TWI628257B - Separator film laminated optical film with adhesive layer - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical film with an adhesive layer which is less indentation under pressure, and particularly has an excellent effect of preventing damage and dents caused by foreign matter during storage, transportation or transportation.

The optical film of the adhesive layer of the laminated separation membrane of the present invention comprises: a separation membrane (C) laminated on at least one side of the optical film (A) via an adhesive layer (B); wherein the separation membrane ( The film thickness of C) is 45 μm or more, and the film thickness of the optical film (A) is 100 μm or less.

Description

An optical film with an adhesive layer attached to the separation membrane

The present invention relates to an optical film of an adhesive layer of a laminated separation film.

An optical film typified by a polarizing plate in which a transparent resin film is bonded to a single surface or a two-layer layer of a polarizing material is widely used as an optical member constituting an image display device such as a liquid crystal display device. In many cases, an optical film such as a polarizing plate or a retardation film is formed as an "optical film with an adhesive layer" provided with an adhesive layer on one surface thereof, and is often formed via the adhesive layer. It is used by being bonded to a display element such as a liquid crystal cell or an organic EL display element. In such an optical film with an adhesive layer, in order to protect the adhesive layer before the display member, a separator film is usually laminated, which is peeled off when the adhesive layer is used (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2009/069799

In recent years, the image display device tends to be thinner, and therefore, the optical film system is expected to have a thickness of, for example, 100 μm or less. An adhesive film is provided on such a thin optical film, and a separation film is laminated thereon to form an optical film (an optical film with an adhesive layer attached to the separation film). In many cases, it is wound into a roll. Store, transport or transport in a state of shape. In this case, when the optical film with the adhesive layer of the laminated separation film is wound in a state in which foreign matter such as dust adheres to the outer surface of the separation membrane, the film is stored under pressure. When the optical film is pressed during transportation or transportation, damage or dents due to foreign matter remain on the optical film even after the pressure is removed. Further, there is a case where the optical film attached to the adhesive layer of the laminated separation film is cut into a size corresponding to the size of the display element to which it is attached, and stored and transported. In this case, if foreign matter is present between the optical films of the pressure-sensitive adhesive layer deposited in the laminated separation film, damage or dents due to foreign matter remain on the optical film. Such a damage or a dent caused by a foreign matter causes defects in the optical properties of the optical film. Therefore, a laminated separation film having a high degree of "damage to the optical film due to foreign matter and prevention of dents" is required. An optical film with an adhesive layer attached thereto.

Accordingly, it is an object of the present invention to provide an optical film which is adhered to an adhesive layer of a laminated separation film, which has less depression under pressure, particularly for damage caused by foreign matter during storage, transportation or handling. The prevention of the marks is good.

The inventors of the present invention have completed the present invention in order to solve the above problems and have intensively reviewed the results.

That is, the present invention includes the following preferred aspects [1] to [3].

[1] An optical film comprising an adhesive layer of a laminated separation film, comprising: a separation membrane (C) laminated on at least one side of an optical film (A) via an adhesive layer (B); wherein the separation membrane The film thickness of (C) is 45 μm or more, and the film thickness of the optical film (A) is 100 μm or less.

[2] The optical film of the adhesive layer of the laminated separation membrane according to [1], wherein the separation membrane (C) is a separation membrane having a Vickers hardness of 15 or more on the surface.

[3] The optical film of the adhesive layer of the laminated separation membrane according to [1] or [2], wherein the separation membrane (C) is a separation membrane having a bending rigidity of 1 mg or more.

[4] The optical film of the adhesive layer of the laminated separation film according to any one of [1] to [3] wherein the storage elastic modulus G' of the adhesive layer (B) at 25 ° C is 0.4MPa or less.

According to the present invention, it is possible to provide an optical film which is adhered to an adhesive layer of a laminated separation film, which has less depression under pressure, particularly for damage or dent caused by foreign matter during storage, transportation or handling. Prevents good results.

1‧‧‧ Optical film with adhesive layer attached to the separation membrane

2‧‧‧ polarizer

3‧‧‧(1) Resin film

4‧‧‧(2nd) resin film

5‧‧‧Protective film

6‧‧‧hard coating

10‧‧‧Optical film

20‧‧‧Adhesive layer

30‧‧‧Separation membrane

Fig. 1 is a schematic cross-sectional view showing an example of an optical film of an adhesive layer of a laminated separation membrane of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of an optical film of an adhesive layer of a laminated separation membrane of the present invention.

<Optical film with adhesive layer attached to laminated film>

An optical film of an adhesive layer of a laminated separation film of the present invention, comprising: an optical film (A); and a separation film laminated on at least a surface of the optical film (A) via an adhesive layer (B) C).

In the optical film with the adhesive layer of the laminated separation membrane of the present invention, the separation membrane (C) has a thickness of 45 μm or more. When the film thickness of the separation membrane (C) is less than 45 μm, the depression caused by foreign matter or the like adhering to the surface of the separation membrane easily spreads to the adhesive layer, and it is difficult to sufficiently ensure the damage to the optical film and the prevention of the dent. . In the optical film with the adhesive layer of the laminated separation membrane of the present invention, the thickness of the separation membrane (C) is preferably 45 μm or more, more preferably 47 μm or more, and particularly preferably 50 μm or more. The upper limit of the film thickness of the separation membrane (C) is not particularly limited, but is usually 200 μm or less. From the viewpoint of facilitating peeling at the time of peeling off the separation membrane, for example, it is preferably 150 μm or less, more preferably 100 μm. the following.

In the optical film with the adhesive layer of the laminated separation film of the present invention, the film thickness of the optical film (A) is 100 μm or less. In the optical film with the adhesive layer of the laminated separation membrane of the present invention, the thickness of the optical film (A) is preferably 80 μm or less, more preferably 70 μm or less. Film of optical film (A) The lower limit of the thickness is usually 5 μm or more, and is preferably 10 μm or more, and more preferably 15 μm or more from the viewpoint of easy handling.

In the present invention, the optical film refers to a film that functions for image display (display screen or the like) (for example, a film that functions to improve visibility of an image), and means that it can be incorporated. A film having various optical characteristics in an image display device such as a liquid crystal display device may be, for example, a single layer structure (a polarizing member, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light collecting film, etc.). The optical functional film or the like may be a multilayer structure (for example, a polarizing plate, a phase difference plate, or the like).

In the present invention, the "film thickness of the optical film (A)" means the thickness of the single layer when the optical film has a single layer structure, and the thickness of all the layers constituting the multilayer structure when it is a multilayer structure. Sum. In addition, when the optical film has a multilayer structure, when the optical film is incorporated in an optical laminate or a display device, a layer (for example, a protective film or the like) which is finally removed by peeling off is not considered to constitute an optical film (A). The layer is not considered when calculating the film thickness of the optical film (A). Therefore, for example, in the optical film with the adhesive layer of the laminated separation film of the present invention shown in Fig. 1, the thickness of the optical film (A) is the polarizer 2, the first resin film 3, and the second resin film. The total thickness of 4. Further, in the optical film with the adhesive layer of the laminated separation film of the present invention shown in Fig. 2, the film thickness of the optical film (A) is the polarizer 2, the first resin film 3, and the second resin film 4. And the total thickness of the hard coat layer 6.

In the present invention, the thicker the film thickness of the separation membrane (C), the higher the effect of preventing damage due to foreign matter and the dent, and the film thickness of the optical film (A) is obtained. The balance can effectively improve the prevention of damage and dents caused by foreign matter. For example, the ratio (T _C /T _A ) of the film thickness T _{C of the} separation membrane to the film thickness T _A of the optical film is preferably 0.4 or more, more preferably 0.5 or more, still more preferably 0.6 or more. This ratio (T _C /T _A ) is usually 4 or less.

The optical film of the adhesive layer of the laminated separation membrane of the present invention includes the optical film (A) and a separation membrane (C) laminated on at least one surface of the optical film (A) via the adhesive layer (B). Further, the configuration may have a usual function of the optical film, that is, the configuration is not limited. The optical film is preferably a polarizing plate, a polarizing member, a phase difference plate or a retardation film, and particularly preferably a polarizing plate or a polarizing member.

For example, when the configuration of a preferred embodiment of the present invention is described with reference to FIGS. 1 and 2, the optical film 1 with the adhesive layer of the laminated separation film shown in Fig. 1 is optical. The film 10 and the separation film 30 laminated on one surface of the optical film via the adhesive layer 20 are formed. Further, in the optical film 10, the resin films 3 and 4 are laminated on both sides of the polarizer 20, and the area of the resin film 4 opposite to the polarizer 2 on the side opposite to the resin film having the adhesive layer 20 is not in contact with the polarizer 2. Layer protective film 5. Further, the optical film 1 with the adhesive layer of the laminated separation film shown in Fig. 2 is composed of an optical film 10 and a separation film 30 laminated on one surface of the optical film via the adhesive layer 20, and optical. In the film 10, resin films 3 and 4 are laminated on both sides of the polarizing member 20, and an area layer hard coat layer of the resin film 4 on the opposite side to the resin film having the adhesive layer 20 is not in contact with the polarizing member 2. 6. Further, a protective film 5 is laminated on the hard coat layer 6. Further, the resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer (not shown).

The respective layers (members) of the "optical film to which the adhesive layer of the laminated layer is adhered" of the present invention are not particularly limited, and can be appropriately determined in accordance with the characteristics of a desired optical film. Hereinafter, the respective constituents of the "optical film with the adhesive layer of the laminated separation film" of the present invention will be described in detail.

[1] optical film (A) [1-1] Polarizer

In the present specification, the polarizing plate refers to a resin film or a resin layer in at least one area of the polarizing material. The polarizer refers to a film having a property of absorbing a linearly polarized light having a vibration plane parallel to its absorption axis and penetrating a linearly polarized light having a vibration plane perpendicular to its absorption axis (parallel to the transmission axis). For example, a film obtained by adsorbing a dichroic dye to a polyvinyl alcohol-based resin film can be used. Examples of the dichroic dye include iodine and a dichroic organic dye.

The polyvinyl alcohol-based resin can usually be obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may, for example, be a polyvinyl acetate which is a homopolymer of vinyl acetate; a monomer copolymerizable with vinyl acetate (for example, an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated) A copolymer of sulfonic acid, (meth)acrylamide having an ammonium group, and the like, and a copolymer of vinyl acetate.

The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 100 mol%, preferably about 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, an aldehyde-modified polyvinyl formal (polyvinyl) Formal) or polyvinyl acetal. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, preferably from about 1,500 to 5,000. Further, the average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.

Usually, a film made of a polyvinyl alcohol-based resin as a raw material film of a polarizer can be used. The polyvinyl alcohol-based resin can be formed into a film by a known method. The thickness of the raw material film is usually from 1 to 150 μm, and is preferably 10 μm or more in view of easiness of stretching and the like.

The polarizer is, for example, a step of stretching the raw material film by one axis, a step of dyeing the film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with an aqueous boric acid solution, and a step of washing the film, and finally It is made by drying it. In the present invention, the thickness of the polarizer is usually from 1 to 50 μm, and from the viewpoint of film formation of the optical film, it is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less.

The polarizer in which the dichroic dye is adsorbed to the polyvinyl alcohol-based resin film can be obtained by the method of the following 1), or can be obtained by the following method 2): 1) A single film of a polyvinyl alcohol-based resin film is used as a raw material film, and the film is subjected to a one-axis stretching treatment and a dyeing treatment of a dichroic dye; and 2) a coating liquid containing a polyvinyl alcohol-based resin is applied to the substrate film ( After drying the aqueous solution or the like to obtain a base film having a polyvinyl alcohol-based resin layer, the substrate film is stretched together with the base film, and a dichroic dye is applied to the stretched polyvinyl alcohol-based resin layer. The dyeing treatment is followed by a method of peeling off the substrate film. As the base film, a thermoplastic resin similar to the thermoplastic resin which can constitute a resin film described later can be used. membrane. A film composed of the following resin or the like is preferably a polyester resin such as polyethylene terephthalate, a polycarbonate resin such as a polycarbonate resin or triethyl fluorenyl cellulose, or a decene-based resin. A cyclic polyolefin resin, a polystyrene resin, or the like. According to the method of the above 2), the production of the polarizer of the film can be facilitated, and for example, the polarizer having a thickness of 7 μm or less can be easily produced.

The resin film may be, for example, a film composed of a resin having light transmissivity (preferably optically transparent), for example, a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.), A polyolefin resin such as a cyclic polyolefin resin (such as a decene-based resin); a fiber-based resin (such as a cellulose ester resin); a polyester resin (polyethylene terephthalate or polyethylene naphthalate) Ethylene glycol, polybutylene terephthalate, etc.); polycarbonate resin (for example, polycarbonate derived from bisphenol such as 2,2-bis(4-hydroxyphenyl)propane); Acrylic resin; styrene resin; polyether ether ketone resin; polyfluorene resin, or a mixture or copolymer thereof. In particular, the resin film is preferably a film composed of a cyclic polyolefin resin, a polycarbonate resin, a fiber resin, a polyester resin, a (meth)acrylic resin, or the like, and particularly preferably a fiber resin. And a film composed of a cyclic polyolefin resin or the like.

The chain-like polyolefin resin may, for example, be a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin, or a copolymer composed of two or more kinds of chain olefins.

The cyclic polyolefin resin contains decene, tetracyclododecane (alias: dimethanooctahydronaphthalene) Or a generic term for the resin in which the derivative is a representative cyclic olefin as a polymerization unit. Examples of the cyclic polyolefin-based resin include a ring-opened (co)polymer of a cyclic olefin, a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin, and a chain olefin such as ethylene or propylene. A copolymer of a vinyl aromatic compound, and a modified (co)polymer modified with an unsaturated carboxylic acid or a derivative thereof. Among these, a norbornene-based resin having a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is preferably used.

The cellulose resin is preferably a cellulose ester resin, that is, a partially or fully esterified cellulose, and the like, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. . Among these, triethyl fluorenyl cellulose, diethyl acetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are more preferable.

The polyester resin is a resin other than the cellulose ester resin having an ester bond, and is generally composed of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. , propylene naphthalate, dimethyl dimethyl terephthalate, cyclohexane dimethyl phthalate, and the like.

The polycarbonate resin is a polyester formed of carbonic acid and a diol or bisphenol. Among these, from the viewpoint of heat resistance, weather resistance, and acid resistance, an aromatic polycarbonate having a diphenyl alkane in a molecular chain is preferred. Polycarbonate, for example, from 2,2-bis(4-hydroxyphenyl)propane (alias: Bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutyl A polycarbonate derived from a bisphenol such as an alkane or a 1,1-bis(4-hydroxyphenyl)ethane.

The (meth)acrylic resin which can constitute a resin film may be a polymer mainly composed of a constituent unit derived from methacrylate (for example, 50% by weight or more thereof), and is preferably copolymerized with other copolymerized components. a copolymer. The (meth)acrylic resin may contain two or more constituent units derived from methacrylate. The methacrylate may, for example, be a C ₁ to C ₄ alkyl methacrylate such as methyl methacrylate, ethyl methacrylate or butyl methacrylate.

As the copolymerization component which can be copolymerized with a methacrylate, an acrylate is mentioned, for example. The acrylate is preferably a C ₁ to C ₈ alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. Specific examples of the other copolymerization component include unsaturated carboxylic acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyltoluene; ) vinyl cyanide such as acrylonitrile; unsaturated carboxylic anhydride such as maleic anhydride or methyl maleic anhydride; unsaturated phenyl maleimide, cyclohexyl maleimide, etc. A compound other than an acrylate having one polymerizable carbon-carbon double bond in a molecule such as quinone. The copolymerization component may be used singly or in combination of two or more.

The (meth)acrylic resin has a ring structure in the polymer main chain from the viewpoint of improving the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic quinone imine structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include, for example, a glutaric anhydride structure and a succinic anhydride structure, and specific examples of the cyclic quinone imine structure include a glutarylene imine structure and an amber quinone structure, and a lactone ring structure. Specific examples thereof include a butyrolactone ring structure and a valerolactone ring structure.

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film forming properties of the film, impact resistance of the film, and the like. The acrylic rubber particles are particles in which an elastic polymer mainly composed of acrylate is regarded as an essential component, and for example, a single-layer structure consisting essentially of only the elastic polymer or an elastic polymer is used. Made of a multi-layered structure of one layer. Examples of the elastic polymer include a crosslinked elastic copolymer in which an alkyl acrylate is used as a main component and which is copolymerized with another vinyl monomer and a crosslinkable monomer copolymerizable therewith. The alkyl acrylate which is a main component of the elastic polymer may, for example, be a C ₁ to C ₈ alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. The alkyl group preferably has 4 or more carbon atoms.

The other vinyl monomer copolymerizable with the acrylate may, for example, be a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, a methacrylate such as methyl methacrylate. For example, an aromatic vinyl compound such as styrene, a vinyl cyanide such as (meth)acrylonitrile or the like. The crosslinkable monomer may, for example, be a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, for example, ethylene glycol di(meth)acrylate or butanediol (meth) acrylate such as di(meth)acrylate or the like (meth) acrylate such as allyl (meth) acrylate, divinyl benzene or the like.

The content of the acrylic rubber particles is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more based on 100 parts by mass of the (meth)acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, the solvent resistance to the organic solvent in the surface treatment agent may be lowered. Therefore, the content of the acrylic rubber particles is usually 80 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the (meth)acrylic resin.

The resin film may contain additives conventional in the technical field of the present invention. Examples of the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, a heat stabilizer, and the like. The ultraviolet absorber may, for example, be a salicylate compound, a benzophenone compound, a benzotriazole compound, a triazine compound, a cyano (meth) acrylate compound, a nickel wrong salt or the like.

The resin film may be an unstretched film or a film extending through one or two axes. The resin film may be a protective film for protecting the polarizer, or may be a protective film having an optical function as a retardation film to be described later. Further, when the polarizing plate includes a plurality of resin films, the resin films may be the same or different films.

Further, the resin film may have a surface treatment layer such as a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, an antifouling layer, a conductive layer, or the like on the outer surface thereof (the surface opposite to the polarizing member). (coating layer). The thickness of the resin film is usually from 1 to 70 μm, preferably from 5 to 50 μm, and further preferably from 30 μm or less.

The resin film can be bonded to the polarizer via an adhesive layer or an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive or an active energy ray-curable adhesive can be used.

The water-based adhesive agent may, for example, be a conventional water-based adhesive (for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsifier, an aldehyde compound, an epoxy compound, or a melamine system). a compound, a methylol compound, an isocyanate compound, an amine compound, a crosslinking agent such as a polyvalent metal salt, or the like). Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be suitably used. Further, when a water-based adhesive is used, it is preferred to carry out a drying step in order to remove water contained in the water-based adhesive after bonding the polarizer and the resin film. After the drying step, a ripening step of, for example, aging at a temperature of about 20 to 45 ° C may be provided.

The active energy ray-curable adhesive agent is an adhesive which is cured by irradiation with an active energy ray such as ultraviolet rays or electron beams, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, and a photoreaction. The curable composition of the resin, the curable composition containing the binder resin and the photoreactive crosslinking agent, and the like are preferably an ultraviolet curable adhesive.

When an active energy ray-curable adhesive is used, after the polarizer and the resin film are bonded, a drying step is performed as needed, and then a hardening step of curing the active energy ray-curable adhesive by irradiating the active energy ray is performed. The light source of the active energy ray is not particularly limited, but is preferably an ultraviolet ray having a light-emitting distribution at a wavelength of 400 nm or less.

The method of bonding the polarizer and the resin film may be, for example, a method of performing surface activation treatment such as saponification treatment, corona treatment, or plasma treatment on at least one of the bonding surfaces. When the resin film is bonded to both surfaces of the polarizer, the adhesive for bonding the resin films may be the same type of adhesive or may be a different type of adhesive.

For the polarizing plate, other films or layers may be laminated. In addition to the retardation film described later, there are also a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-concentrating film, an adhesive layer other than the adhesive layer (B), a coating layer, and protection. Membrane and the like. The protective film is a film which is used for the purpose of protecting the surface of the optical film such as a polarizing plate from damage and contamination, and is generally removed by attaching the optical film of the adhesive layer to, for example, a metal layer or a substrate. It.

The protective film is usually composed of a base film and an adhesive layer laminated thereon. The base film may be a thermoplastic resin (for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; or a polycarbonate resin; Resin; (meth)acrylic resin, etc.).

[1-2] phase difference plate

In the present specification, the retardation plate refers to a resin film or a resin layer in at least one area of the retardation film. The retardation film included in the retardation film is an optical film exhibiting optical anisotropy, and may be a stretched film obtained by extending a resin film composed of the following resin to about 1.01 to 6 times: The thermoplastic resin exemplified above for the resin film Further, for example, a polyvinyl alcohol resin, a polyarylate resin, a polyimide resin, a polyether oxime resin, a polyfluoroethylene/polymethyl methacrylate resin, or a liquid crystal polyester system may be mentioned. Resin, ethylene-vinyl acetate copolymer saponified product, polyvinyl chloride resin, or the like. Among these, a polycarbonate film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is preferably a stretched film which is formed by one-axis stretching or biaxial stretching. Further, in the present specification, a zero retardation film is also included in the retardation film (it can be used only as a protective film). Further, a film called a one-axis retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, or the like can also be suitably used as the retardation film.

The zero retardation film refers to a film in which the in-plane retardation value R _e and the thickness direction retardation value R _th are both -15 to 15 nm. This retardation film is suitable for use in an IPS mode liquid crystal display device. The in-plane phase difference value R _e and the thickness direction phase difference R _{th are} preferably from -10 to 10 nm, more preferably from -5 to 5 nm. Here, the in-plane phase difference value R _e and the thickness direction phase difference value R _th refer to a value at a wavelength of 590 nm.

The in-plane phase difference value R _e and the thickness direction phase difference value R _th are respectively defined by the following formula: R _e =(n _x -n _y )×d R _th =[(n _x +n _y )/2- n _z ] × d where n _x is the refractive index in the slow axis direction (x-axis direction) in the film plane, and n _y is the fast axis direction in the film plane (the y-axis direction perpendicular to the x-axis in the plane) The refractive index, n _z is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the thickness of the film.

For the zero retardation film, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin or a cyclic polyolefin resin, a polyethylene terephthalate resin or a (meth)acrylic resin can be used. A resin film made of a resin or the like. In particular, since it is easy to control the phase difference and it is easy to obtain, a cellulose resin, a polyolefin resin, or a (meth)acrylic resin is preferably used.

In addition, a film which exhibits optical anisotropy by coating/alignment of a liquid crystal compound or a film which exhibits optical anisotropy by application of an inorganic layered compound can also be used as a retardation film. Such a retardation film is known as a temperature-compensated retardation film, and a rod-shaped liquid crystal sold by JX Nippon Mining & Energy Co., Ltd. under the trade name "NH FILM" is obliquely aligned. A disc-shaped liquid crystal sold by Fujifilm Co., Ltd. under the trade name "WV FILM" is a tilt-aligned film, and a full two-axis alignment type sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC FILM". The film is a biaxial alignment type film which is sold by Sumitomo Chemical Co., Ltd. under the trade name "new VAC FILM". Further, the resin film laminated on at least one surface of the retardation film may be, for example, the above-mentioned protective film.

[2] Adhesive layer (B)

The adhesive which constitutes the adhesive layer (B) (the adhesive layer 20 in FIGS. 1 and 2) which is laminated on at least one surface of the optical film (A) of the present invention can be used without any particular limitation. As the known adhesive, for example, an acrylic type, a rubber type, an urethane type, a silicone type, or the like can be used. An adhesive for a matrix polymer such as a polyvinyl ether. Further, it may be an energy ray-curable adhesive or a thermosetting adhesive. Among these, an adhesive which is excellent in transparency, adhesion, reworkability, weather resistance, heat resistance, and the like as a matrix polymer is suitable. In a preferred embodiment of the present invention, the adhesive layer (B) is composed of an adhesive composition comprising a (meth)acrylic resin (a), a crosslinking agent (b), and a decane compound (c). The reaction product is composed.

[2-1] (Meth)acrylic resin (a)

In the present invention, the (meth)acrylic resin (a) which may be contained in the adhesive composition constituting the adhesive layer (B) is preferably one represented by the following formula (I) (A) a structural unit of an alkyl acrylate (hereinafter also referred to as a structural unit (I)) as a main component (for example, a polymer containing 50% by weight or more) (hereinafter also referred to as "(meth) acrylate polymer") :

(wherein R ¹⁰ represents a hydrogen atom or a methyl group, and R ²⁰ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may have any of a linear, branched or cyclic structure, and the hydrogen atom of the alkyl group It can be substituted by an alkoxy group having 1 to 10 carbon atoms).

In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)" such as (meth) acrylate has the same meaning.

The (meth) acrylate represented by the formula (I) may, for example, be propylene. Methyl ester, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate , isooctyl acrylate, 2-ethylhexyl acrylate, n- and iso-decyl acrylate, n-decyl acrylate, isodecyl acrylate, n-dodecyl acrylate, cyclohexyl acrylate, isodecyl acrylate, Stearyl acrylate, 3 butyl acrylate, and the like. Examples of the alkoxy group-containing alkyl acrylate include 2-methoxyethyl acrylate and ethoxymethyl acrylate.

The (meth) acrylate polymer may further contain two or more types of structural units (I). Further, from the viewpoint of simultaneously establishing adhesion and durability, it is preferred that the glass transition temperature T _g of the structural unit and the homopolymer having a glass transition temperature T _{g of the} homopolymer of 0 ° C or more is less than 0 ° C. Copolymer of the structural unit. The structural unit having a glass transition temperature (T _g ) of the homopolymer of 0 ° C or higher may, for example, be methyl acrylate, cyclohexyl acrylate or isodecyl acrylate. From the viewpoint of durability, acrylic acid is preferred. Methyl ester or isodecyl acrylate. The structural unit of the homopolymer having a glass transition temperature _{Tg of} less than 0 ° C may, for example, be ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, acrylic acid. n-Hexyl ester, isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, n-decyl acrylate, isodecyl acrylate, N-dodecyl acrylate or the like, which preferably contains n-butyl acrylate or 2-ethylhexyl acrylate, and particularly preferably contains n-butyl acrylate.

(meth) acrylate polymer, may also contain structural units A structural unit derived from another monomer other than (I). The structural unit derived from another monomer may be one type or two or more types. Specific examples of other monomers which the (meth) acrylate polymer may contain are shown below.

1) Monomers with polar functional groups

The (meth) acrylate polymer may comprise a structural unit derived from a monomer having a polar functional group. The monomer having a polar functional group may, for example, be a (meth) acrylate having a polar functional group. The polar functional group may, for example, be a hydroxyl group, a carboxyl group, a substituted amino group, an unsubstituted amino group or the like. The polar functional group may, for example, be a heterocyclic group such as an epoxy group. The (meth) acrylate having such a polar functional group may, for example, be 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or 4-hydroxy(meth)acrylate. Butyl ester, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate a monomer having a hydroxyl group such as diethylene glycol mono(meth)acrylate; acryloylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, (meth)acrylic acid Tetrahydrofuran methyl ester, caprolactone-modified methyl tetrahydrofuran methyl ester, 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc. a monomer of a heterocyclic group; an aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, etc. Or an unsubstituted amino group monomer; a monomer having a carboxyl group such as (meth)acrylic acid or carboxyethyl (meth)acrylate. Among them, a monomer having a hydroxyl group is more preferably a hydroxyl group from the viewpoint of reactivity of the (meth)acrylic resin (a) and the crosslinking agent. (Meth) acrylate.

In the (meth) acrylate polymer, the other monomer having a polar functional group may be contained in combination with the (meth) acrylate having a hydroxyl group, but from the separation film which prevents the layer which can be deposited on the outer surface of the adhesive layer From the viewpoint of the peeling force, it is preferred that the monomer having an amine group is not substantially contained. Here, "substantially not included" means 1.0 part by mass or less of 100 parts by mass of all constituent units constituting the (meth)acrylic resin (a). Further, from the viewpoint of improving the corrosion resistance to a transparent electrode such as ITO, it is preferred that the monomer having a carboxyl group is not substantially contained. Here, "substantially not included" means 2.0 parts by mass or less of 100 parts by mass of all constituent units constituting the (meth)acrylic resin (a).

The content of the structural unit derived from the monomer having a polar functional group in the (meth) acrylate polymer is preferably 20 parts by mass or less based on 100 parts by mass of all the constituent units of the (meth) acrylate polymer. It is more preferably 0.1 parts by mass or more and 20 parts by mass or less, still more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 10 parts by mass or less.

2) Monomers having an aromatic group

The (meth) acrylate polymer may contain a structural unit derived from a monomer having an aromatic group. The monomer having an aromatic group may, for example, have one (meth)acryl fluorenyl group and one or more aromatic rings (for example, a benzene ring or a naphthalene ring) in the molecule and have a phenyl group, a phenoxyethyl group or a benzyl (meth) acrylate. By including these structural units, polarization during endurance testing can be suppressed The white spot phenomenon of the board.

The (meth) acrylate having a phenoxyethyl group may, for example, be 2-phenoxyethyl (meth)acrylate or 2-(2-phenoxyethoxy)ethyl (meth)acrylate. Ethylene oxide-modified nonylphenolate of (meth)acrylic acid, 2-(o-phenylphenoxy)ethyl (meth)acrylate, and the like. The structural unit having a benzyl group may, for example, be benzyl acrylate or the like. Among them, from the viewpoint of suppressing white spots, 2-phenoxyethyl (meth)acrylate and 2-(2-phenoxyethoxy)ethyl (meth)acrylate are preferred.

The content of the structural unit derived from the aromatic group-containing monomer in the (meth) acrylate polymer is preferably 50 parts by mass or less based on 100 parts by mass of all the constituent units of the (meth) acrylate polymer. It is more preferably 4 parts by mass or more and 50 parts by mass or less, and still more preferably 4 parts by mass or more and 25 parts by mass or less.

3) Acrylamide monomer

The (meth) acrylate polymer may comprise a structural unit derived from a monomer having a acrylamide group. The monomer having a acrylamide group may, for example, be N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, N-( 4-hydroxybutyl) acrylamide, N-(5-hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl decylamine, N,N- Diethyl acrylamide, N-isopropyl acrylamide, N-(3-dimethylaminopropyl) acrylamide, N-(1,1-dimethyl-3-oxetyl butyl Base) acrylamide, N-[2-(2-o-oxy-1-imidazolidinyl)ethyl]propenylamine, 2-propenylamino-2-methyl-1-propane sulfonic acid, N-(methoxymethyl) acrylamide, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(1-methylethoxymethyl)propenylamine, N-(1-methyl Propyloxymethyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide [alias: N-(isobutylmethyl) acrylamide], N-(butoxymethyl) Acrylamide, N-(1,1-dimethylethoxymethyl)propenylamine, N-(2-methoxyethyl)propenylamine, N-(2-ethoxyethyl) Acrylamide, N-(2-propoxyethyl)propenylamine, N-[2-(1-methylethoxy)ethyl]propenylamine, N-[2-(1-methyl) Propyl)ethyl]propenylamine, N-[2-(2-methylpropoxy)ethyl]propenylamine [alias: N-(isobutoxyethyl) acrylamide], N -(2-Butoxyethyl) acrylamide, N-[2-(1,1-dimethylethoxy)ethyl]acrylamide, and the like. By including these structural units, it is possible to suppress the bleeding of an additive such as an antistatic agent. Among them, N-(methoxymethyl) acrylamide, N-(ethoxymethyl) acrylamide, N-(propoxymethyl) acrylamide, N-(butoxy) are preferably used. Methyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide, and the like.

Further, the structural unit derived from another monomer other than the structural unit (I) may, for example, be a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, or a plurality of (methyl) molecules derived from the molecule. A structural unit of a monomer of an acrylonitrile group.

The styrene monomer may, for example, be styrene; for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl An alkyl styrene such as styrene, butyl styrene, hexyl styrene, heptyl styrene or octyl styrene; such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene, etc. Styrene; nitrostyrene; ethenyl styrene; methoxy phenyl Alkene; and divinylbenzene.

Examples of the vinyl monomer include vinyl acetate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; and halogenation of ethylene chloride or ethylene bromide. Ethylene; vinyl halide such as vinylidene chloride; nitrogen-containing heteroaromatic ethylene such as vinylpyridine, vinylpyrrolidone or vinylcarbazole; conjugated diene such as butadiene, isoprene, chloroprene, etc. ; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The monomer having a plurality of (meth) acrylonitrile groups in the molecule may, for example, be 1,4-butanediol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate. 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, a monomer having two (meth) acrylonitrile groups in a molecule such as tripropylene glycol di(meth)acrylate; and three (meth) acrylonitrile in a molecule such as trimethylolpropane tri(meth)acrylate Base monomer and the like.

The weight average molecular weight (Mw) of the (meth)acrylic resin (a) is preferably from 500,000 to 2,500,000. When the weight average molecular weight is 500,000 or more, the durability of the adhesive layer in a high-humidity heat environment can be improved. When the weight average molecular weight is 2.5 million or less, the handleability at the time of applying the adhesive solution is improved. The molecular weight distribution (Mw/Mn) expressed by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2 to 10. The weight average molecular weight can be analyzed by a gel permeation chromatography (GPC), which is a value converted to standard polystyrene.

The (meth)acrylic resin (a) is dissolved in ethyl acetate When the solution has a concentration of 20% by weight, the viscosity at 25 ° C is preferably 20 Pa‧s or less, more preferably 0.1 to 15 Pa‧s. The viscosity of such a range is advantageous for improving the durability of the optical film with the adhesive layer and the optical laminate including the same, and is advantageous for the reworkability of the optical film with the adhesive layer. The above viscosity can be measured by a Brookfield viscometer.

The glass transition temperature of the (meth)acrylic resin (a) is preferably from -10 ° C to -60 ° C from the viewpoint of establishing both adhesion and durability. Further, the glass transition temperature can be measured by a differential scanning calorimeter (DSC).

The (meth)acrylic resin (a) can be usually produced by a conventional polymerization method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. In the production of the (meth)acrylic resin (a), polymerization is usually carried out in the presence of a polymerization initiator. The amount of the polymerization initiator to be used is usually 0.001 to 5 parts by mass based on 100 parts by mass of the total of all the monomers constituting the (meth)acrylic resin (a). The (meth)acrylic resin (a) can be produced, for example, by a method of polymerizing with an active energy ray such as ultraviolet rays.

The polymerization initiator may, for example, be a thermal polymerization initiator, a photopolymerization initiator or the like. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone or the like. The thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis (cyclohexane) Alkan-1--1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy Azoline such as valeronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) a compound such as lauryl peroxide, tert-butyl peroxide, benzammonium peroxide, butyl benzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, peroxide Organic peroxides such as dipropyl carbonate, 3:butyl peroxy neodecanoate, 3 butyl peroxypivalate, and 3,5,5-trimethylhexyl peroxide; such as persulfuric acid An inorganic peroxide such as potassium, ammonium persulfate or hydrogen peroxide. Further, a redox initiator such as a peroxide and a reducing agent may be used as a polymerization initiator.

The (meth)acrylic resin (a) is preferably produced by a solution polymerization method. Specifically, a desired monomer is mixed with an organic solvent, and a thermal polymerization initiator is added to the resulting solution under a nitrogen atmosphere. The obtained mixture is stirred at about 40 to 90 ° C (preferably about 60 to 80 ° C) for about 3 to 10 hours to obtain a (meth) acrylate polymer. In order to control the polymerization reaction, the monomer, the thermal polymerization initiator, or both may be added to the reaction system continuously or intermittently in the polymerization reaction, or may be added in a state of being dissolved in an organic solvent. The organic solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene; an ester solvent such as ethyl acetate or butyl acetate; an aliphatic alcohol solvent such as propanol or isopropanol; such as acetone or methyl ethyl ketone; A ketone solvent such as methyl isobutyl ketone.

The (meth)acrylic resin (a) may contain two or more kinds of (meth)acrylate polymers. Such a (meth) acrylate polymer may, for example, be a lower molecular weight having a structural unit (I) derived from (meth) acrylate as a main component and having a weight average molecular weight of 50,000 to 300,000 ( Methyl) acrylate polymer.

[2-2] Crosslinking agent (b)

The adhesive composition forming the adhesive layer (B) preferably contains a crosslinking agent (b). The crosslinking agent (b) may, for example, be a conventional crosslinking agent (for example, an isocyanate compound, an epoxy compound, an aziridine compound, a metal clamp, a peroxide, etc.), particularly from an adhesive composition. The isocyanate compound is preferable from the viewpoint of the pot life and the durability of the optical film with the adhesive layer, the crosslinking speed, and the like.

The isocyanate compound is preferably a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include an aliphatic isocyanate compound (for example, hexamethylene diisocyanate) and an alicyclic isocyanate compound (for example). Isophorone diisocyanate), an aromatic isocyanate compound (for example, tolyl diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthene Diisocyanate, triphenylmethane triisocyanate, etc.). Further, the crosslinking agent (b) may be an adduct of a polyol compound of the above isocyanate compound (for example, an adduct such as glycerol or trimethylolpropane) or an isocyanurate. a compound, a biuret type compound; an amine obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, or the like A derivative of an ester prepolymer type isocyanate compound or the like. The crosslinking agent (b) may be used singly or in combination of two or more. Among these, from the viewpoint of durability, tolyl diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like polyol compounds or the trimer isocyanate compounds are preferable.

The ratio of the crosslinking agent (b) may be, for example, 0.01 to 10 parts by mass (for example, 0.05 to 5 parts by mass), preferably 0.1 to 3 parts by mass, per 100 parts by mass of the (meth)acrylic resin (a). (e.g., 0.1 to 2 parts by mass), more preferably 0.1 to 1 part by mass (e.g., 0.1 to 0.8 parts by mass). When it is at most the upper limit value, the durability (peeling resistance) is improved, and when it is at least the lower limit value, the foaming resistance and the reworkability are improved.

[2-3] decane compound (c)

The adhesive composition contains a decane compound (c). Thereby, the adhesiveness of an adhesive layer, a glass substrate, etc. can be improved. Two or more kinds of decane compounds (c) can also be used.

The decane compound (c) may, for example, be vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane or 3-glycidoxypropyltrimethoxy. Baseline, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylethoxymethyl Decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene Methoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

The decane compound (c) may include a polyoxyxene oligomer type. Specific examples of the polyoxymethylene oligomers are as follows: 3-mercaptopropyltrimethoxydecane-tetramethoxydecane oligomer, 3-mercapto group, if the monomers are combined with each other. Propyltrimethoxydecane-tetraethoxydecane oligomer, 3- Mercaptopropyl-containing oligomer such as mercaptopropyltriethoxydecane-tetramethoxydecane oligomer, 3-mercaptopropyltriethoxydecane-tetraethoxydecane oligomer; mercaptomethyl Trimethoxydecane-tetramethoxydecane oligomer, mercaptomethyltrimethoxydecane-tetraethoxydecane oligomer, mercaptomethyltriethoxydecane-tetramethoxydecane oligomer, mercapto group a fluorenylmethyl group-containing oligomer such as methyltriethoxydecane-tetraethoxydecane oligomer; 3-glycidoxypropyltrimethoxydecane-tetramethoxydecane copolymer, 3- Glycidoxypropyltrimethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropyltriethoxydecane-tetramethoxydecane copolymer, 3-epoxypropoxy Propyltriethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropylmethyldimethoxydecane-tetramethoxydecane copolymer, 3-glycidoxypropyl Methyldimethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-glycidoxypropyl Methyldiethoxy hydrazine a copolymer containing 3-glycidoxypropyl group, such as an alkane-tetraethoxydecane copolymer; 3-methacryloxypropyltrimethoxydecane-tetramethoxydecane oligomer, 3- Methyl propylene methoxy propyl trimethoxy decane - tetraethoxy decane oligomer, 3-methacryloxypropyl triethoxy decane - tetramethoxy decane oligomer, 3-methyl Acryloxypropyltriethoxydecane-tetraethoxydecane oligomer, 3-methacryloxypropylmethyldimethoxydecane-tetramethoxydecane oligomer, 3 -Methyl propylene methoxy propyl methyl dimethoxy decane - tetraethoxy decane oligomer, 3-methyl propylene methoxy propyl methyl diethoxy decane - tetramethoxy decane oligo Oligomer, 3-methacryloxypropylmethyldiethoxydecane-tetraethoxydecane oligomer, etc. oligomer containing methacryloxypropyl group; 3-propenyloxy group Propyltrimethoxydecane-tetramethoxydecane oligomer, 3-propenylmethoxypropyltrimethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropyltriethoxy矽-tetramethoxy decane oligomer, 3-propenyl methoxypropyl triethoxy decane-tetramethoxy decane oligomer, 3-propenyl methoxy propyl methyl dimethoxy decane - Tetramethoxydecane oligomer, 3-propenylmethoxypropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropylmethyldiethoxydecane- An acryloxypropyl group-containing oligomer such as a tetramethoxy decane oligomer or a 3-propenyloxypropylmethyldiethoxydecane-tetraethoxydecane oligomer; vinyltrimethoxy Pyridinium-tetramethoxydecane oligomer, vinyltrimethoxydecane-tetraethoxydecane oligomer, vinyltriethoxydecane-tetramethoxydecane oligomer, vinyltriethoxy a decane-tetraethoxy decane oligomer, a vinyl methyl dimethoxy decane-tetramethoxy decane oligomer, a vinyl methyl dimethoxy decane-tetraethoxy decane oligomer, Vinylmethyl Vinyl-containing oligomer such as diethoxynonane-tetramethoxydecane oligomer, vinylmethyldiethoxydecane-tetraethoxydecane oligomer; 3-aminopropyltrimethoxy a decyl-tetramethoxydecane copolymer, a 3-aminopropyltrimethoxydecane-tetraethoxydecane copolymer, a 3-aminopropyltriethoxydecane-tetramethoxydecane copolymer, 3-aminopropyltriethoxydecane-tetraethoxydecane copolymer, 3-aminopropylmethyldimethoxydecane-tetramethoxydecane copolymer, 3-aminopropylmethyl Dimethoxydecane-tetraethoxydecane copolymer, 3-aminopropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-aminopropylmethyldiethoxydecane- An amine group-containing copolymer or the like such as a tetraethoxysilane copolymer.

The content of the decane compound (c) in the adhesive composition, It is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, still more preferably 0.1 to 1 part by mass, per 100 parts by mass of the (meth)acrylic resin (a). Share. When the content of the decane compound (c) is 0.01 parts by mass or more, the effect of improving the adhesion between the pressure-sensitive adhesive layer and the substrate (glass or transparent electrode) is easily obtained. Further, when the content is 10 parts by mass or less, the inhibited decane compound (c) bleeds out from the adhesive layer.

[2-4] Antistatic agent

The adhesive composition forming the adhesive layer (B) may further contain an antistatic agent. By including an antistatic agent, the antistatic property of the optical film adhering to the adhesive layer of the laminated separation film can be improved, and for example, it is possible to suppress a problem caused by static electricity generated when the separation membrane or the protective film is peeled off.

The antistatic agent may, for example, be a conventional one, and is preferably an ionic antistatic agent. The cationic component constituting the ionic antistatic agent may, for example, be an organic cation or an inorganic cation. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a pyrrolidinium cation, a piperidinium cation, a phosphonium cation, a phosphonium cation, and the like. Examples of the inorganic cation include an alkali metal cation such as a lithium cation, a potassium cation, a sodium cation or a phosphonium cation; an alkaline earth metal cation such as a magnesium cation or a calcium cation. The anion component constituting the ionic antistatic agent may be any of an organic anion and an inorganic anion. However, from the viewpoint of excellent antistatic function, an anion component containing a fluorine atom is preferred. The anion component containing a fluorine atom may, for example, be a hexafluorophosphate anion (PF ₆ ^- ), a bis(trifluoromethanesulfonyl) quinone imine anion [(CF ₃ SO ₂ ) ₂ N ^- ], or a bis (fluorosulfonate) Indenyl) anthracene anion [(FSO ₂ ) ₂ N ^- ], tetrakis(pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B ^- ], and the like. These antistatic agents may be used singly or in combination of two or more.

From the viewpoint of good stability of the antistatic function of the adhesive composition, it is preferred to use an ionic antistatic agent which is solid at room temperature. The ratio of the antistatic agent is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.5 to 4 parts by mass, per 100 parts by mass of the (meth)acrylic resin (a).

[2-5] Other ingredients

The adhesive composition forming the adhesive layer (B) may contain one or more solvents, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, and the like. Additives such as pigments, inorganic fillers, light-scattering fine particles, and rust inhibitors. Further, an ultraviolet curable compound is blended in the adhesive composition, and after the adhesive layer is formed, it is cured by irradiation with ultraviolet rays, and is used to form a harder adhesive layer.

The thickness of the adhesive layer is usually 2 to 40 μm, and is preferably 5 to 30 μm, more preferably 10 to 25 μm from the viewpoint of durability, workability, and the like of the optical film with the adhesive layer of the laminated separation film. . When it is at most the upper limit value, the reworkability of the optical film with the adhesive layer of the laminated separation film is improved, and when it is at least the lower limit value, the durability is improved.

The storage elastic modulus of the adhesive layer (B) preferably has a storage elastic modulus G' at 25 ° C of 0.4 MPa or less, more preferably 0.3 MPa or less, and more preferably 0.01 MPa or less. When it is 0.4 MPa or less, the stress relaxation property of the adhesive becomes good, and the shrinkage by the polarizing plate can be alleviated. The upward warpage of the liquid crystal panel (liquid crystal cell bending). On the other hand, when the storage elastic modulus G' is low (for example, 0.4 MPa or less), there is a tendency that dents due to foreign matter tend to occur, but the present invention is controlled by the film thickness of the separation membrane (C). Even when an adhesive layer having a low storage modulus is used, an optical film of an adhesive layer of the laminated separation film having a good dent prevention effect can be provided.

The storage elastic modulus G' at 25 ° C of the adhesive layer (B) can be measured, for example, by the method described in the examples.

The storage elastic modulus G' of the adhesive layer (B) can be formulated by, for example, an adhesive composition constituting the adhesive layer (B) ((meth)acrylic resin, crosslinking agent, polyfunctional active energy The type/amount of the linear hardening type compound is controlled.

[3] Separation membrane (C)

The separation membrane (C) constituting the "optical film with the adhesive layer of the laminated separation membrane" of the present invention preferably has a surface hardness of 15 or more in Vickers hardness. When the Vickers hardness is 15 or more, the separation membrane (C) has a high surface hardness, and even if it is pressurized in a state in which foreign matter adheres to the surface, it is less likely to cause dents, and damage or dents due to foreign matter due to the optical film. Prevents good results. In the present invention, the Vickers hardness of the surface of the separation membrane (C) is preferably 15 or more, more preferably 17 or more, and particularly preferably 19 or more. When the Vickers hardness of the separation membrane (C) is high, since the separation membrane (C) is easily broken, it is usually 200 or less, preferably 150 or less. Further, the Vickers hardness can be measured, for example, according to the method described in the examples.

The surface hardness of the separation membrane (C) can be controlled to a desired range by, for example, selection of a plastic film constituting the separation membrane. Specifically, for example, the strength of the film is increased by increasing the stretching ratio at the time of film formation, or the crystal grain size is increased by slow cooling during film formation, or the molecular weight of the resin to be used is increased. It can increase the surface hardness.

The separation membrane (C) constituting the "optical film with the adhesive layer of the laminated separation membrane" of the present invention preferably has a bending rigidity of 1 mg or more. When the bending rigidity is equal to or higher than the above value, the curl of the optical film can be suppressed. In the present invention, the aforementioned bending rigidity of the separation membrane is more preferably 1.5 mg or more. The upper limit of the bending rigidity of the separation membrane (C) is usually 100 mg or less, preferably 50 mg or less, and more preferably 30 mg or less because the separation membrane can be easily peeled off when the separation membrane is peeled off. Further, the bending stiffness is a value measured by the method described in the examples.

The bending rigidity of the separation membrane (C) can be controlled to a desired range by, for example, the thickness of the plastic film constituting the separation membrane or the film forming conditions (especially, elongation conditions). Specifically, for example, by increasing the thickness of the substrate or increasing the tensile modulus of the substrate, the bending rigidity can be increased.

In the present invention, the separation membrane (C) is preferably composed of a plastic film and a release layer. The plastic film may, for example, be a polyester film such as a polyethylene terephthalate film, a polybutylene terephthalate film or a polyethylene naphthalate film, or a polyolefin film such as a polypropylene film. Among them, from the viewpoint of optical characteristics and quality, a polyethylene terephthalate film is preferable, and further, since the dimensional stability is good, a biaxially stretched polyethylene terephthalate is preferred. membrane. Further, the release layer can be formed, for example, from a composition for forming a release layer, and is formed into a peeling layer. The main component (resin) of the composition for forming a layer is not particularly limited, and examples thereof include a polyoxymethylene resin, an alkyd resin, an acrylic resin, and a long-chain alkyl resin. Among them, polyfluorene oxide resin is preferred.

The polyoxyxylene resin may, for example, be a polyfluorene oxide resin having dimethylpolysiloxane as a basic skeleton. Further, the polyoxyxene resin is an addition reaction type, a condensation reaction type, an ultraviolet curing type, an electron beam curing type, or the like. Among them, the addition reaction type polyoxynoxy resin has the advantages of high reactivity, good productivity, and a small change in peeling force after production, and no curing shrinkage when compared with a condensation reaction type. Preferably.

Specific examples of the above-mentioned addition reaction type polynonoxyl resin include, for example, two or more carbon atoms, allyl groups, propylene groups, and hexenyl groups at the terminal and/or side chain of the molecule having 2 to 10 carbon atoms. Alkenyl organic polyoxane, and the like. When such an addition reaction type polyoxyxylene resin is used, it is preferred to use a crosslinking agent and a catalyst together.

The above-mentioned crosslinking agent may, for example, be an organic polyoxyalkylene having at least two hydrogen atoms bonded to a halogen atom in one molecule, and specific examples thereof include a dimethyl group in which a dimethylhydroquinone group is blocked at the end. a decane-methylhydroquinoxane copolymer, a trimethyl methoxy-terminated dimethyl oxane-methyl hydrazine copolymer, and a trimethyl methoxy-terminated methyl hydrogen Polyoxane, poly(hydrosesquioxanes), and the like.

The catalyst may, for example, be particulate platinum, finely divided platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified platinum chloride acid, chloroplatinic acid olefin complex, palladium, rhodium. A platinum metal compound or the like. By using such a catalyst, peeling layer formation can be performed more efficiently The hardening reaction with the composition.

When a polyxanthene resin is used for the composition for forming a release layer, it is preferred to add a release modifier such as an MQ resin.

Further, in the composition for forming a release layer, an additive may be appropriately formulated. The additive may, for example, be a catalyst, a dye, a dispersant or the like. In addition, in the composition for forming a release layer, a dispersion medium or a solvent may be appropriately contained in order to make the viscosity at the time of application into an appropriate range.

Examples of the dispersion medium or solvent include aromatic hydrocarbons such as toluene, fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone (MEK), and organic solvents such as aliphatic hydrocarbons such as hexane and heptane.

The separation membrane (C) can be produced, for example, by coating a side of a plastic film with a composition for forming a release layer diluted in a solvent by the following method. For example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, an air knife coating method, a roller coating method, a knife coating method, a gate roll coating method, and a die can be mentioned. Coating method, etc. Among these, a gravure coating method and a bar coating method are preferred, and a gravure coating method is more preferred.

Further, the heating/drying method of the composition for forming a release layer may be, for example, a method of performing thermal drying by a hot air drying furnace or the like. The drying temperature is, for example, 50 ° C or more and 150 ° C or less. Moreover, the drying time is, for example, preferably from 10 seconds to 5 minutes.

The film thickness of the separation membrane (C) can be controlled by the thickness of the plastic film and the thickness of the release layer. Among them, the thickness of the plastic film is dominant, and can be controlled by selecting a polyester film having a target thickness. The thickness of the plastic film is preferably 45 μm or more, more preferably 47 μm or more, and still more preferably 50 μm. the above. The upper limit of the film thickness of the plastic film is not particularly limited, and is usually 200 μm or less. From the viewpoint of facilitating peeling at the time of peeling off the separation film, for example, it is preferably 150 μm or less, and more preferably 100 μm or less. The thickness of the release layer (when dried) is preferably from 40 to 300 nm, more preferably from 50 to 200 nm, particularly preferably from 80 to 150 nm. By setting the thickness of the release layer to 40 nm or more, unevenness in peeling force due to fluctuation in the amount of coating can be suppressed, and by making it 300 nm or less, agglomeration can be suppressed.

[4] Configuration and manufacturing method of optical film with adhesive layer attached to laminated film

For example, as shown in FIG. 1, the optical film 1 with the adhesive layer of the laminated separation film includes the optical film 10 and the adhesive layer 20 laminated on at least one side of the optical film 10, and on the adhesive layer 20 The outer surface layer separates the membrane 30. The single-layer adhesive layer 20 of the optical film 10. When the adhesive layer 20 is laminated on the surface of the optical film 10, it is preferable to form an undercoat layer on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, or to perform surface activation treatment (for example, Plasma treatment, corona treatment, etc.), especially for corona treatment.

An antistatic layer may be additionally disposed between the optical film 10 and the adhesive layer 20. As the antistatic layer, a ruthenium-based material such as polyoxyalkylene oxide; an inorganic metal-based material such as tin-doped indium oxide or tin-doped cerium oxide; polythiophene, polystyrenesulfonic acid, polyaniline, or the like can be used. Organic polymer material.

The optical film 1 with the adhesive layer attached to the separation film can be obtained, for example, by the following process: an adhesive constituting the adhesive layer (B). Each component of the composition is dissolved or dispersed in a solvent to prepare a solvent-containing adhesive composition, which is then applied to the release-treated surface of the separation membrane 30, dried to form an adhesive layer 20, and the adhesive is adhered thereto. The agent layer 20 is laminated (transferred) to the surface of the optical film 10.

The optical film of the adhesive layer of the laminated separation film of the present invention preferably has a surface hardness of 15 or more. When the Vickers hardness is 15 or more, the optical film with the adhesive layer has a high surface hardness, and even if it is pressurized in a state in which foreign matter adheres to the surface, it is less likely to cause dents, causing damage or concave to foreign matter due to the optical film. The prevention of the marks is good. In the present invention, the Vickers hardness of the surface of the optical film with the adhesive layer of the laminated separation film is more preferably 17 or more, still more preferably 19 or more. When the Vickers hardness is high, the upper limit of the Vickers hardness of the optical film with the adhesive layer of the laminated separation film is high, the optical film of the adhesive layer of the laminated separation film is easily broken, so it is usually 200 or less. Preferably, it is 150 or less. Further, the Vickers hardness can be measured, for example, according to the method described in the examples.

The surface hardness of the optical film attached to the adhesive layer of the separation membrane can be controlled to a desired range by, for example, selection of a plastic film constituting the separation membrane. Specifically, for example, the strength of the film is increased by increasing the stretching ratio at the time of film formation, or the crystal grain size is increased by slow cooling during film formation, or the molecular weight of the resin to be used is increased. It can increase the surface hardness.

[Examples]

Hereinafter, the present invention will be more specifically described by showing examples and comparative examples, but the present invention is not limited to these examples. The following, indicating the amount of use, The parts and % of the content are based on the mass basis unless otherwise noted.

Separation membrane (1) Production of separation membrane

(i) Modulation of composition for forming a release layer

An organic polysiloxane having a vinyl group, an organopolysiloxane having a hydrosilyl group, and a polyoxyxylene resin solution containing a heavy release additive (manufactured by Toray Dow Corning Co., Ltd., trade name: BY24-571, solid type) 30 parts by mass of the solid content was converted into 30 parts by mass in terms of solid content, and the mixture was diluted and mixed with a solvent of toluene/MEK = 1/1 to have a solid content concentration of 1.0% by mass. To the solution, 2 parts by mass of a platinum-based catalyst (manufactured by Toray Dow Corning Co., Ltd., trade name: SRX-212, solid content: 100% by mass) was added to prepare a composition for forming a release layer.

(ii) Production of separation membrane 1

A biaxially stretched polyethylene terephthalate (PET) film A (PET50T-193 manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm, an end azimuth angle of 8 degrees, and a haze of 5% was prepared. Then, on the one side of the biaxially stretched PET film A, the composition for forming a release layer obtained above was applied by a bar coater, and the thickness after drying was 0.1 μm, and dried at 120 ° C for 1 minute to form a release layer. The membrane 1 was separated.

(iii) Production of separation membrane 2

Prepare two axes with a thickness of 38 μm, an end azimuth of 6 degrees, and a haze of 10%. Extended polyethylene terephthalate (PET) film B (PET38R-64 manufactured by Toray Co., Ltd.). Then, the obtained release layer-forming composition was applied to one surface of the biaxially stretched PET film B by a bar coater, and the thickness after drying was 0.1 μm, and dried at 120 ° C for 1 minute to form a release layer. The membrane 2 was separated.

(2) Determination of physical properties of the separation membrane

(i) surface hardness

The separation membrane 1 and the separation membrane 2 produced above were each cut into a size of 40 mm × 40 mm, and then the release-treated surface (peeling layer) of the separation membrane was bonded to a glass of 40 mm × 40 mm through an adhesive layer having a thickness of 20 μm. Then, the evaluation sample attached to the glass was subjected to an ultra-micro hardness tester (FISCHERSCOPE HM2000: manufactured by Fischer Instruments Co., Ltd.) at a temperature of 55% at 23 ° C, and added at 0.1 N/5 s. After the load was applied at the pressing speed, the load was maintained for 5 seconds while maintaining a load of 0.1 N, and the Vickers hardness was measured. The results are shown in Table 1.

(ii) Bending stiffness

<Measurement preparation>

The separation membrane 1 and the separation membrane 2 produced above were each cut into test pieces having a size of 25.4 mm × 25.4 mm, and one end of the test piece was attached to a Gurley type test machine (Gurley stiffness tester (electric type)). 2094-M: The chuck of the movable arm of Kumagai Industrial Co., Ltd.). Fix the chuck by aligning the position of the movable arm A with the scale 1吋 (25.4mm), so that the test piece moves to the pendulum first. The position of the vertex of B. Then, a 5 g weight is attached to the position of the load mounting hole a (1 吋) at the lower portion of the fulcrum of the pendulum B to make it a vertical state without vibration.

<Measurement operation>

Move the movable arm to the right or left at a constant speed of 2 times/min. The lower portion of the test piece is in contact with the pendulum B, and the scale R when the pendulum B is removed is read, and the bending stiffness is calculated by the following conversion formula. The results are shown in Table 1.

S=((aWa+bWb+cWc)/5)×(l ² /b)×11.1×R (mg)

S: bending stiffness (mg)

a, b, c: the distance between the load mounting hole and the fulcrum of the pendulum (吋)

Wa, Wb, Wc: mass of the hammer mounted on the load mounting hole

l: test piece length - 1/2" (吋)

b: width of the test piece (吋)

R: reading of the scale

2. Production of optical film and optical film with adhesive layer attached to laminated film (1) Modification of (meth)acrylic resin A for the adhesive layer

In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 87.5 parts by mass of n-butyl acrylate, 5 parts by mass of methyl acrylate, and 5 parts by mass of 2-phenylethyl acrylate were placed. 2.5 parts by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, and the air in the reaction container was replaced with nitrogen. The reaction solution was heated to 60 ° C while stirring in a nitrogen atmosphere, and allowed to react for 16 hours, followed by cooling to room temperature. Here, a part of the obtained solution was measured for molecular weight by the method described later, and it was confirmed that a (meth) acrylate polymer having a weight average molecular weight of 2 million was produced.

The weight average molecular weight (Mw) of the (meth) acrylate polymer is a weight average molecular weight of the converted polystyrene measured by the following conditions using a gel permeation chromatography (GPC).

[Measurement conditions]

‧GPC measuring device: HLC-8020 manufactured by Tosoh

‧GPC column (through the following order): Tosoh company

TSK guard column HXL-H

TSK gel GMHXL (x2)

TSk gel G2000HXL

‧ Determination of solvent: tetrahydrofuran

‧Measurement temperature: 40 ° C

(2) Production of adhesive layer

(a) Modulation of the adhesive composition (A)

100 mass of the (meth) acrylate polymer obtained in the above step (1) The fraction (converted value of the solid content; the same applies hereinafter), and the xylylene diisocyanate modified by trimethylolpropane as the isocyanate crosslinking agent (B) (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name "TAKENATE D-110N" ” 0.20 parts by mass of co-condensation product of 3-mercaptopropyltrimethoxydecane and methyltriethoxysilane as a decane coupling agent (C) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X41-1810”) 0.30 The parts by mass were mixed and thoroughly stirred, and diluted with ethyl acetate to obtain a coating solution of the adhesive composition (A).

(b1) Production of Adhesive Layer 1 (Adhesive Sheet 1)

After the above-mentioned (a) prepared adhesive composition (A) is applied to the release-treated surface (peeling layer) of the separation membrane 1 obtained as described above by the applicator so that the thickness after drying is 20 μm, It was dried at 100 ° C for 1 minute to obtain an adhesive layer 1 as an adhesive sheet 1.

(b2) Production of adhesive layer 2 (adhesive sheet 2)

The adhesive layer 2 was obtained as the adhesive sheet 2 in the same manner as the production of the adhesive layer 1 except that the separation membrane 2 obtained above was used in place of the separation membrane 1.

(3) Fabrication of an optical film with an adhesive layer of a laminated separation film (I) Example 1: Optical film A1 with an adhesive layer of a laminated separation film

(i) Modulation of polarizing film (polarizer) A

A polyvinyl alcohol film having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 75 μm ("Kuraray Poval Film VF-PS #7500", Kuraray (Kuraray Co., Ltd.) was immersed in pure water at 37 ° C, and then immersed in an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100) at 30 ° C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizing film A having a thickness of about 28 μm in which iodine was adsorbed to polyvinyl alcohol. The elongation was mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

(ii) Modulation of optical film A

On one surface of the obtained polarizing film A, a transparent protective film made of a triethylenesulfonated cellulose film ("KC4UYW", Ke) having a thickness of 40 μm was bonded to an adhesive layer made of an aqueous solution of a polyvinyl alcohol resin. Nylon Minolta Optical Co., Ltd., and a circular olefin resin film ("ZF14-023", manufactured by Japan ZEON Co., Ltd.) having a thickness of 23 μm is bonded to the surface opposite to the transparent protective film to produce optical Film A (polarizer). The thickness of the optical film A was about 91 μm.

(iii) Fabrication of an optical film A1 (polarizing plate) with an adhesive layer of a laminated separation film

The surface of the obtained optical film A to which the cyclic olefin resin film was bonded, and the surface of the adhesive sheet 1 produced in the above (b1) opposite to the separation membrane 1 (adhesive layer) was laminated by a laminator. After bonding, the film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film A1 (polarizing plate) having an adhesive layer of the laminated separation film having a layer structure shown in Table 2. The The surface hardness (Vickers hardness) of the optical film A1 attached to the adhesive layer of the laminated separation film was 20.4.

(II) Comparative Example 1: Optical film A2 with an adhesive layer of a laminated separation film

Except for the use of the adhesive sheet 2 produced in the above (b2) in place of the adhesive sheet 1, the same operation as the production of the optical film A1 of the adhesive layer of the laminated separation film was carried out, and the layer composition shown in Table 2 was obtained. The optical film A2 of the adhesive layer attached to the laminated film. The surface hardness (Vickers hardness) of the optical film A2 attached to the adhesive layer of the laminated separation film was 13.5.

(III) Example 2: Optical film B1 with an adhesive layer of a laminated separation film

(i) Modulation of polarizing film (polarizer) B

A polyvinyl alcohol film ("Kuraray Poval Film VF-PE #3000", manufactured by Kuraray Co., Ltd.) having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm was immersed in pure water at 37 ° C. It was immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at 30 °C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizing film B having a thickness of about 12 μm in which iodine was adsorbed to polyvinyl alcohol. The elongation was mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

(ii) Modulation of optical film B

On one side of the obtained polarizing film B, via a polyvinyl alcohol-based resin A transparent protective film ("25KCHCN-TC", manufactured by Toppan Printing Co., Ltd.) obtained by applying a hard coat layer of 7 μm to a triacetonitrile-based cellulose film having a thickness of 25 μm is bonded to the adhesive agent of the aqueous solution, and On the opposite surface of the transparent protective film, a cyclic olefin resin film ("ZF14-023", manufactured by Japan Zeon Co., Ltd.) having a thickness of 23 μm was bonded to each other to prepare an optical film B (polarizing plate). The thickness of the optical film B was about 67 μm.

(iii) Production of an optical film B1 (polarizing plate) with an adhesive layer of a laminated separation film

The surface of the obtained optical film B to which the cyclic olefin resin film was bonded, and the surface of the adhesive sheet 1 produced in the above (b) opposite to the separation membrane 1 (adhesive layer) was laminated by a laminator. After bonding, the film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film B1 (polarizing plate) having an adhesive layer of the laminated separation film having a layer structure shown in Table 2. The surface hardness (Vickers hardness) of the optical film B1 attached to the adhesive layer of the laminated separation film was 18.7.

(IV) Comparative Example 2: Optical film B2 with an adhesive layer of a laminated separation film

Except for the use of the adhesive sheet 2 produced in the above (b2) in place of the adhesive sheet 1, the same operation as the production of the optical film B1 of the adhesive layer of the laminated separation film described above was carried out, and the layer composition shown in Table 2 was obtained. The optical film B2 of the adhesive layer attached to the laminated film is laminated. The surface hardness (Vickers hardness) of the optical film B2 attached to the adhesive layer of the laminated separation film was 12.7.

(V) Reference Example 1: Optical film C1 with an adhesive layer attached to a laminated film

(i) Modulation of polarizing film (polarizer) C

A polyvinyl alcohol film ("Kuraray Poval Film VF-PS #7500", manufactured by Kuraray Co., Ltd.) having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 75 μm was immersed in pure water at 37 ° C, and then immersed in pure water at 37 ° C. It was immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at 30 °C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizing film C having a thickness of about 28 μm in which iodine was adsorbed to polyvinyl alcohol. The elongation was mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

(ii) Modulation of optical film C

On one surface of the obtained polarizing film C, a transparent protective film made of a triethylenesulfonated cellulose film ("KC6UAW", Ke) having a thickness of 60 μm was bonded to an adhesive layer made of an aqueous solution of a polyvinyl alcohol resin. Nylon Minolta Optical Co., Ltd., and a circular olefin resin film ("ZB12-050135", manufactured by Japan ZEON Co., Ltd.) having a thickness of 50 μm is bonded to the surface opposite to the transparent protective film to produce optical Film C (polarizer). The thickness of the optical film C was about 138 μm.

(iii) Fabrication of an optical film C1 (polarizing plate) with an adhesive layer of a laminated separation film

The obtained optical film C is bonded to a cyclic olefin resin film. The surface of the adhesive sheet 1 produced in the above (b) is bonded to the surface (adhesive layer) on the opposite side of the separation membrane 1 by a laminator, and then aged at a temperature of 23 ° C and a relative humidity of 65%. After 7 days, an optical film C1 (polarizing plate) having an adhesive layer of a laminated separation film having a layer structure shown in Table 2 was obtained.

(VI) Reference Example 2: Optical film C2 attached to the adhesive layer of the laminated separation film

Except that the adhesive sheet 2 produced in the above (b2) was used in place of the adhesive sheet 1, the same operation as the production of the optical film C1 on the adhesive layer of the laminated separation film was carried out, and the layer composition shown in Table 2 was obtained. The optical film C2 of the adhesive layer attached to the laminated film is laminated.

The surface hardness of the optical films A1, A2, B1, B2, C1, and C2 attached to the adhesive layer of the laminated separation film prepared above is "separate each film into 40 mm × 40 mm, and then separate from the bonding." The film side was the opposite surface, and it adhered to the glass of 40 mm*40 mm via the adhesive layer of the film thickness of 20 micrometers, and the evaluation sample adhered to glass was used the ultramicro hardness tester in the environment of 55% of 23 degreeC ( FISCHERSCOPE HM2000: manufactured by Fisher Instruments Co., Ltd.), after applying a load at a pressurization speed of 0.1 N/5 s, the Vickers hardness measured while maintaining a load of 0.1 N for 5 seconds.

3. Evaluation of damage/dentation prevention effect of optical film with adhesive layer attached to laminated film

The damage/dentation preventing effect of the optical film attached to the adhesive layer of the laminated separation film was evaluated according to the following method.

The optical film A1 (Example 1), B1 (Example 2), A2 (Comparative Example 1), B2 (Comparative Example 2), C1 (Reference Example 1), and C2 (with the adhesive layer of the laminated separation film) Reference Example 2) was cut into a size of 120 mm × 75 mm so that the direction of the extension axis of the polarizing plate became a long side, and was placed on a solid flat surface so that the surface of the separation film faced upward. The squeezing hardness tester (hardness test pencil model 318/318S manufactured by Erichsen Co., Ltd.) was used for the anti-collapsing property on the separation film surface of the "optical film with the adhesive layer of the laminated separation film". test. The test is based on the separation membrane table At any point on the face (having a radius of about 0.75 mm), a hemispherical tungsten carbide tip was pressed with a prescribed fixing force to confirm whether or not there was a test for generating a dent.

After the scratch hardness tester was pressed against the surface of the separation membrane with a pressure of 0.1 N for 5 seconds, the scratch hardness tester was allowed to leave the surface of the separation membrane. This operation was carried out at 5 places of the optical film of the adhesive layer of the laminated separation film, respectively, and 5 indentations were given on the surface of the separation film. After the tester was just left from the surface of the separation membrane (initial) and after leaving for 24 hours, the state of the depression remaining on the surface of the separation membrane was visually confirmed, and when there was residual depression, it was judged as "not extinguished", and when it was not left, it was judged as "wipe out". The "unkilled number" of each time is shown in Table 3.

The optical film of the adhesive layer of Examples 1 and 2 having a film thickness of the separation film of 45 μm or more and a film thickness of the polarizing plate (optical film) of 100 μm or less is used to separate the scratch hardness tester from the surface of the separation film. After 24 hours, even one dent (depression) did not remain. In contrast, the separation membrane The optical films of the adhesive layers of Comparative Examples 1 and 2 having a film thickness of less than 45 μm had residual dents after leaving the scratch hardness tester away from the surface of the separation film for 24 hours. In particular, in Comparative Example 2, all the dents remained after 24 hours. Further, an optical film having a thickness of more than 100 μm (Reference Examples 1 and 2) is thick in thickness (138 μm) of the optical film itself, so that it is less likely to cause dents, regardless of the thickness of the separation film, dents after 24 hours. They are all eliminated.

<Measurement of storage elastic modulus>

A plurality of layers of the adhesive layer were laminated so as to have a thickness of 0.6 mm. A cylindrical body (having a height of 0.6 mm) having a diameter of 8 mm was punched out from the obtained adhesive layer, and this was used as a sample for measurement for storing the elastic modulus G'.

The storage elastic modulus (MPa) was measured by the torsional shear method according to JIS K7244-6 using a viscoelasticity measuring apparatus (MCR300, manufactured by Physica Co., Ltd.) under the following conditions.

[Measurement conditions]

Measurement frequency: 1 Hz

Measuring temperature: 25 ° C

The storage elastic modulus of the adhesive layer formed of the above adhesive composition (A) was 0.085 MPa.

(VII) Example 3: Optical film A3 with an adhesive layer of a laminated separation film (1) Modification of (meth)acrylic resin B with an adhesive layer

With mixer, thermometer, reflux cooler, drip device and nitrogen 94 parts by mass of n-butyl acrylate, 5.0 parts by mass of 2-hydroxyethyl acrylate, 1.0 part by mass of acrylic acid, 200 parts by mass of ethyl acetate, and 2,2'-azobisisobutylate were placed in the reaction container of the gas introduction tube. 0.08 parts by mass of the nitrile, and the air in the above reaction vessel was replaced with nitrogen. The reaction solution was heated to 60 ° C while stirring in a nitrogen atmosphere, and allowed to react for 16 hours, followed by cooling to room temperature. Here, a part of the obtained solution was measured by the method described above, and it was confirmed that a (meth) acrylate polymer having a weight average molecular weight of 2 million was produced.

(2) Modulation of the adhesive composition (B)

100 parts by mass of the (meth) acrylate polymer obtained in the above step (1) (converted value of solid content; the same applies hereinafter), and modified by trimethylolpropane as an isocyanate crosslinking agent (B) Toluene diisocyanate [manufactured by Konica Chemical Co., Ltd., trade name "L-45"] 1.0 part by mass, γ-glycidoxypropyltrimethoxydecane as a decane coupling agent (C) [manufactured by Shin-Etsu Chemical Co., Ltd. "KBM403"], as a polyfunctional active energy ray-curable compound, 10 parts by weight of a polyfunctional active energy ray-curable compound (manufactured by Toagosei Co., Ltd., trade name "M-315"), 10 parts by mass, as 1-hydroxycyclohexyl phenyl ketone of a photopolymerization initiator (manufactured by CIBA Specialty Chemical Co., Ltd., trade name "Irgacure 184"), 1 part by mass, mixed well, and diluted with ethyl acetate to obtain adhesion A coating solution of the agent composition (B).

(3) Production of adhesive layer (adhesive sheet 3)

After the above-mentioned (a2) prepared adhesive composition (B) is applied to the release-treated surface (peeling layer) of the separation membrane 1 obtained as described above by the applicator so that the thickness after drying is 20 μm, After drying at 100 ° C for 1 minute, an adhesive layer 3 was obtained as an adhesive sheet 3. The adhesive sheet 3 was produced by irradiating ultraviolet rays (UV) from the side of the release sheet under the following conditions.

<UV irradiation conditions>

‧Fusion company's electrodeless lamp, using H bulb

‧illuminance 600mW/cm ² , light quantity 150mJ/cm ²

The UV illuminance ‧ light meter uses "UVPF-36" manufactured by Eye Graphics.

<Measurement of storage elastic modulus>

The storage elastic modulus at 25 ° C of the adhesive layer formed of the adhesive composition (B) was measured in the same manner as the above measurement method of the adhesive composition (A). The storage modulus of the adhesive layer formed of the adhesive composition (B) at 25 ° C was 0.55 MPa.

(4) Production of optical film A3 (polarizing plate) with an adhesive layer attached to a laminated separation film

The surface of the obtained optical film B to which the cyclic olefin resin film is bonded, and the surface of the adhesive sheet 3 produced in the above (3) opposite to the separation membrane 1 (adhesive layer) is laminated by a laminator. After bonding, the film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film A3 (polarizing plate) having an adhesive layer of the laminated separation film having a layer structure shown in Table 4.

The laminated layer was subjected to the same method as in Example 1. Evaluation of the damage/dentation preventing effect of the optical film attached to the adhesive layer of the film. The results are shown in Table 4.

Claims (3)

An optical film comprising an adhesive layer of a laminated separation film, comprising: a separation film (C) laminated on at least one side of an optical film (A) via an adhesive layer (B); wherein the separation film (C) The film thickness is 45 μm or more, the film thickness of the optical film (A) is 100 μm or less, and the separation film (C) is a separation film having a Vickers hardness of 15 or more on the surface alone. The optical film of the adhesive layer of the laminated separation membrane according to the first aspect of the invention, wherein the separation membrane (C) is a separation membrane having a bending rigidity of 1 mg or more. The optical film of the adhesive layer of the laminated separation film according to the first or second aspect of the invention, wherein the adhesive layer (B) has a storage elastic modulus G' at 25 ° C of 0.4 MPa or less.