JP2011028069A - Method for producing adhesive optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing an adhesive optical film in which an adhesive layer adheres with high adhesive force to a surface of an optical film made of an optical compensation film or to a surface of an optical compensation film layer or an optical compensation membrane layer in a surface of a laminate type optical film, so that no adhesive deposit of the adhesive layer occurs. <P>SOLUTION: The method for producing an adhesive optical film includes: subjecting a surface of an optical film made of an optical compensation film as a simple body or a surface of an optical compensation film layer or an optical compensation membrane layer in a laminate type optical film having the optical compensation film layer or the optical compensation membrane layer in a surface thereof to adhesive roll contact treatment or rubbing treatment; and applying an adhesive to the optical compensation film surface or the optical compensation membrane surface which has been subjected to adhesive roll contact treatment or rubbing treatment, thereby forming an adhesive layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an adhesive optical film, an adhesive optical film obtained thereby, and an image display device using the adhesive optical film. More specifically, the present invention relates to an optical compensation film layer of a laminated optical film having an adhesive layer on an optical film made of a single optical compensation film, or having an optical compensation film layer or an optical compensation film layer on the surface. Or it is related with the manufacturing method of the adhesive optical film which has an adhesive layer on an optical compensation film layer, the adhesive optical film obtained by it, and the image display apparatus using the said adhesive optical film.

  In recent years, optical compensation films (such as retardation films, viewing angle enhancement films, color compensation films, brightness enhancement films, etc.), optical compensation film layers, or optical compensation have been developed from the viewpoint of improving the viewing angle and contrast of liquid crystal display devices. A laminated optical film (such as a polarizing plate) having a film layer on the surface is used. In these optical films, a pressure-sensitive adhesive layer is provided on the surface of a single optical compensation film or an optical compensation film layer or an optical compensation film layer of a laminated optical film to form a pressure-sensitive adhesive optical film. Adhesion to a liquid crystal panel or the like is performed by the adhesive layer. When the adhesive optical film is attached to a liquid crystal panel or the like, there are cases in which wrinkles, bubbles, foreign matter, etc. are bitten and the attachment position is misaligned. The optical film is peeled off and the sticking operation is performed again, or the expensive liquid crystal panel is collected and reused after the adhesive optical film is peeled off. When peeling an adhesive optical film, the adhesive layer of the adhesive optical film is required to be peeled cleanly without leaving any adhesive on a liquid crystal panel, etc., with good adhesion to the optical film side. .

  However, in the pressure-sensitive adhesive optical film in which the pressure-sensitive adhesive layer is provided on the surface of the optical compensation film alone, the pressure-sensitive optical film in which the pressure-sensitive adhesive layer is provided on the optical compensation film layer of the laminated optical film or the optical compensation film layer, , Adhesive strength (adhesive strength) of the adhesive to the optical compensation film alone, optical compensation film layer or optical compensation film layer is insufficient, peel off the adhesive optical film stuck on the liquid crystal panel, etc. When recovering and reusing a liquid crystal panel from which an adhesive optical film has been peeled off, the adhesive layer of the adhesive optical film is used as a single optical compensation film or the optical compensation film surface or optical compensation of a laminated optical film. In many cases, problems such as separation from the film surface and adhesive residue on the liquid crystal panel side occur.

As a method of improving the adhesive strength of the adhesive layer to a substrate such as a film, the surface of the substrate is subjected to corona discharge treatment or plasma treatment, and then the adhesive is applied to the surface to form an adhesive layer. There is a known method (see Patent Document 1).
However, according to this method, it is necessary to use an expensive and high voltage device such as a corona treatment device or a plasma treatment device, which is costly. Further, the control and management of the device, safety, and adverse effects on the human body. It is necessary to pay great attention in terms of prevention of the occurrence (for example, safety management against generation of harmful ozone generated by corona discharge treatment).

JP-A-7-173441 JP 2004-198511 A JP-A-6-93060 Japanese Patent Publication No. 7-25859 JP-A-11-335432

“Macromol. Chem. Phys.”, 2000, 201, p. 1108 to 1114

  An object of the present invention is to safely and easily use a device such as a corona discharge treatment or a plasma treatment without using an expensive and high voltage apparatus, and on the surface of a single optical compensation film or a laminated type. Adhesive optics with an adhesive layer that adheres and laminates with high adhesion on the optical compensation film layer or optical compensation film layer on the surface of the optical film so that no adhesive remains on the liquid crystal panel, etc. It is to provide a method for producing a film.

In order to solve the above problems, the present inventors have made various studies. As a result, an adhesive roll is applied to the surface of the optical compensation film layer or the optical compensation film layer in the surface of the optical film comprising the optical compensation film alone, or in the laminated optical film having the optical compensation film layer or the optical compensation film layer on the surface. After performing the contact treatment or rubbing treatment, the adhesive applied to the release film is transferred to the optical compensation film surface or optical compensation film surface subjected to the adhesive roll contact treatment or rubbing treatment, or the adhesive When the pressure-sensitive adhesive layer is formed by directly coating the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is bonded and laminated with high adhesive force on the optical compensation film or on the optical compensation film layer or the optical compensation film layer on the surface of the laminated optical film. The inventors have found that an adhesive optical film in which the adhesive is not separated from the optical compensation film or the laminated optical film can be obtained.
And when the present inventors performed the test which peels from the liquid crystal panel etc., after once sticking to the liquid crystal panel etc. through the adhesive layer, the adhesive type optical film obtained by that was the adhesive type optical film. It has been found that the pressure-sensitive adhesive layer in the film can be peeled cleanly without leaving any adhesive on a liquid crystal panel or the like while firmly adhered to the optical film side.

Furthermore, the present inventors performed an adhesive roll contact treatment or a rubbing treatment on the surface of the optical compensation film alone or the surface of the optical compensation film layer or the optical compensation film layer in the laminated optical film, and then the adhesive roll. The above-mentioned method found by the present inventors to produce a pressure-sensitive adhesive optical film by forming a pressure-sensitive adhesive layer on the optical compensation film surface or the optical compensation film surface subjected to the contact treatment or the rubbing treatment is a method for producing a monomer having a fluoroalkyl group. When a pressure-sensitive adhesive layer is formed on the surface of a single optical compensation film containing a polymer-containing material having a structural unit derived therefrom, and in the surface of the optical compensation film layer or in the optical compensation film layer TABLE OF LAMINATED OPTICAL FILM CONTAINING POLYMER HAVING STRUCTURAL UNIT DERIVED FROM MONOMER HAVING FLUOROALKYL GROUP When forming an adhesive layer to produce a pressure-sensitive adhesive optical film was found to be particularly effective.
Further, the present inventors have determined that the ratio of the fluorine element on the surface of the optical compensation film alone or on the surface of the optical compensation film layer or the optical compensation film layer of the laminated optical film by the adhesive roll contact treatment or the rubbing treatment. We found that it was reduced.

  Furthermore, the present inventors can use various pressure-sensitive adhesives in the production of the above-mentioned pressure-sensitive adhesive optical film. Among them, at least a methacrylic acid alkyl ester polymer block (A) having a glass transition temperature of 100 ° C. or higher is used. A pressure-sensitive adhesive containing one acrylic block copolymer having at least one alkyl acrylate polymer block (B) having a glass transition temperature of −20 ° C. or lower and a proportion of 60% by mass or more is suitable. The present invention was completed based on these various findings.

That is, the present invention
(1) A method for producing an adhesive optical film, the surface of an optical film comprising an optical compensation film alone, or an optical compensation film layer in a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface, or The surface of the optical compensation film layer is subjected to an adhesive roll contact treatment or rubbing treatment, and then the adhesive layer is applied to the optical compensation film surface or optical compensation film surface subjected to the adhesive roll contact treatment or rubbing treatment. It is the manufacturing method of the adhesion type optical film characterized by forming.

And this invention,
(2) The method for producing an adhesive optical film according to (1), wherein the adhesive roll contact treatment is performed using an adhesive roll having an adhesive strength of 50 g or more;
(3) The optical film comprising the optical compensation film alone, or the optical compensation film layer or the optical compensation film layer on the surface of the laminated optical film contains a polymer having a structural unit derived from a monomer having a fluoroalkyl group. A method for producing the adhesive optical film of (1) or (2); and
(4) By X-ray photoelectron spectroscopy on the surface of an optical film made of a single optical compensation film or on the surface of an optical compensation film layer or optical compensation film layer of the laminated optical film by an adhesive roll contact treatment or rubbing treatment. The method for producing a pressure-sensitive adhesive optical film according to any one of (1) to (3), wherein the measured ratio of elemental fluorine is reduced by 5% or more compared to before performing the pressure-sensitive adhesive roll contact treatment or rubbing treatment;
It is.

Furthermore, the present invention provides
(5) The pressure-sensitive adhesive applied to the surface of the optical compensation film or the surface of the optical compensation film subjected to the adhesive roll contact treatment or the rubbing treatment is an alkyl methacrylate ester polymer block (A) having a glass transition temperature of 100 ° C. or higher. The pressure-sensitive adhesive containing 60% by mass or more of an acrylic block copolymer having at least one acrylic acid alkyl ester polymer block (B) having a glass transition temperature of −20 ° C. or lower (B). It is a manufacturing method of the adhesive optical film in any one of 1)-(4).
And this invention,
(6) An adhesive optical film obtained by the production method of any one of (1) to (5); and
(7) An image display device using the adhesive optical film of (6);
It is.

In the case of the production method of the present invention, the pressure-sensitive adhesive is adhesively laminated on the optical compensation film or on the optical compensation film layer or the optical compensation film layer on the surface of the laminated optical film with a high adhesive force. Alternatively, an adhesive optical film in which the adhesive is not separated from the laminated optical film can be manufactured easily, safely, and smoothly at a low cost without using a plasma processing apparatus or a corona discharge processing apparatus. .
The pressure-sensitive adhesive optical film obtained by the present invention has a pressure-sensitive adhesive layer firmly adhered to the optical film side, and therefore, after the pressure-sensitive adhesive optical film is attached to a liquid crystal panel or the like, the pressure-sensitive adhesive optical film is peeled off to work. When reusing or reusing an expensive liquid crystal panel after peeling off the adhesive optical film, the adhesive does not remain on the liquid crystal panel. Can be performed smoothly.
The method of the present invention in which an optical film is subjected to an adhesive roll contact treatment or a rubbing treatment before forming an adhesive layer is an optical compensation film containing a material containing a polymer having a structural unit derived from a monomer having a fluoroalkyl group In the optical compensation film layer or in the optical compensation film layer in a laminated optical film containing a polymer having a structural unit derived from a monomer having a fluoroalkyl group in the surface or in the optical compensation film layer on the surface or in the optical compensation film layer This is particularly effective when an adhesive optical film is produced by forming an adhesive layer on the surface of the film layer.
In the present invention, at least one methacrylic acid alkyl ester polymer block (A) having a glass transition temperature of 100 ° C. or higher and an acrylic acid alkyl ester polymer block (B) having a glass transition temperature of −20 ° C. or lower are used as the pressure-sensitive adhesive. When an adhesive containing at least one acrylic block copolymer having a ratio of 60% by mass or more is used, it exhibits high cohesion without performing chemical cross-linking treatment, reworkability, adhesive properties, An adhesive optical film excellent in heat resistance, optical characteristics (light unevenness, transparency, etc.), durability, etc. can be produced with good processability and high productivity.

The present invention is described in detail below.
The present invention uses, as a base film, an optical film from a single optical compensation film, or a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface, and the optical compensation film surface or optical compensation film surface of the base film. This is an improved technique for producing a pressure-sensitive adhesive optical film by applying a pressure-sensitive adhesive on the substrate.
Here, in the present invention, the “optical compensation film alone” before forming the pressure-sensitive adhesive layer means that the other layers are not laminated and are composed only of the optical compensation film.
Further, in the present invention, before forming the pressure-sensitive adhesive layer, “a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface” is a laminated optical film, one or An optical film having an optical compensation film layer or an optical compensation film layer on both surfaces. When this laminated optical film is a laminated optical film having an “optical compensation film layer” on one or both surfaces, one or two are provided on the optical film such as a polarizing film or a protective film thereof. An optical film in which two optical compensation films are laminated so as to be positioned in the outermost layer. In addition, when the laminated optical film is a laminated optical film having an “optical compensation film layer” on one or both surfaces, the coating process is performed on the optical film such as a polarizing film or a protective film thereof. An optical film in which one or two optical compensation films formed by adopting the above are laminated so as to be positioned in the outermost layer.

The number of layers in the laminated optical film having the optical compensation film layer or the optical compensation film layer on the surface, the material of each layer other than the optical compensation film layer on the surface or the optical compensation film layer, physical properties, etc. are not particularly limited. It can be selected and determined according to the use and usage of the optical film. Although not limited, as a laminated optical film before forming the pressure-sensitive adhesive layer that can be used in the present invention, for example,
<< 1 >> Optical compensation film layer (optical compensation film layer) / protective layer [TAC layer (triacetylcellulose layer) etc.] / Polarizing film layer (PVA polarizing film layer etc.) / Protective layer (TAC layer etc.)] Laminated laminated optical film (polarizing plate, etc.);
<< 2 >> Laminated optical film (polarizing plate, etc.) laminated in the order of optical compensation film layer (optical compensation film layer) / polarizing film layer (PVA polarizing film layer, etc.) / Protective layer (TAC layer, etc.);
<< 3 >> Laminated optical film laminated in the order of optical compensation film layer (optical compensation film layer) / polarizing film layer (PVA polarizing film layer, etc.) / Optical compensation film layer (optical compensation film layer);
And so on.

The type of the optical compensation film used in the present invention or the type of the optical compensation film or the optical compensation film constituting the optical compensation film layer on the surface of the laminated optical film is not particularly limited, and the liquid crystal display device (LCD), organic EL, electronic paper, touch panels, etc. Conventionally used retardation films and retardations for the purpose of providing optical compensation functions such as improving the viewing angle, improving contrast, and color compensation. An optical compensation film or an optical compensation film such as a film, a viewing angle improving film, a viewing angle improving film, a color compensation film, a color compensation film, a brightness enhancement film, and a brightness enhancement film can be used.
Examples of the optical compensation film or the optical compensation film include an optical compensation film and optical compensation film based on TAC (triacetyl cellulose), an optical compensation film and optical compensation film based on CAP (mixed fatty acid cellulose ester), and TAC. (Triacetylcellulose) and LPC (liquid crystal polymer) based optical compensation film and optical compensation film, TAC and liquid crystal compound (such as discotic compound) based optical compensation film and optical compensation film, norbornene resin and others Optical compensation film and optical compensation film based on COP (cycloolefin polymer), optical compensation film and optical compensation film based on acrylic resin, optical compensation film and optical compensation film based on PC (polycarbonate) Has been known for a long time, The optical compensation film alone to be used in the invention, or an optical compensation film layer or an optical compensation film layer in the optical film of the multilayer may be formed from any of them.
The optical compensation film layer or the optical compensation film layer in the optical compensation film alone or in the laminated optical film may be optically anisotropic.

A polymer having a structural unit derived from a monomer having a fluoroalkyl group in an optical film or in a film layer provided on the surface of the optical film as a leveling agent, a refractive index adjusting agent, etc. There are those that contain addition. When a polymer having a structural unit derived from a monomer having a fluoroalkyl group is contained in an optical film or a film layer provided on the surface of the optical film, surface smoothness, thin film coating property, high-speed coating property, precision Improvement of coatability, film thickness uniformity, optical compensation function, reduction of surface defects (unevenness, repelling, pinholes, etc.), control of refractive index, etc. are achieved.
At that time, as a polymer having a structural unit derived from a monomer having a fluoroalkyl group, a fluoroalkyl ester of (meth) acrylic acid, a fluoroalkylthioester of (meth) acrylic acid, a fluoroalkylamide of (meth) acrylic acid , Other polymers having one or more structural units derived from a monomer having a fluoroalkyl group (such as a polymerizable unsaturated monomer having a fluoroalkyl group) (hereinafter referred to as “fluoroalkyl”). Group-containing polymer ”).
If a fluoroalkyl group-containing polymer is added in the optical film or in the film layer provided on the surface of the optical film, the adhesive strength of the adhesive to the optical film is reduced, and the adhesive of the adhesive layer to the liquid crystal panel, etc. The rest is likely to occur, and this is no exception in optical films having an optical compensation film or an optical compensation film layer.
In addition, an optical film composed of a single optical compensation film, or a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface thereof is subjected to a saponification treatment in order to improve the adhesiveness to the polarizing film. There is. At that time, if the optical compensation film (layer) or the optical compensation film layer contains a polymer having a structural unit derived from a monomer having a fluoroalkyl group, depolymerization proceeds or ester bonds are caused by saponification treatment. The adhesive portion of the pressure-sensitive adhesive layer to the optical compensation film (layer) or the optical compensation film layer may be reduced, because the low molecular component having a fluorohydrocarbon group is generated by cutting the bond portion with the main chain, etc. is there.

In an experiment conducted by the present inventors, an adhesive roll contact treatment or a rubbing treatment was applied to an optical film or a laminated optical film containing a fluoroalkyl group-containing polymer in the optical compensation film (layer) or optical compensation film layer. When it did, it was confirmed that the ratio of the fluorine element in the surface of an optical compensation film (layer) or an optical compensation film layer reduces compared with before performing an adhesive roll contact process or a rubbing process.
From the above points, in the case of the method of the present invention, a fluoroalkyl group-containing polymer or a low molecular component having a fluoroalkyl group on the surface of the optical compensation film (layer) or the optical compensation film layer is subjected to adhesive roll contact treatment or rubbing treatment. Therefore, it is presumed that the pressure-sensitive adhesive layer adheres to the optical compensation film (layer) or the optical compensation film layer with high adhesive force.
Therefore, after performing adhesive roll contact treatment or rubbing treatment on the optical compensation film surface or optical compensation film surface, an adhesive layer is formed on the optical compensation film surface or optical compensation film surface to produce an adhesive optical film. The method of the present invention is a technique for producing a pressure-sensitive adhesive optical film using an optical film comprising a single optical compensation film containing a fluoroalkyl group-containing polymer, or a fluorocarbon in an optical compensation film layer or an optical compensation film layer on the surface. This is extremely effective in a technique for producing an adhesive optical film using a laminated optical film containing an alkyl group-containing polymer.

  At that time, as the fluoroalkyl group-containing polymer contained in the optical compensation film layer or the optical compensation film layer in the optical compensation film alone or in the laminated optical film, a part of hydrogen atoms of the alkyl group is substituted with fluorine atoms. And a polymer having a structural unit derived from a monomer having a fluoroalkyl group and / or a monomer having a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The number of carbon atoms of the fluoroalkyl group in the monomer having a fluoroalkyl group is not particularly limited, but the number of carbon atoms of the fluoroalkyl group is preferably 3 or more, more preferably 6 or more, and more preferably 6-15. preferable. Further, the number of fluorine atoms bonded to carbon atoms in the fluoroalkyl group is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more.

  The kind of the monomer having a fluoroalkyl group constituting at least a part of the fluoroalkyl group-containing polymer is not particularly limited. For example, a fluoroalkyl ester of (meth) acrylic acid, a fluoroalkylthioester of (meth) acrylic acid, (meta ) A fluoroalkylamide of acrylic acid can be mentioned, and the fluoroalkyl group-containing polymer can have a structural unit derived from one or more of the aforementioned fluoroalkyl-containing monomers.

The fluoroalkyl group-containing polymer may be formed only from a structural unit derived from a monomer having a fluoroalkyl group, or may have a structural unit derived from another monomer together with a structural unit derived from a monomer having a fluoroalkyl group. You may do it.
When the fluoroalkyl group-containing polymer has a structural unit derived from another monomer together with a structural unit derived from a monomer having a fluoroalkyl group, examples of the structural unit derived from the other monomer include acryl. Vinyl monomers having a carboxyl group such as acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, etc., and vinyl monomers obtained by esterification, thioesterification, and amidation of the carboxyl group in the vinyl monomer having the carboxyl group , Aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, conjugated diene monomers such as butadiene and isoprene, olefin monomers such as ethylene and propylene, and lactone monomers such as ε-caprolactone and parelactone The structural unit derived from 1 type or 2 types or more of these can be mentioned.
Among them, the structural unit derived from another monomer is preferably a structural unit derived from one or more of (meth) acrylic acid ester, (meth) acrylic acid thioester, and (meth) acrylic acid amide. In that case, (meth) acrylic acid ester, (meth) acrylic acid thioester, ester group, thioester group, and amide group in (meth) acrylic acid amide are linear, branched or 4 to 20 carbon atoms. A cyclic alkyl group or an ester group having a poly (oxyalkylene) group in which the alkylene group is a linear or branched alkylene group having 2 to 4 carbon atoms, a thioester group or an amide group is preferred. In that case, the alkyl group or poly (oxyalkylene) group may be a hydroxyl group, a carboxyl group, an aryl group, a carbonyl group, a nitro group, a cyano group, an amino group, an alkyl ether group, an alkyl ester group, a halogen, if necessary. You may have an atom.
The fluoroalkyl group-containing polymer preferably has a structural unit derived from a monomer having a fluoroalkyl group in a proportion of 5 mol% or more, more preferably in a proportion of 5 to 70 mol%. preferable.
The weight average molecular weight of the fluoroalkyl group-containing polymer is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and 5,000 to 70,000. Is more preferable.

Patent Document 2 discloses an optical film having an optically anisotropic layer (optical compensation film layer) formed from a layer containing a liquid crystal compound such as a discotic compound on a support, the optically anisotropic layer ( in the optical compensation film layer), the general _{formula: CH 2 = C (R 1} ) -CO-X- (CH 2) m - (CF 2 CF 2) n F [ wherein, R ₁ represents a hydrogen atom or a methyl group , X is an oxygen atom, sulfur atom or —N (R ₂ ) — (wherein R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), m is an integer of 1 to 6, and n is an integer of 2 to 4. Indicates. And a structural unit derived from poly (oxyalkylene) acrylate and / or poly (oxyalkylene) methacrylate, optionally further derived from another monomer. An optical film having a polymer having a structural unit is disclosed, but before forming the pressure-sensitive adhesive layer on the optical anisotropic layer (optical compensation film layer) of the optical film, the optical anisotropic layer on the surface An adhesive roll contact treatment or rubbing treatment is performed on the (optical compensation film layer), and then an adhesive layer is formed on the optical anisotropic layer (optical compensation film layer) subjected to the adhesive roll contact treatment or rubbing treatment. When the method of the present invention is applied, the adhesive strength of the pressure-sensitive adhesive to the optical film is improved, the pressure-sensitive adhesive is separated from the optical film, and no adhesive remains on the liquid crystal panel side. Can be trouble can be prevented.
In view of this, the present invention uses an optical film as disclosed in Patent Document 2 and performs an adhesive roll contact treatment on the surface of the optical film [surface optical anisotropic layer (optical compensation film layer)]. Alternatively, a method for producing an adhesive optical film by forming an adhesive layer thereon after rubbing is included in the scope of the present invention.

  In the present invention, as described above, the above-mentioned optical compensation film alone or the above-mentioned laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface is used as an optical film for applying an adhesive (base material). Used as a film), the surface of the optical compensation film alone, or the surface of the optical compensation film layer or the surface of the optical compensation film layer on the surface of the laminated optical film, It is important to perform an adhesive roll contact treatment or a rubbing treatment on the surface of the optical compensation film layer or the optical compensation film layer in the laminated optical film.

Here, the “adhesive roll contact treatment” in the present invention means an adhesive roll (on the roll surface) on the surface of the optical compensation film alone, or on the surface of the optical compensation film layer or optical compensation film layer in the laminated optical film. The pressure-sensitive adhesive layer adheres to the surface of the optical compensation film alone or the surface of the optical compensation film layer or the surface of the optical compensation film layer in the laminated optical film. Remove the causative substances (such as those based on a polymer having a structural unit derived from a monomer having a fluoroalkyl group or a low molecular component having a fluoroalkyl group) by transferring (transferring) to the surface of the adhesive roll. Say.
In the present invention, the “rubbing treatment” (rubbing treatment) refers to a rubbing means or a rubbing device (wiping off) the surface of a single optical compensation film or the surface of an optical compensation film layer or optical compensation film layer in a laminated optical film. Means wiping using a means or a wiping device).

When forming an adhesive layer only on one surface of the optical compensation film, the adhesive roll contact treatment or rubbing treatment is performed only on the one surface, and the adhesive layer is formed on both surfaces of the optical compensation film alone. When forming, it is good to perform an adhesive roll contact process or a rubbing process on both surfaces.
When the laminated optical film has the optical compensation film layer or the optical compensation film layer only on one surface, the surface of the optical compensation film layer or the optical compensation film layer on the one surface is an adhesive roll. Contact treatment or rubbing treatment. In addition, when both surfaces of the laminated optical film have an optical compensation film layer or an optical compensation film layer and an adhesive layer is formed on both surfaces, the optical compensation film layer or optical The compensation film layer may be subjected to an adhesive roll contact treatment or a rubbing treatment. Furthermore, when both surfaces of the laminated optical film have an optical compensation film layer or an optical compensation film layer, when an adhesive layer is formed only on one surface, only on one surface on which the adhesive layer is formed Adhesive roll contact treatment or rubbing treatment is performed.
Adhesive roll contact treatment or rubbing treatment on the surface of an optical compensation film alone or on the surface of an optical compensation film layer or optical compensation film layer in a laminated optical film does not cause degradation of optical compensation function or other performance. In addition, the adhesion of the pressure-sensitive adhesive to the surface of the optical film is improved by an adhesive roll contact treatment or a rubbing treatment.

In the adhesive roll contact treatment, the optical compensation film layer or the optical compensation film layer on the surface of the rotating optical roll or the surface of the laminated optical film is placed under a predetermined pressure on the surface of the rotating adhesive roll. A method of pressing and contacting is adopted. At that time, the adhesive roll may be disposed at a predetermined position, and the optical compensation film alone or the laminated optical film may be contact-treated while being continuously transferred, or the optical compensation film alone. Alternatively, the laminated optical film may be fixed and the contact treatment may be performed while rotating the adhesive roll on the surface of the optical film.
The pressure-sensitive adhesive roll has a pressure-sensitive adhesive layer on the surface, and the pressure-sensitive adhesive roll is brought into contact with the surface of the optical compensation film alone or the surface of the laminated optical film having the optical compensation film layer or the optical compensation film layer on the surface. The adhesive on the surface of the adhesive roll does not move to the optical film side, while the causative substance that causes a decrease in the adhesive strength of the adhesive on the surface of the optical film is caused by the adhesive force on the surface of the adhesive roll. Any of the adhesive rolls that can be transferred (transferred) and removed can be used. The pressure-sensitive adhesive layer on the surface of the pressure-sensitive roll can be formed from a conventionally known pressure-sensitive adhesive such as rubber, silicon, urethane, and acrylic. It is preferable that the adhesive layer on the surface of the adhesive roll is replaceable when the adhesive force is reduced due to dirt or the like.
In particular, when an adhesive roll contact treatment is performed using an adhesive roll having an adhesive strength of 50 g or more, more preferably 80 to 500 g, particularly 100 to 300 g as an adhesive roll, the optical compensation film after the adhesive roll contact treatment A pressure-sensitive adhesive layer can be formed with good adhesive force on the surface of a single body or on the surface of a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface.
Various adhesive rolls having an adhesive strength of 50 g or more have been commercially available.
If the adhesive strength of the adhesive roll is lower than 50 g, it will be difficult to achieve the effects of the present invention. On the other hand, if the adhesive strength of the adhesive roll is too high, the adhesive roll is contacted with the adhesive roll. There is a tendency that the process passability at the time of carrying out the process becomes poor or leads to deformation of the polarizing plate.
Here, the value of the adhesive strength of the adhesive roll in this specification refers to the adhesive strength measured by the method described in the following examples.

In the rubbing treatment, rubbing means or a rubbing apparatus is generally applied to the surface of the optical compensation film or the surface of the optical compensation film layer on the surface of the optical compensation film alone or the surface of the laminated optical film. A rubbing process (wiping process) is performed while moving in the surface direction under a predetermined contact pressure, or a rubbing means or a rubbing device is fixedly arranged at a predetermined position, and an optical compensation film layer or an optical compensation film layer on the surface of the optical compensation film alone or on the surface A method of performing a rubbing process while moving or transporting a laminated optical film having a contact with a rubbing means or a rubbing device under a predetermined contact pressure can be employed.
As the rubbing means or rubbing apparatus, rubbing means or rubbing equipment used for wiping dirt and other materials in factories, laboratories, laboratories, and homes can be used. For example, synthetic fiber nonwoven fabric (polypropylene) Non-woven fabrics, lyocell non-woven fabrics, etc.), rubbed sheets and fabrics such as velvet, various rubbing fabrics and papers (wiper fabrics and wiper papers) themselves such as paper (pulp), rubbing devices (wiper devices) attached with them, rubbing Rolls (wiper rolls), brushes, rubber wipers, and the like can be used.

The adhesive roll contact treatment or rubbing treatment may be performed batchwise or continuously, depending on the size and form of the optical compensation film alone or the laminated optical film.
When the adhesive roll contact treatment or the rubbing treatment is performed in a batch system, the above-mentioned adhesive roll or rubbing material (wiper material) itself, the rubbing means or device (wiper means or device) to which the same is attached, etc. are used. The surface of the optical compensation film layer or the surface of the optical compensation film layer on the surface of each optical compensation film alone or the surface of the laminated optical film is contacted with an adhesive roll or wiped by using a hand or a machine. It is good to do.
When the optical compensation film alone or the laminated optical film is a long continuous film, the adhesive roll contact treatment method is the same as or larger than the width of the optical compensation film alone or the laminated optical film. Using an adhesive roll having a width (roll width), the surface of the optical film is brought into contact with the rotating surface of the adhesive roll while continuously transporting a long optical compensation film alone or a laminated optical film. For example, a rubbing means (rubbing device) can be used as a rubbing treatment method that is equal to or more than the width of a single optical compensation film or a laminated optical film. Roll form, belt form, or long sheet form having a large width, and the rubbing means (rubbing device) The surface of the optical compensation film alone or the surface of the optical compensation film layer or the surface of the optical compensation film layer in the laminated optical film is brought into contact with the surface of the optical film by a predetermined distance or a predetermined pressure along the transport direction of the optical film. Thus, a method of wiping the surface of the optical compensation film layer or the surface of the optical compensation film layer on the surface of the optical compensation film alone or the surface of the laminated optical film can be employed.

The adhesive roll contact treatment or rubbing treatment may be performed only once, or may be repeated twice or more as long as the optical compensation function and other characteristics are not degraded. Moreover, you may perform both a rubbing process and an adhesive roll contact process.
The conditions for the adhesive roll contact treatment or rubbing treatment are as follows: adhesive roll contact means (apparatus) or rubbing means (apparatus), adhesive material and wiping part material, means and apparatus structure, optical compensation film alone or surface Depending on the type and material of the optical compensation film layer or the laminated optical film having the optical compensation film layer, the material of the adhesive layer to be formed later on the optical film, conditions suitable for each situation are adopted. It is good to do.
In addition, the timing of performing the adhesive roll contact treatment or rubbing treatment in the present invention is not particularly limited, but in the case where surface treatment such as saponification or heat treatment is performed on the optical film because the effect exerted by the method of the present invention is great. Is preferably subjected to an adhesive roll contact treatment or a rubbing treatment after a surface treatment step such as saponification or heat treatment, and in particular, an adhesive roll contact treatment or a rubbing treatment is performed immediately before forming the adhesive layer on the optical film. It is more preferable.

In addition, when the optical compensation film alone or the optical compensation film layer on the surface of the laminated optical film contains a polymer having a structural unit derived from a monomer having a fluoroalkyl group, etc. X-ray photoelectron spectroscopy on the surface of an optical film made of a single optical compensation film or on the surface of the optical compensation film layer or optical compensation film layer of the laminated optical film by performing an adhesive roll contact treatment or a rubbing treatment It is desirable that the ratio of the elemental fluorine measured in step 1 is reduced as compared with that before the adhesive roll contact treatment or rubbing treatment, and the reduction ratio of the elemental fluorine at that time is preferably 5% or more. % Or more is more preferable, and it is further more preferable that it is 10% or more. When the adhesive compensation roller contact treatment or the rubbing treatment is performed so that the reduction rate of the fluorine element on the surface of the optical compensation film layer or the surface of the optical compensation film layer on the surface of the optical compensation film alone or the laminated optical film becomes the above value, The adhesive force of the pressure-sensitive adhesive to the optical compensation film layer or the optical compensation film layer on the surface of the optical compensation film or the laminated optical film is improved, and a pressure-sensitive adhesive optical film free from adhesive residue can be obtained smoothly.
Here, “the ratio of fluorine element measured by X-ray photoelectron spectroscopy on the surface of the optical film consisting of a single optical compensation film or on the surface of the optical compensation film layer or optical compensation film layer of the laminated optical film” It refers to the proportion of fluorine element (unit: atomic%) measured by the method described in the following examples.
Further, the reduction rate of the fluorine element is determined by the optical compensation film layer on the surface of the optical compensation film alone or the laminated optical film before the adhesive roll contact treatment or rubbing treatment or the fluorine element on the surface of the optical compensation film layer. The ratio is F ₀ (Atomic%), and the ratio of the same fluorine element after the adhesive roll contact treatment or rubbing treatment is F ₁ (Atomic%).

Reduction rate of elemental fluorine (%) = {(F ₀ −F ₁ ) / F ₀ } × 100 (1)

In the present invention, the optical compensation film layer or the optical compensation in the laminated optical film having the optical compensation film layer or the optical compensation film layer on the surface of the optical compensation film alone subjected to the adhesive roll contact treatment or the rubbing treatment. An adhesive is applied to the surface of the film layer to form an adhesive layer.
As the pressure-sensitive adhesive applied to the optical film, any of the pressure-sensitive adhesives used in the pressure-sensitive optical film can be used. For example, acrylic pressure-sensitive adhesive, polyester pressure-sensitive adhesive, rubber pressure-sensitive adhesive (natural rubber, SBR, recycled) Rubber-based pressure-sensitive adhesives) and silicone-based pressure-sensitive adhesives. Moreover, from the usage form of the pressure-sensitive adhesive, it can be classified into a syrup-type pressure-sensitive adhesive, an ultraviolet curable pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, a solvent-coated pressure-sensitive adhesive, and the pressure-sensitive adhesive used in the present invention is as described above. Any form may be sufficient.
Among them, in the present invention, at least one methacrylic acid alkyl ester polymer block (A) having a glass transition temperature of 100 ° C. or higher and an acrylic acid alkyl ester polymer block having a glass transition temperature of −20 ° C. or lower are used as the pressure-sensitive adhesive. It is preferable to use a pressure-sensitive adhesive containing an acrylic block copolymer having at least one (B) at a solid content ratio of 60% by mass or more, and the pressure-sensitive adhesive exhibits high cohesive force, reworkability, Excellent adhesive properties, optical properties (light unevenness, transparency, etc.) and durability.

  At that time, as the acrylic triblock copolymer which is the main component of the pressure-sensitive adhesive, at least one methacrylic acid alkyl ester polymer block (A) having a glass transition temperature of 100 ° C. or higher and a glass transition temperature of −20 are used. Any acrylic block copolymer having at least one acrylic acid alkyl ester polymer block (B) at a temperature not higher than ° C., for example, a methacrylic acid alkyl ester polymer block (A) and an acrylic acid alkyl ester polymer A diblock copolymer in which one block (B) is bonded, a triblock copolymer in which two methacrylic acid alkyl ester polymer blocks (A) and one acrylic alkyl ester polymer block (B) are bonded. 1 unit of polymer, alkyl methacrylate ester polymer block (A) and acrylic acid A triblock copolymer in which two of the alkyl ester polymer blocks (B) are bonded, two or more alkyl methacrylate polymer blocks (A) and two or more alkyl alkyl ester polymer blocks (B). A polyblock copolymer having a tetrablock or more bonded can be used.

  Among them, in the present invention, as the pressure-sensitive adhesive, (A)-(B)-(, wherein one methacrylic acid alkyl ester polymer block (A) is bonded to both ends of the acrylic acid alkyl ester polymer block (B). A pressure-sensitive adhesive containing 60% by mass or more of the triblock copolymer of A) is more preferably used. This pressure-sensitive adhesive does not require chemical cross-linking treatment, exhibits high cohesion even without chemical cross-linking treatment, is excellent in reworkability, adhesive properties, heat resistance, durability, etc., and excellent in storage stability of the pressure-sensitive adhesive solution Due to the drying process and storage conditions (temperature, air volume, line speed, storage period, etc.), cross-linking unevenness does not occur and it has uniform and high-performance adhesive properties. By using this adhesive, high quality The pressure-sensitive adhesive optical film can be produced with good processability and high productivity.

In particular, in the present invention, an acrylic having the following requirements (E1), (E2), (E3) and (E4) described in Japanese Patent Application No. 2008-546793, which is filed by the present applicant, as an adhesive. It is further preferable to use a non-chemically crosslinked optical film pressure-sensitive adhesive containing the triblock copolymer (I) in a proportion of 60% by mass or more based on the total mass of the total solids contained in the pressure-sensitive adhesive. .
○ Acrylic triblock copolymer (I) :
(E1) The following general formula (1);
A1-B-A2 (1)
(In the formula, A1 and A2 each independently represent a methacrylic acid alkyl ester polymer block having a glass transition temperature of 100 ° C. or higher, and B represents an acrylic acid alkyl ester polymer block having a glass transition temperature of −20 ° C. or lower. )
An acrylic triblock copolymer represented by:
(E2) The content of the polymer block B is 50 to 95% by mass;
(E3) the weight average molecular weight (Mw) is from 50,000 to 300,000; and
(E4) The molecular weight distribution (Mw / Mn) is 1.0 to 1.5.

  The acrylic triblock copolymer (I) having the above requirements (E1), (E2), (E3) and (E4), preferably used in the present invention, is contained at a ratio of 60% by mass or more in terms of solid content The optical film pressure-sensitive adhesive does not require chemical crosslinking treatment, exhibits high cohesion without chemical crosslinking treatment, and has excellent reworkability, adhesive properties, heat resistance, durability, etc. By using the pressure-sensitive adhesive, a uniform and high-performance pressure-sensitive adhesive optical film having no variation in pressure-sensitive adhesive performance can be produced with good processability and high productivity while omitting the crosslinking step.

Here, the adhesive mainly composed of the acrylic triblock copolymer (I) preferably used in the present invention and the acrylic block copolymer (I) mainly composed of the adhesive will be described in detail.
[Acrylic triblock copolymer (I) and pressure-sensitive adhesive mainly composed thereof]
In the acrylic triblock copolymer (I), the polymer blocks A1 and A2 are methacrylic acid alkyl ester polymer blocks having a glass transition temperature of 100 ° C. or higher, more preferably 100 to 200 ° C., particularly 100 to 150 ° C. Are preferable from the viewpoints of durability, heat resistance, followability to deformation of the substrate, and moderate stress relaxation properties.
In the acrylic triblock copolymer (I), the two polymer blocks A1 and A2 have the same polymer [molecular weight, monomer composition, steric structure (syndiotacticity, etc.), etc. One or more of different polymers [molecular weight, monomer composition, steric structure (and syndiotacticity, etc.), etc. It may be composed of different alkyl methacrylate polymers].

Examples of the methacrylic acid alkyl ester units constituting the polymer blocks A1 and A2 include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, methacrylic acid. Examples thereof include units composed of methacrylic acid alkyl esters such as cyclohexyl acid, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and isobornyl methacrylate. Polymer block A1 and A2 may be formed from only one kind of the above-mentioned methacrylic acid alkyl ester unit, or may be formed from two or more kinds.
Among them, the polymer blocks A1 and A2 are made of polymethyl methacrylate, the raw material methyl methacrylate is easily available at an economical price, and polymethyl methacrylate has excellent durability. It is preferable from the point of having weather resistance.

The polymer block B constituting the acrylic triblock copolymer (I) is an acrylic acid constituting the polymer block B as long as it is a polymer block composed of an alkyl acrylate ester and having a glass transition temperature of −20 ° C. or lower. The kind and component composition of the alkyl ester unit are not particularly limited.
The polymer block B having a glass transition temperature of −20 ° C. or lower imparts excellent flexibility and wettability to the acrylic triblock copolymer (I) that forms a microphase-separated structure at a normal use temperature, The pressure-sensitive adhesive for optical films of the present invention (hereinafter sometimes simply referred to as “the pressure-sensitive adhesive of the present invention” or “pressure-sensitive adhesive”) exhibits appropriate adhesive strength and good reworkability.
Among them, the polymer block B is preferably made of an acrylic acid alkyl ester polymer having a glass transition temperature of −30 ° C. or lower, particularly −40 to −80 ° C. from the viewpoint of excellent durability under low temperature conditions.

Examples of the acrylic acid alkyl ester unit constituting the polymer block B include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, and cyclohexyl acrylate. , 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, and the like. It may be formed from only one type of unit, or may be formed from two or more types.
Among them, the polymer block B is composed of one or more units composed of propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. The glass transition temperature of the block B is −20 ° C. or lower, the adhesive strength and tack at low temperatures of the pressure-sensitive adhesive are good, and the adhesive strength increase at the time of high-speed peeling and the zipping phenomenon can be suppressed.
In particular, the polymer block B is composed of n-butyl acrylate units and / or 2-ethylhexyl acrylate units, so that n-butyl acrylate and 2-ethylhexyl acrylate are available as general-purpose chemicals at low cost. In addition, the phase separation between the polymer block A and the polymer block B becomes clear, and the pseudo-crosslinking point of the polymer block A is not broken, and the cohesive force as an adhesive is high and the durability is excellent. To preferred.

  The polymer blocks A1 and A2 and the polymer block B constituting the acrylic triblock copolymer (I) are in a small amount (usually 10% by mass or less based on the mass of each polymer block) within a range not impairing the effect. Ratio), other monomer units may be included. Examples of other monomer units that the polymer blocks A1 and A2 and the polymer block B may have include, for example, methoxyethyl (meth) acrylate (methoxyethyl acrylate or methoxyethyl methacrylate). Similarly, ethoxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) (Meth) acrylic acid ester having a functional group such as tetrahydrofurfuryl acrylate; vinyl monomer having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, (meth) acrylamide, etc. -; Styrene, α-methylstyrene, p-methyl Examples include units composed of aromatic vinyl monomers such as tylene; conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene and propylene; and lactone monomers such as ε-caprolactone and valerolactone. One or more of these monomer units can be included as required.

The ratio of the polymer block B in the acrylic triblock copolymer (I) is 50 to 95% by mass based on the mass of the acrylic triblock copolymer (I) [the above requirement (E2)]. 60 to 85% by mass, and more preferably 65 to 80% by mass.
When the content ratio of the polymer block B in the acrylic triblock copolymer (I) is within the above range, the adhesive force of the pressure-sensitive adhesive becomes stable.
When the content of the polymer block B in the acrylic triblock copolymer (I) is less than 50% by mass, the adhesive strength of the pressure-sensitive adhesive is reduced, and when it exceeds 95% by mass, the polymer becomes a pseudo-crosslinking point. Since the content ratios of the blocks A1 and A2 are relatively reduced, the cohesive force is reduced, and the durability of the pressure-sensitive adhesive is lowered.

The acrylic triblock copolymer (I) has a weight average molecular weight (Mw) of 50,000 to 300,000 [the above requirement (E3)], and from the viewpoint of both durability and reworkability, 60 It is preferable that it is 150,000-250,000, and it is more preferable that it is 70,000-200,000.
When the weight average molecular weight (Mw) of the acrylic triblock copolymer (I) is less than 50,000, the cohesive force of the adhesive becomes insufficient, and the optical film is attached to the adherend using the adhesive. Or when the protective film is attached to the optical film, it becomes easy to peel off and becomes inferior in durability. On the other hand, when the weight average molecular weight (Mw) of the acrylic triblock copolymer (I) is larger than 300,000, the adhesive force gradually increases during storage of the product, and soot, bubbles, and foreign matter are caught. And rework when removing the optical film and the protective film and re-attaching them to eliminate misalignment. On the other hand, when the weight average molecular weight (Mw) of the acrylic triblock copolymer (I) is larger than 300,000, the solution viscosity becomes high and coating at a high concentration becomes impossible, and the amount of solvent used increases. .

The molecular weight distribution (Mw / Mn) of the acrylic triblock copolymer (I) is 1.0 to 1.5 [the above requirement (E4)], and the cohesive force at high temperature of the pressure-sensitive adhesive is increased, resulting in durability. The molecular weight distribution (Mw / Mn) is preferably from 1.0 to 1.4, more preferably from 1.0 to 1.3, from the viewpoint that the property becomes superior.
When the molecular weight distribution (Mw / Mn) of the acrylic triblock copolymer (I) is larger than 1.5, the influence of low molecular weight components cannot be ignored, and there are problems such as a decrease in cohesive force and adhesive residue during rework. Is likely to occur.
Here, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the acrylic triblock copolymer and the acrylic diblock copolymer described below are as follows: It is the value calculated | required by the method described in the following Examples.

The acrylic triblock copolymer (I) constituting the main component of the pressure-sensitive adhesive may consist of one kind of acrylic triblock copolymer that satisfies the above requirements (E1) to (E4), or the above It may consist of two or more types of acrylic triblock copolymers that satisfy the requirements (E1) to (E4).
In particular, the acrylic triblock copolymer (I) having the following requirements (E1), (E2), (E3 ′) and (E4) as the acrylic triblock copolymer (I), and the following requirements: An acrylic triblock copolymer (Ib) comprising (E1), (E2), (E3 ″) and (E4) is converted into an acrylic triblock copolymer (Ia): an acrylic triblock copolymer ( Ib) = 45: 55 to 75:25, preferably 50:50 to 70:30, more preferably 60:40 to 70:30 Adhesive properties (adhesive strength, creep, etc.), bulk properties (dynamic viscoelasticity, etc.) can be adjusted to desired physical properties more easily and smoothly, and the durability and reworkability of adhesives are further improved. improves.

○ Acrylic triblock copolymer (Ia) :
(E1) The following general formula (1);
A1-B-A2 (1)
(In the formula, A1 and A2 each independently represent a methacrylic acid alkyl ester polymer block having a glass transition temperature of 100 ° C. or higher, and B represents an acrylic acid alkyl ester polymer block having a glass transition temperature of −20 ° C. or lower. )
An acrylic triblock copolymer represented by:
(E2) The content of the polymer block B is 50 to 95% by mass;
(E3 ′) the weight average molecular weight (Mw) is 50,000 or more and less than 100,000; and
(E4) The molecular weight distribution (Mw / Mn) is 1.0 to 1.5.

○ Acrylic triblock copolymer (Ib) :
(E1) The following general formula (1);
A1-B-A2 (1)
(In the formula, A1 and A2 each independently represent a methacrylic acid alkyl ester polymer block having a glass transition temperature of 100 ° C. or higher, and B represents an acrylic acid alkyl ester polymer block having a glass transition temperature of −20 ° C. or lower. )
An acrylic triblock copolymer represented by:
(E2) The content of the polymer block B is 50 to 95% by mass;
(E3 ″) the weight average molecular weight (Mw) is 100,000 or more and 300,000 or less; and
(E4) The molecular weight distribution (Mw / Mn) is 1.0 to 1.5.

  When the acrylic triblock copolymer (I) is blended with the acrylic triblock copolymer (Ia) and the acrylic triblock copolymer (Ib), the acrylic triblock copolymer is used. The union (Ia) has the above requirements (E1), (E2) and (E4) and has a weight average molecular weight (Mw) of 50,000 to 90,000, more preferably 55,000 to 85,000, particularly 60 And the acrylic triblock copolymer (Ib) has the above-mentioned requirements (E1), (E2) and (E4), and has a weight average molecular weight (Mw). ) Is 100,000 to 200,000, more preferably 105,000 to 190,000, and particularly preferably 110,000 to 180,000. . Thereby, durability of the adhesive, reworkability, and followability to expansion and contraction of the optical film due to the influence of temperature and humidity are further improved.

  Moreover, in using what mix | blended acrylic triblock copolymer (Ia) and acrylic triblock copolymer (Ib) as acrylic type triblock copolymer (I), content of polymer block B Is used by blending an acrylic triblock copolymer (Ia) having a content of 50 to 70% by mass and an acrylic triblock copolymer (Ib) having a content of the polymer block B of 65 to 95% by mass. And the molecular weight of the polymer blocks A1 and A2 of the acrylic triblock copolymer (Ia) and the molecular weight of the polymer blocks A1 and A2 of the acrylic triblock copolymer (Ib) are close to each other. Compatibility between polymer blocks responsible for physical crosslinking of copolymer (Ia) and acrylic triblock copolymer (Ib) is increased, Triblock copolymer (Ia) and the acrylic triblock copolymer network structure by physical cross-linking of (Ib) is formed, is further improved durability of the adhesive.

  In addition, when the acrylic triblock copolymer (Ia) and the acrylic triblock copolymer (Ib) are blended and used as the acrylic triblock copolymer (I), the acrylic triblock copolymer (Ib) And an acrylic triblock copolymer (Ib-1) having the above requirements (E1), (E2) and (E4) and having a weight average molecular weight (Mw) of 100,000 or more and less than 120,000 An acrylic triblock copolymer (Ib-2) having the above requirements (E1), (E2) and (E4) and having a weight average molecular weight (Mw) of 120,000 to 200,000 is acrylic Triblock copolymer (Ib-1): Acrylic triblock copolymer (Ib-2) = 10: 90 to 90:10, preferably 50:50 to 90: Using a mixture of 0, more preferably 60:40 to 80:20 in a mass ratio makes it easier to achieve adhesive properties (adhesive strength, creep, etc.) and bulk properties (dynamic viscoelasticity, etc.) of the adhesive. In addition, the desired physical properties can be adjusted smoothly, and the durability and reworkability are excellent, coating at a high concentration is possible, and the amount of solvent used can be reduced.

  Acrylic triblock copolymer (I), Acrylic triblock copolymer (Ia), Acrylic triblock copolymer (Ib), Acrylic triblock copolymer (Ib-1) or Acrylic triblock In the copolymer (Ib-2), the syndiotacticity of the alkyl methacrylate polymer block constituting these triblock copolymers is preferably 65% or more, and preferably 70 to 95%. More preferred. When the syndiotacticity of the polymer block is 65% or more, the durability of the pressure-sensitive adhesive (persistence of pressure-sensitive adhesive properties) is improved.

The pressure-sensitive adhesive used in the present invention contains the above-described acrylic triblock copolymer (I) in a proportion of 60% by mass or more based on the total mass of the total solids contained in the pressure-sensitive adhesive. Preferably, it is contained at a ratio of 75 mass%, more preferably 80 mass% or more.
When the content of the acrylic triblock copolymer (I) is less than 60% by mass based on the total mass of the total solids contained in the pressure-sensitive adhesive, the cohesive force decreases, and the durability of the pressure-sensitive adhesive ( The durability of the adhesive strength may decrease.

The pressure-sensitive adhesive used in the present invention is an acrylic diblock having the following requirements (F1), (F2), (F3) and (F4) as necessary together with the above-described acrylic triblock copolymer (I). A block copolymer (II) can be contained.
○ Acrylic diblock copolymer (II) :
(F1) The following general formula (2);
CD (2)
(In the formula, C represents a methacrylic acid alkyl ester polymer block, and D represents an acrylic acid alkyl ester polymer block.)
An acrylic diblock copolymer represented by:
(F2) The content of the polymer block D is 50 to 95% by mass;
(F3) the weight average molecular weight (Mw) is from 50,000 to 300,000; and
(F4) The molecular weight distribution (Mw / Mn) is 1.0 to 1.5.

When the pressure-sensitive adhesive used in the present invention further contains an acrylic diblock copolymer (II) together with the acrylic triblock copolymer (I), the content of the acrylic diblock copolymer (II) Is preferably 3 to 25% by mass, more preferably 3 to 20% by mass based on the total mass of the total solid content contained in the pressure-sensitive adhesive.
When the acrylic diblock copolymer (II) is contained in the amount described above, the wettability of the pressure-sensitive adhesive to the adherend is improved, the change in adhesive force with time is reduced, and the optical film has excellent reworkability. A pressure-sensitive adhesive can be obtained. When the content of the acrylic diblock copolymer (II) exceeds 25% by mass, the cohesive force of the pressure-sensitive adhesive is lowered, and durability (maintaining a long-term adhesion state) may be deteriorated.

In the acrylic diblock copolymer (II), the polymer block C is preferably a polymer block made of a methacrylic acid alkyl ester polymer having a glass transition temperature of 50 ° C. or higher, and the polymer block D is A polymer block made of an acrylic acid alkyl ester polymer having a glass transition temperature of −20 ° C. or lower is preferred.
Further, the polymer block C of the acrylic diblock copolymer (II) is compatible with the polymer block A of the acrylic triblock copolymer (I) that is the main component in the pressure-sensitive adhesive. The polymer block D of the acrylic diblock copolymer (II) is preferably compatible with the polymer block B of the acrylic triblock copolymer (I).
As a result, the polymer block C of the acrylic diblock copolymer (II) is constrained by the constrained phase comprising the polymer blocks A1 and A2 in the acrylic triblock copolymer (I), thereby preventing a decrease in cohesive force. To do. Further, the polymer block D of the acrylic diblock copolymer (II) is present in an unconstrained phase composed of the polymer block B of the acrylic triblock copolymer (I), and is an interface with the adherend. In the bonding process, the wettability is improved and a stable adhesive force is expressed from the initial stage of bonding.

  In the acrylic diblock copolymer (II), examples of the methacrylic acid alkyl ester unit constituting the polymer block C include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and methacrylic acid t. -Units consisting of methacrylic acid alkyl esters such as butyl, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate The polymer block C may be formed from only one kind of the above-described methacrylic acid alkyl ester units, or may be formed from two or more kinds. Among them, the polymer block C is composed of polymethyl methacrylate, the raw material methyl methacrylate can be easily obtained at an economical price, and polymethyl methacrylate has excellent durability and weather resistance. From the point of having.

In the acrylic diblock copolymer (II), examples of the acrylic acid alkyl ester unit constituting the polymer block D include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid t -Units consisting of acrylic acid alkyl esters such as butyl, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate The polymer block D may be formed from only one kind of the above-described alkyl acrylate units, or may be formed from two or more kinds.
Among them, the polymer block D is preferably composed of one or more units composed of propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, As a result, the glass transition temperature of the polymer block D becomes −20 ° C. or lower, the adhesive strength and tack at a low temperature of the pressure-sensitive adhesive are improved, and the adhesive strength increase and zipping phenomenon at the time of high-speed peeling can be suppressed. . Among the above-described monomers, n-butyl acrylate and 2-ethylhexyl acrylate are available as inexpensive general-purpose chemicals.

  The polymer block C and polymer block D constituting the acrylic diblock copolymer (II) are in a small amount (usually a ratio of 10% by mass or less with respect to the mass of each polymer block) as long as the effect is not impaired. If so, it may have other monomer units. Examples of other monomer units that the polymer block C and the polymer block D may have include, for example, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( (Meth) acrylic acid ester having a functional group such as 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; (meth) Vinyl monomers having a carboxyl group such as acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid and (meth) acrylamide; aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene Conjugated diene monomers such as butadiene and isoprene; ethylene Olefin monomers such as propylene; .epsilon.-caprolactone, can be mentioned a unit consisting of a lactone monomer such as valerolactone may have optionally one or two or more of these monomer units.

The content ratio of the polymer block D in the acrylic diblock copolymer (II) is 50 to 95% by mass based on the mass of the acrylic diblock copolymer (II) [the above requirement (F2) ], Preferably 70 to 95% by mass.
When the content ratio of the polymer block D in the acrylic diblock copolymer (II) is within the above range, the adhesive force of the pressure-sensitive adhesive is stabilized.
When the content of the polymer block D in the acrylic diblock copolymer (II) is less than 50% by mass, the adhesive strength of the pressure-sensitive adhesive is reduced, while when it exceeds 95% by mass, the polymer becomes a pseudo-crosslinking point. Since the content ratio of the block C is relatively reduced, the cohesive force is reduced, and the durability of the pressure-sensitive adhesive may be inferior.

The acrylic diblock copolymer (II) has a weight average molecular weight (Mw) of 50,000 to 300,000 [the above requirement (F3)], and from the viewpoint of both durability and reworkability, 60 It is preferable that it is 150,000-250,000, and it is more preferable that it is 70,000-200,000.
If the weight average molecular weight (Mw) of the acrylic diblock copolymer (II) is less than 50,000, the cohesive force of the pressure-sensitive adhesive becomes insufficient, and the acrylic diblock copolymer (I) together with the acrylic diblock copolymer (I). When an optical film is attached to an adherend using an adhesive containing a block copolymer (II), or when a protective film is attached to an optical film, it becomes easy to peel off and becomes inferior in durability. . On the other hand, when the weight average molecular weight (Mw) of the acrylic diblock copolymer (II) is larger than 300,000, the wettability decreases, so that the adhesive force gradually increases during storage of the product. In addition, it becomes difficult to rework when peeling off the optical film or the protective film and re-bonding them in order to eliminate the occurrence of bubbles and foreign matters.
The acrylic diblock copolymer (II) has a molecular weight distribution (Mw / Mn) of 1.0 to 1.5 [the above requirement (F4)], excellent cohesion, and adherend contamination (adhesive residue). From the viewpoint of low adhesion of low molecular weight components, etc., it is preferably 1.0 to 1.4, more preferably 1.0 to 1.3.

  For the acrylic triblock copolymer (I) and the acrylic diblock copolymer (II), a method according to a known method can be adopted. Generally, as a method for obtaining a block copolymer having a narrow molecular weight distribution, a method of living polymerizing a monomer as a constituent unit is employed. Examples of such living polymerization methods include a method of polymerizing using an organic rare earth metal complex as a polymerization initiator (see Patent Document 3), and an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator. A method of anionic polymerization in the presence of a mineral acid salt (see Patent Document 4), a method of anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see Patent Document 5), atoms A moving radical polymerization method (ATRP) (see Non-Patent Document 1), and the like.

  Among the above production methods, in the case of anionic polymerization in the presence of an organoaluminum compound, there is little deactivation during the polymerization, so there is little mixing of the deactivating component homopolymer. High transparency. Moreover, since the polymerization conversion rate of a monomer is high, there are few residual monomers in a product, and when using it as an adhesive for optical films, generation | occurrence | production of the bubble after bonding can be suppressed. Furthermore, the molecular structure of the methacrylic acid alkyl ester polymer block is highly syndiotactic and has the effect of enhancing durability when used in an optical film pressure-sensitive adhesive. And because living polymerization is possible under relatively mild temperature conditions, it is possible to reduce the environmental burden (mainly the electric power applied to the refrigerator for controlling the polymerization temperature) for industrial production. There is. From the above points, the acrylic triblock copolymer (I) and the acrylic diblock copolymer (II) used in the present invention are preferably produced by a method of anionic polymerization in the presence of an organoaluminum compound.

Examples of the anionic polymerization method in the presence of the above organoaluminum compound include an organolithium compound and the following general formula (III):
AlR ¹ R ² R ³ (III)
Wherein R ¹ , R ² and R ³ are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl which may have a substituent. A group, an aralkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent or an N, N-disubstituted amino group, or R ¹ is any of the groups described above, and R ² and R ³ are combined to form an aryleneoxy group which may have a substituent.
In the presence of an organoaluminum compound represented by formula (2), an ether compound such as dimethyl ether, dimethoxyethane, diethoxyethane, or 12-crown-4; if necessary, in the reaction system; triethylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, pyridine, 2,2 ′ -A method of polymerizing a (meth) acrylic acid alkyl ester by further adding a nitrogen-containing compound such as dipyridyl can be employed.

  Examples of the organic lithium compound include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, isobutyl lithium, tert-butyl lithium, n-pentyl lithium, and n-hexyl. Alkyllithium and alkyldilithium such as lithium, tetramethylenedilithium, pentamethylenedilithium and hexamethylenedilithium; aryllithium and aryl such as phenyllithium, m-tolyllithium, p-tolyllithium, xylyllithium and lithium naphthalene Dilithium; benzyl lithium, diphenylmethyl lithium, trityl lithium, 1,1-diphenyl-3-methylpentyl lithium, α-methylstyryl lithium, diisopropyl Aralkyllithium and aralkyldilithium such as dilithium produced by the reaction of phenylbenzene and butyllithium; lithium amides such as lithium dimethylamide, lithium diethylamide and lithium diisopropylamide; methoxylithium, ethoxylithium, n-propoxylithium, isopropoxylithium, n -Butoxylithium, sec-butoxylithium, tert-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, 4-methylbenzyloxylithium, etc. Lithium alkoxide of the following. These may be used alone or in combination of two or more.

  Examples of the organoaluminum compound represented by the general formula (III) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tris-butylaluminum, tri-t-butylaluminum, triisobutylaluminum, n-hexylaluminum, tri-n-octylaluminum, tri-2-ethylhexylaluminum, trialkylaluminum such as triphenylaluminum, dimethyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, dimethyl (2,6 -Di-tert-butylphenoxy) aluminum, diethyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-tert-butylphenoxy) aluminum, Isobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-tert-butylphenoxy) aluminum, di-n-octyl (2,6-di-tert-butyl-) 4-methylphenoxy) aluminum, dialkylphenoxyaluminum such as di-n-octyl (2,6-di-tert-butylphenoxy) aluminum, methylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, Methylbis (2,6-di-tert-butylphenoxy) aluminum, ethyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, ethylbis (2,6-di-tert-butyl- 4-methylphenoxy) aluminum, ethylbis 2,6-di-tert-butylphenoxy) aluminum, ethyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di-tert-butyl-4) -Methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, n-octylbis (2 , 6-Di-tert-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-tert-butylphenoxy) aluminum, n-octyl [2,2′-methylenebis (4-methyl-6- tert-Butylphenoxy)] Alkyl diphe such as aluminum Noxyaluminum, methoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-di-tert-butylphenoxy) aluminum, methoxy [2,2′-methylenebis (4-methyl) -6-tert-butylphenoxy)] aluminum, ethoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-di-tert-butylphenoxy) aluminum, ethoxy [2,2 '-Methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isopropoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isopropoxybis (2,6-di-tert) -Butylphenoxy) Aluminum, A Propoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, tert-butoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, tert-butoxybis (2, Alkoxydiphenoxyaluminum such as 6-di-tert-butylphenoxy) aluminum, tert-butoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, tris (2,6-di-) and triphenoxyaluminum such as tert-butyl-4-methylphenoxy) aluminum and tris (2,6-diphenylphenoxy) aluminum. Among these organoaluminum compounds, isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2 ′ -Methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, etc. is easy to handle and allows the polymerization of (meth) acrylic acid esters to proceed without deactivation under relatively mild temperature conditions. It is particularly preferable in that These may be used alone or in combination of two or more.

  The pressure-sensitive adhesive mainly composed of the acrylic triblock copolymer (I) preferably used in the present invention contains only the acrylic triblock copolymer (I) as a solid content (component other than the organic solvent). It may be necessary to contain only the acrylic triblock copolymer (I) and the acrylic diblock copolymer (II), or if necessary, tackifying One or more of resins, plasticizers and other additives may be further contained. When components other than the acrylic triblock copolymer (I) are contained, the total content of the other components may be 40% by mass or less based on the total mass of the total solids contained in the pressure-sensitive adhesive. Preferably, it is more preferably 25% by mass or less, and further preferably 20% by mass or less.

When tackifying resin is mix | blended with the adhesive which has acrylic triblock copolymer (I) as a main component, adjustment of a tack, adhesive force, and holding power becomes easy. As the tackifying resin, any of the conventionally used tackifying resins in pressure-sensitive adhesives can be used. For example, natural resins such as rosin resins and terpene resins; petroleum resins, coumarone-indene resins, phenolic resins Examples thereof include synthetic resins such as resins, xylene resins, and styrene resins, and only one of them may be used, or two or more may be used in combination.
Among the above-mentioned tackifying resins, terpene resins such as hydrogenated terpene resins and terpene phenols are highly compatible with the acrylic triblock copolymer (I) and exhibit stable adhesive strength; water Rosin resins such as rosin ester, disproportionated rosin ester and polymerized rosin; petroleum resins such as C5 / C9 petroleum resin and aromatic petroleum resin; α-methylstyrene polymer, styrene / α-methylstyrene copolymer, etc. A tackifying resin such as a styrene resin is preferably used. These may be used alone or in combination of two or more.
The softening point of the tackifying resin is preferably 50 ° C. to 150 ° C. in order to develop a high adhesive force.

  The blending amount of the tackifying resin in the pressure-sensitive adhesive can be appropriately selected according to the type of adherend, but when the blending amount is increased, the cohesive force is reduced, resulting in inconvenience such as occurrence of adhesive residue during rework. Therefore, based on the total mass of the total solids contained in the pressure-sensitive adhesive, it is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

Examples of the plasticizer that can be used as needed for the pressure-sensitive adhesive include dibutyl phthalate, di-n-octyl phthalate, bis-2-ethylhexyl phthalate, di-n-decyl phthalate, and diisodecyl phthalate. Phthalates, adipates such as bis-2-ethylhexyl adipate, di-n-octyl adipate, sebacates such as bis-2-ethylhexyl sebacate, di-n-butyl sebacate, bis Fatty acid esters such as azelaic acid esters such as 2-ethylhexyl azelate; Paraffins such as chlorinated paraffin; Glycols such as polypropylene glycol; Epoxy such as epoxidized soybean oil and epoxidized linseed oil Polymer plasticizer; phosphoric acid such as trioctyl phosphate and triphenyl phosphate Stealth; Phosphites such as triphenyl phosphite; Ester oligomers such as esterified product of adipic acid and 1,3-butylene glycol; n-butyl poly (meth) acrylate, poly (meta ) Acrylic oligomers such as 2-ethylhexyl acrylate; polybutene; polyisobutylene; polyisoprene; process oil; naphthenic oil and the like. These may be used alone or in combination of two or more. May be.
The blending amount of the plasticizer in the pressure-sensitive adhesive is preferably 25% by mass or less, and more preferably 10% by mass or less, based on the total mass of the total solids contained in the pressure-sensitive adhesive. When the blending amount of the plasticizer is increased, the cohesive force is lowered, and inconvenience such as occurrence of adhesive residue at the time of rework tends to occur.

  In addition, the pressure-sensitive adhesive mainly composed of the acrylic triblock copolymer (I) can contain an isocyanate compound, if necessary. When the isocyanate compound is contained, the isocyanate group content in the isocyanate compound is high. It is preferable that the amount is 0.0015% by mass or more and less than 0.35% by mass based on the mass of the solid material of the pressure-sensitive adhesive. An optical compensation film layer or optical compensation in an optical compensation film alone or in a laminated optical film by containing an isocyanate compound in an amount in the above range in an adhesive mainly comprising an acrylic triblock copolymer (I). The adhesive force with respect to the film layer can be further increased.

  In recent years, it has been emphasized that an antistatic agent is added for the purpose of preventing static electricity from being generated when the protective film is peeled off or reworked. From this point, also in the present invention, it is preferable to add an antistatic agent to the adhesive note. Examples of the antistatic agent preferably used in the present invention include ionic conductive agents composed of alkali metal salts, ionic liquids, surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. . Among these, from the viewpoint of permanent chargeability and no coloration, an ionic conductive agent or ionic liquid made of an alkali metal salt is more preferably used. The above-mentioned antistatic agents may be used alone or in combination of two or more.

  The pressure-sensitive adhesive mainly composed of the acrylic triblock copolymer (I) preferably used in the present invention can further contain other components in addition to those described above. Examples of the other components include weather resistance. Antioxidants and UV absorbers for further improving heat resistance and oxidation resistance; inorganic powder fillers such as calcium carbonate, titanium oxide, mica and talc; fibrous fillers such as glass fibers and organic reinforcing fibers And so on. Moreover, in order to improve adhesiveness with the glass under high humidity, you may contain a silane coupling agent. Furthermore, you may contain a light-diffusion agent, a near-infrared absorber, a coloring agent, an electroconductivity imparting agent, etc. as a compounding agent for providing a desired function to an adhesive layer.

  In the case of pressure-sensitive adhesives that do not involve chemical cross-linking, there is no chemical cross-linking reaction after application to the optical film base, so that if the optical film base contains a fluoroalkyl group-containing polymer, the optical film base In the case of using the method of the present invention, the adhesive force between the optical film substrate and the pressure-sensitive adhesive is sufficiently high even when a pressure-sensitive adhesive without chemical crosslinking is used. Thus, an adhesive optical film having no adhesive residue can be produced smoothly.

  An optical compensation film or a laminated optical film having an optical compensation film layer on the surface, or an adhesive roll contact treatment or rubbing treatment, followed by the adhesive roll contact treatment or rubbing treatment. In forming an adhesive layer by applying an adhesive to the compensation film surface or the optical compensation film surface, the method for forming the adhesive layer is not particularly limited. For example, (i) it is dissolved in a solvent or heated on the surface of a single optical compensation film that has been subjected to adhesive roll contact treatment or rubbing treatment, or on the surface of the optical compensation film layer or optical compensation film layer of the laminated optical film. A method for producing a pressure-sensitive adhesive optical film by coating a pressure-sensitive adhesive that has been melted to form a liquid; (ii) a pressure-sensitive adhesive on a release film such as a polyethylene terephthalate film that has been pre-released Is applied to the surface of a single optical compensation film which has been subjected to adhesive roll contact treatment or rubbing treatment, or is transferred to the optical compensation film surface or the optical compensation film surface of the laminated optical film, thereby producing an adhesive optical film. (Iii) The surface of a single optical compensation film which has been subjected to adhesive roll contact treatment or rubbing treatment or the above laminated optical film Of the surface of the optical compensation film layer or an optical compensation film layer, it can be adopted a method of melt extruding an adhesive.

  When an adhesive mainly composed of acrylic triblock copolymer (I) is used as the adhesive, for example, the coating operation is performed using a solution dissolved in an organic solvent such as toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, or the like. The pressure-sensitive adhesive optical film may be manufactured by heating, or the pressure-sensitive adhesive is heated and melted to a temperature of 160 to 250 ° C., and the melt is used to perform a coating operation to manufacture the pressure-sensitive adhesive optical film. Alternatively, the pressure-sensitive adhesive may be melt extruded onto the optical film.

  The thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive optical film produced by the method of the present invention is not particularly limited, and the thickness of the optical compensation film alone or the laminated optical film forming the pressure-sensitive adhesive layer, the pressure-sensitive adhesive optics obtained It can be determined according to the purpose of the film. In general, the thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive optical film is preferably about 5 to 500 μm, more preferably about 10 to 100 μm, from the viewpoint of stress relaxation, adhesive strength, optical characteristics, and the like.

  The pressure-sensitive adhesive optical film obtained by the production method of the present invention can be used effectively when producing a liquid crystal display device, organic EL, electronic paper, plasma display (PDP), touch panel, retroreflective plate and the like.

  The method of the present invention is not limited to a single optical compensation film or a laminated optical film having an optical compensation film layer or an optical compensation film layer on the surface, and can be applied to any optical film. Applicable optical films include, for example, antiglare film, antireflection film, reflective film for backlight, light guide film, polarizing film, transparent conductive film, brightness enhancement film, diffusion film, protective film, prism film, fingerprint resistance A film, an electromagnetic wave shielding film, a hard coat film, a sealing film, an anisotropic film, a near-infrared cut film, etc. can be mentioned.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
The acrylic triblock copolymers used in Examples and Comparative Examples were synthesized by the following synthesis examples using chemicals dried and purified by a conventional method.
Further, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), composition (n-butyl polyacrylate in the acrylic triblock copolymer) of the synthesized acrylic triblock copolymer Content ratio of block), syndiotacticity [stereoregularity (rr)] of polymethyl methacrylate block in triblock copolymer, glass transition temperature of each polymer block, polymerization conversion rate of charged monomer, Measurement or evaluation of the ratio of the fluorine element on the surface, the adhesive strength of the adhesive roll, the adhesive strength of the adhesive layer in the adhesive optical film and the adhesive residue was performed as follows.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of acrylic triblock copolymer:
The weight average molecular weight (Mw) of the acrylic triblock copolymer was measured by gel permeation chromatography (GPC) using the following apparatus and conditions using a solution of the acrylic triblock copolymer dissolved in tetrahydrofuran. ) And number average molecular weight (Mn).
-Apparatus: Gel permeation chromatograph "HLC-8020" manufactured by Tosoh Corporation
-Column: TSKgel GMHXL, G4000HXL and G5000HXL manufactured by Tosoh Corporation connected in series-Eluent: Tetrahydrofuran-Eluent flow rate: 1.0 ml / min-Column temperature: 40 ° C
・ Detection method: Differential refractive index (RI)
-Calibration curve: created using standard polystyrene

(2) Molecular weight distribution of acrylic triblock copolymer (Mw / Mn):
The molecular weight distribution (Mw / Mn) was determined by dividing the weight average molecular weight (Mw) value of the acrylic triblock copolymer by the number average molecular weight (Mn) value.

(3) Composition of acrylic triblock copolymer:
An acrylic triblock copolymer is dissolved in deuterated chloroform, using a nuclear magnetic resonance apparatus ("JNM-LA400") manufactured by JEOL Ltd., deuterated chloroform as a solvent, and proton nuclear magnetic resonance ( ¹ H- The composition of the acrylic triblock copolymer (content ratio of polymethyl methacrylate block and poly (n-butyl acrylate block) in the acrylic triblock copolymer) was measured by NMR spectroscopy.
At that time, in the ¹ H-NMR spectrum, signals in the vicinity of 3.6 ppm and 4.0 ppm are respectively an ester group of a methyl methacrylate unit (—O—C H ₃ ) and an ester of an n-butyl acrylate unit. was assigned based on _{(-O-C H 2 -CH 2} -CH 2 -CH 3), was determined the content of the copolymerization component by the ratio of the integrated value.

(4) Syndiotacticity [stereoregularity (rr)] of polymethyl methacrylate block in acrylic triblock copolymer:
Acrylic triblock copolymer is dissolved in deuterated chloroform, and using a nuclear magnetic resonance apparatus ("JNM-LA400") manufactured by JEOL Ltd., a methyl methacrylate polymer block in the acrylic triblock copolymer ( The syndiotacticity [stereoregularity (rr)] of the polymer blocks A1 and A2) was determined.
At that time, in the ¹³ C-NMR spectrum, signals around 44.5 ppm, 44.8 ppm and 45.5 ppm are attributed to the quaternary carbon of the polymethyl methacrylate block, and stereoregularity rr, mr and mm, respectively. And stereoregularity rr was determined by the ratio of the integral values. The stereoregularity can also be determined by ¹ H-NMR method.

(5) Glass transition temperature (Tg) of each polymer block:
In the curve obtained by DSC measurement using a Mettler DSC measuring device (DSC-822) at a temperature rising rate of 10 ° C./min, the extrapolation start temperature (Tgi) is the glass transition temperature (Tg). ).

(6) Polymerization conversion rate of charged monomers:
A part of the reaction solution at the stage where the formation reaction of each polymer block has been completed is collected, and the amount of monomer remaining in the reaction solution is measured by employing the following apparatus and conditions. The polymerization addition rate was determined.
・ Equipment: Gas chromatograph “GC-14A” manufactured by Shimadzu Corporation
Column: GL Sciences Inc. “INERT CAP 1” [Inner Diameter 0.25 mm × Length 60 m, Film Thickness (df) 0.4 μm]
Analytical conditions: injection 300 ° C., detector 300 ° C., 60 ° C. (0 minute hold) → 5 ° C./minute→100° C. (0 minute hold) → 15 ° C./minute→300° C. (2 minute hold)

(7) Ratio of fluorine element on the surface of the optical film having the optical compensation film:
Regarding the derivation of the surface element ratio, the surface of the polarizing plate was measured by X-ray photoelectron spectroscopy using a scanning X-ray photoelectron spectrometer (“Quants SXM” manufactured by ULVAC-PHI Co., Ltd.).
In the measurement, 100 μm-25W-15 kV was adopted as the X-ray excitation condition, and Al was used for the counter cathode. The X-ray irradiation range of the sample was 100 μm × 100 μm, and the photoelectron detection angle was 45 °.
In the measurement of the polarizing plate surface, there is a concern about damage to the sample due to X-rays. Therefore, the survey spectrum is separately performed at the sample surface position different from the element measurement, and the survey spectrum measurement is not performed in the measurement of the surface element ratio. It was decided. The measurement was performed in the order of 1 s of F, 1 s of O, 1 s of N, and 1 s of C, and the irradiation time of the X-rays to the total sample in the total element measurement was within 30 minutes.
For the data processing, analysis software “Multipack V8, 2C” (manufactured by ULVAC-PHI Co., Ltd.) was used. As binding energy correction, the main peak position of neutral carbon C1s was adjusted to 285.0 eV. The background used the Shirley type and derived atomic% of F, O, N, and C elements. Here, the element ratio was derived by setting the atomic% of the total of F, O, N, and C elements as 100%.

(8) Adhesive strength of the adhesive roll:
A commercially available cellophane having a width of 50 mm is wound (attached) on the surface of a cylindrical adhesive roll having an outer diameter of 50 mm × width of 50 mm, and the wound cellophane is rewound (peeled) at a speed of 100 mm / min. The force (g) required for the measurement was measured as the adhesive strength (g).

(9) Adhesive strength of the pressure-sensitive adhesive layer in the optical film having the optical compensation film:
(I) The optical film pressure-sensitive adhesive prepared in the following examples was coated on a polyethylene terephthalate film (PET film) (thickness 50 μm), dried at 60 ° C. for 30 minutes, and pressure-sensitive adhesive layer / PET film An adhesive optical film composed of layers was prepared. This adhesive optical film was cut into a size of width × length = 25 mm × 200 mm to obtain a test piece.
(Ii) The test piece prepared in (i) above is an adherend of a polarizing plate (a polarizing plate with a rubbing treatment on the surface of the optical compensation film layer on the polarizing plate surface or a polarizing plate without the rubbing treatment). Overlaid on the optical compensation film layer through an adhesive layer, a 2 kg roller was attached to the adhesive optical film by reciprocating twice at a speed of 10 mm / second, and the temperature was 23 ° C. and the humidity was 50% RH. After being left under atmospheric pressure for 24 hours, the 180 ° peel adhesion was subsequently measured at a peel rate of 300 mm / min in accordance with JIS Z0237.

(10) Adhesive residue of adhesive optical film:
(I) The optical film pressure-sensitive adhesive prepared in the following example is applied to a release PET film (thickness 38 μm), dried at 60 ° C. for 30 minutes, and consists of an optical film pressure-sensitive adhesive / PET film. A laminate was produced.
(Ii) Laminate and polarizing plate obtained in (i) above (polarizing plate or adhesive roll contact treatment or rubbing treatment in which the surface of the optical compensation film layer on the polarizing plate surface is subjected to an adhesive roll contact treatment or rubbing treatment) Is laminated at a speed of 10 mm / second at a pressure of 70 psi using a laminator ("LL-100" manufactured by Chem Instruments), and is an adhesive optical film composed of PET film / adhesive / polarizing plate. Was made. This adhesive optical film was cut into a size of width × length = 25 mm × 200 mm to obtain a test piece.
(Iii) The release PET film on one surface of the test piece prepared in (ii) above is peeled off and attached to a glass plate (an alternative to a liquid crystal plate) as an adherend, and a 2 kg roller is applied at a speed of 10 mm / sec. The adhesive type optical film was reciprocated twice to be pasted, left at atmospheric pressure at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours, and subsequently peeled at 300 mm / min in accordance with JIS Z0237. And 180 ° peeled off. By visually observing whether the adhesive remains on the glass plate surface after peeling, if the adhesive remains, evaluate that there is adhesive residue, while no adhesive remains The case where it peeled off neatly was evaluated as “no adhesive residue”.

<< Synthesis Example 1 >> [Synthesis of Acrylic Triblock Copolymer (α)]
(1) After attaching a three-way cock to a 2 L three-necked flask and replacing the inside with nitrogen, 868 g of toluene, 43.4 g of 1,2-dimethoxyethane, isobutylbis (2,6-di-t-butyl-4 at room temperature) -Methylphenoxy) 60.0 g of a toluene solution containing 40.2 mmol of aluminum was added, and 3.68 g of a mixed solution of cyclohexane and n-hexane containing 6.37 mmol of sec-butyllithium was further added. Subsequently, 49.9 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. At this time, the polymerization conversion rate of methyl methacrylate was 99.9% or more. Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 212 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition. At this time, the polymerization conversion rate of n-butyl acrylate was 99.9% or more. Further, 49.9 g of methyl methacrylate was added thereto, and after stirring overnight at room temperature, 3.50 g of methanol was added to terminate the polymerization reaction. At this time, the polymerization conversion rate of methyl methacrylate was 99.9% or more. The obtained reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. Thereafter, a white precipitate was collected by filtration and dried to obtain 310 g of a triblock copolymer [acrylic triblock copolymer (α)].

(2) As a result of measuring by the above-mentioned method, the acrylic triblock copolymer (α) obtained in (1) above is a triblock copolymer composed of PMMA-PnBA-PMMA, and has a weight average molecular weight ( Mw) was 63,000, the number average molecular weight (Mn) was 50,000, and the molecular weight distribution (Mw / Mn) was 1.26.
The mass ratio of each block in the acrylic triblock copolymer (α) is PMMA (16.0% by mass) -PnBA (68.0% by mass) -PMMA (16.0% by mass), The content of the PnBA block was 68.0% by mass.
Further, the glass transition temperature of the PMMA block in the acrylic triblock copolymer (α) was 101.8 ° C., and the glass transition temperature of the PnBA block was −44.6 ° C.
Moreover, the syndiotacticity [stereoregularity (rr)] of the PMMA block was 70.5%.

<< Synthesis Examples 2 and 3 >> [Synthesis of Acrylic Triblock Copolymers (β) and (γ)]
The same operation as in Synthesis Example 1 (1) was performed, and the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), PnBA block content, glass transition temperature of each polymer block and Acrylic triblock copolymers (β) and (γ) having syndiotacticity of PMMA were respectively synthesized.

  The contents of the acrylic triblock copolymers (α) to (γ) obtained in Synthesis Examples 1 to 3 are summarized in Table 1 below.

Example 1
(1) A polarizing plate A [a polarizing plate containing a polymer having a structural unit derived from a monomer containing a fluoroalkyl group in the surface optical compensation film layer (optically anisotropic layer)] was prepared. When the proportion of fluorine element on the surface of the optical compensation film layer (optically anisotropic layer) of this polarizing plate A was measured by the method described above, it was 21.4 Atomic%.
(2) On the surface of the optical compensation film layer (optically anisotropic layer) of the polarizing plate A prepared in (1) above, an adhesive roll (“Tackey Roll H” manufactured by Odaka Rubber Industries, Ltd., adhesive strength = 230 g) The adhesive roll contact treatment was performed 10 times in the vertical direction with a load of 500 g. When the ratio of the fluorine element on the surface of the optical compensation film layer (optically anisotropic layer) of the polarizing plate A subjected to the adhesive roll contact treatment was measured by the above method, it was 17.5 Atomic%, and the above formula (1) The reduction rate of the fluorine element calculated | required from 18.2%.
(3) The acrylic triblock copolymer (α) obtained in Synthesis Example 1, the acrylic triblock copolymer (β) obtained in Synthesis Example 2, and the acrylic triblock obtained in Synthesis Example 3 For the optical film, the copolymer (γ) is used in a mass ratio of (α) :( β) :( γ) = 65: 25: 10 and dissolved in toluene so that the solid content is 45% by mass. An adhesive (adhesive solution) was prepared.

(4) (i) The optical film pressure-sensitive adhesive prepared in (3) above is coated on a PET film (thickness 50 μm) and dried at 60 ° C. for 30 minutes. From the pressure-sensitive adhesive layer / PET film layer A pressure-sensitive adhesive optical film was prepared, and the pressure-sensitive adhesive optical film was cut into a size of width × length = 25 mm × 200 mm to obtain a test piece.
(Ii) The test piece obtained in (i) above is overlaid on the optical compensation film layer in the polarizing plate A after the adhesive roll contact treatment obtained in (2) via an adhesive layer. Adhesion of the adhesive layer after a 2 kg roller was reciprocated twice on the adhesive optical film at a speed of 10 mm / second and left at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. When the force was measured by the method described above, it was as shown in Table 2 below.

(5) (i) The optical film pressure-sensitive adhesive (pressure-sensitive adhesive solution) prepared in the above (3) is applied to a release PET film (thickness: 38 μm) and dried at 60 ° C. for 30 minutes to obtain an optical film. The laminated body which consists of an adhesive / PET film for manufacture was manufactured.
(Ii) The laminated body obtained in the above (i) and the polarizing plate after the adhesive roll contact treatment obtained in the above (2) are 70 psi using a laminator (“LL-100” manufactured by Chem Instruments). A pressure-sensitive adhesive optical film composed of PET film / adhesive / polarizing plate was produced. This adhesive optical film was cut into a size of width × length = 25 mm × 200 mm to obtain a test piece.
(Iii) The release PET film on one surface of the test piece prepared in (ii) above is peeled off and attached to a glass plate (an alternative to a liquid crystal plate) as an adherend, and a 2 kg roller is applied at a speed of 10 mm / sec. After the adhesive optical film was reciprocated twice on the adhesive optical film, the adhesive residue was evaluated by the above-mentioned method after being left under atmospheric pressure at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. 2 as shown.

Example 2
(1) A rubbing cloth (“JK Wiper 150-S” manufactured by Nippon Paper Crecia Co., Ltd.) is used on the surface of the optical compensation film layer (optical anisotropy layer) of the same polarizing plate A used in Example 1. Then, rubbing treatment (wiping treatment) was performed 20 times in the vertical direction with a load of 500 g. When the ratio of the fluorine element on the surface of the optical compensation film layer (optical anisotropic layer) of the polarizing plate A after the rubbing treatment was measured by the above method, it was 9.3 Atomic%, which was obtained from the above formula (1). The reduction rate of fluorine element was 56.5%.
(2) As the polarizing plate, the polarizing plate A after the rubbing treatment obtained in the above (1) is used, and otherwise, in the same manner as in (3) to (5) of Example 1, Preparation of adhesive optical film (test piece) for measuring adhesive strength of adhesive layer and measurement of adhesive strength, and preparation of adhesive optical film (test piece) for evaluation of adhesive residue and evaluation of adhesive residue Was done.
The results are shown in Table 2 below.

<< Comparative Example 1 >>
(3) to (5) of Example 1 except that the same polarizing plate A prepared in (1) of Example 1 was used as it was without performing any adhesive roll contact treatment or rubbing treatment. In the same manner as above, preparation of pressure-sensitive adhesive, preparation of pressure-sensitive adhesive optical film (test piece) for measuring the adhesive strength of pressure-sensitive adhesive layer and measurement of pressure-sensitive adhesive force, and pressure-sensitive adhesive optical film for evaluation of adhesive residue (test) Piece) and evaluation of adhesive residue.
The results are shown in Table 2 below.

<< Comparative Example 2 >>
(1) Use an air gun (nozzle inner diameter = 3 mm, “Joplaster II” manufactured by Joplux) on the surface of the optical compensation film layer (optical anisotropy layer) of the same polarizing plate A used in Example 1. Then, a cleaning process was performed by blowing compressed air in the longitudinal direction for 10 seconds at an air pressure of 5 kg / cm ² . When the ratio of the fluorine element on the surface of the optical compensation film layer (optically anisotropic layer) of the polarizing plate A after the cleaning treatment was measured by the method described above, it was 21.4 Atomic%, and the ratio of the fluorine element was absolutely It was not reduced [reduction rate of fluorine element determined from the above formula (1) = 0%].
(2) The polarizing plate A after the cleaning treatment by air blowing obtained in (1) above was used as the polarizing plate, and the rest was the same as in (3) to (5) of Example 1 except that Preparation of adhesive, preparation of adhesive optical film (test piece) for measurement of adhesive strength of adhesive layer and measurement of adhesive strength, and preparation of adhesive optical film (test specimen) for evaluation of adhesive residue and adhesive The remaining property was evaluated.
The results are shown in Table 2 below.

As seen from the results in Table 2 above, in Examples 1 and 2, the optical compensation film layer on the surface of the optical film (polarizing plate A) was subjected to the adhesive roll contact treatment or rubbing treatment, and then the optical By producing an adhesive optical film by applying an adhesive on the compensation film layer, the adhesive optical film obtained in Example 1 and Example 2 was bonded to the optical film (polarizing plate A). When the adhesive type optical film was peeled off after being adhered to the glass plate, the adhesive did not remain on the glass plate and could be removed cleanly from the glass plate.
On the other hand, in Comparative Example 1, the optical compensation film layer on the surface of the optical film (polarizing plate A) was subjected to the adhesive on the optical compensation film layer as it was without performing the adhesive roll contact treatment or rubbing treatment. Since the pressure-sensitive adhesive optical film was produced, the pressure-sensitive adhesive optical film obtained in Comparative Example 1 had a weak adhesive force of the pressure-sensitive adhesive layer to the optical film (polarizing plate A). When peeling from the glass plate, the adhesive remained on the glass plate.
Further, in Comparative Example 2 in which compressed air was sprayed on the optical compensation film layer on the surface of the optical film (polarizing plate A), the adhesive force of the pressure-sensitive adhesive layer to the optical film (polarizing plate A) was weak, and the glass plate When the adhered adhesive optical film was peeled off from the glass plate, the adhesive remained on the glass plate.

Example 3
To the optical compensation film layer of polarizing plate A in the same manner as in (1) to (5) of Example 1 except that each of the three types of adhesive rolls shown in Table 3 below was used as the adhesive roll. Adhesive roll contact treatment, preparation of pressure-sensitive adhesive, preparation of pressure-sensitive adhesive optical film (test piece) for measuring the adhesive strength of pressure-sensitive adhesive layer, measurement of pressure-sensitive adhesive force, and pressure-sensitive adhesive optical film for evaluation of adhesive residue (Test specimen) was prepared and the adhesive residue was evaluated.
The results are shown in Table 3 below.

Example 4
(1) Polarizing plate B [A polarizing plate containing a polymer having a structural unit derived from a monomer containing a fluoroalkyl group in the surface optical compensation film layer (optically anisotropic layer) was prepared. When the proportion of fluorine element on the surface of the optical compensation film layer (optically anisotropic layer) of the polarizing plate B was measured by the method described above, it was 22.1 Atomic%.
(2) Using the polarizing plate B prepared in (1) above, an adhesive roll contact treatment was performed in the same manner as in (2) of Example 1. When the ratio of the fluorine element on the surface of the optical compensation film layer (optical anisotropic layer) of the polarizing plate B subjected to the adhesive roll contact treatment was measured by the above method, it was 15.7 atomic%, and the above formula (1) The reduction rate of the fluorine element calculated | required from 29.0% was 29.0%.
(3) Preparation of pressure-sensitive adhesive and pressure-sensitive adhesive in the same manner as in (3) to (5) of Example 1 except that the polarizing plate B after the pressure-sensitive adhesive roll contact treatment obtained in (2) above was used. Preparation of adhesive optical film (test specimen) for measuring the adhesive strength of layers and measurement of adhesive strength, and preparation of adhesive optical film (test specimen) for evaluation of adhesive residue and evaluation of adhesive residue It was.
The results are shown in Table 4 below.

Example 5
(1) Using the same polarizing plate B as used in Example 4, a rubbing process (wiping process) was performed in the same manner as (1) in Example 2. When the ratio of the fluorine element on the surface of the optical compensation film layer (optically anisotropic layer) of the polarizing plate B after the rubbing treatment was measured by the method described above, it was 1.9 Atomic% and was obtained from the above formula (1). The reduction rate of fluorine element was 91.4%.
(2) Preparation of pressure-sensitive adhesive and adhesive strength of pressure-sensitive adhesive layer in the same manner as in (3) to (5) of Example 1 except that the polarizing plate B after rubbing treatment obtained in (1) above was used. A pressure-sensitive adhesive optical film (test piece) for measurement and measurement of adhesive strength, and a pressure-sensitive adhesive optical film (test piece) for evaluation of adhesive residue and evaluation of adhesive residue were performed.
The results are shown in Table 4 below.

<< Comparative Example 3 >>
(3) to (5) of Example 1 except that the same polarizing plate B prepared in (1) of Example 4 was used as it was without performing any adhesive roll contact treatment or rubbing treatment. In the same manner as above, preparation of pressure-sensitive adhesive, preparation of pressure-sensitive adhesive optical film (test piece) for measuring the adhesive strength of pressure-sensitive adhesive layer and measurement of pressure-sensitive adhesive force, and pressure-sensitive adhesive optical film for evaluation of adhesive residue (test) Piece) and evaluation of adhesive residue.
The results are shown in Table 4 below.

As seen from the results in Table 4 above, in Examples 4 and 5, the optical compensation film layer on the surface of the optical film (polarizing plate B) was subjected to the adhesive roll contact treatment or rubbing treatment, and then the optical By producing an adhesive optical film by applying an adhesive on the compensation film layer, the adhesive optical film obtained in Example 4 and Example 5 was bonded to the optical film (polarizing plate B). When the adhesive type optical film was peeled off after being adhered to the glass plate, the adhesive did not remain on the glass plate and could be removed cleanly from the glass plate.
On the other hand, in Comparative Example 3, a pressure-sensitive adhesive optical film was produced by directly applying an adhesive on the optical compensation film layer without rubbing the optical compensation film layer on the surface of the optical film (polarizing plate B). Therefore, the adhesive optical film obtained in Comparative Example 3 has a weak adhesive force of the adhesive layer to the optical film (polarizing plate B), and when the adhesive optical film adhered to the glass plate is peeled off from the glass plate. The adhesive remained on the glass plate.

  In the case of the present invention, the pressure-sensitive adhesive is bonded and laminated on the optical compensation film or on the optical compensation film layer or the optical compensation film layer on the surface of the laminated optical film with a high adhesive force. An adhesive optical film in which the adhesive is not separated from the optical film can be easily and safely manufactured smoothly and inexpensively without using a plasma processing apparatus or a corona discharge processing apparatus, and the present invention. The pressure-sensitive adhesive optical film obtained by the above has a pressure-sensitive adhesive layer firmly adhered to the optical film side, and after sticking the pressure-sensitive adhesive optical film to a liquid crystal panel or the like, the pressure-sensitive adhesive optical film is peeled off and the operation is repeated. Since the adhesive does not remain on the liquid crystal panel or the like when reusing an expensive liquid crystal panel or the like after peeling the adhesive optical film, the present invention It is effective as a method for producing a pressure-sensitive adhesive optical film of the quality.

Claims (7)

  Method for producing adhesive optical film, optical compensation film layer or optical compensation film in surface of optical film comprising optical compensation film alone, or laminated optical film having optical compensation film layer or optical compensation film layer on the surface After the surface of the layer is subjected to an adhesive roll contact treatment or rubbing treatment, an adhesive is applied to the optical compensation film surface or optical compensation film surface subjected to the adhesive roll contact treatment or rubbing treatment to form an adhesive layer. A method for producing a pressure-sensitive adhesive optical film.   The manufacturing method of the adhesive type optical film of Claim 1 which performs an adhesive roll contact process using the adhesive roll which has 50 g or more of adhesive force.   An optical film composed of a single optical compensation film, or an optical compensation film layer or an optical compensation film layer on the surface of the laminated optical film contains a polymer having a structural unit derived from a monomer having a fluoroalkyl group, The manufacturing method of the adhesion type optical film of Claim 1 or 2.   Fluorine measured by X-ray photoelectron spectroscopy on the surface of an optical film made of a single optical compensation film or on the surface of an optical compensation film layer or optical compensation film layer of the laminated optical film by an adhesive roll contact treatment or rubbing treatment The method for producing a pressure-sensitive adhesive optical film according to any one of claims 1 to 3, wherein the ratio of the element is reduced by 5% or more as compared to before performing the pressure-sensitive roll contact treatment or the rubbing treatment.   At least one methacrylic acid alkyl ester polymer block (A) having a glass transition temperature of 100 ° C. or higher is applied to the optical compensation film surface or the optical compensation film surface subjected to the adhesive roll contact treatment or rubbing treatment. And a pressure-sensitive adhesive containing 60% by mass or more of an acrylic block copolymer having at least one alkyl ester polymer block (B) having a glass transition temperature of -20 ° C or lower. The manufacturing method of the adhesion type optical film of any one of these.   A pressure-sensitive adhesive optical film obtained by the production method according to claim 1.   An image display device using the adhesive optical film according to claim 6.