TW201209120A - Adhesive agent compostition for an optical film - Google Patents

Abstract

This invention provides an non-crosslinking type adhesive agent compostiton for an optical film, which initially has an adhesive force suitable for reworking and can be peeled off without adhesive residuals, and after being adhered and kept at this status for a long time, especially exposed at the status of high-temperature, high-humidity, since the adhesive force increases, the adhesive endurance is excellent. An adhesive agent compostiton for an optical film, containing a specific triblock copolymer (I) and a specific diblock copolymer (II). The specific triblock copolymer (I) is respresented by the formula: A1-B-A2, and is formed by binding methacrylic acid alkyl ester polymer blocks A1 and A2, and acrylic acid alkyl eter polymer blocks B, and the content of the polymer blocks B is 5 to 45 % by mass; The specific diblock copolymer (II) is represented by the formula: C-D, and is formed by binding methacrylic acid alkyl ester polymer blocks C and acrylic acid alkyl ester polymer blocks D, and the content of the polymer blocks D is 60 to 85 % by mass. The mass ratio of the specific triblock copolymer (I) and the specific diblock copolymer (II), based on (I)/(II), is within a specific range. Additionally, the ratio of the total mass (X) of the polymer blocks A1, A2 and C, and the total mass (Y) of the polymer blocks B and D, based on (X)/(Y), is within a specific range.

Description

201209120 VI. [Technical Field] The present invention relates to attaching an optical film such as a polarizing plate or a retardation film to an adherend such as a liquid crystal panel, or attaching a protective film to an optical film. The optical film used is an adhesive formed with an adhesive. Moreover, the present invention relates to an adhesive optical film and an optical film protective film having an adhesive layer containing the above-described adhesive composition for an optical film, and an image of the protective film for the adhesive optical film and/or optical film. Display device. [Prior Art] When an optical film such as a polarizing plate or a retardation film is attached to a liquid crystal panel or the like, or a plurality of optical films are attached and laminated, or a protective film is attached to an optical film, an optical film is used for adhesion. Agent. When an optical film is attached, if a sensitive film, air bubbles, foreign matter is caught, or the position of the bonding is deviated, the attached optical film or protective film may be peeled off and reattached. Or, after the optical film is peeled off, an expensive liquid crystal panel is recovered and recycled. From this point of view, the adhesive for an optical film is required to have no residual glue in the manufacturing steps of the image display device such as a display, and can be peeled off with an appropriate peel strength, and the initial reworkability can be reattached. On the other hand, in the case where the adhesive for an optical film is attached between the optical film and the actual use, it is required to be blister-free or not peeled off from the adherend even when exposed to heat and humidity. -4 - 201209120 Moreover, the adhesive for optical films requires high transparency or optical isotropic (no birefringence) in order not to impair the function of the optical film. Heretofore, a hot-melt type adhesive containing an acrylic triblock copolymer has been known (see Patent Documents! and 2). However, in these documents, the use of a hot-melt type adhesive for an optical film has not been specifically examined, and the characteristics of the solution-type adhesive containing an acrylic triblock copolymer disclosed in these documents are completely unclear. Further, a member including an optical film, a substrate, and an adhesive layer containing an acrylic block copolymer is known (see Patent Document 3). However, in this document, although the effect of suppressing interlayer peeling and foaming of the adhesive layer when the substrate is a gas release substrate such as polycarbonate or polymethacrylic acid is discussed, it is used for an optical film. The initial redoability of the adhesive was not explored. In the above-mentioned circumstances, the inventors of the present invention have developed an adhesive for a non-chemically crosslinked optical film having a specific acrylic acid-based triblock copolymer as a main component, and have previously filed an application (see Patent Document 4). The non-chemically crosslinked optical film adhesive has no problem of uneven adhesion due to uneven crosslinking, shows good cohesiveness, and initial reworkability, adhesive properties, heat resistance, durability It is excellent in properties, and is useful as an adhesive for optical films. However, even this non-crosslinking type of adhesive sometimes has a situation in which initial reducibility and durability are insufficient. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Chem. Phys. 201, p.l108~1 1 14 [Problem to be Solved by the Invention] An object of the present invention is to provide an adhesive composition for a non-crosslinked optical film which does not require cross-linking The treatment is excellent in adhesion to the optical film substrate even without chemical crosslinking treatment, and when the optical film is attached to the attached body or the protective film is attached to the optical film, etc. The adhesion of the adhesive can be peeled off with a suitable peel strength without residual glue, and when it is kept in a state after being attached for a long period of time, especially when exposed to a high temperature state or a hot and humid state, it may be due to adhesion. Next having excellent durability. , especially the purpose of the invention is to provide a non-crosslinking type adhesive agent for optical film and light film of 4 film m, which will expand even if it is used due to environmental changes such as temperature or humidity. The shrinkable optical film is highly durable even when it is bonded to a substrate which is less likely to expand or contract due to changes in the environment. -6 - 201209120 Further, an object of the present invention is to provide an adhesive optical film and an optical film protective film having an adhesive layer containing the adhesive composition for a non-crosslinked optical film, and the above-mentioned adhesive optical fiber. An image display device for a protective film for a film and/or an optical film. [Means for Solving the Problem] The inventors of the present invention have found that the above problem can be solved by including a specific acrylic triblock copolymer and a specific acrylic diblock copolymer in a specific ratio. The block copolymer, that is, the alkyl acrylate polymer block having a glass transition temperature of -2 0 ° C or less is used as the central block, and the glass transition temperature of each of the two ends is 100 C or more. The acrylic acid triblock copolymer of the propylene acrylate 1 and the weight average molecular weight (Mw) is 30,0 〇〇~300,000, and the molecular weight distribution (]^/1411) is 1. 〇~1.5 and a central acrylic acid ester polymer block content of 5 to 45% by mass of an acrylic triblock copolymer, and the specific acrylic diblock copolymer, that is, a methacrylic acid vinegar polymer segment and an alkyl acrylate polymer block having a weight average molecular weight (Mw) of 30,000 to 300,000 and a molecular weight distribution (Mw/Mn) of 1.0 to 1.5, and The content of the alkyl acrylate polymer block is 60 to 85% by mass. Block copolymers. " That is, the present invention is: (1) An adhesive composition for an optical film, which is: (〇〇 contains the following acrylic triblocks having the elements (El), (E2), (E3), and (E4) Copolymer (I), and the following acrylic diblock copolymers (II) having the elements (Fl), (F2), (F3) and (F4), 201209120 (β) acrylic acid triblock copolymer (1) The mass ratio (1)/(11) to the acrylic diblock copolymer (II) is 75/25 to 30/70, and is contained in the (γ) acrylic triblock copolymer (I). The total mass (X) of the polymer block A1 and the polymer block A2 and the polymer contained in the acrylic diblock copolymer, and the polymer contained in the acrylic triblock copolymer (I) The ratio of the total mass of the segment B to the polymer block D contained in the acrylic diblock copolymer (11) is 30/70 to 50/50; 1 Acrylic triblock copolymer (I): (Ε 1 An acrylic triblock copolymer represented by the following general formula (1): A 1-B-A2 (1) (In the formula (1), A1 and A2 are each independently and the glass transition temperature is 100 ° C or more. Alkyl methacrylate polymer block, b The content of the polymer block B is (5 to 45% by mass); 30,000 to 300,000; and (E4) molecular weight distribution (Mw/Mn) of 1.0 to 1.5; acrylic diblock copolymer (H): (F1) an acrylic diblock copolymer represented by the following formula (2) : CD (2) (In the formula (2), 'C represents a mercaptoalkyl acrylate polymer block, and d represents a propionate polymer block; (F2) a polymer block 〇 content of 60 ～5% by mass; (卩3) weight average molecular weight (=^^) is 30,000 to 300,000; and (F4) molecular weight distribution (Mw/Mn) is 1. 〇~1.5. 201209120 The present invention is: (2) as described above (1) An adhesive composition for an optical film comprising a microphase-separated structure comprising a hard polymer phase and a soft polymer phase, the hard polymer phase being embedded in a polymer of an acrylic triblock copolymer (1) The polymer block C of the segments A1 and A2 and the acrylic diblock copolymer (π) is formed as a main body, and the soft polymer phase is an acrylic triblock copolymer (I). The polymer block Β and the polymer block D of the acrylic diblock copolymer (II) are formed as a main body, and the hard polymer phase and the soft polymer phase together form a continuous structure. (3) The adhesive composition for an optical film according to the above (1) or (2), wherein the mass ratio of the acrylic triblock copolymer (1) to the acrylic diblock copolymer (II) is (1)/(11) ) is 59/41 to 30/70. The adhesive composition for an optical film according to any one of the above (1) to (3), wherein the polymer block A丨, the polymer block A2 contained in the adhesive composition And the total mass (χ) of the polymer block c and the total mass (γ) of the polymer block Β and the polymer block D contained in the adhesive composition (Χ) / (Υ) ' 33/67~45/55. The present invention is the adhesive block of the optical film according to any one of the above (1) to (4), wherein the polymer block A 1 and the polymer contained in the adhesive composition are: Ratio (X) / (Y) of the total mass (x) of the block A2 and the polymer block c to the total mass (γ) of the polymer block B and the polymer block D contained in the adhesive composition ), from 39/61 to 43/57. The adhesive composition for an optical film according to any one of the above (1) to (5), wherein the polymer block contained in the acrylic triblock copolymer (I) is a polymer block. Among A1 and polymer block A2, the weight average molecular weight (Mw (Al〇w)) of the polymer block having a small weight average molecular weight and the weight average molecular weight of the polymer block having a larger weight average molecular weight (Mw (Ahigh)) The weight average molecular weight (Mw(C)) of the polymer block C contained in the acrylic diblock copolymer (Π) satisfies the following relationship:

Mw(Alow)x〇.5SMw(C)SMw(Ahigh)x2. The adhesive composition for an optical film according to any one of the above items (1) to (6), wherein the weight average molecular weight of the polymer block c of the acrylic diblock copolymer (Mw) (C)) is 9,000 to 30,000. The present invention is: (8) An adhesive type optical film comprising the adhesive layer of the adhesive composition for an optical film according to any one of the above (1) to (?). (9) A protective film for an optical film, comprising an adhesive-type optical film comprising the adhesive composition for an optical film according to any one of the above (1) to (7), and/or [effect of the invention] 10) A video display device comprising the protective film for an optical film of the above (9) as described above.

The adhesive composition for an optical film of the present invention has an appropriate adhesion force capable of being reworked when the bonding optics is thinner than the initial period, and when this state is maintained, the adhesion is increased with the increase of the adhesion force to indicate that the repetitive and durable protective film is required. The composition of the preparation has the excellent retention of the problem and is recycled and reused in the adhesive tank. The composition of the agent is not the same as the line speed and the storage period. Therefore, it is not possible to omit the high durability of the 201209120. The adhesive optical film or optical film which is effectively used in both, the optical film of the present invention is characterized by an adhesive for an adhesive cross-linking optical film, and the residual agent can be used in this state when the adhesive optical film is manufactured. During the storage period, the drying process or the storage conditions (temperature and air volume may cause uneven crosslinking to cause uniformity and adhesion properties of the product adhesion. Further, the optical film of the present invention is treated by a viscous chemical crosslinking process and It shows a high degree of agglutination force and high productivity. Moreover, the adhesive composition for an optical film of the present invention becomes a solution as an organic solvent. In the case of the adhesive, even if the concentration of the solution is high, the concentration of the organic solvent can be reduced, and a solution type having a concentration of the solution-type adhesive component higher than the conventional solid content concentration of 35 mass% or more can be prepared. Adhesive), excellent in processability such as coating workability and wire speed improvement. By reducing the amount of organic solvent used, it is possible to reduce the problems caused by organic solvents, environmental deterioration or ring dyeing, and to reduce the time required for the solvent removal step after coating or thermal energy, etc., and to form a high solid concentration. The solution agent can reduce the transportation cost and reduce the feeding of the adhesive tank. Further, the adhesive optical film or the protective film for an optical film comprising the adhesive layer of the adhesive composition for an optical film described above has a long history. It is necessary to dissolve in a low-lying state, and it is necessary to cope with the low-lying state of the smear. Or when the protective film for an optical film expands or contracts due to environmental changes such as temperature, the stress received by the film or the optical member can be relaxed by the adhesive to suppress warpage or birefringence, and the display quality can be suppressed. [Embodiment] The present invention will be described in detail below. The adhesive composition for optical enamel according to the present invention means that an adhesive layer is formed on part or all of one or both sides of the film. The adhesive composition used for attaching a film to other adherends, a general term for the adhesive composition used to adhere the protective film to the surface of the optical film in order to protect the surface of the optical film. Refers to each film generally used for optical applications, such as polarizing film, polarizing plate, retardation film, phase difference viewing angle expansion film, brightness enhancement film, anti-reflection Membrane, anti-film, color filter, light guide plate, diffusion film, ruthenium film, wave shielding film, near-infrared absorbing film, near-infrared reflection thin composite functional optical film with most optical functions, etc. The protective film is a film which is attached to the optical film in order to protect the surface of the optical film. The propylene triblock copolymer (I) contained in the adhesive composition for optical thin films of the present invention has the following (E1) to (E4). (E1) Acrylic triblock copolymer A1-B-A2 represented by the following general formula (1) or wet optical stress optical optics and thin thin plate, glare Electromagnetic film and various acid compounds: (1) -12- 201209120 (In the formula (1), A1 and A2 are independent, and the alkyl methacrylate polymer block having a glass transition temperature of 100 ° C or higher, b The glass transition temperature is _2 (the alkyl acrylate polymer block of TC or less). The content of the polymer block b of (E2) is 5 to 45% by mass. (E3) The weight average molecular weight (Mw) is 30,000 to 300,000. (E4) The molecular weight distribution (Mw/Mn) is 1.0~1. 5. In the acrylic triblock copolymer (I), both polymer blocks Ai and A2' are polymers containing a mercapto acrylate acid ester polymer having a glass transition temperature of 100 ° C or higher. When the glass transition temperature of the polymer blocks A 1 and A 2 is 1 〇 (TC or more, the adhesive composition for an optical film of the present invention (hereinafter simply referred to as "adhesive composition") is usually used. In the microphase-separated structure formed by the temperature and the adhesive composition, the polymer blocks act in the form of a component of the restraint phase (physical pseudo-crosslinking point) and exhibit a cohesive force. Excellent adhesion and durability. From the viewpoints of durability, heat resistance, followability of substrate deformation, and moderate stress relaxation, the glass transition temperatures of the polymer blocks A 1 and A2 are preferably 100 to 200 ° C, respectively, and 100. ~150 ° C is better. The above polymer blocks A1 and A2 can be obtained by polymerizing a thioglycolic acid ester. The alkyl methacrylate, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid Cyclohexyl ester, 2-ethylhexyl methacrylate, n-octyl methacrylate, methyl lauric acid laurel vinegar, methyl propylene tridecyl vinegar, stearyl methacrylate and methacrylic acid isophthalic acid Ester and the like. -1 3- 201209120 From the viewpoint of being economical and easy to obtain, the obtained polymer blocks A 1 and A 2 have excellent durability and weather resistance, and the like, in the above alkyl methacrylate, methacrylic acid The ester is preferred. The polymer blocks A1 and A2 may be polymerized by only one type of alkyl methacrylate, or may be polymerized by two or more types. Further, the molecular weight of the polymer blocks A1 and A2', the unit composition of the polymer block to be formed, and the like may be the same or different. Further, when the polymer blocks A1 and A2' are not mutually miscible with the polymer block b, it is preferred from the viewpoint of forming a physical pseudo-crosslinking point. Further, from the viewpoint of exhibiting more physical pseudo-crosslinking properties based on the polymer blocks A1 and A2, the polymer blocks A1 and A2 preferably have no isocyanate-reactive functional groups and the like to contribute to chemical crosslinking. The linked group is preferred. In the acrylic triblock copolymer (1), the polymer block B is an alkyl acrylate polymer block having a glass transition temperature of -20 ° C or lower. If the temperature is -2 0. 〇 In the following, the properties of the microphase-separated structure formed in the adhesive composition, the property and the moisture permeability, and the transfer of the polymer block B to the non-interpolymer block B of the glass transfer adhesion The usual use temperature of the agent composition is such that the polymer block B acts as a softener for the adhesive composition. The polymer blocks A1 and A2 are dissolved. It is preferably -3 0 ° C or less, and the glass transition temperature of the polymer block B is preferably -40 to -80 ° C. The above polymer block B can be obtained by polymerizing an alkyl acetonate. The alkyl acrylate 'for example: decyl acrylate, ethyl acrylate, acrylate, butyl acrylate, acrylic acid third vinegar, acrylic acid n-hexa-14- 201209120 brewing, cyclohexyl acrylate, 2-ethyl acrylate Hexyl ester, acrylic acid, cinnamyl acrylate, tridecyl acrylate and stearyl acrylate. The glass transition temperature from the polymer block B is _ 2 〇t or less, and the adhesion and viscosity of the adhesive composition at a low temperature are good, and the adhesion force and the zipping resistance at the time of high-speed peeling can be suppressed. From the viewpoint of the phenomenon, among the above alkyl acrylates, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate are preferred. The phase separation obtained from the phase in which the polymer block B is at least one component and the phase containing the above-mentioned polymer segment A1 and A2 as components thereof is clearly defined, and the phase containing the polymer blocks A1 and A2 as components thereof is obtained. The physical pseudo-crosslinking does not collapse, and the viewpoint of the adhesive composition having high cohesive force and excellent durability can be obtained. In the above alkyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are especially used. good. The polymer stagnation B' may be polymerized by only one type of acrylonitrile, or may be polymerized by two or more types. The polymer blocks ai, A2, and B constituting the acrylic triblock copolymer (I) may also contain other components in a range that does not impair the effects of the present invention (for example, 10% by mass or less in the polymer block). Monomer unit. 2 other monomers, for example: methoxyethyl (meth)acrylate ethoxylate 9 (ethyl) methacrylate, diethylaminoethyl (meth) acrylate, (meth) acrylate ring Oxypropyl propyl ester, tetrahydrofuran (meth) acrylate, stupid VT |) acrylonitrile other than acryl s hydrazine; styrene, methicillin ^ ^ oxime ethylene, p-methyl benzene An aromatic vinyl monomer such as ethylene; a conjugated diene such as butyl sulphate or isopentyl pentoxide; an olefin such as ethylene or propylene. -15- 201209120 In the acrylic diblock copolymer (1), the content of the polymer block B is 5 to 45% by mass, preferably 20 to 45% by mass, more preferably 30 to 43% by mass. When the content of the polymer block B is 5 to 45% by mass, an appropriate adhesion force to the initial redoing can be imparted to the adhesive composition of the present invention, and durability can be increased as the long-term adhesion force increases. characteristic. When the content of the polymer moiety B is less than 5% by mass, the adhesion or viscosity of the adhesive composition may be lowered. On the other hand, when it exceeds 45 mass%, durability is lowered. In the acrylic triblock copolymer (1), the total content of the polymer blocks A i and A 2 is 95 to 55 mass. /. , 8 〇 ~ 55 mass% better '7 〇 ~ 57 mass% better. The weight average molecular weight (Mw) of the acrylic triblock copolymer (1) is from 30,0 Å to 300,000. When the Mw is less than 3 〇, _, the cohesive force of the adhesive composition becomes insufficient, and when the optical film and the adherend are attached to the adhesive composition, the film is easily peeled off and the durability is poor. On the other hand, if Mw exceeds 300, 〇〇〇', when the acrylic triblock copolymer (1) is dissolved in an organic solvent, the viscosity of the solution becomes high, so that a high concentration of the acrylic triblock copolymer (I) is applied. The solution will become difficult. The Mw of the acrylic triblock copolymer (I) is preferably from 40, 〇〇〇 to 250,000, more preferably from 50,000 to 200,000, from the viewpoint of durability and reworkability. The molecular weight distribution (Mw/Mn) of the acrylic triblock copolymer (1) is from 1.0 to 1.5. When the molecular weight distribution (Mw/Mn) of the acrylic triblock copolymer (1) exceeds 1.5, the influence of the low molecular weight component cannot be ignored, and the residual force at the time of reduction in cohesive force or rework may occur. -16- 201209120 Molecular weight distribution of propylene bismuth citrate triblock copolymer (I) from the viewpoint that the viscosity of the adhesive composition ^ Λ β is improved at the temperature of the enthalpy, and the durability is further improved (Mw/Mri ), preferably 1 〇. Preferably, 1.0 to 1.3 is better, and 1.0 to 1.2 is better. Here, in the description, the weight average molecular weight (Mw) and the number average molecular weight of the 'acrylic triblock copolymer, the following S-supported acrylic acid two-in-one' copolymer] (Mn) and molecular weight distribution (Mw/Mn) are obtained by the method described in the examples below. The present invention is a New Zealand, & 1 W, 'acrylic acid three contained in the product. The block copolymer (I) may be a mixture of two or more elements (El) to (Ε4), and may be a single type or a mixture of two or more types. The stereoregularity of the polymer blocks A1 and A2 of the triblock copolymer (1) is not particularly limited, but is preferably 65% or more, more preferably 70 to 95%, and more preferably polymer blocks A1 and A2. When the amount of the alignment is 65% or more, the durability of the adhesive composition tends to be good. The acrylic acid-based diblock copolymer (II) used in the adhesive composition of the present invention has The following (F1) to (F4) are required. (F1) The acrylic diblock copolymer CD (2) represented by the following general formula (2) (in the formula (2), C represents 曱The alkyl acrylate polymer block, d represents an alkyl acrylate polymer block. (F 2) The content of the polymer block D is 60 to 85% by mass. 03) The weight average molecular weight (1 / ^) is 3 〇 , 〇〇〇~3〇〇, 〇〇〇. (F4) Molecular weight distribution (Mw/Mn) is 1.0 to 1.5. -17- 201209120 Acrylic diblock copolymer (II), polymer block c system A polymer block comprising a mercapto acrylate polymer. The glass transition temperature of the polymer block C is preferably 5 〇〇C or more, and is more than 〇. The above polymer block c is borrowed. Obtained from the polymerization of alkyl methacrylates. For example, alkyl methacrylates such as methyl methacrylate, ethyl decyl acrylate, propyl propyl acrylate, n-butyl decyl acrylate, hydrazine Tert-butyl acrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, Sterolyl methacrylate, isodecyl methacrylate, etc. Obtained from the viewpoint of economical and easy to obtain The polymer blocks A 1 and A 2 have excellent durability and weather resistance, etc., and among the above alkyl methacrylates, methyl methacrylate is preferred. The polymer block C ' may be one type only. In the case of polymerizing an alkyl methacrylate, it may be polymerized by two or more kinds. In the acrylic diblock copolymer (Π), the polymer block D is a polymer containing an alkyl acrylate polymer. The glass transition temperature of the above polymer block D is _2 〇. Preferably, the above polymer block D ' is obtained by polymerizing an alkyl acrylate. The alkyl acrylate such as methyl acrylate or acrylic acid B. Ester, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, tridecyl acrylate, And stearyl acrylate and the like. The glass transition temperature from the polymer block D becomes _2 (rc or less, and the adhesion and viscosity of the adhesive composition at low temperature become good, and the -18-201209120 can be suppressed by the high-speed brake. The idea of rising and stripping sound phenomena,

From the viewpoint of obtaining an adhesive composition having excellent agglutination power and excellent durability, among the above alkyl acrylates, n-butyl acrylate and ethyl hexyl acrylate are particularly preferable. The polymer block D' may be polymerized by one type of alkyl acrylate or may be polymerized by two or more types. The polymer blocks c and D constituting the acrylic diblock copolymer (II) may contain other monomers in a range that does not impair the effects of the present invention (for example, 10% by mass or less in the polymer block) unit. The above other monomers are, for example, the same as those which may be contained in the polymer blocks A1, A2 and B. In the acrylic diblock copolymer (II), the content of the polymer block D is from 60 to 85% by mass, preferably from 70 to 80% by mass. In the acrylic diblock copolymer (II), the content of the polymer block D is 60 to 85 mass. /. Further, the mutual solubility with the acrylic triblock copolymer (1) is increased, and the adhesive composition is excellent in transparency. If the content of the polymer private portion D is less than 60% by mass, the adhesion of the adhesive composition is lowered. On the other hand, when the content of the polymer block D exceeds 85% by mass, the content ratio of the polymer block C which is at least one component of the phase which becomes a cross-linking point is relatively decreased, and thus the cohesive force is reduced, and the adhesive is reduced. The composition -19-201209120 has poor durability, and the miscibility with the acrylic triblock copolymer (i) is lowered, and transparency necessary for the adhesive may not be obtained. In the acrylic diblock copolymer (II), the content of the polymer block c is preferably 40 to 15% by mass, and preferably 30 to 20% by mass. The weight average molecular weight (Mw) of the acrylic diblock copolymer (II) is 30,000 to 300,000. When the Mw is less than 30,000, the cohesive force of the adhesive composition becomes insufficient, and when the optical film and the adherend are attached to the adhesive composition, the adhesive film is easily peeled off and the durability is poor. On the other hand, if Mw exceeds 300,000, the mutual solubility with the acrylic triblock copolymer is lowered, and when the solution type adhesive is prepared from the adhesive composition, it is divided into two layers and cannot be uniformly coated, or even uniformly coated. Will separate during the drying process and have poor transparency. The acrylic diblock copolymer (11) has a MW of 40,000 to 200,000, more preferably 40,000 to 120,000, from the viewpoint of compatibility with the acrylic triblock copolymer (I). The molecular weight distribution (Mw/Mn) of the acrylic diblock copolymer (Π) is 1. 〇 1.5. When the molecular weight distribution (Mw/Mn) of the acrylic diblock copolymer (Mw/Mn) exceeds 1.5, the influence of the low molecular weight component cannot be neglected, and the residual rubber when the cohesive force is lowered or reworked may occur. The molecular weight distribution (Mw/Mn) of the acrylic diblock copolymer (II) is from the viewpoint of improving the cohesive force of the adhesive composition and reducing the contamination of the adherend (residual adhesion of the residual rubber or the low molecular weight component). 1.0 to 1.4 is better, 1.0 to 1.3 is better, and 1. 〇 to 1.2 is better. The mass ratio of the acrylic triblock copolymer (I) to the acrylic diblock copolymer (II) in the adhesive composition of the present invention is (Ι)/(Π) and -20-201209120 a, 75/25~30/70, 70/30~30/70 is better, 65/35~35/65 is better, and 59/41~40/60 is better. When the ratio of the amount of the acrylic triblock copolymer (1) to the acrylic diblock copolymer (11) is 75/25 to 30/70 in terms of (Ι)/(Π), the copolymer is contained. The adhesive composition is attached to the adherend with an appropriate adhesion force at the time of the initial re-entry, and the force is increased by maintaining the state after the attachment, and is high if it is kept in the attached state for a long time. Force 'shows high durability. The ratio of the acrylic triblock copolymer (1) to the acrylic diblock copolymer (11) is 1 ratio, and in the case of (Ι)/(Π), the content of (I) is higher than that of 30/70. When there is little time, the initial adhesion force is too low, and the attachment of the optical film to the adherend becomes difficult. Further, in the case of (1)/(11), when the content of (1) is more than 75/25, the cohesive force of the adhesive composition is lowered, and the durability is lowered (for example, it is difficult to maintain the subsequent state for a long period of time). The total mass of the polymer block A 1 and the polymer segment A2 contained in the acrylic triblock copolymer (I) and the polymer segment C contained in the acrylic diblock copolymer (π) ( X), and the ratio of the total mass (γ) of the polymer block B contained in the acrylic triblock copolymer (1) to the polymer block D contained in the acrylic diblock copolymer (π), 30 /70~50/50 '33/67~45/55 is better, 35/65~43/57 is better, 39/61~43/57 is better. In the mass ratio (Χ)/(Υ), if the content of (X) is less than 30/70, the durability becomes insufficient, and if the content of (X) is more than 50/50, then the initial Then the force is too low 'sometimes can't continue, or peel off immediately after picking up. -2 1 - 201209120 The adhesive composition of the present invention has an appropriate adhesion force suitable for re-doing after a period of bonding, and if it is maintained after the bonding, it will continue to rise with time and exhibit high durability. Sex. This property is not exhibited in the adhesive composition containing only the acrylic triblock copolymer, but by containing a specific ratio of the acrylic triblock copolymer (1) and acrylic acid in the adhesive composition. The characteristics exhibited by the diblock copolymer (π). The acrylic triblock copolymer (I) used in the adhesive composition of the present invention has a large proportion of a hard component, and has no adhesive property alone, and is inferior to that of a plastic. By mixing the acrylic diblock copolymer (11) in a specific ratio in the acrylic triblock copolymer (I) and dissolving them, there is an adhesive force suitable for redoing at the beginning, and By attaching this state for a long period of time, the force will rise with time, showing excellent durability. Although the reason is not clear, it is presumed that the reason is that since the entire composition of the adhesive composition is hard, the initial adhesion force can exhibit a low level of adhesion suitable for redoing, on the one hand, when the fit is long. When the time is maintained, especially when placed in an environment such as a high temperature state or a hot and humid state, the interface of the adherend and the adhesive 'acrylic diblock copolymer (π) is gradually wetted by the adherend, and the adhesion is improved. improve. The degree of increase in the adhesion force of the adhesive composition of the present invention over time can be determined by the use of an adhesive optical film to produce a product such as a display (for example, 'adhesive optical film is attached to a liquid crystal cell, and defects are found during inspection). Evaluation of the temperature and time until the optical film is reworked. For example, the adhesion after 24 hours of storage at 23 ° C can be used as a bonding force when -22-201209120 is reworked, and after bonding, 9 (The adhesion force after 24 hours of rc storage is evaluated as the adhesion force after long-term retention. The adhesion force at the time of redoing (for example, the adhesion force after 24 hours of storage at 23 ° C) is the minimum. Adhesiveness, and from the viewpoint of easy rework, the peeling speed in the direction of 18 〇 at a peeling speed of 30 〇mm/min is preferably in the range of 〇.〇3N/25 mm to l_〇N/25 mm. 〇.〇9N/25mm~〇.75N/25mm Better, 〇〇9N/25mm~〇5N/25mm and better, 0.12N/25mm~0.3N/25mm is especially good. (For example, the adhesion after 24 hours of storage at 9〇〇c), from durability The viewpoint of peeling at a peeling speed of 3 〇〇mm/min in a direction of 180° is preferably 1.1 N/25 mm or more, more preferably 1 _6 N/25 mm or more. The adhesive optical film and optical film of the present invention are used. The protective film is 180° at 90° C., after 24 hours, and the peeling force is 23 〇c, and 1800 after 24 hours. The rate of change of the adhesion force expressed by the following formula (1) is preferably compared with the peeling force. More than 200%, more preferably 400% or more. [(9 0 C, 2 8 0 after 1 8 0. Peeling adhesion force) _ (2 3, 2, after 4 hours, 180. Peeling force) Bu (23. 〇, 18 24 after 24 hours. Peeling adhesion force) x 100 [%] (i) By using such an adhesive film, an adhesive optical film for an optical film adhesive composition of the present invention and a protective film for an optical film are used. The month is such that when it is attached to the object to be attached for a long period of time, especially when the road is in a high temperature state or a hot state, the durability is further excellent. In the adhesive composition of the present invention, the acrylic triblock is used. The copolymer (1) and the acrylic diblock copolymer (II) are mutually soluble, and can be uniformly coated. The viewpoint of obtaining a transparent adhesive layer is preferred. -23- 201209120 The weight average molecular weight (Mw(Al)) or polymer embedding of the polymer block A1 of the acrylic triblock copolymer (I) The weight average molecular weight (Mw(A2)) of the segment A2 is close to the weight average molecular weight (Mw(C)) of the polymer block C of the acrylic diblock copolymer (II), and the acrylic triblock copolymer The mutual solubility of (I) and the acrylic diblock copolymer (II) tends to increase. Therefore, from the viewpoint that the adhesive layer is uniformly formed and the adhesive layer becomes transparent, the weight average molecular weight of the polymer block A 1 and the polymer block A2 of the acrylic triblock copolymer (I) is small. The weight average molecular weight (Mw (Alow)) of the polymer block, the weight average molecular weight (Mw (Ahigh)) of the polymer block having a larger weight average molecular weight, and the polymerization of the acrylic diblock copolymer (II) The weight average molecular weight (Mw(C)) of the block C preferably satisfies the relationship of Mw(Alow)x〇.5SMw(C)SMw(Ahigh)x2, and more preferably satisfies Mw(Alow)x〇.8SMw (C) The relationship of SMw(Ahigh)xl.2 is better for satisfying the relationship of Mw(Alow) SMw(C) SMw(Ahigh). Here, the weight average molecular weight of each polymer block can be determined from the weight average molecular weight of the polymer contained in the sample liquid at the stage in which the synthesis of the polymer block is completed in the first polymer block. Further, in terms of the weight average molecular weight of the polymer block which is continuously polymerized, the weight average molecular weight of the first polymer block can be used as a reference, and the weight ratio of each polymer block (formation of each polymer block) The weight ratio of the consumed monomers is calculated in proportion. For example, the weight of the raw material monomer added to form the first polymer block (hereinafter referred to as polymer block 1) is W1, and the weight average molecular weight of the polymer block 1 is set to Mw 1, in order to form a continuous The weight of the raw material monomer added by the successively polymerized polymer block (hereinafter referred to as poly-24-201209120 compound latter stage 2) is determined as 'the weight average molecular weight of the polymer block 2 is set to Mw2, 4 is formed further. The weight of the raw material monomer to be added to the polymer block (hereinafter referred to as polymer block 3) is W3, and the weight average molecular weight 聚合物 of the polymer block 3 is Mw3', and Mw2 and Mw3 are obtained by the following formula. Conversion of monomer added to form Mw2=MwlxW2x polymer block 2/(Wlx conversion of monomer added to form polymer block i) To form Mw3=Mwlx\V3x polymer block 3 Conversion of monomer added / (Wlx conversion of monomer added to form polymer block 1) Weight average molecular weight of polymer block C of acrylic diblock copolymer (II) (Mw (C ()) From the viewpoint of excellent mutual solubility with the acrylic triblock copolymer (I) and high transparency, it is preferably from 9,000 to 30,000, more preferably from 15,000 to 25,000. When the weight average molecular weight (Mw (C)) of the polymer block C is less than 9,000, the durability of the adhesive composition may be insufficient, and if Mw (C) exceeds 300, hydrazine is dissolved in an organic solvent. The viscosity of the solution-type adhesive becomes high, and it becomes impossible to apply the conditions of containing the acrylic-type triblock copolymer (I) and the acrylic diblock copolymer (π) in high concentration, and the solvent usage amount will increase. In the adhesive composition of the present invention, the total content of the acrylic triblock copolymer (I) and the acrylic diblock copolymer (II) is based on the mass of the solid component of the adhesive grade (adhesive composition) The total mass of the total solid content is preferably 75% by mass or more, more preferably 80% by mass or more.

-25- 201209120 The total content of the acrylic triblock copolymer (1) and the acrylic diblock copolymer (II) is reduced according to the mass of the solid content of the adhesive composition, and if it is less than 75% by mass, the cohesive force is lowered. In addition, the durability of the adhesive composition is lowered (for example, the maintenance of the long-term adhering state becomes difficult). The dot composition of the present invention exhibits excellent cohesive force by forming a physical pseudo-crosslinking. Adhesive properties and durability. The physical pseudo-crosslinking is derived from a microphase separation structure formed of an acrylic triblock copolymer (I) and an acrylic diblock copolymer (II), and an acrylic triblock copolymer (I). The hard polymer phase formed by the polymer blocks A1 and A2 and the polymer block C of the acrylic diblock copolymer (11) as a main body contributes to the physical pseudo-crosslinking. Further, the adhesive composition of the present invention has excellent flexibility and moisture permeability. This property is derived from the polymer block B of the acrylic triblock copolymer (1) and the acrylic diblock copolymer ( The polymer block d of j丨) contributes as a soft polymer phase formed as a main body. The microphase separation structure generally forms a spherical structure, a column structure, a co-continuous structure, a stacked structure, and the like in accordance with the mass ratio, volume ratio, degree of polymerization, and the like of each polymer block. In the present invention, the co-continuous structure refers to a spherical structure in which a t-phase exists in a matrix phase, a column structure in which a rod-like phase exists in a matrix phase, and a stacked structure in which two or more phases overlap each other. The structure is typically, for example, a gyr〇id structure, a pL (porous stack) structure, or the like. -26- 201209120 Secret, the structure of the dilute hard polymer phase and the soft polymer phase ° 质量 & block mass ratio, volume ratio, degree of polymerization, etc., sometimes immersed in a group of people The formation of the ι segment is sometimes formed by embedding a plurality of polymers. Hard polymer phase # $ β , continuous 'is increased durability, and if the polymer phase is continuous, but the right mussels show the proper initial adhesion, therefore, the polymer phase It is preferable to use a soft phase to separate the ^ ^ , , , , σ phase to form a continuous structure of the micro phase separation structure. The hard temporary acquisition of the present invention is ^ M ^ ^ ^ i v . The phase/soft polymer phase together form a microfacies of the flail structure W, a Φ ^ structure &, for example, in the base phase formed by the soft polymer, there is a ... Long and continuous rod-like phase composed of negative ΛΚ & (for example, a column structure with a length of 500 nm or more in a rod-like phase, rich in softness Ιμιη or more), a co-continuous structure rich in hard flat, and stacked In the matrix phase composed of the composition, the left-staple is composed of a column which has a longer quality and has a long rod-like phase composed of a soft polymer (for example, the length of the rod-like phase is 5 〇〇ΐμπι or more). Body structure. 马 马 马 马 , , , 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马 马It is preferred to have a co-continuous structure composed of a hard and soft polymer component. & Each of the adhesives of the present invention, New Zhongzha m ^(1) η ^ ^ , an acrylic triblock copolymer (1) not used, and yttrium acrylate Diblock technology κ, θ ^ ρ monomer (Π) manufacturing method, as long as it can be paid The method of the well-known method is given by the method of the well-known method. One and two ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The wood is used as a method for the living polymerization of a monomer which constitutes a unit. Such an activity is changed by the hand of the fengmu baizhong &>, for example, an organic rare earth metal complex is used as a polymerization initiator for polymerization. The method (refer to Patent Document 5), using an organic metal compound as a polymerization initiator, and performing anion polymerization in the presence of a metal or a metal-based metal salt (see Patent Literature &quot J is a method of performing anion polymerization using an organic metal compound as a polymerization initiator and in the presence of an organic bismuth aluminum compound (refer to the patent document Ε ν ^ ^ ^ , W W 驮 7), atomic movement A radical polymerization method (ATRP) (see Non-Patent Document 1), etc. In the above production method, when a method of anionic polymerization is carried out in the presence of an organoaluminum compound, the deactivation in the middle of the polymerization is small, and the incorporation is deactivated. As a result, the amount of the homopolymer is small, and as a result, the adhesive composition has high transparency, and since the conversion rate of the monomer is high, the residual amount in the product is small, and when used as an adhesive composition, the adhesion can be suppressed. Further, the molecular structure of the decyl acrylate polymer block becomes ruthenium alignment, and when used in an adhesive composition, an effect of improving durability can be obtained, and, under mild temperature conditions, The living polymerization is carried out, and when it is industrially produced, it has the advantage of low environmental load (mainly the power consumption required for the refrigerator for controlling the polymerization temperature). From the above viewpoint, the acrylic diblock copolymer (1) and the acrylic system The diblock copolymer is preferably produced by a method of anionic polymerization in the presence of an organoaluminum compound. For the method of performing anionic polymerization in the presence of the above organoaluminum compound, for example, the following method can be employed: an organolithium compound, and the following formula (3) ^(3) A1R'R2R3 -28- 201209120 (wherein R, R2 and R 3 each independently represents a alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent which may have a substituent. An oxy group, an aryloxy group which may have a substituent or an N,N-disubstituted amine group, or R1 is any of the foregoing groups, and R2 and R3 are integrated to form an exoaryldioxy group which may have a substituent. . In the presence of an organic compound, an ether compound such as dioxane, dimethoxyethane, diethoxyethane or 12-crown-4 may be further added to the reaction system as needed; triethylamine, N, N ,N,,N,-tetramethylethylenediamine, N,N,N',N'',N,pentamethyldiethylenetriamine,lu,? A nitrogen-containing compound such as 1 〇, 1 〇 hexamethyldiethylenetetramine, pyridine or 2,2 '-bipyridine is used to polymerize an alkyl (meth) acrylate. There are isopropyl lithium, dilithium, fluorenyl phenyl didiphenyl benzene and dilithium; etc. Lithium amide lithium, oxybell 4-methyl with two kinds of lithium compounds, such as: methyl lithium , ethyl chain, n-propyl lithium, lithium, n-butyl lithium, second butyl lithium, isobutyl lithium, third butyl n-pentyl lithium, n-hexyl lithium, tetradecyl dilithium, penta An alkyl lithium such as hexamethylene dilithium or an alkyl dilithium; an aryl lithium such as phenyl lithium, meta-lithium, p-nonylphenyl lithium, xylyl lithium, or naphthalene; and a benzyl group; Lithylmethyllithium, trityllithium lithium-3-mercaptopentyllithium 'α•mercaptoyllithium, aralkyl lithium and aralkyl formed by the reaction of diisopropenylbutyllithium Lithium bis hydrazide lithium, diethyl guanamine lithium, lithium diisopropyl guanamine oxime, ethoxylate, n-propoxy chain, lithium isopropoxy n-butoxide, second Lithium alkoxide such as lithium oxyhydride, lithium ntoxide, lithium pentoxide, lithium heptoxide, lithium octoxide, lithium benzyloxide or lithium benzyloxide. & etc. can be used alone or in combination. -29- 201209120 An organoaluminum compound represented by the formula (3), for example, tridecyl aluminum, triethyl aluminum, tri-n-butyl aluminum, three second butyl aluminum, three third butyl: aluminum: three different Butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tris-2-ethylhexylamine, etc.; diterpene (2,6-di-t-butyl-4-methylphenoxy aluminum) , dimethyl (2,6-di-t-butylphenoxy), diethyl (2 6 di-t-butyl-4-methylphenyl), diethyl (2, 6 • bis-third base-stupyloxy)aluminum, diisobutyl (2,6-di-t-butyl-4-methylbenzene aldehyde, ^isobutyl (2,6-di- Tributylphenoxy)aluminum di-n-octyldi-t-butyl-4-methylphenoxy)aluminum, di-n-octyl (2,6-di-t-butylphenoxy)aluminum, etc. Dialkylphenoxyaluminum; methyl bis(2,6•di-t-butyrylphenoxy), methyl bis(2,6-di-trisylphenoxyethylmethylene bis( 4_methyl·6·t-butyl phenyloxy)], ethyl (2,6-mono-t-butyl-4-methylphenoxy) aluminum ethyl bis (2,6 two _ tert-butylphenoxy)aluminum, ethyl [2,2'-methylene double (4 Methyl-6 butyl tributyl phenoxy)]aluminum, isobutyl bis(2,6-di-t-butylmethyl phenyloxy, #butyl bis(2,6-di-t-butylbenzene) Oxy), isobutyl = 2'-methylenebis(4_methyl_6 tert-butylphenoxyaluminum, n-octyldi(2,6-mono-t-butyl-4) _Methylphenoxy)aluminum, n-octylbis-di-t-butylphenoxy)aluminium, n-octyl[2,2,-methylenebis(4-methyl-6-a: base Alkyldiphenoxide aluminum such as phenoxy)]aluminum; methoxybis(2,6-di-butyl-4-methylphenoxy)aluminum, methoxybis(2,6-di- Tert-butyl phenoxy)aluminum, methoxy[2,2,·methylenebis(4methyl-6-t-butylphenoxy)]aluminum, ethoxybis(2,6- Di-t-butyl-4-methylphenoxy) ethoxybis(2,6-di-t-butylphenoxy)aluminum, ethoxy[2,2,_methylene Tert-butylphenoxy (10), isopropoxy bis-30- 201209120 (2j_di-t-butyl-4-mercaptophenoxy) aluminum, isopropoxy bis (2,6-di _ Second butyl phenoxy) aluminum, isopropoxy [2,2,-arylene bis(4-methyl-6_ oxa) aluminium, second butoxide Bis(2,6-di-t-butyl-4-methylphenoxy), third butoxybis(2,6-di-t-butylphenoxy)aluminum, third butoxide Alkyl [2,2,-methylenebis(4_fluorenyl-6-t-butylphenoxy)aluminum alkoxydiphenoxyaluminum; ginseng (2,6-di-t-butyl _ 4-phenoxy)aluminum, triphenyloxyaluminum such as bis(2,6-diphenylphenoxy)aluminum, etc., etc., and isobutyl bis (2,6·2·third Butyl-4 -methylphenoxy) s-isobutyl bis(2,6-di-t-butylphenoxy) s, isobutyl [2,2,- fluorenyl (4-mercapto) ·6 • Ternyl butyl phenoxy ruthenium, etc., easy to handle = The viewpoint of the polymerization of (fluorenyl) propylene 'alkyl hydrazine can be carried out under mild temperature conditions without deactivation. These may be used alone or in combination of two or more. The adhesive composition of the present invention may optionally contain an adhesive, such as a fat, a plasticizer, an anabolic acid compound, an antistatic agent, and the like. When the adhesive composition of the present invention contains an adhesion-imparting resin. . 1 Viscosity, joint force and retention will become easier.峨;=! The resin can be used as the "adhesive" used in the past" ""any" such as rosin-based resin 1 olefinic resin, etc.: resin; petroleum resin, couma, keratin resin, cumbersome A synthetic resin such as a resin, a sapphire or a hexene-based resin, etc.. The centering agent has a high mutual solubility, and can be a transparent smear composition, a smear, or a smear. Equivalent resin; hydrogen A 0 -, - rosin, rosin resin such as polymer rosin; C5 / C9 -3 1- 201209120 petroleum resin such as eucalyptus, aromatic petroleum resin; α-fluorenyl A styrene-based resin such as a styrene polystyrene, a stupid ethylene/α-methylstyrene copolymer, or the like may be used as a resin, and may be used alone or in combination of two or more. In the case where the adhesive composition of the present invention contains an adhesive-imparting resin, the content of the adhesive composition of the present invention can be appropriately selected depending on the type of the adherend, etc., but based on The total mass of the total solid content of the adhesive composition is 25 mass In the following, it is more preferably 20% by mass or less, more preferably 1% by mass or less. When the content of the adhesive-imparting resin exceeds 25% by mass, the cohesive force of the adhesive composition is lowered, and residual glue is likely to occur during the rework. "Chemical agent" case.. Dibutyl phthalate, phthalic acid, octyl dicarboxylic acid, bis-diethyl phthalate, phthalic acid Phthalic acid phthalate such as diisoindole formate; adipate such as di-2-ethylhexyl adipate or n-octyl adipate; di-2-ethylhexyl hexahexanoic acid Fatty acid capable of phthalic acid such as n-butyl ester; sebacic acid bismuth oxalic acid; chlorinated paraffin; epoxidized ugly oil 1 oxidized linseed oil and other epoxy Polymer plasticizer; phosphate such as monosodium phosphate, triphenyl phosphate, etc.; bismuth phosphite such as triphenyl phosphite, n-butyl (meth) acrylate, 2-ethyl (meth) acrylate Acrylate-based polymer such as hexyl ester; polybutene; polyisobutylene; polyisoprene; processing oil, decane hydrocarbon oil; polyfluorene polyol, polyether polyol, etc. The alcohol-based compound, a polyolefin-based diol such as polyethylene glycol or polypropylene glycol, etc. The plasticizer may be used singly or in combination of two or more kinds. -32- 201209120 The adhesive agent of the present invention is based on the amount of adhesive The composition of the agent is preferably 25% by mass or less, and if the amount is more than 25% by mass, the residual phenomenon such as residual glue. When the plasticizer is contained, the total mass of the total solid content contained in the plasticizer is 1 〇% by mass or less is more preferable. The cohesive force of the plasticizer is lowered, and if an isocyanate compound is easily formed in the case of remanufacturing, the adhesion of the adherend is improved, and the durability of the adhesive composition of the present invention is related to the optical film base. The optical film of the present invention is also improved. The vinegar compound is attached to the interface between the optical film substrate and the adherend and the adhesive, and is bonded to the functional group and the adhesive of the Zhao side. The isocyanate compound contained can form a chemical bond last name, At which questions the adhesion to the attached body and exhibits higher durability. That is, on the surface of the protective film for an optical film or an optical film, there is an isocyanate-reactive functional group such as an m group, a trans group, a thiol group, an amine group or a guanamine group, and thus an adhesive composition. The isocyanate compound reacts with the surface of the protective film for an optical film or an optical film, and has an effect of improving the interfacial adhesion force of the optical film or the optical film with the adhesive film and the adhesive composition. The isocyanate compound is a compound having one or two or more isocyanate groups in the molecule, and the interface between the adherend and the adherent composition of the substrate is the same as that of the substrate. The regulation 'is an isocyanate compound having two or more cyanate groups, and is more preferably an isocyanate compound having three or more isocyanate groups in the molecule. -3 3 - E; 201209120 The above isocyanate compound 'for example: an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, the aforementioned isocyanate compound (especially a polyisocyanate compound) for a plurality of An adduct of an alcohol, an adduct of an isonic acid s, and the like. Specific examples of the above isocyanate compound include, for example, an aliphatic diisocyanate compound such as butyl diisocyanate or hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate An alicyclic diisocyanate compound; an aromatic diisocyanate compound such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or xylene diisocyanate; trimethylolpropane/stretch a polyisocyanate compound in which a diisocyanate compound is added to a polyol such as a terpene diene isocyanate trimer adduct, a trihydroxyhydrazine propane/hexamethylene diisocyanate trimer adduct or the like; hexamethylene diisocyanate An isocyanate adduct such as an isocyanurate body. Among the above isocyanate compounds, a trimer adduct of trimethylolpropane/extension benzene diisocyanate is a trade name of "CORONATE L", and a tris(hydroxyl) propane/hexamethylene diisocyanate trimer is added. The product is the trade name of "CORONATE HL", the isocyanurate body of toluene diisocyanate, the trade name of "CORONATE 2030" or "CORONATE 223 3", and the difference of hexamethylene diisocyanate The cyanurate body is sold under the trade name of "CORONATE HX" by Japan Polyurethane Industrial Co., Ltd. These isocyanate compounds may be used singly or in combination of two or more. In the adhesive composition of the present invention, when the isocyanate compound is contained, the amount of the isocyanate group in the isocyanate compound is -34 - 201209120 in terms of the content thereof, depending on the mass of the solid component of the adhesive composition (the composition of the adhesive composition) The total mass of the solid components is preferably 5% by mass or less, more preferably 0.35% by mass or less, and still more preferably 22% by mass or less. Here, the content of the isocyanate group in the isocyanate compound can be determined by the following formula < 丨 > depending on the mass of the solid component of the adhesive composition. CNCO (% by mass) = [ { wisoxn(42/Miso)} /Ws]xi〇<1> [wherein, CNCO represents the isocyanate group content in the isocyanate compound according to the solid content of the adhesive composition. (% by mass), W1S〇 represents the amount of isocyanate compound in the adhesive composition (bei amount), Miso represents the molecular weight of the isocyanate compound, n represents the number of isocyanate groups in the isocyanate compound, and ^ represents adhesion. The content (mass) of the solid component in the composition of the agent. In order to increase the reactivity of the above isocyanate compound, it is also possible to further use the reaction to contact the female. The above reaction touches a female, for example, 8-dioxheterobicyclo[5.4. 11 eleven _7), and metal 丄 special. Specific examples of the reaction catalyst are, for example, tetramethylbutanediamine, 14-azabicyclo[2.2.2]octane, dibutyltin dilaurate, tin octoate, & ethyl sulphate, triethylamine ,Ν,Ν,Ν,Ν,_tetramethylbutanediamine, triethylenediamine, cobalt sulphonate, tin chloride („), tetra-n-butyltin, tin chloride UV), trimethyl hydroxide Tin, dimercapto 2, vaporized tin, di-n-butyltin dilaurate, etc. These reaction catalysts may be used singly or in combination of two or more kinds. The adhesive composition of the present invention is an adhesive composition. Antistatic ability to contain antistatic agent can be -35- 201209120 The above antistatic agent, for example: ion-conducting ionic liquid containing alkali metal salt, interface active sword, Mo Gong r hl conductive polymer, metal oxidized carbon black, Nano carbon material 箄.Bu stem ρ μ 1 In the special antistatic agent of Ye Temple, from the viewpoint of permanent and non-colored, the ion-conducting ionic liquid of metal salt is better. The anti-static agent of the green phoenix 丨1 temple can be used alone or in combination. / The adhesive composition of the present invention When the antistatic agent is contained, it contains a few electrostatic effects, etc., and the solid content of the adhesive composition is preferably 0.1 to 10% by mass, more preferably 0.15 to 8 mass%, and more preferably 0.2% by weight. % is more preferable. The adhesive composition of the present invention contains a decane coupling agent, and the adhesion between the mixture and the glass when the moisture is returned to the humidity. The decane coupling agent has an alkoxy group such as a mercapto group or an ethenyl group. Hydrolysis of the alkoxy group to an alcohol group 'partially condensed'. and attached to the surface of the glass or fixed by hydrogen bonding or chemical bonding, which improves durability. The above-mentioned stone-burning coupling agent, for example, 3-epoxy-propyl Oxypropyl propyl trimethoxide, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-propoxypropylmethyldiethoxydecane, 3-epoxypropoxypropyl氧基基石石院,3·s-propylpropyltri-f-decyloxy, vinyltrimethalin*, vinyltriethoxydecane, 3-mercaptopropene oxypropyloxylate, 3- Methyl propylene oxypropyl triethoxy decane, 3 propyl decyloxy oxacyclohexane, 3-aminopropyl triethoxy decane, 3, acid propyl propyl triethoxy decane 3 - acetamidine acetate propyl trioxane oxime * etc. These zexi-burning coupling agents can be used alone, or they can be used together with 2 agents, materials, charged agents and 2 amounts by mass-6 The quality may be generally a key to the gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a gas, a salt, a salt, a When the coupling agent is used, the decane coupling μ a is determined by the reliability of k and the solid content s of the adhesive composition. The quality is better. 0. W mass % is better. 〇1~3 mass 〇 /. Compared with the adhesive composition of the present invention, for example, the other components used in the 隹 丰 丰 ^ ^ ^ 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 n M . .b Α. ... "Oxidative anti-oxidation external absorbing agent; carbonic acid, cerium oxide, mica, talc and other fillers; glass fiber, reinforcing fiber absorbent, coloring agent, etc. Wearing a first diffusing agent, near-infrared, and an adhesive composition of the invention, including an adhesive-imparting resin, a plasticizing J-linking agent, an antistatic agent, a decane coupling agent, and other components, the result is a flaw. The total mass of the total solid content contained in the adhesive composition is preferably 25% by mass or less, more preferably 2% by mass or less, and still more preferably 10% by mass or less. The adhesive composition of the glaze film of this month can be used as a solution adhesive or as a solid adhesive. The solution type adhesive can be prepared, for example, by dissolving the adhesive composition at a relatively low temperature (usually about 〇 to 7 Torr) in an organic/felt agent such as toluene, ethyl acetate, butyl acetate or methyl ethyl ketone. Further, the solid adhesive may be a conventional kneading device such as a kneader ruder, an extruder, a mixing roll or a Banbury mixer, usually in a range of 1 〇〇〇 c 〜 25 ( The temperature of rc is prepared by mixing. The adhesive composition of the present invention is preferably used in the form of a solution-type adhesive, which can be used for substrates, etc. without deformation or deterioration, alignment, residual stress, etc. of the substrate or the attached body. The adherend does not need to be heated at a high temperature to form a thin and uniform thickness of the adhesive layer. -37- 201209120 In particular, the adhesive composition of the present invention, when dissolved in an organic solvent, has a high solid content concentration (for example, '35 mass% The above) still shows a low solution viscosity. For example, when the adhesive composition of the present invention is dissolved in a high concentration solution having a solid concentration of 45 mass%, the viscosity is measured at a temperature of 25 ° C by a b-type viscosity meter. The viscosity of the solution, in the range of a*1000 to 4000 mPa·s, preferably in the range of 15 〇〇 to 35 〇〇mpa • ', more preferably in the range of 2000 to 3500 mPa·s β, therefore the adhesive composition of the present invention, even Reduce organic solvents The amount of use, from the t: a solution-type adhesive with a higher concentration of solid components in the past (solid:: minute wave is more than 35 mass%). When applied, ^^ Λ Λ 钿 钿 钿 or The processability (whether the drying is reduced, the coating speed is increased, the ripening step is omitted, etc.). The adhesive composition of the present invention can be omitted in the manufacturing step of the (iv) product. The conventional cross-linked type C-cats can be omitted. When the composition is made into a solution-type adhesive, the adhesive of the present invention can be used in the production of an adhesive type optical film. In the solution tank, the 3 type adhesive is used in the solution type adhesive a of the composition of the human body. The state of the original state is preserved for a long period of time, or the other side is recovered, and the conventional agent and the cross-linking agent are used. 2 liquid adhesives for the main heart to persuade the sword 'to use the main combination even after the room temperature will enter the spleen' L adhesive in 2 liquid mixed l rewards father and father reaction, use, adhesive properties or coating properties will Change. Therefore, the right ^ is not quickly followed by the 'practical cross-linking reaction in the dry Step frequency or product preservation 4 = agent, due to the above-mentioned dry conditions (temperature, :a into the sputum, it will respond to line speed or storage conditions (storage period, -38- this hair can be made by a part or composition of the film) Or (i) the unevenness of the adhesion of the product caused by the unevenness of the cross-linking of the protective film for the adhesive film for the coating of the present invention, which is applied to the protective film of the present invention, and 35 is the adhesion of the present invention. The adhesive composition does not cause such a good phenomenon. The adhesive film or the optical film substrate or the protective film of the present invention, at least one adhesive layer formed without chemical crosslinking, and the protective film for the optical film, for example, the optical film base described above Or optical bright film composition method, phthalic acid phthalate film isolating composition 'and superimposing it on the light film substrate, and the adhesive layer is transferred onto the protective film substrate, etc. Generally made of plastic materials, such as polyethylene terephthalate (pET), triethylamine (TAC), polyvinyl alcohol (pvA), polycarbonate, cycloaliphatic, =ene- Methacrylate copolymer resin (MS resin), known in the tree, an ultraviolet curable acrylic resin and the like. These plastic materials are distinguished by the function of the optical thin film. Although it is used as a polarizing plate, the two-phase pVA film which is adsorbed with two molecules (mainly iodine) is generally used to improve the degree and suppress the high temperature. • The purpose of stretching and the like in a hot and humid environment, - a multi-layer film of a TAC film having a function of a protective film. When U is used for a polarizing plate having a phase difference function, it is used in a uniform film which is not uniform, and the double-sided adhesive film forming method is used to form a film substrate, and the optical thin material or optical plastic enamel of the present invention is used. Fiber resin, acrylic acid used. The color-developing film is strongly bonded, and when the protective thin-protected single-sided or the above-mentioned adhesive of the present invention is previously applied, the coating substrate or the film-based substrate is formed. For example, a film which can be used for a film, (ii) a film which is coated with a discotic liquid crystal on an optical film of the optical film -39* 201209120 film TAC, or a protective film TAC, or a polycarbonate or a cycloolefin resin. A laminated film obtained by laminating a phase difference film obtained by bonding to a PVA film. In addition, when used as a crepe sheet, for example, a film formed of a photocurable acrylic resin or the like on a PET film or the like is used, and when used as a diffusion plate, a system made of MS resin or polycarbonate is used. film. Further, when used as a diffusion film, for example, a film coated with a particle layer on a PET film or a polycarbonate film or a surface treated with a pET film or a polycarbonate film, or an inner film is used. A film of a diffusing agent or the like. X ′ is used as a light guide plate by using a special film for the surface of a plate (film) made of acrylic resin, and a film made of a reflective sheet made of a pET film is laminated on the lower side of the plate. Light 4·Plastic materials for film protective film substrates, such as: polyethylene terephthalate (PET), polypropylene (pp), high density polyethylene (HDPE), low density polyethylene Polyethylene (PE), polyvinyl chloride (PVC), and ethylene vinyl acetate (EVA), such as thin (LDpE) and linear low density polyethylene (LLDPE). Films comprising such plastic materials may be either single or multi-layered. An adhesive optical film having an adhesive layer and a protective film for an optical film comprising the adhesive composition of the present invention, which are suitable for use in a liquid crystal display device, a plasma display panel (PDP), an organic electrodisplay device, and an electronic paper. Various image display devices. The adhesive optical film and the optical film produced by using the adhesive composition of the present invention are used as a can. Manganese 4 film, not 4 is used for the use of cross-linked acrylic-based -40, 201209120 Adhesives necessary for annealing or aging" can be directly shipped in the form of liquid crystal panels or products that can be attached to other adherends, productivity Excellent. The image display device 'generally includes a laminate of the plurality of optical films described above. The adhesive used when bonding an optical film to a glass substrate or the like or to bonding different types of optical films is preferably a difference in thermal expansion coefficient (dimension change accompanying temperature rise) between the optical film and the glass substrate. The difference in thermal expansion rate between different types of optical films is followed by a difference. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and the like, but the present invention is not limited to the Examples. First, the acrylic triblock copolymer (I) [acrylic triblock copolymer (1-1) to (1-2)] and the acrylic acid triblock copolymer used in the examples and the comparative examples are described. (1-3) to (1-4), and acrylic second-stage copolymer (II) [acrylic diblock copolymer (Π-1) to (II-2)] and acrylic diblock copolymerization A synthesis example of the substance (Π-3)~(Π-5). In the following synthesis examples, each block copolymer is produced by using a drug which is dried and purified by a usual method. The molecular weight, molecular weight distribution, composition, glass transition temperature of each polymer block, and polymerization conversion ratio of the block copolymer synthesized in the following synthesis examples were measured in accordance with the following methods. (1) Determination of number average molecular weight (Μη), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) by gel permeation chromatography (GPC): • Device: Gel Permeation Chromatograph (HLC) manufactured by Tosoh Corporation -8020) • Pipe column: "TSKgel GMHXL, G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation -41- 201209120 • Eluent: Tetrahydrofuran • Eluent flow: l.Omi/min

• Column temperature: 40 ° C * Detection method · Differential refractive index (RI). Calibration line: Made using standard polystyrene (2) Determination of the content of each copolymerized component by proton nuclear magnetic resonance (iH_NMR) spectrometry: • Device: Nuclear Magnetic Resonance Device (JNM-LA400) manufactured by JEOL Ltd. • Solvent: Heavy gas imitation • j-NMR spectrum 'signal near 3.6 ppm and 4.0 ppm' is assigned to the decyl methacrylate unit. The ester group (_〇_CH3) and the ester group of the n-butyl acrylate group - 〇_CH2-CH2-CH2-CH3), the content of the copolymerization component is determined according to the ratio of the integral enthalpy. (3) Measurement of glass transition temperature (Tg): In the curve obtained by differential scanning calorimetry (DSC measurement), the extrapolation start temperature (Tgi) was taken as the glass transition temperature (Tg). • Device: DSC-822 manufactured by Mettler Company • Condition: Heating rate 1 〇 °C / min (4) Determination of conversion rate of monomer added by gas chromatography (G C):

• Equipment: Gas Chromatograph GC-14A manufactured by Shimadzu Corporation • "Inert CAP 1" manufactured by GL Sciences Inc. (df = 0_4μηι, 〇.25mmI.D.x60m) • Analysis conditions: injection port 3〇〇° C, detectors 3〇〇〇c, 6〇. 〇 (Keep the temperature at 5t/min for 0 minutes - 10 (TC (keep 〇 min) - 15 〇 / min) - 30 ° C (for 2 minutes) -42 - 201209120 "Synthesis Example 1" [acrylic hydrazine Synthesis of triblock copolymer (I _ 1)] (1) After replacing the inside of a 2-L three-necked flask with nitrogen, 870 g of toluene and 44 g of 1,2-dimethoxyethane were added at room temperature, and then added. Isobutyl bis(2,6-di-dibutyl-4-methylphenyl)- 26.7]11111〇1 benzene solution 39.8g, then added to the second butyl lithium 3.81 mmol of cyclohexane The mixed solution with Zhengjiao was 2.2 〇g. Then, 36.2 g of decyl methacrylate was added to the mixture. The reaction solution was initially yellow, but was stirred at room temperature for 60 minutes and then became colorless. The conversion ratio of the methyl ester is 99.9% or more. Then, the internal temperature of the reaction liquid is cooled to _3 (rc, A is added dropwise to n-butyl acrylate for 2 hours) 2 〇.丨g, after the completion of the dropwise addition, at -30 The mixture was stirred for 5 minutes at ° C. The conversion of n-butyl acrylate at this time was 99.9% or more. Further, the oxime methacrylate i23 〇g was added thereto, and the mixture was added to the warm sandalwood for one night. 3.50 g of methanol was stopped and the polymerization reaction was stopped. The conversion of decyl methacrylate at this time was 99.9 % or more. The obtained reaction liquid was poured into 15 kg of methanol to precipitate a white precipitate. The white precipitate was recovered by the transition. And drying, thereby obtaining a block copolymer [hereinafter referred to as "acrylic triblock copolymer (11)"] 279 g. (2) Acrylic triblock copolymer obtained in the above (1) (Work-1), 1H-NMR measurement and Qpc measurement were carried out, and the result was a weight average molecular weight (Mw) of a tri-T-segment copolymer containing polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate. It is 7〇, 3〇〇, the average number of knives (Μη) is 62,600, and the molecular weight distribution (Mw/Mn) is 丄12. Further, each polymer in the acrylic acid diblock copolymer (1_丨) The content of the block, the methyl methacrylate polymer enemy (the total of the two polymer blocks A) is 57.3% by mass, and the acrylonitrile n-butyl ester polymer block (polymer block-43-201209120 B) 42.7% by mass. Further, sampling was performed at the time when the initial polymerization of methyl methacrylate was completed. The GPC of the reaction liquid was measured, and as a result, the weight average molecular weight of the mercaptoacetic acid methyl acrylate polymer block (M - 9,800, the number average molecular weight (?η) was 9,5 Å, and the molecular weight distribution (Mw/Mn) was 1.03. The results of the glass transition temperatures of the respective polymer fragments of the acrylic triblock copolymer (^) obtained above were as shown in Table 1. Synthesis Example 2 [Acrylic Triblock Copolymer (1) -2) Synthesis] (1) After replacing the inside of a 2L three-necked flask with nitrogen, 870 g of sulfonate and 44 g of 1,2-methoxypropane bromide were added at room temperature, and then isobutyl bis (2, 38.1 g of 6-di-t-butyl-4-methylphenoxy)aluminum 255 nl m〇l of ruthenium benzene, and adding cyclohexane and hexanol containing second butyl lithium 丨7〇mnl〇l The mixed solution was 0.9 8 g. Then, 28.9 g of methyl methacrylate was added to the mixture. The reaction solution initially appeared yellow, but became colorless after 60 minutes of incubation at room temperature. The conversion ratio of methyl methacrylate at this time was 99.9% or more. Then, the internal temperature of the reaction liquid was cooled to _ 3 Torr. Thereafter, 87.6 g of n-butyl acrylate was added dropwise over 2 hours, and after the completion of the dropwise addition, the mixture was stirred at -30 ° C for 5 minutes. The conversion ratio of n-butyl acrylate at this time was 99.9% or more. Further, 78.1 g of decyl methacrylate was added thereto, and after stirring at room temperature for one night, 3.50 g of decyl alcohol was added to terminate the polymerization reaction. The conversion ratio of decyl methacrylate at this time was 99.9 % or more. The obtained reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. The white precipitate was recovered by filtration and dried to obtain a block copolymer [hereinafter referred to as "acrylic triblock copolymer (I _ 2)"] 149 g. (2) The acrylic triblock copolymer (1-2) obtained in the above (1) was subjected to 1H-NMR measurement and (JPC measurement, and the result was a poly-44-201209120 methyl methacrylate-polyacrylic acid. N-butyl ester _ polymethyl methacrylate diblock copolymer, the average molecular weight (] ^ ~) is 121, 〇〇〇, number average molecular ® (Μη) is 97,7 〇〇 'molecular weight distribution (Mw /Mn) is 1.24. In the 'acrylic triblock copolymer (12), the content of each polymer block 'f-based acrylic polymer block (the combination of two polymer blocks A) is 55.5 mass%, the acrylic acid is vinegar polymer (polymer block B) is 44.5 mass%. In addition, at the time of the initial polymerization of methyl methacrylate, The Gpc of the reaction liquid was measured, and as a result, the weight average molecular weight (Mw) of the methacrylic acid malformed polymer was 18'000, the mass average molecular weight (?n) was 17,000, and the molecular weight distribution (Mw/Mn) was 1H. The results of the glass transition temperatures of the respective polymer blocks of the acrylic acid triblock copolymer (1-2) obtained above are shown in Table 1. <<Synthesis Example 3>> Synthesis of Acrylic Triblock Copolymer (1_3) (1) After replacing the inside of a 2 L two-necked flask with nitrogen, 870 g of toluene, hydrazine, 2-dimethoxyB were added at room temperature. 44g of alkane, then add 43.5g of benzene solution containing = isobutyl bis(2,6-di-tauthyl fluorenyl phenoxy) sulphate 2 2 〇 1 ' and then add the second butyl lithium 4 62 g of a mixed solution of cyclohexane and n-hexane of 62. Then, 36.2 g of methyl methacrylate was added to the mixture. The reaction liquid initially appeared yellow, but became colorless after stirring for 60 minutes in the room and field. The conversion ratio of decyl methacrylate at this time is 99.9% or more. However, the internal temperature of the reaction liquid is cooled to -3 〇 ° C. It takes 2 hours to add 229 butyl acetonate to the mixture. After that, the n-butyl acrylate at -3 (TC stirring for 5 minutes) is 9 9.9 / 〇 or more. Further, methyl methacrylate % 2 ^, -45- 201209120 is added thereto and stirred at room temperature for one night. Thereafter, 3 5 〇g of methanol was added to stop the polymerization reaction. The conversion of decyl methacrylate at this time was 99.9 % or more. The obtained reaction liquid was injected into 15 kg. In the decyl alcohol, a white precipitate was precipitated, and a white precipitate was recovered by a transition and dried to obtain a block copolymer [hereinafter referred to as "acrylic-based tri-segment copolymer j3 〇 lg. (2) (1) The obtained acrylic triblock copolymer (1-3) was subjected to 1H-NMR measurement and GPC measurement, and as a result, it was composed of polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate. The triblock copolymer has a weight average molecular weight of 8 Å, a number average molecular weight (?η) of 65,300, and a molecular weight distribution (Mw/Mn) of 1.23. Further, the content of each polymer block in the acrylic triblock copolymer (1-3) was 2 methacrylate polymer block (the total of two polymer blocks a) was 23.5 mass. /〇, the n-butyl acrylate polymer block (polymer block B) was 76.5 mass%. Further, GPC measurement of the reaction liquid sampled at the time point when the polymerization of the original decyl methacrylate was completed was carried out, and as a result, the weight average molecular weight (Mw) of the thioglycolic acid methyl vinegar polymer was 8,800, and the number average molecular weight (Μη) ) was 7,800 and the molecular weight distribution (Mw/Mn) was 1.13. Further, the glass transition temperatures of the respective polymer blocks of the acrylic triblock copolymer (1-3) obtained above were determined, and the results are shown in Table 1. <<Synthesis Example 4>> Synthesis of Acrylic Triblock Copolymer (丨_4) (1) After replacing the inside of a 2 L three-necked flask with nitrogen, 870 g of toluene and 1,2-dimethoxy group were added at room temperature. 44g of ethane, then add 60.0g' of toluene solution containing isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum 4〇2mm〇i and then add the second butyl group Lithium 3 33ηιηι〇1 Ring-46- 201209120 A mixed solution of hexane and n-hexane was 92 g. Then, 49.9 g of methacrylic acid 曱S曰 was added to the mixture. The reaction solution initially appeared yellow, but became colorless after stirring at room temperature for 60 minutes. The conversion ratio of decyl methacrylate at this time was 99.9 % or more. Then, the internal temperature of the reaction liquid was cooled to -300 ° C, and 1 77 4 g of n-butyl acrylate was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred at - 30 C for 5 minutes. The conversion ratio of n-butyl acrylate at this time was 99.9% or more. Further, 49. 9 g of methyl methacrylate was added thereto, and after stirring overnight at room temperature, the addition of sterol 3 · 50 g was stopped to terminate the polymerization reaction. The conversion ratio of decyl methacrylate at this time was 99.9 % or more. The obtained reaction solution was poured into 15 kg of sterol to precipitate a white precipitate. The white precipitate was collected by filtration and dried to obtain a block copolymer (hereinafter referred to as "acrylic triblock copolymer (1-4)"] 277 g. (2) The 1H-NMR measurement and the GPC measurement were performed on the acrylic triblock copolymer (1-4) obtained in the above (1), and the results were as follows: decyl acrylate-polybutyl acrylate-poly The triblock copolymer of decyl methacrylate has a weight average molecular weight (Mw) of 1〇1, a 〇〇〇, a number average molecular weight (Μη) of 81,500', and a molecular weight distribution (Mw/Mn) of 1.24. Further, in the acrylic triblock copolymer (1-3), the content of each polymer block, the methyl methacrylate polymer block (total of two polymer blocks A) was 36.0% by mass, and acrylic acid The n-butyl ester polymer block (polymer block B) was 64.0% by mass. Further, GPC measurement of the reaction liquid sampled at the time point when the polymerization of the first decyl methacrylate was completed showed that the weight average molecular weight (Mw) of the methyl methacrylate polymer block was 16,800 and the number average molecular weight (?η) The molecular weight distribution (Mw/Mn) was 1,1.2. Further, the acrylic triblock-47-201209120 obtained as described above is obtained by heating the respective ring groups of the different kinds of the cyclic group to the acid-inducing quantum-1) complex copolymer (1-4). The results of the glass transition temperature of the segments are shown in Table 1. Synthesis Example 5 [Synthesis of Acrylic Diblock Copolymer (11_丨)] (1) After replacing the inside of a 2 L three-necked flask with nitrogen, 870 g of toluene and i,2-dimethoxy at room temperature were added. 44g of ethyl ethane, followed by the addition of 26.3g of butyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum I. 6mmol benzene solution, followed by the addition of second butyl lithium 2.52 mmol of a mixed solution of hexane and n-hexane was 1.46 g. Then, 49. 9 g of decyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes in the chamber. At this time, the conversion of methyl methacrylate was 99.9% or more. Then, the internal temperature of the reaction liquid was cooled to -3 ° C, and 87.7 g of n-butyl acrylate was added dropwise over 2 hours. After the addition of the mixture, the mixture was stirred at -3 ° C for 5 minutes, and then 3.5 g of methanol was added. Stop the polymerization should. At this time, the conversion ratio of n-butyl acrylate was 99.9% or more. The obtained reaction solution was then poured into 1 5 k g of methanol to cause a white precipitate. The white precipitate was collected by filtration and dried to obtain a bis-laid copolymer [hereinafter referred to as "acrylic diblock copolymer (II-1)"] 237 g. (2) For the acrylic diblock copolymer obtained by the above, [1H-NMR measurement and GPC measurement], the result is a diblock copolymer comprising poly(decyl propylene acrylate)-polybutyl acrylate. The weight average molecular weight (Mw) was 114,000, the number average molecular weight (Mn) was 98,500, and the component distribution (Mw/Mn) was 1.16. Further, the acrylic diblock copolymer (in the Π, the content ratio of each polymer block 'the methacrylate methacrylate polymer block (polymer block C) is 20.9 % by mass, n-butyl acrylate poly -48-201209120 The polymer block (polymer block D) was 79.1% by mass. Further, GPC measurement of the reaction liquid sampled at the time point when the initial polymerization of methacrylic acid was completed was completed, and as a result, methyl methacrylate was obtained. The polymer block had a weight average molecular weight (Mw) of 21,800 and a number average molecular weight (Mn) of 19,800' molecular weight distribution (Mw/Mn) of 1.10. Further, the acrylic diblock copolymer obtained above (II- was obtained. 1) The glass transition temperature of each polymer block, and the results are shown in Table 1. "Synthesis Example 6" [Synthesis of acrylic diblock copolymer (π·2)] (1) 2 L two-necked flask After replacing the inside with nitrogen, 870 g of toluene and 44 g of 1,2-dimethoxyethane were added at room temperature, followed by the addition of isobutyl bis(2,6-di-t-butyl-4-methyl 54.9g of phenoxy)aluminum 36.8mm〇1 in toluene solution, and then added to the ring containing butyl butyl lithium and 5.25mm〇1 The mixed solution was 3 _ 0 3 g. Then, 49.9 g of methyl methacrylate was added to the mixture. The reaction solution was initially colored yellow, but became colorless after 60 minutes of stirring at room temperature. The conversion ratio of dilute methyl ester is above 9 9 · 9 ° /. Then 'cool the internal temperature of the reaction solution to -3 0 ° C, it takes 2 hours to add n-butyl acrylate 1 6 7.1 g, and drop After the completion of the addition, the mixture was stirred at -3 ° C for 5 minutes, and then the addition of sterol 3 · 5 g was stopped to terminate the polymerization reaction. At this time, the conversion of the acrylic acid was 99.9 % or more. Then, the obtained reaction was carried out. Injecting 15 kg of sterol to precipitate a white precipitate. The white precipitate was recovered by filtration and dried to obtain a diblock copolymer [hereinafter referred to as "acrylic diblock copolymer (II-2)". 216g. (2) The acrylic diblock copolymer (Π-2) obtained above was subjected to 1H-NMR measurement and GPC measurement, and as a result, polymethyl methacrylate-49-201209120 methyl ester-polyacrylic acid was contained. a diblock copolymer of butyl ester having a weight average molecular weight (Mw) of 45,200 and a number average molecular weight (??) 40,000, molecular weight distribution (Mw/Mn) is 1.13. Further, in the acrylic diblock copolymer (π-2), the content ratio of each polymer block, methyl methacrylate polymer block (polymer The block C) was 23.0% by mass, and the n-butyl acrylate polymer block (polymer block D) was 77.0% by mass. Further, sampling was performed at the time when the initial polymerization of methyl methacrylate was completed. The GPC measurement of the reaction liquid revealed that the methyl methacrylate polymer block had a weight average molecular weight (Mw) of 9,900, a number average molecular weight (??) of 9,500, and a molecular weight distribution (Mw/Mn) of 1.04. Further, the glass transition temperatures of the respective polymer blocks of the acrylic acid-based diblock copolymer (Π·2) obtained above were determined, and the results are shown in Table 1. <<Synthesis Example 7>> Synthesis of Acrylic Diblock Copolymer (Π-3) (1) After replacing the inside of a 2 L three-necked flask with nitrogen, 870 g of 1, -1 -1 曱 oxygen was added at room temperature. Ethyl bromide 44g' then added 30.9g of 20.7m mol of toluene solution containing isobutyl bis(2,6--mono-t-butyl-4-indenylphenoxy), followed by the addition of a second butyl group A mixed solution of lithium 5.17 mm 〇i and a mixture of hexane and hexane was 2.9 9 g. Then, 21.7 g of methyl methacrylate was added to the mixture. The reaction solution was initially colored yellow, but became colorless after 60 minutes of room temperature mixing. At this time, the conversion ratio of mercapto-acrylic acid vinegar was 9 9 _ 9 % or more. Then, the internal temperature of the reaction liquid was cooled to -30 ° C, and 288.4 g of n-butyl acrylate was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred at -30 ° C for 5 minutes, and then 3 to 5 g of sterol was added to stop the polymerization. . At this time, the conversion ratio of n-butyl acrylate was 99.9% or more. Then, the obtained reaction liquid was poured into 15 kg of sterol to precipitate an oily precipitate -50 - 201209120. The oily precipitate was collected by decantation and dried to obtain a diblock copolymer (hereinafter, the pants were "acrylic diblock copolymer (II-3)"] 310 g. (2) The acrylic diblock copolymer (11-3) obtained above was subjected to H-NMR measurement and GPC measurement, and as a result, it was a diblock copolymer containing decyl acrylate-n-butyl acrylate. The weight average molecular weight (Mw) is 67,000, the number of bismuth molecular weight (Mn^55 4 〇〇, molecular weight distribution (Mw/Mn) is 1.21. Further, in the acrylic diblock copolymer (π_3), each polymer The content ratio of the block, the methyl methacrylate polymer block (polymer block C) was 6.9% by mass, and the n-butyl acrylate polymer block (polymer block D) was 93.1% by mass. The Gpc of the reaction liquid sampled at the time point when the polymerization of methyl methacrylate was completed was carried out, and as a result, the weight average molecular weight (Mw) of the decyl acrylate polymer block was 4,400, and the number average molecular weight (Mn) was 4. 2〇(), the molecular weight distribution (Mw/Mn) was 1.05 °, and the glass transition temperature of each polymer block of the acrylic diblock copolymer (II-3) obtained above was determined, and the results are shown in Table 1. [Synthesis Example 8] [Synthesis of Acrylic Diblock Copolymer (Π-4)] (1) 2 L After the inside of the flask was replaced with nitrogen, 870 g of toluene and 44 g of 1,2-dimethoxyethane were added at room temperature, followed by the addition of isobutyl bis(2,6-di-t-butyl-4-methyl). 82.4 g of a benzene solution of phenoxy)aluminum 55 2 min ,l, and then added 8.0 3 g of a mixed solution of cyclohexane and n-hexane containing a second butyllithium 13 8 mm〇i. Then, in the mixture 122.9 g of methyl propyl acrylate was added. The reaction solution was initially colored yellow, but became colorless after 60 minutes of stirring at room temperature. At this time, the conversion of methyl methacrylate-51 - 201209120 was 9 9 · Then, the internal temperature of the reaction liquid was cooled to -30 ° C, and 192.2 g of n-butyl acrylate was added dropwise over 2 hours, and after the completion of the dropwise addition, the mixture was stirred at -3 ° C for 5 minutes, and then added. The polymerization reaction was stopped while the methanol was 3 · 5 g. At this time, the conversion ratio of n-butyl acrylate was 9 9 · 9 % or more. Then, the obtained reaction liquid was poured into 15 kg of sterol to precipitate a white precipitate. The white precipitate was recovered by decantation and dried to obtain a diblock copolymer [hereinafter referred to as "acrylic diblock copolymer ( II-4)"] 313g. (2) The 1H-NMR measurement and the GPC measurement were carried out on the acrylic diblock copolymer (Π4) obtained above, and the result was a polyacrylic acid 曱S-polyacrylic acid. The diblock copolymer of n-butyl ester has a weight average molecular weight (Mw) of 31,00 Å, a number average molecular weight (Mn) of 25 Å, and a distribution in the molecule (% of PCT is 124. Further, acrylic In the diblock copolymer (π_4), the content ratio of each polymer block is yttrium methacrylate polymer (polymer segment C) is 39. 〇 mass%, n-butyl acrylate polymer is embedded The segment (polymer block enthalpy) was 61 〇 mass%. Further, the Gpc of the reaction liquid sampled at the time point when the polymerization of the mercapto propyl ketone S 完成 was completed was carried out, and the weight average molecular weight (w ) of the methyl methacrylate polymer block was 9,800. 0. The thousand-average molecular weight (Μη) in the radical *denier is 9,300, and the molecular weight distribution (Mw/Mn) is 1 ^ , _υ5. Further, the glass transition temperature of the κ-block of the acrylic-based two-block copolymer (ΙΙ-4) obtained above was determined, and the results are shown in Table 1. °Example 9&gt; [Synthesis of a second-stage copolymer of acrylic acid (ΙΙ-5)] (1) 2L _ into 870g of toluene, I] The inside of the flask was replaced with nitrogen, and then dimethoxy group was added at room temperature. 44g of ethane, then add 36.0g of toluene solution containing iso-52-201209120 butyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum 24.1111, Xenopus 1 A mixed solution of dibutyllithium 6.02 mmol of cyclohexane and n-hexane was 3.50 g. Then, 53.6 g of methyl thioglycolate was added to the reaction mixture. The reaction solution was initially colored yellow, but became colorless after stirring at room temperature for 60 minutes. At this time, the conversion ratio of methyl methacrylate was 99.9 % or more. Then, the internal temperature of the reaction liquid was cooled to -30 ° C, and 1.5 g of n-butyl acrylate was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred at -30 ° C for 5 minutes, and then 3.5 g of methanol was added to stop the polymerization. reaction. At this time, the conversion ratio of n-butyl acrylate was 99.9 % or more. Then, the obtained reaction liquid was poured into 15 kg of methanol to precipitate a white sediment. Thereafter, the white precipitate was recovered by decantation and dried to obtain a diblock copolymer [hereinafter referred to as "acrylic diblock copolymer (II-5)"] 330 g 〇 (2) for the above The acrylic diblock copolymer (11_5) was subjected to 1 H-NMR measurement and GPC measurement, and the result was a diblock copolymer containing polymethyl methacrylate-n-butyl acrylate, and the weight average molecular weight ( Mw) was 66,000, the number average molecular weight (?n) was 54,500, and the molecular weight distribution (Mw/Mn) was 1.21. Further, in the acrylic diblock copolymer (π_5), the content ratio of each polymer block is such that the methyl methacrylate polymer block (polymer block C) is 16% by mass, and the acrylic acid is positive. The butyl ester polymer block (polymer block D) was 8 4.0% by mass. Further, GPC measurement of the reaction liquid sampled at the time point when the polymerization of methyl methacrylate was completed was carried out. As a result, the weight average molecular weight (Mw) of the methacrylate polymer block was 9,800, and the molecular weight (Mn) was 9,3 Å, the molecular weight distribution (Mw/Mn) was 1.05. Further, the glass transition temperatures of the respective polymer blocks of the acrylic type II-53-201209120 copolymer (II-5) obtained above were determined, and the results are shown in Table 1. The physical properties of the acrylic triblock copolymers (1_1) to (b) and the acrylic diblock copolymers (Π-1) to (Π-5) synthesized in the above Synthesis Examples 1 to 9 are as shown in Table 1. Shown. -54- 201209120 Synthesis Example 9 1(11-5) I CD (N (7) 84.0 66,000 1.21 101.8 νί 1 1 1 9,800 51,500 Synthesis Example 8 (II-4) CD (N (7) 61.0 31,000 1.24 101.7 -44.8 1 1 1 9,800 15,300 Synthesis Example 7 (II-3) CD CN 00 rn On ο ο 1 1.21 1 1-46.6 1 1 1 1 ο ο 寸 &quot; 〇〇\ Synthesis Example 6 (II-2) CD CN (7) 77.0 j 1 45,200 1.13 101.8 -44.9 1 1 1 ο 33,100 Synthesis Example 5 (II-1) CD (N 〇\ 114,000 1.16 110.2 1 -46.9 1 1 1 1 21,800 82,500 Synthesis Example 4 ^P, A1-B-A2 Xfl 64.0 101,000 1.24 108.1 - 45.2 ο OO VO Ο Ο oC ο 00 1 1 Synthesis Example 3 h-1^ A1-B-A2 in 76.5 ο ο S 1.23 100.3 -46.5 o 00Λ OO 1 55,700 1 ! 8,800 1 1 Synthesis Example 2 f7 h— A1- B-A2 44.5 ο ο CN 1.24 ! 115.0 -46.6 o 〇λ OO ο S ο S 1 1 Synthesis Example 1 /-&quot;-N ^-H A1-B-A2 00 42.7 70,300 1.12 105.3 -45.0 9,800 32,500 ο ° Cn m 1 1 [Block copolymer] symbol type structure υ PnBA block content (% by mass) Weight average molecular weight (Mw) 3) Molecular weight distribution (Mw/Mn) 4) TMA of PMMA block (°C) ΡηΒΑ Block Tg (°C) Weight average molecular weight of polymer block A1 (Mw) Weight average molecular weight (Mw) of polymer block 5 5) Weight average molecular weight (Mw) of polymer block Α 2 5) Weight average molecular weight (Mw) of polymer block C Weight of polymer block D Average molecular weight (Mw) 6) S Μ·^φ^ ss^$ tw屮Let the poor cows forget the #铋涑郐难(£ «w&lt;«&gt;s^难¥90&lt;1-17&gt;?-6-0 -3 Gong铋涑^磘^-硪3¥-03-1&lt; Gong铋*趔雄-^(3VH^dqv 养d d: CNS VIAISd-q-vaud-q-vwsd : is $^ίίί 201209120 Further 'documentation of the invention The materials used. • Polyethylene terephthalate (PET) film: Toyo-spun film E 500 (thickness: 50 μm), manufactured by Toyobo Co., Ltd. The following examples and comparative examples are described. The evaluation of the characteristics of the adhesive type optical film obtained in each of the examples and the comparative examples was carried out as follows. [Continuous force] The adhesive optical film produced in the following examples or comparative examples was cut into a width of 25 mm and a length of 200 mm. As a test piece, the shai test piece was rubbed back and forth twice with 2 kg of rubber. On the air surface of the glass plate to be attached. After storage at 24 ° C '50% RH for 24 hours, or 90 C under dry conditions for 24 hours, 180 was measured at a peeling speed of 3 〇 mm/min or 300 mm/min. Peel off the force. The above conditions were measured in accordance with JIS Z0237. Further, the glass plate is a glass plate which has been subjected to inspection and cleaning using a commercially available soda lime glass plate containing an alkali component. [creep test (holding force test)] Adhesive type opticals produced in the following examples or comparative examples The film was cut into a size of 25 mm (horizontal direction: a direction perpendicular to the direction of the load) x l 〇 mm (longitudinal direction, the same direction as the direction of the load), and as a test piece, the test piece was used with a 2 kg rubber roller. The air surface of the glass plate to be attached was attached to the test piece, and the weight of i kg was applied to the test piece, and the creep test was carried out in accordance with JIS Z023 7 under the conditions of a temperature of 9 〇. As a result of the test, when the dropping time was less than 1 minute, the dropping time was measured, and when it was 1000 minutes or more, the position of the test piece after 1 minute was measured. -56- 201209120 This test is used to check the durability of the adhesive (adhesive composition) under heating. The shorter the deviation of the position of the test piece, and the longer the time until the test piece falls off, the adhesive (adhesive) The durability of the agent composition is more excellent. [Observation of Microphase Separation Structure of Adhesive Layer] The adhesive optical film produced in the following examples or comparative examples was placed on the pedestal of the apparatus with the adhesive layer facing up, and the surface of the adhesive layer was observed by SPM. Device··Using SII · Scanning probe microscope (SPM) and environmental control unit (E_sweep) manufactured by nanotechn〇1〇gy.

Measurement mode: DFM using cantilever company) SI-DF20 (inside A1) (sn. nan〇techn〇i〇gy Measurement area: 1 χ 1 μιη Scanning frequency: 1.0 Hz Scanning division number: χ = number of data = 512, γ = number of data = 256 "Example 1" I) The acrylic triple-strand copolymer (Ι-i) and the acrylic diblock copolymer (111) produced in the above Synthesis Example 1 and Synthesis Example 5 were as follows: ^ As shown in Table 2, the ratio of 44 parts by mass and 56 parts by mass was weighed separately. After the adhesive composition was formed, it was diluted with a solid part to make the whole solid component: 35 mass%, and oscillated to prepare a solution type. Sticky (four). The appearance of the solution-type adhesive is transparent, without mixing or separating into two objects? 'Removing the solvent from the above-mentioned solution type adhesive to obtain the (IV) agent -57-201209120 (2) Applying the solution type adhesive obtained in the above (1) to a PET film (thickness 50 μηι) using a bar coater, at 6 (rc) Drying for 3 minutes, making an adhesive optical film containing an adhesive layer/PET film. Adhesive light

In the film, the thickness of the adhesive layer is shown in Table 2. Also, the adhesive layer is transparent. S (3) The results of the adhesion force (peeling adhesion force) and creep test of the adhesive optical film 'obtained in the above (2) for the glass plate are shown in Table 2. (4) Further, the surface of the adhesive layer of the adhesive optical film obtained in the above (2) was observed by the above method, and the image shown in Fig. i was obtained. In the figure i, the black portion is a hard polymer phase composed of the polymer blocks A1 and A2 of the acrylic diblock copolymer (1) and the polymer block c of the propylene I-based block copolymer (Π). The white portion is a soft polymer phase comprising a polymer block B of an acrylic triblock copolymer (1) and a polymer block of an acrylic diblock copolymer (π). Also, Mw(c) is full of "Μ*]. ,. 5Bu 49〇〇)sMw(C) Bu 218 is similar to Mw(Ahigh)x2(= 666〇〇). <<Example 2>> (1) The above-mentioned Synthesis Example 1 and an acrylic triblock yam (1-1) and an acrylic diblock mound manufactured by the smashing of Example 5, and a polymer (Π) -1), as shown in Table 2 below, 'weighed 56 parts by mass and 44 from 4 mils, to prepare the viscous 4, and after the product' was released into the whole with toluene The solid content of the solid content was 35 lbs %, and the mixture was shaken to prepare a liquid-type adhesive. The obtained solution type adhesive agent was transparent in appearance, and was turbid or separated into two layers. Further, the adhesive agent was removed from the above-mentioned solution type adhesive to remove the bathing agent. '58- 201209120 (2) The solution-type adhesive obtained in the above (1) was applied to a PET film (thickness 5 〇μη1) using a bar coater at 6 Torr. The adhesive type optical film containing the adhesive layer/pΕΤ film was produced by drying for 3 minutes. The thickness of the 'adhesive layer' in the adhesive optical film is shown in Table 2. Also, the adhesive layer is transparent. (W) The results of the adhesion force (peeling adhesion force) and the creep test of the adhesive sheet for the adhesive optical film obtained in the above (2) are shown in Table 2.

Mw(C) satisfies Mw(A1ow)x〇.5(= 4900)$Mw(C)(= 21 800)$Mw(Ahigh)x2(= 66600). [Example 3] (1) The acrylic triblock copolymer (I1) and the acrylic diblock copolymer (U1) produced in the above Synthesis Example 1 and Synthesis Example 5 are shown in Table 2 below. Separately, 72 parts by mass and 28 parts by mass were weighed to prepare an adhesive composition, which was diluted with toluene to have a total solid content of 35 mass%, and shaken to prepare a solution type adhesive. The obtained solution type adhesive was transparent in appearance, free from turbidity or separated into two layers. Further, the solvent was removed from the above solution type adhesive to obtain an adhesive composition. (2) The solution-type adhesive obtained in the above (1) was applied onto a PET film (thickness: 50 μm) using a bar coater and dried at 60 °C for 30 minutes to prepare an adhesive optical film comprising an adhesive layer/PET film. The thickness of the 'adhesive layer' in the adhesive optical film is shown in Table 2. Also, the adhesive layer is transparent. (3) For the adhesive optical film obtained in the above (2), the results of the adhesion (peeling adhesion force) and the creep test of the glass plate are shown in Table 2.

Mw(C) satisfies Mw(Alow)χ〇·5( = 4900) ‘Mw(C)( = 21800) gMw(Ahigh)x2(= 66600). -59-201209120 "Example 4" (1) The acrylic triblock copolymer (1-1) and the acrylic diblock copolymer (π_2) produced in the above Synthesis Example 1 and Synthesis Example 6 are as follows. 2, '40 parts by mass and 60 parts by mass, respectively, were prepared and prepared as an adhesive composition, and then diluted with toluene to make the total solid content of 35 masses. /. A solution-type adhesive was prepared by shaking. The obtained solution type adhesive was transparent in appearance, free from turbidity or separated into two layers. Further, the solvent was removed from the above solution type adhesive to obtain an adhesive composition. (2) The solution-type adhesive obtained in the above (1) was applied to a PET film (thickness of 50 μπ〇 after a thickness of 50 μπ〇) at 6 〇. After drying for a minute, an adhesive optical film comprising an adhesive layer/PET film was produced. The thickness of the adhesive layer in the adhesive optical film is shown in Table 2. Further, the adhesive layer is transparent. (3) For the adhesive optical film obtained in the above (2), the adhesion to the glass plate (peeling is followed by The results of the force and creep test are shown in Table 2. Mw(C) satisfies Mw(A1〇w)x〇5(=49〇0)gMw(c)(=99〇〇)$μ&lt;αμ^) χ 2 (= 66600) 〇 "Example 5" ^ (1) Acrylic tri-nake v, λ Κ (i_2) and acrylic diblock copolymer (η丨) produced in the above Synthesis Example 2 and Synthesis Example 5 , as shown in the following Table 2, weighed 40 parts by mass and 60 parts by mass, and prepared an adhesive composition, which was diluted with benzene to a total solid content of 35 lb.%, and oscillated to prepare. Solution-type adhesive ◎ The appearance of the solution-type adhesive obtained is transparent, without turbidity or separation into two layers, and the above solution of bonfire Type of adhesive removes solvent to obtain adhesive group -60- 201209120 (2) The solution adhesive obtained by the above (丨) is applied to a PET film (thickness 50 μm) using a bar coater, and then dried at 60 ° C for 30 minutes. An adhesive optical film comprising an adhesive layer/PET film was produced. The thickness of the 'adhesive layer' in the adhesive optical film is shown in Table 2. Also, the adhesive layer is transparent. (3) For the adhesive optical film obtained in the above (2), the results of the adhesion (peeling adhesion force) and the creep test for the glass plate are shown in Table 2.

Mw(C) satisfies Mw(Alow)x0_5(= 9000)SMw(C)(= 21800)$Mw(Ahigh)x2(=97200) 〇"Comparative Example 1" (1) The propylene produced by the above Synthesis Example 3 Acid-based three-stage copolymer (Ι·3) 'According to the following Table 2, the adhesive composition was prepared in an amount of 1 part by mass, and then diluted with toluene to make the whole solid content into a mass two-vibration preparation. A solution-type adhesive. The obtained solution-type adhesive was transparent in appearance, and was not turbid or separated into two layers. (2) The solution-type adhesive obtained in the above (1) was coated on a PET film (thickness 50 μm) by a bar coater, and then dried at 6 (TC for 30 minutes to produce an adhesive optical film comprising an adhesive layer/PET film). In the adhesive optical film 4, the thickness of the adhesive layer is as shown in Table 2. Further, the adhesive layer is transparent. (j) Adhesive optical film obtained in the above (2), adhesion to the glass plate (peeling) The results of the subsequent force and the creep test are shown in Table 2. Comparative Example 2 The acrylic triblock copolymer (1-4) produced in the above Synthesis Example 4 was prepared as shown in Table 2 below. After 100 parts by mass of the adhesive group -6 1-201209120, the whole solid content was made into μ% by diluting with toluene, and oscillated to prepare a solution type adhesive. The obtained solution was visually transparent, free from turbidity or separated into two layers. (2) The solution-type adhesive obtained in the above (1) was applied to a PET film (thickness: 50 μm) using a bar coater, and then an adhesive type optical film comprising an adhesive layer/PET film was formed at 6 Torr: dry. In the adhesive film, the thickness of the adhesive layer is as shown in Table 2. Also, the adhesion is transparent. (3) For the adhesive optical film obtained in the above (2), the results of the glass adhesion (peeling adhesion) and the creep test are shown in Table 2, "Comparative Example 3" (1) The above synthesis example and synthesis The acrylic segment copolymer (1-1) and the acrylic diblock copolymer (π) produced in Example 5 were weighed in a ratio of 23 parts by mass and 77 parts by mass, respectively, in an amount of 2 parts by weight: After the composition was diluted with toluene, the entire solid was made into a mass of 35% and shaken to prepare a solution type adhesive. Obtained: The appearance of the liquid-type adhesive is transparent, and there is no turbidity or separation into two. The above-mentioned solution-type adhesive removes the solvent and obtains the composition. (2) The solution type adhesive obtained in the above (1) was applied to a PET film (thickness 50 μm) using a bar coater at 6 Torr. Drying for 3 minutes to form an adhesive optical film comprising an adhesive layer/pΕΤ film. The thickness of the 'adhesive layer' in the adhesive film is as shown in |2. &amp;, adhesive is transparent. Adhesive coating, three layers of the molding agent, and the adhesion coating of the obtained layer, the molding agent layer-62-201209120 (3) The adhesive optical film obtained by the above (2), The adhesion of the glass plate (peeling adhesion force) and the results of the creep test are shown in Table 2.

Mw(C) satisfies mw(Alow) X 0· 5( = 4900) Mw(C)( = 21 faces) $ Mw(Ahigh) χ2(= 66600). Comparative Example 4 (1) The acrylic triblock copolymer (Μ) and the acrylic diblock copolymer (11_丨) produced in the above Synthesis Example 1 and Synthesis Example 5 are shown in Table 2 below. The ratio of 77 parts by mass and 23 parts by mass was weighed, and an adhesive composition was prepared, and the solid content was 35 % by mass, and the mixture was shaken to prepare a solution type adhesive. The obtained &gt; valley liquid type adhesive was transparent in appearance, and was not turbid or separated into two layers. Further, the solvent was removed from the above solution type adhesive to obtain an adhesive composition. U) The solution-type adhesive obtained in the above (1) was coated on a PET film (thickness 50 μm) by a bar coater and then dried at 60 ° C for 30 minutes to produce an adhesive optical film comprising an adhesive layer/PET film. . The thickness of the 'adhesive layer' in the adhesive optical film is shown in Table 2. Also, the adhesive layer is transparent. (3) With respect to the adhesive optical film obtained in the above (2), the adhesion to the glass plate (peeling adhesion force) was measured by the above method, and as a result, the adhesion force to the glass was too low, and the adhesion could not be measured. (4) Further, in the adhesive optical film obtained in the above (2), the creep test was carried out by the above method, but the adhesion force to the glass was too low, and the creep test could not be carried out. Mw(C) satisfies Mw(Alow)x〇.5(= 4900)SMw(C)(= 21800)$Mw(Ahigh)x2(= 66600). -63-201209120 "Comparative Example 5" (1) The acrylic triblock copolymer (I-1) and the acrylic diblock copolymer (11_3) produced in the above Synthesis Example 1 and Synthesis Example 7 were subjected to As shown in the following Table 2, the ratio of 55 parts by mass and 45 parts by mass was weighed to prepare an adhesive composition, and then the total solid content was 35 % by mass diluted with toluene and oscillated to prepare a solution type adhesive. Agent. The obtained solution type adhesive has a turbid appearance, and if left to stand, it is separated into two layers. Further, the solvent is removed from the solution-type adhesive to obtain an adhesive composition. (2) The solution-type adhesive obtained in the above (1) was coated on a PET film (thickness 50 μm) using a bar coater and then dried at 60 ° C for 30 minutes to produce an adhesive type optical film including an adhesive layer/PET film. film. In the adhesive optical film, the thickness of the adhesive layer is as shown in Table 2, and the adhesive layer is microscopically phase-separated and opaque. The adhesive optical film has low transparency.

Mw(Alow)x〇.5 = 4900, Mw(C)= 4400, Mw(C) is not satisfied Mw(Alow)x〇.5SMw(C)$Mw(Ahigh)x2. Comparative Example 6 (1) The acrylic triblock copolymer (1-1) and the acrylic diblock copolymer (π_4) produced in the above Synthesis Example 1 and Synthesis Example 8 are shown in Table 2 below. A ratio of 72 parts by mass to 28 parts by mass was weighed, and an adhesive composition was prepared, and the solid content was 35 % by mass, and the mixture was shaken to prepare a solution-type adhesive. The obtained solution-type adhesive was transparent in appearance, and was not turbid or separated into two layers. Further, the solvent was removed from the above &gt; valley liquid type adhesive to obtain an adhesive composition. -64- 201209120 (2) The solution adhesive obtained in the above (1) was applied to a PET film (thickness 50 μm) using a bar coater, and then dried at 6 ° C for 3 minutes to prepare an adhesive layer/PET. Adhesive optical film for film. # 、, The thickness of the adhesive layer in the cat-type optical film is shown in Table 2, and the adhesive layer is clear. (3) In the adhesive optical film obtained in the above (2), the adhesion force (peeling adhesion force) to the glass plate was measured in the above-described speed. As a result, the adhesion force to the glass was too low, and the adhesion could not be measured. (4) Further, with respect to the adhesive optical film obtained in the above (2), the creep test was carried out by the above method, but the adhesion force to the glass was too low, and the creep test could not be carried out.

Mw(C) satisfies Mw(A1ow)x〇.5(= 4900) Mw(C)(= 9800)$Mw(Ahigh)x2(= 66600). Comparative Example 7 (1) The acrylic triblock copolymer (1-1) and the acrylic diblock copolymer (π_5) produced in the above Synthesis Example 1 and Synthesis Example 9 are not shown in Table 2 below. The ratio of 31 parts by mass and 69 parts by mass was weighed, and after the preparation of the adhesive was prepared, the mixture was diluted with toluene so that the total solid content was 35 % by mass and oscillated to prepare a solution-type adhesive. The obtained solution type adhesive was transparent in appearance, and was not turbid or separated into two layers. The above-mentioned bath type dot removing agent was used to remove the solvent to obtain an adhesive composition. (2) The solution-type adhesive obtained in the above (1) was applied to a PET film (thickness 5 μm μη) using a bar coater at 6 Torr. The crucible was dried for 3 minutes to prepare an adhesive optical film comprising an adhesive layer/ruthenium film. Adhesive type -65- 201209120 In the film, the thickness of the adhesive layer is shown in Table 2. Also, the adhesive layer is transparent. (3) For the adhesive optical film obtained in the above (2), the results of the adhesion (peeling adhesion force) and the creep test for the glass plate are shown in Table 2.

Mw(C) satisfies Mw(A1ow)x〇.5(= 4900)$Mw(C)(= 9800)SMw(Ahigh)x2(= 66600). Comparative Example 8 (1) The acrylic triblock copolymer (1-4) and the acrylic diblock copolymer (Π-1) produced in the above Synthesis Example 4 and Synthesis Example 5 are as shown in Table 2 below. The adhesive composition was prepared by weighing the ratio of 72 parts by mass and 28 parts by mass, and then diluted with toluene to make the total solid content of 35% by mass, and oscillated to prepare a solution-type adhesive. The obtained solution-type adhesive was transparent in appearance, and was not turbid or separated into two layers. Further, the solvent was removed from the solution-type adhesive to obtain an adhesive composition. (2) The solution type adhesive obtained in the above (1) was applied to a p ET film (thickness 50 μτη) using a bar coater at 6 Torr. The adhesive was dried for 30 minutes to prepare an adhesive optical film comprising an adhesive layer/PET film. In the adhesive type optical film, the thickness of the adhesive layer is as shown in Table 2. Also, the adhesive layer is transparent. 〇) For the adhesive optical film obtained in the above (2), the results of the adhesion (peeling adhesion force) and the creep test for the glass plate are shown in Table 2.

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The adhesive optical film of Comparative Example 1 and Comparative Example 2 produced by using an adhesive composition containing only an acrylic triblock copolymer has a low adhesion force before heat treatment and has a suitable weight The adhesive force is not peeled off, but can be peeled off with an appropriate peel strength. On the other hand, the adhesion force after the heat treatment is increased, and the adhesive strength can be firmly followed, and the durability in the creep test is excellent. The mass ratio (1)/(11) of the tris-segment copolymer (I) to the propionic acid-based diblock copolymer (II) falls within the range specified by the present invention to the acrylic triblock copolymer (I). The adhesive optical film of Comparative Example 3 produced by the adhesive composition having a small content is low in durability in the creep test. Further, the acrylic triblock copolymer (I) and the acrylic two-embedded film are used. The mass ratio (1)/(11) of the segment copolymer (II) falls within the scope of the invention. The adhesive optical film of Comparative Example 4 produced by the adhesive composition having a large content of the acrylic acid-based triblock copolymer (I) has low adhesion and cannot be attached to a liquid crystal panel or the like. A plurality of optical films are attached and laminated. Further, the acrylic diblock copolymer (Π-) which does not have (F2) is contained in the requirements (FI), (F2), (F3) and (F4) specified in the present invention. 3) The adhesive composition of Comparative Example 5, the acrylic triblock copolymer (I-1) and the C-69-201209120 dilute acid diblock copolymer (Π-3) have low miscibility, and the system is low in compatibility. When it is a solution-type adhesive, the 'appearance turbidity' will be divided into two layers, and the adhesive cannot be uniformly applied. Further, the adhesive layer of the adhesive optical film is microscopically separated to be opaque, and the adhesive optical film has low transparency. The total mass (X) of the polymer block C contained in the polymer block A1, the polymer block Α2, and the acrylic diblock copolymer (Π) contained in the acrylic triblock copolymer (I) 'The ratio of the total mass (Y) of the polymer block B contained in the acrylic triblock copolymer (I) to the polymer block D contained in the acrylic diblock copolymer (π) (χ)/ (γ), the adhesive optical film of Comparative Example 6 produced by the adhesive composition which is one of the more (X) than the range specified in the present invention, has low adhesiveness and cannot be attached to a liquid crystal panel or the like, or Most optical films cannot be attached and laminated. Further, an adhesive type optical film of Comparative Example 7 produced by using (黏)/(Υ) an adhesive composition which is one of the lesser than the range specified in the present invention, was used for the durability of the creep test. low. Further, 'the use of an adhesive composition containing the acrylic triblock copolymer (1_4) which does not have (Ε2) among the requirements (El), (Ε2), (Ε3) and (Ε4) specified in the present invention is used. In the adhesive optical film of Comparative Example 8, the adhesive force before the heat treatment was high, and the reworkability was somewhat poor, and the durability was poor in the creep test. [Industrial Applicability] The adhesive composition for an optical film of the present invention contains non-chemically crosslinked optical fibers of an acrylic triblock copolymer (I) and an acrylic diblock copolymer (11). The adhesive for film can be initially applied with a bonding force suitable for redoing, and it can be peeled off with a good peeling strength when it is reworked, and it is peeled off at a proper peeling strength of 70-201209120 degrees. In particular, when exposed to a high temperature state or a hot and humid state, the force is increased and the durability is excellent. Therefore, the adhesive film and the protective film for an optical film can be effectively used. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a microphase separation structure (phase image measured by DFM) of an adhesive layer of an adhesive optical film obtained in Example 1. Fig. 2 is a view showing the microphase separation structure (phase image measured by DFM) of the adhesive layer of the adhesive optical film obtained in Comparative Example 1. [Main component symbol description] jifr- 〇 4 »*&gt; -7 1-

Claims (1)

201209120 VII. Patent application scope: 1. An adhesive composition for an optical film, wherein the (α) contains the following propylene I-based diblock copolymers having the elements (E1), (E2), (E3) and (e4); (1), and the following acrylic diblock copolymer (11) having the elements (η), (f2), (F3) and (F4), (β) acrylic diblock copolymer (1) and acrylic two-embedded The mass ratio (1)/(11) of the segment copolymer (π) is 75/25 to 3 Å/7 Å, and the polymer block Α1 contained in the (γ) acrylic acid-based three-drum segment copolymer (1) The total of the polymer block C contained in the polyblock block Α2 and the acrylic diblock copolymer (9) is contained in the (3)' and the acrylic triblock copolymer (I). The ratio of the total mass (Υ) of the polymer flag.β I 甘 入 amp Β Β 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸/(Υ) is 30/70 to 50/50; Acrylic triblock copolymer (I): (Ε1) An acrylic triblock copolymer Α1-Β-Α2 (1) represented by the following formula (丨) In formula (1), Α1 and Α2 are each The glass transition temperature is represented by the alkyl methacrylate polymer block on CX, and the Β represents the glass transition temperature of "2〇 °p |, / &quot;C々工# ' UC below the alkyl acrylate polymer embedded (E2) polymer block. B content is 5 to 45 mass%; (E3) weight average molecular weight (Mw) is 30,000 to 300,000; and (E4) molecular weight distribution (Mw/Mn) is l.oq Acrylic diblock copolymer (II): (F 1) Acrylic diblock copolymer represented by the following formula - 72 - 201209120 (in the formula (7) 'C β methyl propionate The vinegar polymer section, D represents the alkyl acrylate polymer block); (4) the content of the polymer block D is 6 〇 to 85% by mass; (F3) the weight average molecular weight (Mw) is 3 〇, 〇〇〇 〜 3〇〇〇〇〇; and (F4) the molecular weight distribution (Mw/Mn) is J 〇~丨5. 2. The adhesive composition for an optical film according to the invention of claim i, which has a microseparation structure comprising a hard polymer phase and a soft polymer phase. The hard solid umbrella phase is formed by the acrylic acid-based three-coupling copolymer (1), the oxime 肷筱A1 and A2, and the acrylic diblock copolymer (π) polymer, which is formed as a main body. The polymer phase is formed by the polymer block D of the acrylic acid triblock copolymer (1) and the polymer block D of the acrylic acid-block copolymer (II) as the main body, and the hard polymer phase and The soft polymer phases together form a continuous configuration. 3. The adhesive composition for an optical film according to claim 1 or 2, wherein the mass ratio (1)/(11) of the acrylic triblock copolymer (1) to the acrylic diblock copolymer (II) is 59. /41~30/70. 4. The adhesive composition for an optical film according to any one of claims 1 to 3, wherein the total mass (χ) of the polymer block Α丨, the polymer block Α 2 and the polymer block C, The ratio (Χ)/(Υ) of the mass (Υ) to the total of the polymer block Β and the polymer enemy D is 33/67 to 45/55 〇' as in the first to fourth patent applications. An adhesive composition for an optical film, wherein the total mass (χ) of the polymer block A丨' polymer block Α2 and the polymer block C, and the polymer block Β and the polymer block D The mass (Υ) / (Υ) of the total mass (Υ) is 39/61 to 43/57 〇-73- 201209120 The optical film for the optical film (I), the weight average molecular weight CM w (A1 〇w)) and a weight-weight average molecular weight of 6. The composition of any one of claims 1 to 5, wherein the acrylic triblock block A1 and the polymer block A2 are small (Mw(Ahigh)) of the polymer block having a weight average molecular weight and a large average molecular weight of the polymer block, which is contained with respect to the acrylic diblock copolymer (11) The weight average molecular weight (Mw(C)) of the polymer block C satisfies the relationship of Mw(Al〇w)x〇.5SMw(C)$Mw(Ahigh)x2 as in the claims 1 to 6 of the patent application. - a dot composition for an optical film, wherein the weight average molecular weight (Mw(c)) of the polymer block c of the acrylic diblock copolymer (1) [) is 9, 〇〇〇~3〇 Hey. An adhesive-type optical (4) having an adhesive layer comprising the adhesive composition for an optical film according to any one of claims 1 to 7. 9. A protective film for an optical film, which is blown by a soybean meal, and which has an adhesive comprising an adhesive composition for a coating film of a coating film according to any one of claims 1 to 7 of the patent application. Floor. An image display device having an adhesive optical film as claimed in claim 8 and/or a protective film for an optical film according to the ninth application of the patent application. '74-