TW201229171A - Acryl-based pressure sensitive adhesive composition, acryl-based pressure sensitive adhesive and optical component containing pressure sensitive adhesive layer - Google Patents

Abstract

To provide an acryl-based pressure sensitive adhesive composition for forming a pressure sensitive adhesive layer which can prevent occurrence of light leakages due to shrinkage of polarizing plate and can be suitably used for polarizing plate composing liquid crystal display apparatuses. Provided is an acryl-based pressure sensitive adhesive composition that contains (A) a first (meth)acrylic ester polymer having Mw of 100 to 250 millions, (B) a second (meth)acrylic ester polymer having Mw of 20 to 150 thousands and (C) an isocyanate-based crosslinking agent having features of: (1) the second (meth)acrylic ester polymer (B) is a tri-block copolymer having a (meth)acrylate-based monomer unit containing a hydroxyl group, (2) a content of the second (meth)acrylic ester polymer (B) is less than 40 parts by mass per 100 parts by mass of the first (meth)acrylic ester polymer (A) and (3) a gel fraction of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition is more than 40%.

Description

.201229171 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to an acrylic acrylate-based acrylic acid-based adhesive, and a viscous material, which is thermally cross-linked, and the present invention relates to Optical member for the two' layer. Further, the adhesive composition, the adhesive::: an acrylic polarizing plate or the like of the coating layer can prevent: two: a phenomenon that constitutes a liquid crystal display device; and a whitening agent which is caused by stretching of the acrylic: plate And an acryl-based adhesive having an um & agent and a product, and an optical member to which the adhesive layer is attached. [Prior Art] If the internal stress of the adhesive layer cannot be absorbed, the effect of the residual stress on the polarizing plate, which is caused by the expansion and contraction of the polarizing plate, is not scooped. The stress will be concentrated in the peripheral part of the government. More than the central: the reason is 'the liquid crystal display is left white. As a wide-ranging liquid crystal display device, it is considered to be a cause of whitening of the liquid display device, and it is considered that the stress is generated in the optical functional film and the adhesive layer j (the occurrence of birefringence, etc.) ). Patent Document 1 discloses that an adhesive composition for a polarizing plate formed of a low molecular weight acrylic copolymer of 30,000 or less in a high-molecular-weight acrylic copolymer has an average of 30,000 or less. The adhesive composition is difficult to leave white as the size of the polarizing plate changes. However, the adhesive composition described in Patent Document 1 has a large amount of a low molecular weight acrylic polymer having a weight average of 30,000 or less (4) to prevent foaming or peeling under high temperature and high humidity. [comparison

-4-S. 201229171 Patent Document 2 discloses that a monomer having an acrylic group having a low glass transition temperature (Tg) having a functional group of at least % by weight is 6% by weight or more of a high Tg propylene conjugate, and The cross-linking agent formed by reacting with the functional group has a gel fraction of less than 3% by weight of the adhesive composition by means of a high Tg acrylic copolymer crosslinked structure of a low Tg acrylic copolymer. The polymer of the ester compound is limited, and it is revealed that the adhesive composition hardly forms a cross between molecules, and it is difficult to prevent whitening. However, it is difficult to suppress the occurrence of foaming or peeling when the cohesive force at a high temperature is low. Patent Document 3 discloses that an adhesive is further composed of 100 parts by weight of an acrylic polymer as a polymer and 1 to 100 parts by weight of the above acrylic low-acid-based oligomer. The block copolymer of the block is formed. The propylene contains a separate glass transition temperature of -5 t or less to fix the adhesive to the adherend, and has no adhesion from the degree of adhesion, and hardly occurs when it is peeled off from the adherend. Contamination is easily peeled off by adhesion. Further, the monomer composition is different from that of the copolymer, and even if a small amount of acrylic acid is used, the above effect is exhibited. It is not clear that such an excellent feeling is exerted, but it is considered that the interaction monomer such as the high compatibility of each block and the compatibility of the acrylic polymer is a mixed weight of a 0.5 weight copolymer and an officially-containing copolymer. The chaotic acid S is a composition of the composition. The intramolecular formation of the substance is subjected to an isocyanin concentration. However, the joint structure, although it is formed in the durability evaluation, is characterized by the formation of an adhesive residue as a main component, and the propylene is a polyacid oligomer of -5 ° C or less due to the copolymer block, The adhesion of the adhesive body to the peeling process can be extremely high, and the polymer block polymer can be used for the purpose of the effect of the effect of the addition, and can be used to exert the viscosity. 201229171 Focus and peeling The above characteristics of force and the like. However, since the oligomer component exists in a free state, durability is poor under wet heat conditions. [Comparative Example 3] [Prior Art Document] [Patent Document 1] Japanese Patent No. 3533589 (Patent Document 2) Japanese Patent Publication No. 2〇〇6_1336〇6 [Patent Document 3] Japanese Laid-Open Patent Publication No. 4,92,152, the disclosure of the present invention is based on the present invention. The present invention is based on the fact that the adhesive is suitable for forming a liquid to prevent the polarizing plate from being formed. The expansion and the acid-based adhesive composition of the acrylic acid-based adhesive composition are proposed, and the purpose is to remove the whitening phenomenon of the polarizing plate of the acrylic-based adhesive composition crystal display device, and the like; Providing the obtained property with the above-mentioned properties [Means for Solving the Problem] The inventors of the present invention have made the following findings in order to devote themselves to the purpose of the investigation, and to repeat the serious research. ^ The second (mercapto) propylene polymer containing a weight average molecular weight at a specific average, and a second molecular weight of the second (mercapto) propylene crosslinker The adhesive composition is such that the tris-dimer of the acrylic vinegar monomer unit has a matrix containing a methyl group (the methyl group is contained in such a ratio... a copolymer) and by the hydroxyl group in the special 201229171 Crosslinking occurs at the joint. It is presumed that a high molecular weight (methane) propylene-based polymer is inserted in the three-dimensional network structure formed by low molecular weight triblock copolymer: cross-linking, Therefore, it is possible to effectively absorb and relax the internal stress generated by the expansion and contraction of the optical member such as the polarizing plate. Further, it has been found that the gel fraction of the adhesive formed of the above-mentioned adhesive composition can be maintained at 40% or more. The absorption and relaxation of the aforementioned internal stresses provide the cohesive force necessary for the optical application of the adhesive. The present invention has been completed based on these findings. That is, the present invention provides: [1] An acrylic adhesive a composition comprising a first (fluorenyl) acrylate polymer (A) having a weight average molecular weight of 1,000,000 to 250,000 and a second having a weight average molecular weight of 20,000 to 150,000 ( The mercapto acrylate polymer and the isocyanate crosslinking agent (c) are characterized in that _(1) the aforementioned second (meth) acrylate polymer (B) has a Three (7) of (meth) acrylate monomer units relative to - parts by mass of the aforementioned first (meth) acrylic acid condensing s (eight) narration of the first (meth) acrylate The content of the polymer (b) is less than 40 parts by mass, and (3) the gel fraction of the adhesive formed of the adhesive composition is 40% or more; [2] The acrylic adhesive as described in the above item (1) The composition 'make' the morphology of the triblock copolymer is b2bi_b2 type or 201229171 type (wherein bl represents a block containing a (meth) acrylate monomer unit having no functional group which becomes a crosslinking point , b2 represents a block comprising a hydroxyl group-containing (fluorenyl) acrylate monomer unit.); [3] The acrylic pressure-sensitive adhesive composition according to the above [2], wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (?η) of the triblock copolymer is 1.0. [1] The acrylic acid-based dot composition as described in any one of the above-mentioned items [1] to [3], wherein the base group of the triblock copolymer The content of the acrylate monomer unit is 1.5 to 20% by mass' and the content of the three-year-old copolymer is 10% with respect to 1 part by mass of the first (meth) acrylate polymer (Α). [5] The acrylic adhesive composition according to any one of the above items, wherein the three-segment copolymer is formed by living radical polymerization, [6] The acrylic pressure-sensitive adhesive composition according to any one of the above-mentioned items, wherein the isocyanate is a cyanide polymer (Β), isocyanate, 100% by mass of the second (meth) propionate polymer (Β) The content of the acid vinegar-based crosslinking agent (C) is 5 to 2 parts by mass; [7] an acrylic adhesive' is characterized by being [1] to [6] as described above The acrylic acid-based adhesive composition according to any one of the preceding claims is formed by thermal crosslinking; and [8] an optical member having an adhesive layer attached thereto, characterized in that a layered layer is laminated on the optical member The acrylic adhesive described in the above item [7]. [Effect of the Invention] 201229171 According to the present invention, it is possible to provide an internal olefinic acid-based pressure-sensitive adhesive composition for forming an adhesive layer, which is suitable for use in a polarizing plate or the like for constituting a liquid crystal display, and can be prevented from being caused by a polarizing plate. And a phenomenon in which the stretching occurs; and an acryl-based article obtained from the acrylic adhesive composition and an optical member to which the adhesive layer is attached. [Embodiment of the Invention] First, the acrylic pressure-sensitive adhesive composition of the present invention will be described. [Acrylic Adhesive Composition] The acrylic pressure-sensitive adhesive composition of the present invention (hereinafter, simply referred to as an adhesive) The composition) comprises a first (meth) acrylate polymer (A) having a weight average molecular weight of from 10,000 to 250,000, and a second (methyl) having a weight average molecular weight of 20,000 to 150,000. An adhesive composition of an acrylic vinegar polymer (b) and an iso-acid vinegar cross-linking agent (C), characterized in that the hydroxyl group (1) the aforementioned second (meth) acrylate polymer (B) a triblock copolymer having a (meth) acrylate monomer unit, (2) a second (meth) acrylate W in combination with 100 parts by mass of the first compound (4); The gel fraction of 40 parts by mass and the small amount of ester aggregation is 40% (3) or more of the adhesive formed of the adhesive composition. It is possible to presume that the adhesive obtained from the adhesive composition is inserted into two or more polymers (A) in the three-network structure by forming a three-dimensional network structure from the polymer (B) and the crosslinking agent (C). In the polymer (formation of a pseudo-crosslinked structure, that is, 'can be presumed to be due to the large octagonal 3 3 between the various 201229171 (A). The sickle does not lick the chemical cross-linking structure, but through the aforementioned three-dimensional network structure The 槠& _仏 is connected by collocation and collocation, so the mobility of the cross-linked part

The pI j it shape is larger than the chemical father. Therefore, the adhesive formed is stress-relieving. It is presumed that in the present invention, by the cross-linking point in the polymer (B), the three-dimensional network-shaped ''circumference' of the formed adhesive can be adjusted to the most suitable size. Thereby, it is possible to simultaneously achieve improvement of stress relaxation in a high dimension and improvement of cohesive force. (First (meth)acrylate polymer (A)) In the acrylic pressure-sensitive adhesive composition of the invention, the (meth) acrylate polymer used as the component (A) is preferably not The (meth) acrylate monomer having a reactive s energy group is a main constituent component. The first polymer may be composed only of a (meth) acrylate monomer having no reactive functional group, but it is preferably a small amount of copolymerized carboxyl group in consideration of adhesion to a glass surface of a liquid crystal glass cell or the like. (meth) acrylate monomer. The (fluorenyl) acrylate monomer having no reactive functional group is not particularly limited, and for example, a (meth) acrylate having an alkyl group of an ester moiety and having 1 to 20 carbon atoms is preferred. Here, examples of the (meth) acrylate having 1 to 20 carbon atoms of the alkyl group of the ester moiety include methyl (meth)acrylate, ethyl (meth) acrylate, and (decyl) acrylate. Propyl ester, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)propionate, cyclohexyl (meth)acrylate, 2-ethylhexanoic acid (meth)acrylate, (methyl) isooctyl acetoate, decyl acrylate, dodecyl (meth) acrylate, myristyl (methyl) propyl phthalate, (meth) acrylate 10-10 - 201229171 Six burns, (methyl) acridine and 18 hydrazine. They may be used singly or in combination of two or more. The dibasin, particularly butyl acrylate, is preferable in that it can obtain an appropriate adhesive property and it is easy to produce a (fluorenyl) acrylate copolymer having a weight average molecular weight of 1,000,000 or more. On the other hand, as a specific example of the carboxyl group-containing (meth)acrylic acid vinegar monomer to be mixed, (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid may be mentioned. Wait. These may be used singly or in combination of two or more. Among them, acrylic acid is preferred from the viewpoint of producing a (meth) acrylate copolymer having a weight average molecular weight of 1,000,000 or more. Further, a hydroxyl group-containing (meth) acrylate monomer, an amine group-containing (meth) acrylate monomer, and a thiol group-containing (meth) acrylate monomer, etc. The (meth) acrylate monomer having a reactive functional group other than the acrylate monomer preferably does not contain a structural unit as the first (fluorenyl) acrylate polymer. This is because the second (meth) acrylate polymer and the isocyanate crosslinking agent (C) may be hindered from forming a three-dimensional network structure. Examples of the monomer having another functional group include non-crosslinkable acrylamide such as (fluorenyl) acrylate having an aromatic ring such as (mercapto)acrylic acid benzoacetic acid, acrylamide or methacrylamide. (曱) Ν Ν, Ν _: methylaminoethyl ester, (meth) propyl acrylate, Ν-dimethylaminopropyl ester and other non-parental secondary amine group (methyl) propyl The dilute vinegar, the ethyl acetate vinegar, the stupid ethylene, etc. can be suitably used in the range which does not impair the effect of this invention. -11 - 201229171 In the (meth) isopropyl phthalate polymer, from the viewpoint of remanufacturability, <reactive functional group (f-based) acrylic acid vinegar monomer monoterpene, and Content ratio of carboxyl group-containing (meth) acrylate monomer unit

'It is better to have a mass ratio of 100:0~8 V, +1 eyepiece X 〇υ. 2 υ之$!!, the above viewpoint plus the long-term view, better for the heart ~ (10): The scope of (7). Further, the first (meth) acrylate polymer (A) is not necessarily obtained by the polymerization of the group (B) as described later, but also by a conventional radical polymerization method. get. Here, the weight average molecular weight of the polymer (4) is required to be 1,000,000 to 250,000. This is because if the weight average molecular weight is less than 1,000,000, the durability may be lowered. If the weight average molecular weight is more than 250,000, the stress relaxation property may be hindered and the light leakage prevention property may be lowered. From the same point of view, the average molecular weight of ♦Huidan is preferably in the range of 1.2 million to 10,000, more preferably in the range of “Ο; ~1.8 million. In addition, the above weight average molecular weight is passed through the gel permeation layer. The polystyrene-converted value measured by the analytical method (GPC). In the adhesive composition of the present invention, the w-factor (A), a single type of first (meth)acrylic polymer can be used alone, It can be used in combination of two or more types. (The second (meth) acrylate polymer is the second (meth) acrylate polymer used in the acrylic adhesive composition τ of the present invention as a horse component,) It is a di-agricultural-to-one-stage copolymer having a surface-containing (fluorenyl) acrylate monomer unit. The triblock copolymer preferably has a form of b2_bl b2 or bi bb 1 (wherein b 1 (meth)acrylic acid represented by a non-reactive functional group

S -12- 201229171 The block formed by the ester type early unit 'b2 represents a block formed of a monomer unit containing hydroxyenoic acid. (Methyl)-propyl: a triblock copolymer of the component (8), using a (meth)acrylic acid vinegar monomer having no s-energy group as a raw material component, and a hydroxyl group-containing (meth) group having a hydroxyl group as a reactive s-energy group Acrylate monomer. Another 2 γ In the present invention, the block copolymer means that the fungal portion formed by the (meth)acrylic acid g-free monomer having no reaction = g energy group is formed by the si-based (meth)acrylic acid. The formation of the ester monomer in each block portion may be composed of a plurality of types of monomers, and the early body of the inner species may be arranged in a block configuration, or may be omitted: from the viewpoint of controlling the three-dimensional network structure. , for the formation of a (meth) acrylate monomer having a reactive s-energy group, or by the formation of a (meth) acrylate-containing monomer containing a thiol group. - Record, #λ, the species is preferably composed of only one monomer. The (mercapto)acrylic acid vinegar monomer having no reactive functional group is not particularly limited. For example, (meth)acrylic acid having an alkyl group of the ester moiety and having 1 to 20 carbon atoms is preferable. wine. Here, examples of the (meth) acrylate having an oxime atomic number of the ester partial alkane 丨 〇 〇 〇 , 可以 可以 可以 可以 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱Acetone, (meth)acrylic acid butyl vinegar, (methyl) propyl acetoacetate, (methyl) propyl, ene g 夂 曰 曰, (methyl) propionic acid ring, (meth)acrylic acid ethylhexanyl (meth)acrylic acid isooctyl ester, (mercapto) decyl acrylate, (mercapto) acrylic acid twelve stealing field # «=!«, (曱基) acrylic meat Soybean ester, (mercapto) hexamic acid hexadeced vinegar, (meth) acrylic acid, ten people burned vinegar, etc. They may be used singly or in combination of two or more. 201229171 Among these compounds, particularly butyl acrylate, it is preferred to obtain a suitable adhesive property in view of good polymerizability. On the other hand, as a specific example of the (meth)-containing acetophenone-containing monomer containing a radical, (meth)acrylic acid 2-hydroxyethyl ester, (methyl, 2-hydroxypropyl acrylate, (meth)acrylic acid (meth)acrylic acid 3-hydroxybutyl acrylate 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, (meth) tert-butyl 4-hydroxybutyl propionate Earth) propylene only 卞. It can be used alone or in combination of two or more. These T t are particularly preferably 2-hydroxyethyl acrylate or 3-hydroxyl-hydroxybutyl acrylate. This is because when the polymer is incorporated, it is considered that the olefin of the olefin 4A 7 is a crosslinking point due to the contact of the adjacent carbon atom or the side chain portion. The triblock copolymer of the component (B) is required to have a weight ranging from 20,000 to 150,000. + are all thermally crosslinked by a composition of a thermally crosslinkable triblock having such a low molecular weight, which is crosslinked in the low molecular weight triblock copolymer Point, while cross-linking occurs between the triblock copolymers.妓*, 纟果疋, it can be considered that by inserting the aforementioned first amount of knives in the three-dimensional network structure formed by crosslinking of the low molecular weight triblock The acrylate polymer can effectively absorb the force: the internal weight of the optical member due to the polarizing plate or the like is moderated, and the weight average molecular weight of the triblock copolymer is preferably 250,000 to 12, more preferably 30,000 to 1 Wan Wan. In addition, from the viewpoint of attempting to homogenize the obtained three-dimensional network 妗 θ, the ratio of the weight average molecular weight (Mw) to the amount of 201229171 average molecular weight (Μη) (Mw/Mn), that is, the molecular weight distribution (pDI) is preferably 1.0-1.8. Further, the weight average molecular weight (Mw) and the number average molecular weight (?η) of the triblock copolymer are values in terms of standard polystyrene measured by gel permeation chromatography (GpC method). <Production of Triblock Copolymer> The ?-diblock copolymer can be efficiently produced by living radical polymerization. Therefore, it is presumed that the size of the mesh of the three-dimensional structure of the polymer (Β) and the crosslinking agent (c) can be adjusted so that the polymer (a) has a certain degree of freedom and is restrained. The right range. Therefore, an adhesive having stress relaxation and excellent cohesive force can be obtained. Further, it is also presumed that the molecular bond length of the compound (B) is uniform and constant, so that the obtained bonded structure can be obtained. Thereby, the adhesive is fully relieved. The living radical polymerization can be used to make the arrangement of the cross-linking sites and the uniform three-dimensional network in the agent. It is expected that the homogenous sentence can be realized as a living radical polymerization method. The method, for example, uses an atom transfer radical method to transfer the galvanic acid as a polymerization control agent to the transfer radical polymerization method (reversible addition of the ATRp chain transfer agent - the gate-strength A), using a reversible addition- Cracking) ' it rn yk Μ ^ Sweat chain transfer polymerization method (raft polymerization method; use organic hydrazine compound for ° ^ in these active free A ¥8 A 13 should be the initiator polymerization method, etc. t polymerization, etc. A method for molecular weight control and water-based initiators. The use of organic ruthenium compounds as a polymerization inverse means the use of organic ruthenium compounds as a polymerization

S -15- 201229171 Method of combining the initiator. <<Reactive radical polymerization using an organic ruthenium compound>> The second (fluorenyl) acrylate polymer (B) [triblock copolymer] is, for example, a living radical polymerization represented by the following formula (1) Reaction initiation ^ (hereinafter 'sometimes called organic ruthenium compound'), making no reactive function

The uniform can be produced by copolymerizing 2 in a predetermined order. R

R4 yl 2 (meth) acrylate monomer and hydroxyl group-containing (meth) acrylate [wherein R 1 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group or an aromatic aryl group The ring groups ^2 and r3 represent a hydrogen atom or a group having a carbon number of 8 . R4 represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an anthracene, an oxo group or a cyano group. ]

The group represented by R1 is specifically shown below. Examples of the alkyl group having a carbon number of 丨8 include an anthracenyl group, a n-propyl group, an isopropyl group, a cyclopropylidene butyl group, a secondary butyl group, a tertiary butyl group, and a cyclobutyl group. Is a ^ ^ ^ pentyl, n-hexyl, n-heptyl, n-octyl and other carbon ^, fluorene, branched or cyclic alkyl. The preferred &amp; base may be a carbon atom; a linear or branched alkyl group having a number of 1 to 4, preferably a methyl group or an ethyl group. Aromatically: '', the aromatic earth may be exemplified by a phenyl group, a naphthyl group or the like; as a substituent: -I is: a phenyl group having a substituent, and a naphthoquinone having a substituent 4 is an aromatic heterocyclic group' A pyridyl group, a furyl group,

-16- S .201229171 嗟. Examples of the substituent of the above-mentioned aryl group having a substituent include a halogen group 1 1 ^ ^ &amp; 5 ' soil, alkoxy group, an amine group, a succinyl group, and a cyano group: a group containing a group represented by jOR5' The group (r5 = a group having 1 to 8 carbon atoms), an alkoxy group having an aryl group having 1 to 8 carbon atoms, an aryloxy group, a mercapto group or a tris-methyl group. As a preferred aryl group, a phenyl group or a trifluoromethyl group-substituted phenyl group may be mentioned. Further, these substituents may be substituted for one or two, preferably para or ortho. The respective groups shown by R2 and R3 are specifically shown below. Examples of the alkyl group having 1 to 8 carbon atoms include the same groups as the alkyl group represented by the above R1. The respective groups shown by R4 are specifically shown below. The aryl group or the substituted aryl group 'aromatic heterocyclic group' may be the same as the group represented by the above R1. Examples of the thiol group include a methyl group, an ethyl group, a benzamidine group and the like. The oxycarbonyl group is preferably a group represented by _COOR6 (R6=H, a group having a carbon number of i~8 or an aryl group), and examples thereof include a thiol group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propylene group. Oxycarbonyl, n-butoxycarbonyl, 2-butoxycarbonyl: a butoxycarbonyl group, a n-pentyloxycarbonyl group, a phenoxycarbonyl group, and the like. As the more oxygen group, it may be a methoxycarbonyl group or an ethoxycarbonyl group. Each group represented by R4 is preferably an aryl group, a substituted aryl group or an oxycarbonyl group. As a preferred aryl group, it may be a phenyl group. Preferably, the aryl group may be a styl group substituted with a tooth atom or a phenyl group substituted with a trifluoromethyl group. In addition, these substituents may be substituted for 1 to $ when they are _ atoms. When it is alkoxy or trifluoromethyl, ' can replace one or two,

S -17- 201229171 When substituting one, it is preferably para or adjacent V. . „ ^ , 勹耵伹 and 郯, when replacing two, it is preferably meta. As a better blue 乂 焱The group may be a methoxycarbonyl group or an ethoxycarbonyl group. The organic hydrazine compound oxime represented by the formula (1) may be an alkyl group having a number of R1 of 1 to 4, and R2 and R3 represent a hydrogen atom or a carbon atom. The alkyl group 'R4' represents an aryl group, a substituted aryl group, or an oxycarbonyl group. Particularly preferably, Ri represents an alkyl group having a carbon number of 4, and r, r3: a non-hydrogen atom or an alkyl group 4 having a carbon number of 4 is a phenyl group, a substituted phenyl group, a fluorenyloxy group or an ethoxycarbonyl group. The organic ruthenium compound represented by the formula (1) is specifically shown below. Examples of the organic ruthenium compound include (methyl benzyl) benzene, (1-methyl decyl-ethyl) benzene, (2-methyl fluorenyl propyl) benzene, and chloro chloride 4 (A). Benzyl-methyl)benzene, hydroxy-4-(methylindenyl-indenyl)benzene, 1-methoxy-4-yl-(methylmercapto-methyl)benzene, anthracene-amino-4- (methyl fluorenyl) phenyl 1 nitro-4_(methylindenyl-methyl)benzene, 1-cyano-4-(methylmercapto-methyl)benzene, 1-methylcarbonyl _4-( Methyl-mercapto-fluorenyl)benzene, 1-phenylcarbonyl-4-(methylmercapto-methyl)benzene, 丨_曱oxycarbonyl_4_(indolyl-methyl)benzene, 1-phenoxy Carbonyl 4-(methylmercapto-methyl)benzene, 1-sulfonyl-4-(methylindolyl-methyl)benzene, 1-trifluoroindolyl-4-(indolyl-yl) Benzene, chloro-4-(1-methylindolyl-ethyl)benzene, hydroxy- 4 (1 fluorenylethyl)benzene, 1-methoxy-4-(1-methyl) Mercapto-ethyl)benzene, hydrazine-amino fluorenyl-ethyl)benzene, hydrazine _nitro_4_(1_fluorenylfluorenyl-ethyl)benzene, decyl cyano-4-(1-曱-mercapto-ethyl)benzene, bromocarbonyl _4_(1_mercaptodecylethyl) benzene, 1-phenylcarbonyl-4-(1-methylindolyl-ethyl)benzene, Oxycarbonyl group _4_ (1_ hoof-yl methyl - ethyl) present, a few phenoxy group _4_ 1_ (1_ hoof-yl methyl - ethyl) benzene

-18- S 201229171, 1-sulfonyl-4-(1-methylindolyl-ethyl)benzene, wi-methyldecyl-ethyl)·3,5-bis(trifluoromethyl) Benzene, pentafluoro-6·(ι-methylfluorenyl-ethyl) stupid, m(2.methylhomolyl'propyl)benzene, 1-hydroxy-4-(2·indolyl-propyl-propyl Benzene, diterpeneoxy_4_(2methyl benzyl-propyl)benzene, iota-amino-4-(2-methylindolyl-propyl)benzene, r-hydrazine-M2-methyl-homo- Propyl) benzene, hydrazine _ cyano _4_(2_mercaptopropyl propyl benzene, 1-indole carbonyl-4-U-fluorenyl fluorenyl-propyl)benzene, b phenylcarbonyl _4_(2_methyl Mercapto-propyl) stupid, oxiranylcarbonyl-4-(2-methylindolyl-propyl)benzene, 1-phenoxycarbonyl-4-(2-mercaptodecyl-propyl) stupid, hydrazine Sulfosyl_4_(2_f-mercapto-propyl)benzene, hydrazine·trifluoromethyl·4_(2-methylindolyl)propyl, 2-(indolyl-methyl) ratio Acridine, 2 (1_methylpyridylethyl glacial, 2-(2-mercaptopurinyl-propyl). Ratio, 2, methyl 2, 2-methylmercaptopropanal, hong methyl -3-mercaptopurinyl-2-indanone, 2-hydroxymethyl phthalic acid decyl ester, 2-methyl decyl decanoyl decanoate, 2 fluorenyl hydrazino-2-yl propionate 2·methyl(meth)acetate Ester, ethyl 2-mercaptodecyl propionate, 2·methylmercapto-2-methylpropionyl-ethyl S-[ethyl-2-indenyl-2-indolinylpropionate], 2_ (n-butyl decyl)-2-methylpropionic acid ethyl acetonate [ethyl 2 - fluorenyl 2 - n-butyl decyl propyl vinegar], 2-mercapto fluorenyl acetonitrile, 2 - methyl hydrazine Propionitrile, 2_fluorenyl-2-methylhydrinopropionitrile, (stupyl-methyl)benzene, (1-phenyl)-(ethyl)benzene, (2-phenylphenyl-propyl) Further, in the above, all the moiethyl group, the fluorenylmethyl fluorenyl group, and the 2, methyl fluorenyl group are respectively changed to ethyl ketone &amp; ! ethyl fluorenyl 2 ethyl group. Anthracene, butyl sulfoyl, butyl butyl ketone, 2-butyl ketone. Preferably, (mercaptomethyl) benzene, (丨_methyl fluorenyl-B

S -19- 201229171 phenyl, (2-fluorenyl fluorenyl propyl) stupid, decyl decyl ethyl) benzene, 1 · trifluoromethyl 4-(1-methylindolyl-ethyl Benzene oxime ^methyl fluorenyl _ ethyl) 4 - difluoro fluorenyl phenyl] 2 - fluorenyl fluorenyl 2 - methyl propyl methacrylate - 2-methyl fluorenyl-2- fluorenyl Ethyl propionate [ethyl 2 - decyl 2 - methyl decyl propionate], ethyl 2-(n-butyl decyl)-2-methylpropanoate [ethyl 2 - methyl _2_ n-butyldecyl-propionate], 1-(1·methylindolyl-ethyl)_3,5•bis(trifluoromethyl)benzene, 1,2,3,4,5-five Fluorine-6-(1-indolyl-yl-ethyl)benzene, 2-mercaptodecylpropionitrile, 2-mercapto-2-methylindolylpropionitrile, (ethylindenyl-fluorenyl)benzene, (1-ethylindenyl·ethyl)benzene, (2·ethylmercapto-propyl)benzene, methyl 2-ethylguanidino-2-methylpropanoate, 2-ethylindenyl-2- _Mercaptopropionate, 2_ethylmercaptopropionitrile, 2-methyl-2-ethylpropanenitrile, (n-butyl fluorene-methyl) benzene, (1-n-butyl fluorenyl-B Benzo, (2-p-butylindenyl-propyl)benzene, methyl 2-n-butyldecyl-2-mercaptopropionate, 2-n-butylindenyl-2-methylpropanoate Ester, 2-n-butyl The mercaptopropionitrile and the 2-methyl-2-n-butylmercaptopropionitrile may be used singly or in combination of two or more kinds. In the polymerization step of the present invention, in addition to the above organic ruthenium compound, an azo polymerization initiator may be added as a polymerization accelerator. The azo polymerization initiator is not particularly limited as long as it is an initiator used in ordinary radical polymerization, and examples thereof include 2,2,·azobis(isobutyronitrile). ΑΙΒΝ), 2, 2, _ rabbit double (2 methyl 戍 guess), 2, 2, - azo bis (2, 4 dimethyl pentane) (advn), ι, ι '- Bis(1-cyclohexylcarbonitrile) (ACHN), dimethyl-2,2,-azobisisobutyrate (MAIB), 4,4,_azobis(4-cyanovaleric acid) (acva) ), 201229171 1,1'-Azobis(1-acetoxy-1-phenylethane), 2,2,·Azobis(2-methylbutylguanamine), 2,2' - azobis(4-methoxy-2,4-dimethylpentidine), 2,2'-azobis(2-methylmethylpropanepropane) dihydrochloride, 2,2,_ Occasional bis[2-(2-imidazolidine-2-yl)propane], 2,2,-azobis[2_fluorenyl-N (2-hydroxyethyl)propanamide], 2,2' - azobis(2,4,4-tridecylpentane), 2-cyano-2-propylazomethanamine, 2,2,-azobis(N-butyl-2-methyl Acetylamine, 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), and the like. When the above azo polymerization initiator is used, the organic ruthenium compound of the formula (1) used as a polymerization initiator for 1 m 〇1 is preferably 0.01 to 100 mol, more preferably ruthenium, further. It is preferably used in a ratio of 〇·1 to 5 m ο 1 . The method of forming the second (fluorenyl) acrylate polymer (B) [triblock copolymer] by living radical polymerization is specifically shown below. In the vessel substituted with the inert gas, the above-mentioned (meth)acrylic acid (tetra) monomer and the active radical polymerization initiator of the formula (1) and the azo polymerization polymerization according to the desired (four) In the reaction system, the polymerization reaction is carried out. In this case, as the inert gas, nitrogen, helium, neon, etc. may be mentioned. Argon and nitrogen are preferred. Nitrogen is particularly preferred. Adding to A, adding Y to become a cross-linking point in Y. After the polymerization reaction, adding a 3 1 group of (meth) acrylates _ h〇k1 , and introducing a polymerization reaction,

(wherein bl represents a block in which the functional group which becomes a crosslinking point is dry-formed due to J 66 rmu, and b2 represents a mono-copolymer of a (meth) acrylate type monomer which has a mesogenic group. The triblock of the segment) 201229171 In addition, the order of the polymerization reaction is 'non-reactive functional group (indenyl) acrylic vinegar monomer, hydroxyl group-containing (fluorenyl) acrylate monomer, and no reactivity A functional group of (mercapto) acrylate monomer can give a bl-b2-b type triblock copolymer. The polymerization is usually carried out without a solvent, and an organic solvent generally used in radical polymerization can also be used. Examples of the solvent that can be used include benzene, toluene, hydrazine, hydrazine-dimethylformamide (DMF), dimercaptosulfoxide (DMSO), acetone, chloroform, carbon tetrachloride, and tetrahydrofuran (THF). Ethyl acetate, trifluoromethylbenzene, and the like. Further, an aqueous solvent may be used, and examples thereof include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, and 1-methoxy-2-propanol. The amount of the solvent to be used may be appropriately adjusted, for example, from 0.01 to 100 ml with respect to the lg monomer, preferably from 5 to 10 ml, particularly preferably from 3 to 5 ml. The molecular weight of the copolymer can be adjusted by the reaction temperature, the reaction time, and the amount of the organic hydrazine compound of the formula (1). The reaction temperature and reaction time can be appropriately adjusted by the molecular weight or molecular weight distribution of the obtained triblock copolymer, and usually, the reaction time is from about 60 to 150 hours, and the total reaction time is from about 5 to about 1,000 hours. Preferably, at 80 ° to 12 ° C, the total reaction time is about 33 〇 hr. At this time, the pressure is usually carried out at normal pressure, or it may be pressurized or decompressed. After completion of the reaction, the target triblock copolymer can be purified by removing the solvent or residual monomer used under reduced pressure by a conventional method, or by precipitation filtration, reprecipitation filtration, or column separation. In the adhesive composition of the present invention, as the component (B), it is possible to independently contain a kind of flute _ erbium (mercapto) acrylate polymer [triblock sputum], It is also possible to combine people ία and ν 3 in two or more categories. The content of the component (B) is less than 40 parts by mass relative to 1 〇 〇 by mass of the first (fluorenyl 彳$ also m) dicaprate polymer (A). In the case of 40 mass parts or more, there is an obstacle to stress relaxation / λ ^. In addition to the viewpoint of the stress relaxation property described above, the content of the component (B) is preferably 5 in terms of a sufficient amount of cohesive force to the adhesive to be applied to the polymer (A). 3 parts by mass, more preferably 10 to 25 parts by mass. Ready. . The content of the hydroxyl group-containing (mercapto) acrylate of the triblock copolymer, such as early hydrazine, is preferably from 5 to 2% by mass, more preferably from 5% to 2% by mass of the obtained adhesive composition. Good for 5~〗 5 mass%. (Isocyanate-based crosslinking agent (c)) In the adhesive composition of the present invention, the oxime-based crosslinking agent which is contained as the component (C) is used for the second (meth)-propyl group: : a "quick (10) triblock copolymer] of a hydroxyl group-containing (meth) acrylate acid π early body monoterpene as a crosslinking point, crosslinking the low molecular weight of the aforementioned three snail copolymer to form a three-dimensional In addition, it can also be considered that when the first (meth)acrylic acid vine polymer has two carboxyl group-containing (mercapto) acrylate monomer units, the carboxyl group serves as a joint to contribute to the aforementioned high molecular weight. Cross-linking of the _(meth)acrylic acid vinegar compound. However, it is presumed that the isocyanate-based crosslinking agent (6) has a higher reactivity with a hydroxyl group than a carboxyl group, so the post-crosslinking agent ( The blending amount of C) is mostly consumed in the soil reaction with the polymer (Β), and is extremely small in reacting with the carboxyl group of the polymer (Α). The isocyanate crosslinking agent (C) includes a polyisocyanate compound.

S -23- 201229171 Examples of the Α Λ long isocyanate vinegar compound include aromatic toluene diisocyanate vinegar, diphenylmethane diisocyanate vinegar, stupid dimethyl diisocyanate s Polyisocyanuric acid vinegar, field and /, sulfhydryl monoisocyanate and other aliphatic polyisomeric acid S 曰, different 嗣 嗣 diisoindene ^ ^ 7P (four) a hamster acid ester, deuterated diphenyl decane diisocyanate Such as alicyclic polyisocyanic acid, scutellaria, etc., as well as the special diuret, diglycolic acid (tetra), and with ethylene glycol, propanol, neopentyl glycol, hydrazine A reactant of a low molecular weight active hydrogen-containing compound such as a cannabis oil, that is, an adduct or the like. In the present invention, the isocyanate crosslinking agent (C) may be used singly or in combination of two or more. Further, the amount of the polyisocyanate compound is preferably 2 to 20 parts by mass based on 100 parts by mass of the above-mentioned (de)-methyl-propionate polymer (B) [triblock copolymer]. A range of 30 parts by mass. When the amount is less than 2 parts by mass, the thermal crosslinking of the triblock copolymer is insufficient, and an adhesive composition having the desired properties of the old y + u Ah can not be obtained; on the other hand, if it exceeds 3 Å暂县&gt;\_ α, ,. m , negative injury, the use period will be shorter 'so it is difficult to apply 〇 安 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; r r r The amount of the bismuth mass of the polymer (B) '13⁄4 isocyanate crosslinking agent (c) is acetylated with polyisocyanate. Preferably, it is 5 to 2 parts by mass, more preferably 7 to 15 parts by mass. Further, as described above, from the viewpoint of allowing the crosslinking agent (C) to react only with the hydroxyl group of the polymer (Β), Cypress's Μ 1 Λ Λ is obtained with respect to the hydroxyl group in 100 mol of the polymer (β). The portion of the parent junction of the parent agent (c) is preferably 1 〇〇1 or less, particularly preferably 8Omo X. In addition, from the viewpoint of obtaining sufficient agglutination force by the crosslinked structure with the polymer (8) Look, relative to i〇〇m〇l polymer (7))

The hydroxyl group in the middle portion is a portion of the crosslinking agent ^^t A ), preferably 30 m ο 1 or more, more preferably 4 Å or more, and particularly preferably 50 mol or more. -24-201229171 (decane-based coupling agent) ^ In the adhesive composition of the present invention, a decane-linked oxime-helane coupling agent may be further contained, for example, for use in the adhesive sheet of the present invention! Even under the thermal conditions, an optical member such as a polarizing plate can be adhered to the glass substrate of the liquid crystal cell with good adhesion. Examples of the coupling agent of the Shi Xiyuan include, for example, triethoxy oxalate ethoxy ethoxy ethoxy) shixiyuan, r-methacryloxypropyltrimethoxy decane, 7_ Glycidoxypropyltrimethoxydecane cold (3,4% oxygen% hexyl)ethyltrimethoxydecane, Μ·cold·(aminoethyl)-i-propylpropyltrimethoxy sylvestre, NK Aminoethyl)amino group: ylmethyl bis-oxy cleavage, r-aminopropyltriethoxy sylvestre, benzoic acid 7 aminopropyl dimethoxy decane, decyl propyl tri Oxydecane, r_gas propyl tridecyloxydecane, and the like. It is also possible to use 3_isocyanatepropyltriethoxydecane, 3-isocyanatopropyl (meth)diethoxy oxane, 2-isocyanate ethyl-ethoxy decane , 2-isocyanate ethyl (methyl) diethoxy oxime, 3-glycidoxy propyl triethoxy monoxide, 3 • glycidoxypropyl (methyl) diethoxy decane , 2' glycidoxyethyl triethoxy decane, 2-glycidoxyethyl (meth) diethoxy decane, 3-(3,4-epoxycyclohexyl) propyl triethoxy Basestone, 3 (3,4-epoxycyclohexyl)propyl(methyl)diethoxydecane, 2_(3,4-epoxycyclohexyl)ethyltriethoxy Shi Xiyuan, 2-( 3,4-epoxycyclohexyl)ethyl(methyl)diethoxy oxime, and the like, and a sulphuric acid compound in which the ethoxy group of these money compounds is replaced with a methoxy group. These Shi Xi Xuan coupling agents can be used alone or in combination.

-25- S .201229171 or more. Further, the amount of the solid content of the adhesive composition of the present invention is usually 〇〇〇1 to 1 〇 parts by mass, preferably 0.1 to 7 parts by mass, based on the mass% of the adhesive composition of the present invention. The preparation of the coating liquid containing the adhesive composition is particularly limited, and the composition of the adhesive of the present invention is particularly limited, for example, by methyl) acrylate polymer (A), | (B) [triblock copolymer , a decane coupling agent used for isocyanic acid, more, an ultraviolet absorber, a light stabilizer, a flame retardant, and an antifoaming agent. The coating composition of the invention is used as the solvent, and the hydrocarbon can be listed. An aromatic halogenated hydrocarbon such as toluene or xylene, an ester such as methanol, ethanol, propanol, 2-pentanone, isophorone or cyclohexanolate, or a cellulolytic glycol ether solvent such as ethyl cellulolytic. These solvents are used in combination of two or more. The viscosity of the coating liquid as a solid in the coating liquid is not particularly limited, and the method for preparing the coating liquid for the adhesive [adhesive] of the present invention is not added to the solvent, and the first stable &lt; 5 two kinds are added. The methyl group-containing acrylate polymer-based cross-linking agent (C) and various additives such as an antioxidant, a leveling agent, an antistatic agent, and the like are stirred and mixed to prepare a liquid-containing solution. Examples include aliphatic hydrocarbons such as hexane and heptane, alcohols such as di-methane and dichloroethane, butanol, ketones such as propyl I and methyl ethyl ketone, and ethyl acetate, butyl acetate, and propylene glycol monomethyl ether. Alternatively, one type may be used alone or as a component concentration, as long as it is suitable for coating. The agent is explained. The adhesive of the present invention is obtained by thermally crosslinking the adhesive composition containing the adhesive J obtained in (1) with the coating liquid of the composition. -26- λ .201229171 The method described later, the above-mentioned adhesive-containing agent is separated from the sheet by, under 60~1 lot:, at 23 to 30 ° C, it takes 1 to 2 weeks to heat the left cross, which can be borrowed, for example. The coating liquid of the composition is applied to the drying for about 1 to 1 minute, and then the right curing time is completed. x South has a poor durability under wet conditions, and is ~85%, more preferably 40 to 70% from the viewpoint of remanufacturability and durability. The value measured by the method described below. The adhesive of the present invention requires a gel fraction of less than 40%, which is also insufficient in a high temperature thermal shock test. Further, the gel fraction is preferably 4 Å. Further, the gel fraction is &lt;measurement of gel fraction&gt; The fraction is 40% or more. If the ', take out the adhesive into the weighing, the weight at this time is taken as -. Put it into acetic acid vinegar, use a Soxler extraction apparatus, and after refluxing for 16 hours or more, remove only the solvent contained in the insoluble component after drying, and then weigh it and discriminate it.曰l Reset at this time as M2. The gel fraction is expressed by (M2/M 1 ) x 1 00 (%). (Adhesive sheet), using, for example, a bar coating method, a doctor blade coating method, a subtracting method, a doctor blade coating method, a die coating method, a gravure coating method, etc., coating the above-mentioned coating material containing the adhesive composition on the release layer of the release sheet W drink heat and dry, cross-linking to form an adhesive layer. Then, Ding... Futian in the sticky sword drawer 匕 制 制 制 制 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 剥离 @ @ @ @ @ @ @ @ @ @ @ @ @ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ The adhesive sheet of the η 火 fire 耆 adhesive layer. In addition, the thick sound of the adhesive sheet into the 4 丨 private 御 Η ...... 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷Preferably, it is 10 to 5 Ο μιη. As the above-mentioned release sheet, it can be exemplified in the poly(p-benzoic acid)

S -27- 201229171 Alcohol ester (hereinafter, sometimes referred to as PET), polybutylene terephthalate, polynaphthalene, formic acid glycol vinegar and other polyester film, polypropylene, polyethylene, etc. A plastic film such as a hydrocarbon film is coated with a release agent such as a polyoxymethylene resin, and a release layer is provided. The thickness of the release sheet is not particularly limited and is usually about 20 to 15 Ο μηη. Next, an optical member with an adhesive layer of the present invention will be described. [Optical member to which an adhesive layer is attached] The present invention also provides an optical member with an adhesive layer having a layer formed of the above-described adhesive of the present invention on an optical member. Examples of the optical member include a polarizing plate, a retardation plate, an optical compensation film, a reflection sheet, and a brightness enhancement film. Among them, a polarizing plate and a phase difference plate are preferably used. Further, the thickness of the adhesive layer formed of the adhesive of the present invention is usually about 5 to 1 〇〇μηι, preferably 10 to 50 μm η, more preferably 10 to 3 μm. The optical member to which the adhesive layer is attached can be manufactured, for example, as follows. On the release layer of the release sheet, an adhesive composition layer is provided according to the above method, heated, dried, and thermally crosslinked to form an adhesive layer, and the adhesive can be produced by attaching an optical member thereon. The optical member of the agent layer. The dot-agent of the present invention is suitable for a polarizing plate formed of a polarizing film alone. The polarizing plate can be bonded to a liquid crystal cell, for example, and is particularly suitable for a polarizing plate in which a polarizing film and a viewing angle-expanding film are integrated. 'The polarizing plate can be preferably used, for example, to follow the liquid crystal cell. The polarizing plate 28-201229171 obtained by integrating the polarizing film and the viewing angle-enhancing film may be formed by laminating a film of triethylenesulfonyl cellulose (TAC) on both sides of a polyvinyl alcohol-based polarizer. On one surface of the polarizing film, for example, by coating a viewing angle-enhancing functional layer formed of a disk-shaped liquid crystal, or by adhering a viewing angle with an adhesive, the film may be enlarged. In this case, the adhesive of the present invention is provided on the side of the viewing angle expanding function layer or the viewing angle expanding film side. As described above, by bonding the polarizing plate to the crystal display device, even if the high temperature is high, and the polarizing plate and the liquid crystal glass cell can improve the viewing angle characteristics, the phase difference plate is disposed between the liquid crystal cells, and the present invention can be Adhesive polarizing plate and phase difference plate, and phase difference plate and commissure phase difference plate and liquid crystal glass cell of the optical film are used to use the ordinary polarizing plate and liquid crystal dense 〇 using the adhesive of the present invention in the liquid crystal glass cell In the liquid-wet environment manufactured above, it is also excellent in adhesion and light retention which is not easy to cause light leakage. Further, the adhesive of the present invention is suitably used even in the case of a polarizing plate by an adhesive. In other words, the optical film is formed by a polarizing film alone, and the liquid crystal glass cell can be attached by an adhesive. Here, the adhesive is not particularly limited, and the adhesive used in the bonding of the glass cells may be used. [Examples] The present invention is not limited by these examples; Further, various properties of the agent are based on the following &lt;processing method&gt; A coating liquid containing a composition such as a composition, a blending composition shown in Table 1 and an adhesive prepared by coating with a knife coater to a thickness of 38 μm -29 - 201229171 1 SP-PET382050"] 25 μιη » drying temperature is A release sheet formed of PET [manufactured by Lintec Co., Ltd., the drying time of the dried adhesive layer was i minutes. The polarizing film of the J-disc liquid crystal layer is connected to the above-mentioned viscous = (tetra) liquid crystal layer. After the bonding, (4) ‘: During the two-week maintenance period, a polarizing plate with a coating layer is obtained.

&lt;Adhesive force&gt; The polarizing plate with the adhesive layer is sampled as a width X 1 〇〇 _ long 'peeling peeling film' attached to the non-test glass [Corning company, "Eagle XG" tile In the case of the "High Pressure 荃" manufactured by Kurihara Manufacturing Co., Ltd., it is 55 MPa, 5 〇. . , 2 〇 conditions to increase pressure. After that, at 23. (:, placed in a 50% Rh environment for 24 hours' using [Orientec, "Tensii〇n"], the adhesion was measured under the following conditions: Peeling speed: 300 mm/min, peeling angle: 180. The placement conditions before the force measurement (24 hours in the environment of 23 ° C and 50% Rh) were changed to 2 days in an environment of 23 ° C, 50% Rh, not 14 days, 50 ° C, and 50% Rh. The same adhesive force measurement was carried out together. &lt;Evaluation of durability&gt; The polarizing plate with the adhesive layer was adjusted to 233 mm x 3 0 9 using a super cutter (manufactured by Takino Seisakusho Co., Ltd.). The size of the mm. Then, the peeling sheet is peeled off and the exposed adhesive layer is attached to the non-test glass [Eagle Xg, manufactured by Corning, Inc.], -30-201229171, manufactured by [Kurohara Seisakusho Co., Ltd., "Autoclave" In the case of pressurization under the conditions of 0.5 Mpa, 50 ° C, and 20 minutes, it was placed under each endurance condition, and after 20 hours, it was observed with a magnifying glass of 1 〇. The appearance change was γ. As a benchmark, &amp; 〇. In the outer end of the four sides, 0 6mm or more △: In the case of any of the four sides, the circumference is 6 mm or more, and the appearance of the adhesive of 0.5 mm or less, such as floating, peeling, foaming, etc., is abnormal, and γ is absent. 43 X: On the other side of the four sides 〇6mm or more, there are floating, peeling, foaming, etc. The appearance of the adhesive of '6mm or more is abnormal, the durability of the defect is 60°C, 90%Rh environment 8 〇°C, dry environment HS· -3 5C0 7O° C. Each 30-minute thermal shock test machine 2 〇〇 cycle using a continuous automatic cutting machine [manufactured by Takino Seisakusho Co., Ltd.] The polarizing plate with the adhesive layer described above was adjusted to a ruler of 233 mm x 3 〇 9 mm. Then, peeling off In the film, the exposed adhesive layer is attached to the alkali-free I glass [made by Corning, "Eagle XG"], and then [manufactured by Kurihara Manufacturing Co., Ltd., "High Pressure Dad"], MPa.5MPa, 5(rc, In the case of bonding, the polarizing axis is in a state of being 2 cross-polarized light inside and outside the glass, and the light-shielding plate with the adhesive layer peeling off the peeling sheet is bonded to the peeling sheet. 8 (TC, placed in a dry environment 2 〇〇 =, after the time, the method shown below Light leakage prevention. Using the "MCPD" manufactured by Otsuka Electronics Co., Ltd. -31-201229171, the difference in brightness and brightness of each area shown in Fig. 1 was measured: AL* was used as the light leakage prevention property. (Where, A, B C, D, and E are the predetermined measurement points (one position at the center of each area) of the A area, the B area, the c area, the D area, and the E area, respectively. In addition, the maximum value § has been loaded as L*max. Further, the light leakage prevention property was evaluated by the following criteria. (§) · Δ L*D 1.0 〇: 1.0 &lt; Δ L* [I| 2.0 X : Δ L* &gt; 2.0 &lt;gel fraction&gt; The gel fraction was determined according to the method described herein. &lt;Haze value&gt; The haze value of the adhesive layer having a thickness of 25 μm was measured by the method shown below. In the manufacturing step of the polarizing plate with the adhesive layer described in the above-described processing method, 'the liquid crystal layer is replaced by laminating another peeling sheet [SP-PET38 1 1 30" manufactured by Lintec Co., Ltd.] The polarizing film was used to produce a release sheet/adhesive layer/release sheet structure. Then, the curing time of the same conditions as in the case of the polarizing plate to which the adhesive layer is attached is used. After that, the peeling sheet of the structure ("SP-PET381130" manufactured by Lintec Co., Ltd.] was peeled off and attached to the sodium dance glass (made by 曰本板硝子)'Manufacture of soda lime glass/adhesive/ Strip the film. Then, another peeling sheet ("sp_PET382〇5〇 201229171" manufactured by Lintec Co., Ltd.) was peeled off, and a haze meter ("NDH-2000" manufactured by Sakamoto Denshoku Industries Co., Ltd.] was used, and the haze value was measured in accordance with JIS K 7136. When used as an adhesive for a polarizing plate, it is preferable that the haze value is smaller. Examples 1 to 10 and Comparative Examples 1 to 5 (1) Production of Acrylate Copolymer (A) Using a ratio (mass ratio) shown in Table 1 using butyl acrylate (BA) and acrylic acid (AA) The copolymerization was carried out according to a conventional method to produce a butyl acrylate/acrylic acid random copolymer of weight average molecular weight (Mw) shown in Table 1. (2) Production of acrylate copolymer (B) (a) Production of triblock copolymer by living radical polymerization In Examples 1 to 10 and Comparative Examples 4 and 5, butyl acrylate was used. 2-Hydroxyethyl acrylate (HEA) or 4-hydroxybutyl acrylate (4HBA), as a living radical polymerization initiator, the following organic hydrazine compound (ethyl-2-methyl-2-positive) was used. Butyl mercapto-propionate) and 2,2'-azobisisobutyronitrile were produced having the weight average molecular weight (Mw) and molecular weight distribution (PDI) shown in Table 1, and were in the form shown in Table 1. Triblock copolymer. &lt;Synthesis of ethyl-2-mercapto-2-n-butyl-propionic acid g&gt; 6.38 g (50 mmol) of metal (manufactured by Aldrich, product name: Tellurium (-40 mesh)) was suspended in In 50 ml of tetrahydrofuran (THF), 34.4 ml (55 mmol) of n-butyl hydride [manufactured by Aldrich '1.6 mol/L hexane solution) was slowly added dropwise thereto at room temperature. The reaction solution was stirred until the metal ruthenium completely disappeared. Into this reaction solution, l〇_7 g (55 mmol) of ethyl 2-bromoisobutyrate was added at room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, and then distilled under reduced pressure to give 8.9 g of yellow oil.

S-33- 201229171 Ethylethyl-2-methyl-2-n-butyl-homopropionic acid vinegar (yield 59.5%). (b) Comparative Example 2 is a butyl acrylate homopolymer obtained by a radical polymerization method, and Comparative Example 3 is a random copolymer of butyl acrylate and lauryl acrylate obtained by a living radical polymerization method. Comparative Example: Only the acrylate copolymer (A) was used, and the acrylate copolymer (B) was not used. (3) Preparation of adhesive composition Preparation of the blending composition shown in Table 1, according to the aforementioned addition

The gel fraction of the adhesive. &gt;Adhesive (solid content conversion)

-34- 201229171 [I Yu] Adhesive composition (addition amount: parts by mass) 矽 olefin coupling agent ΚΒΜ-043 Addition amount CN 〇&lt;N Ο cs ο CN 〇(N 〇(N 〇CS o CN Ο CN c&gt ; &lt;N Ο (N o CN 〇(Ν 〇CN 〇TDI(C) hydroxy equivalent ※ in 卜 in 〇沄1 1 I m (N addition amount ※lo 1 12.0 1 1 13.0 1 1 12.0 I 〇οό O ) 1 12.0 1 Ο) O) «Η 1 in οό 1 CN cs (N ro addition amount (mass) vq inch (N cn inch &lt;N »-Η rH inch rj vq i H vq t H m &lt;N i 4 0.30 1 0.86 J 0.63 Acrylate copolymer (B) Addition amount (parts by mass) Ο 宕闵o 宕ο PDI l ·Η &gt;&quot; Η 1—^ \D yn \q F—H 1 (N ΟΟ Inch · Mw 4.7 million 47,000 1 4.7 million 1 2_6 million 4-5 million: 4.9 million 1 4.4 million | 471,000 112,000 4.4 million sec n (N 〇 \ 47,000 I 4.7 million | polymer form block b2- Bl-b2 block b2-bl-b2 block b2-bl-b2 block b2-bl-b2 block bl-b2-bl block b2-bl-b2 block b3-bl-b3 block b2-bl -b2 block b2-bl-b2 block b2-bl-b2 1 individual polymer (free radical) random bl-b4 (active) block b2-b L-b2 block b2-bl-b2 content (% by mass) 1 1 1 1 I 1 1 1 1 1 1 1 1 1 丨4ΗΒΑ| 1 1 1 1 1 〇1 1 1 1 1 1 1 1 HE A Ο ο 〇〇Ο 1 〇〇1 1 1 〇〇冢茬On 00 1 Ο § 1 Acrylate copolymer (A) Addition amount (mass) Ο Ο Ο 〇〇〇〇Ο ο 〇〇〇o 〇ooooo 〇〇Ο 1-Η 〇〇2 〇〇Mw 1 1.5 million 1 11503⁄4 1 1 1.5 million 丨 10,000 1 1.5 million | 1.5 million | Yangshuo Wan 1 11903⁄4 I 1 1.5 million 1 | 1.5 million 1 | 1.5 million I 1.5 million 1.35 million \i5〇n I il50 million 1 _ r〇m in ΓΛ m Γ〇» ^ m φ4 ♦3 BA 1 〇\ On 〇\ On 〇\ Os 〇\ 〇\ 〇\ σ\ ON r- 〇\ Example 1 "Example 2 1 1 Example 3 1 1 Example 4 | Example 5 | Example 6 1 Example 7 1 "Example 8 Π 1 Example 9 i Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 "Comparative Example 4 "Comparative Example 5 j . f#qJLilr^4ElB4is^^萚玩忘(^蘅箨蘅箨忐砩澍盂^巴令哒桕啭:(七)※ 二牟#铋)¥和哙忘(υ)ΙαΗ· (βφ哒牟峒铋001衾葙要伥&lt; :一※ _ s 201229171 [Note] BA: butyl acrylate AA: Acrylic acid HEA: 2-hydroxyethyl acrylate 4HBA: Acrylic 4-butyl butyl acrylate LA: Acrylic laurel TDI (C): Trimethylolpropane-modified terpene diisocyanate [Nippon Polyurethane Industry, "Conate Lj] KBM-403: 3-glycidoxypropyltrimethoxy oxalate [manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403"] [Table 2]

S It is understood from Table 2 that the adhesive of the present invention (in the evaluation of the durability and the light leakage prevention property of the embodiment, both are r Δ" or more, and the adhesives of Examples 1 to 5 have at least one of 36 in the aforementioned evaluation. - 201229171 [Industrial Applicability] The adhesive composition of the present invention is suitably used for a polarizing plate or the like constituting a liquid crystal display device, and an adhesive layer capable of preventing a whitening phenomenon due to expansion and contraction of the polarizing plate can be formed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a method of evaluating light leakage prevention of a polarizing plate with an adhesive layer obtained in Examples and Comparative Examples. [Explanation of main component symbols] I Light leakage portion

S -37

Claims (1)

201229171 VII. Patent application scope: 1. An acrylic adhesive composition comprising a first (fluorenyl) acrylate polymer (A) having a weight average molecular weight of 10 million to 2.5 million, and a weight a second (meth) acrylate polymer (B) having an average molecular weight of 20,000 to 150,000 and an isocyanate crosslinking agent (C) characterized by (1) the second (meth)acrylic acid The ester polymer (B) is a triblock copolymer having a (meth) acrylate monomer unit containing a substituent, and (2) the first (fluorenyl) acrylate relative to 1 part by mass The polymer (A) 'the content of the second (meth) acrylate polymer (B) is less than 40 parts by mass, and (3) the gel fraction of the adhesive formed from the adhesive composition is 4 0% or more. 2. The acrylic adhesive composition according to claim 2, wherein the triblock copolymer is in the form of b2-bl_b2 or bl b2 blS (b represents a functional group having no crosslinking point) The (meth) propylene is a segment of the monomer unit, and b2 represents a block comprising a monomer group containing a (meth) acrylate group. 3. The acrylic adhesive composition according to claim 1, wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (?η) of the triblock copolymer is 1.0 to 1.8. . 4. The acrylic adhesive composition according to claim 2, wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (?η) of the triblock copolymer is 1.0 to 1.8. . The acrylic adhesive composition according to any one of claims 1 to 4, wherein the content of the hydroxyl group-containing (mercapto) acrylate monomer unit in the triblock copolymer is 1.5. ～20% by mass, and the content of the triblock copolymer is from 10 to 30 parts by mass based on 100 parts by mass of the first (fluorenyl) acrylate polymer (A). 6. The propylene-based adhesive composition according to any one of claims 1 to 4, wherein the triblock copolymer is formed by living radical polymerization. 7. The acrylic adhesive composition according to any one of claims 1 to 4, wherein the isocyanate is crosslinked with respect to 100 parts by mass of the second (meth) acrylate polymer (B). The content of the crosslinking agent (C) is 5 to 20 parts by mass. An acrylic adhesive characterized by being thermally crosslinked by the acrylic adhesive composition according to any one of claims 1 to 7. An optical member to which an adhesive layer is attached, characterized in that, in the optical member, the layered laminate is an acrylic-based adhesive of claim 8 of the patent application. -39-