TW201114866A - Adhesive composition for optics, optical adhesive and optical film - Google Patents

Abstract

To provide an optical adhesive composition, an optical adhesive and an optical film having the no necessity of post-curing, preventing efficiently the light leakage while environmental changes, and having the good transparency. Thus, the present invention relates to an optical adhesive composition and the like, including the following components (A) to (D); (A) 100 parts by weight of (meta)acrylic ester polymer having a weight average molecular weight is 200,000 to 2500,000, (B) 1 to 50 parts by weight of reactive (meta)acrylic ester polymer having a chain of reactive ethylenic double bond, having a weight average molecular weight is 30,000 to 1500,000, (C) 0.1 to 50 parts by weight of multifunctional (meta)acrylic ester compound, and (D) 0.1 to 10 parts by weight of a photo-initiator.

Description

201114866 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a bribe energy ray = a combination agent and an optical film. In particular: === The occurrence of light leakage, and the optical adhesive having excellent transparency has 3 adhesives and optical films. $口", and α观尤子 [Prior Art] In order to achieve good image age for liquid crystal display charging, it is necessary to optically uniformly apply a polarizing plate to the liquid crystal cell to maintain optical properties. In the case of a display device or the like, the unevenness of the adhesion of the bonding portion due to the change in the size of the polarizing plate, or the residual stress unevenness caused by the change in the size of the polarizing plate becomes a so-called "light leakage", which is easily caused directly. Reduced product quality. Therefore, in a liquid crystal display device or the like, it is necessary to maintain the optical properties of the polarizing plate without being affected by environmental changes or the like. Therefore, the photocurable composition which can be cured in a short time by light irradiation is widely used as a binder or an adhesive for bonding a polarizing plate (for example, refer to Patent Documents 1 to 2). That is, Patent Document 1 discloses a pressure-sensitive adhesive sheet which is a pressure-sensitive adhesive sheet which can shorten the aging treatment time and can be used for various applications such as permanent adhesives and re-peeling. It can also be used for the bonding of polarizing plates. More specifically, a pressure-sensitive adhesive sheet formed by forming a film on a support or a release sheet and performing radiation crosslinking is disclosed, which has a carbon atom with respect to 100 parts by weight. An acrylic polymer obtained by polymerizing a monomer having 1 to 18 alkyl groups (alkyl) alkyl acrylate as a main component, and blending at least 1 to 100 parts by weight of a radiation-polymerizable group on a side chain Formed from a complex of a dilute acid polymer. 201114866 It is also difficult to produce light leakage in a warm and humid environment. x ° IM 离线 间 间 ' ' 先前 先前 先前 先前 先前 先前 先前 先前 ' ' ' ' ' ' ' ' ' ' ' ' ' ' 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利 利(Scope of the Invention) [Brief Description of the Invention] However, the pressure-sensitive adhesive sheet disclosed in Patent Document 1 is an acrylic polymer having a radiation polymerizable group in a side chain, and is a (fluorenyl) group. The acrylic acid-based polymer obtained by polymerizing a monomer having a main component of acrylonitrile is low in compatibility. When a polarizing plate used as an optical material is bonded, a problem of lack of transparency has been found. Further, in the pressure-sensitive adhesive disclosed in Patent Document 1, since the acrylic polymer having a radiation polymerizable group in the side chain is directly photocrosslinked, the crosslinking density is high and the exposure is changed to the environment. Under the circumstance, it is difficult to obtain sufficient durability, and it is found that there is a problem that light leakage is likely to occur. Further, the adhesive for polarizing plates disclosed in Patent Document 2 is an acrylic copolymer having an active energy ray-polymerizable group in a side chain, and the compatibility with the acrylic copolymer is low, and it has been found that it is not obtained. Adequate transparency issues. On the other hand, the binder for polarizing plate disclosed in Patent Document 2 is successful in improving durability and suppressing occurrence of light leakage to some extent by using a thermal crosslinking agent such as isocyanate (see the examples). 201114866 However, in this case, the problem that the aging treatment time for thermal crosslinking must be set to about one week occurs. In view of the above, an optical adhesive which does not require aging treatment and which is effective in suppressing light leakage even when exposed to environmental changes and having excellent transparency is required. Therefore, the inventors of the present invention have conducted a thorough review in view of the above circumstances, and as a result, found that (A) a (meth) acrylate polymer having a predetermined weight average molecular weight, and (B) a reaction having a predetermined weight average molecular weight 曱a acrylic acid vinegar polymer, (c) a polyfunctional (fluorenyl) acrylic acid vinegar compound, and (D) a photopolymerization initiator are compounded in a prescribed ratio so as to be affected by environmental changes even without aging treatment. Good adhesive properties, and transparency are also improved to complete the present invention. That is, the object of the present invention is to provide an optical adhesive composition which is excellent in brightness and excellent in light leakage, and which is not required to be subjected to aging treatment, and which is effective in suppressing light leakage when exposed to a ring. In the case of the present invention, there is provided an optical adhesive composition containing the following (A), which solves the above problems. The weight average molecular weight is from 200,000 to 2.5 million (mercapto)acrylic acid polymer. Partial weight average molecular weight of 4,000 to 15 G in the side chain with ethylene double bond reactive (meth) acrylate polymer 丨 ~ 5 〇 parts by weight (C) polyfunctional (f-based) acrylic acid Ester compound 〇 丨 〇 〇 〇 〇 〇 〇 〇 光 光 光 光 光 光 光 光 光 光 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 (8) Compared with the cross-linking (4) of the age, the cross-linking density can be more effectively carried out to cross-link the components between the components (8). The result is 'unexpected thermal cross-linking of cyanic acid, ie, expectation Strongly dissipative energy storage mold fresh adhesion _ Thus, excellent transparency can also be obtained. 1 201114866 Further, since (A) component and (B) component have a predetermined weight average molecular weight ' ^ (6) component participates in the photocrosslinking of the component (8), which is effective in enhancing the durability of the photocured adhesive composition. Therefore, in the case of the optical adhesive composition of the present invention, the aging treatment is not required, and the occurrence of light can be effectively suppressed even when exposed to environmental changes, and excellent results can be obtained. Further, in the case of constituting the optical adhesive composition of the present invention, it is preferred that the component (A) contains a (mercapto)acrylic acid having a value of an alkyl group having a carbon number of 丨 within a penalty range, and has an intramolecular component. The monomer of the county group selected from the group consisting of a hydroxyl group, a county, an amino group and an amino group as a structural unit, and the copolymerization ratio (weight basis) s is further reduced to a value in the range of 99. 9:0.1 to 80:20. With such a configuration, not only the durability of the photocurable adhesive composition can be more effectively improved, but also the adhesive properties such as the desired adhesive strength and the storage elastic modulus can be more effectively obtained. The invention When the binder composition is used, it is preferred that the component (B) contains a (mercapto)acrylic acid Sa having a value of from 1 to 20 in the home group and a monomer having an ethylenic double bond in the side chain as a structural unit. At the same time, the copolymerization ratio (weight basis) is set to a value in the range of 99:1 to 50:50. With such a configuration, not only the durability of the photocurable adhesive composition can be more effectively improved, but also It is more effective to obtain the adhesive properties such as the desired adhesive strength and storage elastic modulus. And the monomer having an ethylenic double bond in the side chain also includes such a monomer: after copolymerization, it becomes ethyl in the side chain. In the form of a double bond, and in the case of constituting the optical adhesive composition of the present invention, it is preferred that the ethylenic double bond in the side chain of the component (B) is a ruthenium group introduced via an isocyanate group. Base or (fluorenyl) propylene oxime. With such a configuration, the distance between the crosslinking points of the light cross-linking of the component (B) and the component (C) can be adjusted to a suitable range. And 'the preferred component (C) is selected from the group consisting of tris(propylene oxyethyl) isocyanuric acid 201114866 bis propylene oxyethyl) hydroxyethyl isocyanurate, isocyanuric acid epoxy = modified Diacrylate, isocyanuric acid ethylene oxide modified triacrylate caprolactone modified tris(propylene oxyethyl) isocyanurate to the combination of this composition, (8) component and (6) The light cross-linking of the ingredients to a more suitable range can also effectively improve the durability of the photocurable adhesive composition. Further, the compatibility of the (Β) component with the (Α) component can be further improved to obtain superior transparency. Less promotion

Further, in the case of constituting the optical adhesive composition of the present invention, it is preferred that one step contains a decane coupling agent as a (Ε) component, and the (ε) component is added to a weight of (〇〇) component. The content is set to a value within the range of 〇〇1 to 〇1. According to this configuration, the adhesion between the polarizing plate, the retardation film, and the like, which is used as the optical adhesive, and the liquid crystal cell can be effectively improved. Further, another aspect of the present invention is an optical adhesive which is obtained by curing the optical adhesive composition, and is formed by the steps (1) to (3). (1) a step of preparing an optical binder composition containing the following components (A) to (D), and a σ-aggregation=flat weight average amount of 2 to 10,000 to 2.5 million (meth)acrylic acid (Β) a weight average molecular weight of 30,000 to 1.5 million in a side chain having a reactive double bond (reactive (meth) acrylate polymer 1 to 5 parts by weight ^ (C) polyfunctional (meth)acrylic acid Ester compound 〇·ι 5 〇 weight "^ parts (D) Photopolymerization initiator 0.01 to 10 parts by weight 73 (2) Step (3) of applying the optical binder composition to the detached ruthenium at 50 to 1000 mJ/ The step of irradiating the active rays in the range of cm2 to obtain the optical adhesive, that is, by the configuration, the adhesive for the optical 201114866 can be stably obtained on the release film, and the optical adhesive is exposed to the ring. The case of the treatment is seven, and the other is excellent in transparency. Since the valley effectively suppresses the occurrence of light leakage, it is effective to use light such as a polarizing plate, and there is a Japanese tree layer/gu. The film substrate is provided with the above-mentioned optical film, which is a film, and is characterized by a value in a range of light to be adhered. The thickness of the crucible 5 is further reduced to 1 to 100"m. The strength of the sheet is more than: the desired adhesion can be achieved and the film substrate is polarized. [First Embodiment] The present embodiment relates to an optical binder composition containing the following components (4) to (9).

(Α) Weight average molecular weight is 2G 10,000 to 25G 10,000 (mercapto) acrylate polymer 1 〇〇 by weight (Β) Weight average molecular weight is 30,000 ~ 15 million in the side chain with ethylenic double bond Reactive (fluorenyl) acrylate polymer 1 to 5 parts by weight (C) Doluyue*=·(meth)acrylic acid from the compound 〇. 1 to 5 parts by weight (D) Photopolymerization initiator 〇 1 to 10 parts by weight or less, the first embodiment of the present invention will be specifically described with reference to the drawings. l. (A) component (1) Kind (Α) component is a (mercapto) acrylate polymer, a so-called acrylic acid polymer. 8 201114866 Further, as for the difference from the component (B) described later, the component (a) is characterized in that it does not have a non-reactive double bond in the side chain. Therefore, the component (A) is not used for photocrosslinking, which contributes to the improvement of the bonding property and durability. It is to be noted that the (mercapto) acrylate in the present invention means both acrylate and methacrylate. The (meth)acrylic acid vinegar which is a structural unit of the component (A) is not particularly limited. A conventionally known one can be suitably used. For example, it is preferably derived from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (mercapto) propylene / amyl acetate, (A Ethyl acrylate, cyclohexyl (decyl) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, (decyl) acrylate At least one of a dialkyl ester, (mercapto)acrylic acid myristyl ester, (meth)acrylic palmitic vinegar, and (meth) stearyl stearyl ester. Further, it is preferably a monomer having a functional oxime in the molecule. For example, as for the functional group, at least one of a hydroxyl group, a carboxyl group, an amino group, and a decylamino group is preferable. Specific examples thereof include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. , (mercapto) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Hydroxyalkyl acrylate; acrylamide, mercapto acrylamide, N-mercapto acrylamide, N-mercaptomethyl decylamine, N-hydroxydecyl acrylamide, N-methylolmethyl Acrylamide such as acrylamide; monodecylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, (meth)acrylic acid Monoalkylaminoalkyl (meth) acrylate such as monoethylaminopropyl acrylate; ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or citraconic acid. Further, the (A) component preferably contains at least one selected from the group consisting of a (meth) acrylate having an alkyl group having a carbon number of 1 to 20 and a molecule having a hydroxyl group, a carboxyl group, a 201114866 amino group and a decyl group. The value of the range of the range of 99. 9:0. 1~80:20. The reason for this is that by configuring the component (A) in this way, not only the durability of the photocurable adhesive composition can be more effectively improved, but also the desired one can be more effectively obtained without thermal crosslinking. Adhesive strength and storage elastic modulus 荨 adhesive properties. In other words, when the number of carbon atoms of the alkyl group in the (fluorenyl) acrylate exceeds 20, the storage elastic modulus is too low, and the durability may be lowered. On the other hand, when the number of carbon atoms of the alkyl group is too small, the storage elastic modulus is too high and the durability may be lowered. Therefore, it is preferred to set the number of carbon atoms of the alkyl group in the (fluorenyl) acrylate to a value in the range of 2 to 18, and it is particularly preferable to set the value in the range of 3 to 12. And if the copolymerization ratio of (mercapto) acrylate exceeds 99. 9:0. 1, the compatibility with other components may be lowered. Further, the interaction with an auxiliary agent such as a decane coupling agent is also weak, and it is difficult to sufficiently exert the effects of a decane coupling agent or the like, and the durability may be lowered. On the other hand, when the copolymerization ratio of (mercapto) acrylate is less than 8 Å: 2 Å, compatibility with other components is lowered, and optical properties and durability may be lowered. Therefore, it is preferred that Copolymerization ratio of (meth) acrylate having a value of the alkyl group having a carbon number of from 1 to 2 Å to a monomer having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and a decyl group in the molecule (weight Benchmark) Set the value in the range of 9^5:0.5 to 85:15, and it is preferable to set the value in the range of 99:1^〇. · In this case, the (meth) acrylate having an alkyl group having a carbon number in the range of 丨 to deduction means that it is as green as methyl (meth) acrylate, and does not have green, county, Amino group and a group of (meth)(tetra) acid^ Further, the above copolymerization ratio means that the value is calculated from the single charge amount of each structure. W early body 201114866 (2) weight average molecular weight within the circumference =). The weight average molecular weight of the component is set to 200,000 to 50,000. The weight average molecular weight of the component is less than 20. The durability of the component is insufficient when the temperature is changed.

Ϋίίΐ When the molecular weight is more than 2.5 million, it is sometimes difficult to obtain the desired bond strength and storage elastic modulus 2 (I can't be used.) Therefore, the weight average molecular weight can be obtained by It is determined by gel permeation chromatography (GPC) method in terms of polystyrene. 2· (Β) component (1) The type (Β) component is a reactive (subunit) acrylate having an ethylenic double bond in the side chain. a polymer, a so-called reactive acrylic polymer. The (Β) component participates in photocrosslinking by a radical reaction with a ruthenium component, thereby increasing the agglomeration strength of the binder and contributing to its durability. The '(Β) component can be obtained by the following method. That is, first, a copolymer of (meth)propionate and a monomer having a functional group such as a group or a carboxyl group in the molecule is prepared. a compound having an ethylenic double bond, an isocyanate group or an epoxy group in the molecule, and an addition reaction of a substituent such as a hydroxyl group or a carboxyl group of the prepared copolymer via the isocyanate group or the epoxy group; , thereby obtaining (Β) ingredients. The ratio of the addition reaction is preferably set to a value within a range of 50 to 100 mol% of a monomer having a functional group having a hydroxyl group or a carboxyl group in the molecule of 201114866, preferably 60 to 100%. a value in the range of 95% by mole, particularly preferably in the range of 70 to 90% by mole. One and the case where the substituent of the copolymer is a carboxyl group, it is preferably a medium, a cyanate group or an epoxy group. The compound is subjected to an addition reaction with a compound having an ethylenic double bond in the molecule; in the case where the substituent of the copolymer is a hydroxyl group, it is preferred to add a compound having an ethylenic double bond in the molecule via an isocyanate group. In the case where the substituent of the copolymer is an amino group or a substituted amino group, it is preferred to carry out an addition reaction of a compound having an ethyl-reactive double bond in the molecule via an isocyanate group. Further, as (mercapto) acrylate and The monomer having a functional group in the molecule may be the same as in the component (A). Further, it is preferred that the component (B) contains a (mercapto) acrylate having a value of a carbon atom in the range of 1 to 2 Å. Ethylene double on the side chain The monomer is used as a constituent unit, and the copolymerization ratio (weight basis) is set to a value in the range of 99:1 to 50:50. The reason is that the composition of (B) is not only more effective. The durability of the adhesive composition after photocuring is improved, and the adhesive properties such as the desired adhesive strength and storage elastic modulus are more effectively obtained. It is necessary to have an ethylenic double bond on the side chain. The monomer also includes such a monomer which, after copolymerization, has a form of an ethylenic double bond in the side chain, that is, if the alkyl group of the (meth) acrylate has more than 20 carbon atoms. If the value of the storage elastic modulus is too small, the durability may be easily lowered. On the other hand, if the number of carbon atoms of the alkyl group is small, the value of the storage elastic modulus is too large, and the durability may be easily lowered. . Therefore, it is preferred to set the number of carbon atoms of the alkyl group in the (fluorenyl) acrylate to a value in the range of 2 to 18, and it is particularly preferable to set the value in the range of 3 to 12 to 0 and 'this is because' When the copolymerization ratio of the (meth)(tetra) acid is more than the value of 201114866 99:1, the bonding between the component (B) and the component (C) is too small, and it may be difficult to obtain sufficient long-lasting properties and desired adhesion. Agent characteristics. On the other hand, when the copolymerization ratio of (mercapto)acrylic acid vinegar is less than 50:50, the bonding between the (β) component and the (cerium component is too large, and it may be difficult to obtain desired binder properties. It is preferable that the (mercapto) acrylate having a value of a carbon atom in the range of 1 to 2 Å and the mound having a monomer having an ethylenic double bond in a side chain are set as: 5~ The value in the range of 60:40 is more preferably set to a value in the range of 90:10 to 70:30. It should be noted that the above copolymerization ratio represents the theoretical value calculated from the amount of feed. The amount of the monomer having an ethylenic double bond in the side chain represents the amount of the compound when the ethylenic double bond is subjected to the addition reaction of the monomer having a substituent, and the (meth) acrylate and the side chain The theoretical value calculated from the amount of the monomer copolymerized with the ethylenic double bond, and the ethylenic double bond in the side chain of the '(Β) component is preferably a (meth) acrylonitrile introduced via an isocyanate group. Or (mercapto) acryloxy group. The reason is that 'by this composition' can be (Β) ingredients and The crosslinking density of the photocrosslinking of component C) is adjusted to a more suitable range. That is, 'this is because 'is a (fluorenyl) acrylonitrile or (meth) propylene oxime scale', that is, a moderate anti-ship , can be carried out efficiently. Lu - more specifically, it should be propylene oxyethyl isocyanate, propylene oxypropyl isocyanate, decyl propylene oxyethyl isocyanate and decyl propylene propylene The addition reaction of the hydroxyl group of the copolymer prepared in advance is carried out by a lactic acid ester or the like. It is to be noted that the addition reaction is preferably carried out at a temperature of, for example, 25 to 60 ° C for about 6 to 48 hours. When necessary, an organotin compound such as dibutyltin dilaurate or a substituted amine compound may be used as a catalyst. (2) The weight average molecular weight is characterized by 'the weight average molecular weight of the component (B) is set to 30,000 13 201114866 to 1.5 million When the weight average molecular weight of the component (8) is less than 30,000, the durability in the case of exposure to environmental changes may be insufficient, and it may be difficult to effectively suppress light leakage. occur. When the average molecular weight of one side is more than 15G 10,000, the desired adhesive strength and storage elastic modulus are obtained in a timely manner, and the weight average molecular weight of the (Β) component is set to 100,000 to 120. The value in the range of 10,000 is particularly preferably set to a value in the range of 30,000 to 10,000. It should be noted that the weight average molecular weight can be determined by gel permeation chromatography (GPC) in terms of polystyrene. (3) Contents: The content of the (Β) component is set to a value in the range of 1 to 50 parts by weight based on 1 part by weight of the component. When the content of the (Β) component is less than 丨 by weight, the crosslinking reaction may not proceed sufficiently, and the aggregation strength may be insufficient. On the other hand, when the content of the component (B) exceeds 50 parts by weight, The reaction is excessively carried out, and the adhesiveness and durability are sometimes lowered. Therefore, it is preferable to set the content of the component (B) to a value in the range of 2 to 40 parts by weight based on 100 parts by weight of the component (A), and it is particularly preferable to set the value in the range of 5 to parts by weight. The component (B) may be used singly or in combination of two or more kinds of monomer components or molecular weights. 3. (0 component (1) type (C) component is a polyfunctional (meth) acrylate The (C) component participates in photocrosslinking by a radical reaction with the component (B), and contributes to an increase in the agglutination strength and a storage elastic modulus of the binder. Further, the polyfunctional group of the present invention) The acrylate compound means a monomer or oligomer having 2 or more (meth) acrylonitrile groups in one molecule in 201114866. 〇 and 'for monomers having 2 or more (meth) acrylonitrile groups in one molecule The polyfunctional (meth) acrylate monomer having a molecular weight of less than 1,000 is preferably used. The polyfunctional (fluorenyl) acrylate monomer having a molecular weight of less than 1,000 is exemplified by, for example, 1,4-butane. Alcohol di(meth)acrylate, 1,6-hexanediol di(methyl) Ethyl ester, neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, neopentyl glycol adipate di(methyl) acrylate, hydroxypivalic acid Neopentyl glycol di(indenyl) acrylate, dicyclopentanyl di(methyl) 1 enoate, caprolactone modified dicyclopentenyl di(meth)acrylic acid ester, modified ethylene oxide Dimethyl (meth) acrylate, bis(propylene oxy ethionate, allylated cyclohexyl di (meth) acrylate, etc. Ester, dipentaerythritol tris(曱二)=_acidate, propionic acid modified dipentaerythritol tris(decyl) acrylate, quaternary (methyltetrapropyl, epoxidized fluorene modified tri-methyl propyl sulphate Bismuth, di(acrylic acid ethyl) isocyanate, bis (acrylic ethyl isocyanurate, isocyanuric acid ethylene oxide modified - acrylate, isocyanuric acid epoxy丨王一内:等=型: • (4) Modified tetrabasic) propylene vinegar and other 4-functional plastics: pentaerythritol hexahydrate (methyl methacrylate) 5-functional; two seasons propylene riding 6-functional ^ Change The second quarter of the fine alcohol hexa(indenyl) = 'especially in the framework structure with 酉曰, ε-caprolactone modification = r 虱 and then an acrylic acid isocyanuric acid vinegar structure of mono-dioxyethyl) Isocyanine slightly has a monomethylol dicyclopentane dienoic acid 15 201114866 Ethylene oxide modified hexahydrophthalic acid diacrylate, tricyclic terpinediol acrylate, neopentyl glycol Modified trihydroxymercaptopropane dipropylene, cycloalkane diacrylate, etc. In particular, if it is a compound having an isocyanurate structure, the component (B) and the component (C) can be used. Adjusting the crosslink density of photocrosslinking to a suitable range can also improve the resistance of the photocurable adhesive composition more effectively, and further improve the compatibility of the component (B) with the component (A). Sexuality can provide better transparency, so it is more appropriate.

Among them, the effect of exhibiting excellent effects in terms of improving the optical properties and improving the durability or adhesion to the adherend is more preferably a 3 ^ energy type monomer having an isocyanurate structure. . In the present invention, these polyfunctional (meth)acrylate monomers may be used alone or in combination of two or more. In addition, as for the oligomer having two or more (meth) acrylonitrile groups in one molecule, a polyester acrylate type, an epoxy acrylate type, a urethane acrylate type, and a polycondensation having a weight average molecular weight of 20,000 or less may be mentioned. An ether acrylate type, a polybutadiene acrylate type, an organic hydrazine acrylate type, etc. Here, as for the polyester acrylate-based oligomer, for example, a hydroxy ester of a polyester oligomer having a hydroxyl group at both terminals can be obtained by condensing a polyvalent carboxylic acid with a polyhydric alcohol with (meth)acrylic acid. Alternatively, it may be obtained by esterifying a terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. The epoxy acrylate-based oligomer can be obtained, for example, by reacting an epoxidized ring of a bisphenol-type epoxy resin or a novolak-type resin having a low (fluorenyl)acrylic acid amount. Further, an epoxy _-scale obtained by partially modifying the oxy acrylate-based oligomer with a dicarboxylic acid anhydride can also be used. The urethane acrylate-based oligomer can be obtained, for example, by using a poly(10) polyol or a polymer polyol and a poly-IU oligomer derived from a polyisotopic acid with an acid. The acrylic polymer 201114866 can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. Further, the weight average molecular weight of the above acrylate-based oligomer is preferably 2 Å or less, more preferably 1,000 to 10,000, particularly preferably in terms of a standard polystyrene value measured by a GPC method. Selected in the range of 3000~5000. Further, these oligomers may be used alone or in combination of two or more. (2) Content Further, the content of the component (C) is set to a value within a range of from 1 to 50 parts by weight based on 100 parts by weight of the component (A).

This is because if the content of the component (C) is less than 〇1 parts by weight, the combination between the component (B) and the bismuth component is too small, and it is difficult to obtain durability in the case of exposure to environmental changes. Alternatively, the compatibility of the component (B) with respect to the component (A) is excessively lowered, and it may be difficult to obtain sufficient transparency. On the other hand, when the content of the component (C) exceeds 5 parts by weight, Further, if the combination between the component (B) and the component (C) is excessive, it may be difficult to obtain the adhesive properties such as the desired adhesive strength and the storage elastic modulus. Therefore, it is preferably relative to 100 parts by weight of the component (A). , component (c)

The content is set to a value in the range of 1 to 40 parts by weight, particularly preferably in the range of -30 parts by weight. π W 4. (D) Component (1) The component (D) is a so-called photopolymerization initiator. The component (D) is based on irradiation with an active energy ray to help initiate a radical anti-w between the (Β) component and the (C) component and, as for the CD; Benzene methoxyl ether, benzoin ethyl ether, benzoin isopropyl ether, stupid cumin not ^ 偶 异 异 、, acetophenone, monomethyl acetophenone, 2 2- dimethyl window Phenylacetophenone, 2,2-diethoxy-2-phenyl stilbene, 2:; ^_ _ methyl-p-phenylpropane- ketone, hydroxycyclohexyl phenyl ketone; Methyl 201114866 -l-[4-(indolyl)phenyl]-2-morpholino-propanone, 4-(2-hydroxyethoxy)benyl 2-(yl-2-yl)酉, benzophenone _, p-phenyl dibenzophenone, 4,4'-diethylaminodibenzophenone, dibenzobenzophenone, fluorenyl hydrazine, 2-ethyl hydrazine, 2 -tert-Butyl hydrazine, 2_amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-oxythioxanthone, 2,4-dimethylthioxanthone = 2'4 -Diethylthioxanthone, benzoin dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo[2-hydroxy-2-methyl-didecylvinyl )benzene ] Propanone], 2, 4, 6-trimethyl Yue trityl group Dukes group - two US Ben _ phosphine oxide. Further, it is characterized in that the content of the component (D) is set to a value within a range of 〇·01 to 1 〇 by weight with respect to 1 part by weight of the component (A). The reason for this is that when the content of the component (D) is less than 0.01 part by weight, the crosslinking reaction between the component (B) and the component (C) may not be effectively carried out. On the other hand, when the content of the component (D) is more than 1 part by weight, the cross-linking reaction between the component (B) and the component (C) is excessively performed, and the adhesive property and durability may be excessive. Will be reduced. Therefore, it is preferable to set the content of the component (D) to a value in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the component (A), and it is particularly preferable to set the value in the range of 〇. 2 to 3 parts by weight. . 5. (E) Ingredients (1) In addition, it is also preferred to contain a so-called decane coupling agent. The decane coupling agent contributes to an effective improvement of the adhesion between an object formed of glass such as a liquid crystal cell and an optical film such as a polarizing plate. Further, as for the decane coupling agent, an organic hydrazine compound having at least one alkoxyalkylene group in the molecule which is compatible with the binder composition and has light transmissivity is preferable. More specifically, it is preferred to use vinyl trimethoxy decane, vinyl triethoxy decane, decyl propylene oxypropyl tri methoxy decane, 3-epoxy 201114866 based Wei \ 2 · (3, 4 _epoxycyclohexyl^5曱^ propyl trimethyl sulfonyl hydrazine bis-methyl decyl decane, N-(2Uf )-3 methoxy wei, 3- qi ^xin (2 methoxyethyl propyl propyl) Methyl one (2) content of gas propyl trimethoxy decane, etc. Μ〇Ϊ!^ 100 The reason is A 〇 the value in the range of parts by weight. When the content of the component is sometimes less than 〇· 〇〇 1 part by weight The effect of improving the compatibility is such that the polarizing plate or the like and the liquid crystal amount are more than 10 weights of 1-5, which is because when the component (E) is 3, the adhesive property and durability are lowered. Λ , «34 · ^ ~ 5 parts by weight of the value, further preferably within the range of 0.1 to 3 parts by weight. 6. Antistatic agent electric agent ^ The optical (four) mixture composition of the present invention is also suitable In the case where the antistatic agent is contained, when a polarizing plate or the like having a binder layer is bonded to a liquid crystal cell or the like as an adherend, it is possible to suppress, for example, La peeling electrostatic protective release layer of adhesive which was generated due to, stable results can prevent a case where: the polarization of the easily attached to the surface of dust, or a liquid crystal alignment disorder prone to static charge damage of peripheral circuit elements.

(1) Kind N Further, as for the type of the antistatic agent, it is preferred to use a potassium/fluorine-containing amine salt and a lithium/fluorine-sulfonimide salt, or any one of them. The reason for this is that if it is a compound such as this, excellent antistatic properties can be obtained for a long period of time. Especially in the case of long-term exposure to a warm environment, it inhibits the bleeding in the optical adhesive layer obtained from the photocuring, and the 201114866 can effectively prevent the bonding strength and the specified environment. Reduced durability. Further, as the potassium/fluorinated sulfonium imide salt, potassium imidate, potassium bis(trifluoromethylsulfonyl)imide, potassium iodide, and the like are preferable. Further, as the lithium/fluorinated sulfonium imide salt, for example, lithium sulfonium iodide, lithium bis(trifluoromethylsulfonyl)imide, and bis(i)imide material are preferable. w Iethyl 35 (2) content Further, it is preferably as the (A) component enoate polymer with respect to 1 part by weight, and the antistatic agent is set to a range of 0 05 to 15 #"曰^ Value. The reason for the J-injury is that if the content of the antistatic agent is less than 〇〇5, the antistatic property imparted to the optical adhesive composition is insufficiently cured, and the antistatic property is insufficient. It is difficult to stabilize the occurrence of ^. On the other hand, when the content of the antistatic agent exceeds 15 parts by weight, the optical adhesive for optical curing of the optical adhesive composition has an adhesive strength and durability under a predetermined condition. In some cases, it is preferable to set the value of the antistatic agent to a value in the range of from 0 5 to 101 parts by weight relative to 100 parts by weight of the (A) component (the mercaptoacrylate polymer). (3) Dispersing aid Further, in order to improve the dispersibility of the antistatic agent in the optical adhesive composition for curing the optical adhesive composition and curing it, it is preferable to further A dispersing aid is added. Further, as the dispersing aid, a polyoxyethylene glycol-polyoxypropylene glycol block copolymer or the like may be used, but it is preferred to use a calcined diol dialkyl ether. When the right is the base button of the second and second hospitals, the antistatic property of the potassium/fluorinated sulfonium imide salt can be effectively improved, and the self-optical adhesive of the dispersing aid itself can be effectively inhibited. Mid-exudation. 201114866 Also, as for the alkylene glycol dialkyl ether Specific examples thereof include octaethylene glycol dibutyl hydrazine, octaethylene glycol diethyl ether, octaethylene glycol diterpenoid scale, hexaethylene glycol dibutyl ether, hexaethylene glycol diethyl ether, hexaethylene glycol dimethyl ether, and tetraethylene glycol diol. Any one of butyl ether, tetraethylene glycol diethyl ether, tetraglyme dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dioxime ether, etc., or such combination. And 'part of which is particularly tetraethylene glycol diethyl ether Further, as for the addition ratio, it is preferred to set the ratio of the antistatic agent to the alkane devoladiol dialkyl ether (mol ratio) to be in the range of 30:70 to 70:30. It is preferable to set the ratio in the range of 40:60 to 60:40, and it is preferable to set the ratio in the range of 45:55 to 55:45.

7. Additives As for the additives, it is preferred to contain a tackifier, an antioxidant, a near-infrared absorber, a UV absorber, a light stabilizer, a softener, a filler, and the like. Further, the "in this case" varies depending on the type of the additive, but it is preferably set to a value within a range of from 〇·丨 to the weight of the component with respect to 100 parts by weight of the component. Further, the optical adhesive composition of the present invention exhibits sufficient performance by only photocrosslinking, so that it is not necessary to add a thermal crosslinking agent. Therefore, in the present invention, aging processing time is not required. [Second Embodiment] The second embodiment of the present invention is an optical adhesive which is an optical adhesive obtained by curing an optical adhesive composition, which is characterized by the step (1). (3) made. Group ^ Prepare an optical adhesive containing the following (Α) to (D) components (A) Weight-average molecular weight of 200,000 to 2.5 million (meth)acrylic acid ruthenium polymer 1 part by weight (B) Weight The average molecular weight is 30,000 to 15 million. The reactivity of the side chain has an ethylenic double bond (methyl;) acrylate polymer 丨 ~ training weight (C) g g 匕 匕 (methyl) propyl acrylate Compound 〇. 1 to 5 〇 parts by weight 201114866 (D) Photopolymerization initiator 0.01 to 10 parts by weight Step (2) Step of applying the optical adhesive composition to the ruthenium removal step (3) in the range of 50 to 1000 mJ/cm 2 The following steps will be specifically described with reference to the accompanying drawings, and the second warning of the present invention will be specifically described. 1. Step (1) (Preparation step of optical adhesive composition) Step 1 is a step of preparing an optical composition containing the following components (A) to (D). (four) "agent

(Β) a weight average molecular weight of 30,000 to 15 million in the side chain of the reactivity of the oxime-bonded double bond (mercapto) acrylate polymer 丨 ~ 5 〇 weight; ^ ° (C) polyfunctional (曱) acrylate compound 〇. parts by weight 77 (D) photopolymerization initiator 〇. 〇 〜 10 parts by weight, that is, 'this is because' the composition of the optical adhesive combination can be obtained when curing It requires aging treatment, and on the other hand, under the environmental change reading conditions, the village has a _ _ _ light occurrence of the optical adhesive can be obtained with excellent transparency. I·3·

Further, the specifics of the optical adhesive composition described above have been described in the first embodiment, and therefore will not be described here.甶 2. Step (2) (Coating step of optical adhesive composition) As shown in Fig. 1a, the step (2) is a step of applying the photoactive composition 1 to the release film 2. The film 'is exemplified by a polyethylene phthalate such as polyethylene terephthalate, a polyethylene naphthalate, or the like, and a peeling off range such as a poly-membrane-coated Wei resin. The thickness of the film is usually set to 22 201114866. The cloth used is ~ mold = compound gravure =: cloth 2 to ^, the thickness of the film for the optical adhesive composition should be 1 to 〗 〖 A value in the range 〇/im. (10) ° and seconds ~ ^ bell to dry conditions, usually should be 50 ~ boots drying 10 acetic acid should be an example of "benzene, dimethyl stearate, ethyl acetate, the addition of solvent with optical adhesive composition For δ, it is converted into a value in the range of 5 to 30% by weight. The agricultural degree and *,, ·, the younger j: the person shown in Fig. 1 'is suitable for coating the release film 2 for optical use after drying It is expected that the optical composition is photo-cured by stably producing the optical alignment agent set in the laminated state, and as shown in the sword 6, it is preferable to apply the optical adhesive "study" mixture to the release film 2. ,. Furthermore, the additional stripping _ 2 stacking is generally considered not only in the necessity of transporting only the optically viscous curing, but also in the case of the use of the optical adhesive and the use of the optical adhesive. The way is appropriate. (3) Step (3) (Step of light-irradiating the optical adhesive composition) As shown in Fig. 1c, the step (3) is in the range of 5 〇 to 1 〇〇〇 mJ/cm 2 The radiation dose irradiation 4 ray 'cures the optical adhesive composition 1 coated with the lion membrane 2 to form the optical adhesive 10 . Examples of the active energy ray include ultraviolet rays, electron emission 23 201114866 lines, and the like, and when ultraviolet rays are used, they can be obtained by using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like. It can be obtained by an electron beam accelerator or the like. Further, the active energy ray is irradiated with an irradiation amount in the range of 50 to 1000 mJ/cm 2 because the irradiation amount of the active energy ray is less than 50 mJ/cm 2 , and it is difficult to sufficiently carry out the component (B) and (c) The reaction of the ethylenic double bond between the components may make it difficult to obtain the durability and the desired adhesive properties in the case of exposure to environmental changes. On the other hand, when the irradiation amount of the active energy ray exceeds 10 μm/cm 2 , the binder and the substrate may be easily broken. Therefore, it is preferred to irradiate the optical adhesive composition with an active energy ray with an irradiation amount in the range of 1 Torr to 7 〇〇mj/cm 2 , and it is particularly preferable to irradiate with an irradiation amount in the range of 12 Å to 500 mJ/cm. . The photogram-C is shown as 'active energy cleavage from the side of the release film 2'. When the self-polarization 4 #optical illumination is applied, there may be damage from the two, and the active energy ray is absorbed by the optical film. The efficiency of time curing is reduced. 4. Adhesive properties (1) Gel rate range 2 values ίί明 The gel ratio of the optical adhesive is 7°~", when: the value of the gel due to the viscosity of the learning adhesive Values in the 8G~ range are particularly in the range of 85 to 98%. In addition, the measurement of the condensate is in the embodiment. 24 201114866 (2) Adhesive strength It is preferable to set the bonding strength of the optical adhesive to a value in the range of 0.1 to 50 N/25 mm. The reason for this is that when the adhesive strength is less than 0·1 N/25, it is sometimes difficult to sufficiently suppress the occurrence of light leakage in the case of exposure to environmental changes. On the other hand, if the adhesive strength exceeds 50 N/25 mm, the reworkability may be excessively lowered. Therefore, it is preferable to set the bonding strength of the optical adhesive to a value in the range of 0.5 to 40 N/25 mm, and it is particularly preferable to set the value in the range of 1 to 3 〇 N / 25 mm. • The method of measuring the adhesion strength is described in the examples. (3) Unnecessary aging treatment ^ and 'It is preferable to manufacture the optical adhesive (more specifically, after the active energy ray irradiation, the same below) the gel fraction after one day and after manufacturing 7 The difference in gel fraction after the day was set to a value smaller than 15% of the gel fraction one day after the production. The reason is that if the difference in gel fraction is 15% or more, the change in the characteristics of the adhesive over time after curing is large, and therefore it may be determined that an aging treatment time is required to stabilize the adhesive properties. Therefore, it is preferable to set the difference between the gel fraction after one day after manufacture and the gel fraction after 7 days after manufacture to be less than 1% by mole of the gel fraction one day after the production, and particularly preferably Set to a value less than 5%. Further, for the same reason, it is preferable to set the difference between the bonding strength after the manufacturing and the bonding strength after 7 days after the manufacturing to a value smaller than i〇n/25_, preferably to be less than 5N/25. The value is preferably set to a value less than 0 to 2 N/25 faces. [Third Embodiment] A third embodiment of the present invention is an optical film in which an optical film comprising a binder layer containing the optical adhesive of the second embodiment is provided in a film substrate. The thickness of the adhesive layer is set to a value within the range of __ 25 201114866. The film is appropriately incorporated into the third embodiment of the fourth (4). The film substrate (8)' of the film can be effectively suppressed in the occurrence of light leakage if it is used for light polarization = even if the film substrate is subjected to the test. Benzene: ΐ ί ί Ξ = = = = 聚 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = Amine, polyphenylene, poly-hard, poly-, poly-, sulphur, sulphur, sulphur, alicyclic, alicyclic, alicyclic, alicyclic, alicyclic, alicyclic, alicyclic The iodine-containing polyvinyl alcohol tree used as a raw material of the polarizing plate can be used as the optical film of the present invention, and the single surface of the polarizer is covered with a protective film such as triethylene glycol cellulose f-ethylene glycol ester. The polarizer or the like is also the same: ... - 4 and ΐ: As for the thickness of the film material, although it is not limited, it is usually set to a value in the range of 1 to 1000 Å. J 1 逋 其 The reason is that if the thickness of the wire is less than _, the Johnson will be excessively reduced, or it is difficult to form both. On the other hand, if the thickness of the substrate is too large, the operability may be excessively lowered, or economically disadvantageous. Therefore, it is preferable to set the thickness of the film substrate to 5 to 5 〇〇. The value inside is particularly preferably set to a value in the range of 10 to 200 WJJJ. Further, it is preferable to subject the film substrate 101 to surface treatment. 26 201114866 Although such a surface treatment may, for example, be a primer treatment, a corona treatment, a flame treatment or the like, it is preferably a primer treatment. The reason is that the adhesion of the adhesive layer to the substrate film can be further improved by using the substrate on which the undercoat layer is formed. Further, examples of the material constituting the undercoat layer include cellulose esters (for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, and the like), polyacrylic acid, and Polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl acetal, polyvinyl ether, polyvinyl ketone, polyvinyl carbazole, polyvinyl butyral, and combinations thereof. Further, the thickness of the undercoat layer is not particularly limited, but it is usually necessary to set the value in the range of 0·05β"ΐ~lO/zm. 2. Adhesive layer ϋ: The adhesive layer of the optical film of the present invention is characterized by the fact that the optical _ mixture described in the second embodiment has formed the specific content of the optical adhesive for 渝古述Since it is explained in the first and second embodiments, it is omitted here. The coffee ^ lies in 'the thickness of the adhesive layer 1 设定 is set to 1~ • 挥 ==== 合 7_~° 疋 疋 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Moreover, as for the adhesive layer, it is optically and is the most smooth to form an optical adhesive composition layer! 27 201114866 A state in which the optical film substrate 101 is laminated, and then photocuring is performed thereon. Further, as shown in FIG. 1e, when the release film 2 is laminated on both surfaces of the optical adhesive layer 1 , the release film 2 having a small peel strength can be peeled off, and the optical adhesive layer 1 can be removed. The exposed surface of the crucible is attached to the optical film substrate 101 to be laminated. Further, as for the method of bonding the obtained optical film to the adherend, as shown in FIGS. 1 c to d, the release film 2 laminated on the optical adhesive layer is first peeled off, and then, for optical use. The exposed surface of the adhesive layer is attached to the adherend 200 to be bonded. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. [Examples 1 to 14 and Comparative Example 1] 1. Preparation of optical adhesive composition As shown in Table 1, the predetermined (A) to (F) components were mixed at a predetermined ratio to prepare an optical adhesive composition. Hereinafter, the contents of the components (A) to (F) in Table 1 are shown. • (A) Ingredient (I) BA/AA=95/5 Mw=1.5 million According to a conventional method, 95 parts by weight of butyl acrylate (BA) and 5 parts by weight of acrylic acid (AA) are polymerized to give a weight average molecular weight of 150,000. (fluorenyl) acrylate copolymer. For the preparation of the optical adhesive composition, a 18% by weight solution of ethyl acetate was used. 5重量份的苯乙酯酯。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (HEA) was polymerized to obtain a (fluorenyl) acrylate polymer having a weight average molecular weight of 1.5 million. For the preparation of the optical adhesive composition, a 18% by weight solution of ethyl acetate was used. • (B) Component (III) BA/HEA=85/15 (addition of methacrylinyl group to 80 mol% of HEA amount) Mw=800,000 201114866 85 parts by weight of butyl acrylate according to a conventional method (μ And 15 parts by weight of 2-hydroxyethyl acrylate (HEA) were polymerized to obtain a (meth) acrylate polymer. 5重量份之间。 Relative to 100 parts by weight of the resulting (mercapto) acrylate polymer in ethyl acetate solution (solids concentration of 30% by weight), adding fluorenyl propylene oxyethyl isocyanide - 4. 8 parts by weight It is equivalent to 2-hydroxyethyl acrylate (1 〇 equivalent) in 1QQ. and then. The addition of 1 part by weight of dibutyltin dilaurate as a catalyst was carried out at 25 C for 24 hours to obtain a solution of a reactive (meth) acrylate polymer having a weight average molecular weight of 800,000. For the preparation of the optical adhesive composition, a 18% by weight solution of ethyl acetate was used. • (B) Ingredient (IV) BA/HEA=80/20 (addition of mercaptopropenyl group to 80 mol% of HEA amount)_=800,000 80 parts by weight of butyl acrylate (BA) and 2 according to a conventional method The weight of the oxime, 2, is polymerized by the basis of g (g) to obtain a (mercapto) acrylate polymer. ,, relative to 100 parts by weight of the obtained (meth)acrylic acid vinegar polymerized L solution (solid concentration concentration of 30 wei), added methyl propyl acrylate 6.7,4 parts by weight (relative to 100 equivalents of acrylic acid 2 _ hydroxy group) B from the single 70, is 8 〇 equivalent). A solution of a reactive (meth) acrylate polymer having a weight average molecular weight of 800,000 was obtained by adding 0.014 parts by weight of dibutyl laurate 3 24 /] as a catalyst. = 18% ethyl ester solution was used when preparing the optical adhesive composition. • (C) Ingredient (V) Tris(propylene oxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., Aronix m_315) • (C) Ingredient (VI) 29 201114866 Trihydroxydecylpropane triacrylate (Manufactured by East Asia Synthetic Co., Ltd., Aronix M-309) • (D) Ingredients: a ketone/1-cyclohexyl phenyl ketone = ι:ι (by weight) mixture (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 500) • (E) Ingredient (VII) 3-glycidoxypropyltrimethoxysulfide Shisha (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) • (E) Ingredient (VIII) 3-Acrylonitrile (3) succinyl sulfonate (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103) • (F) component trihydroxy decylpropane modified stumylene sulfhydryl diisocyanate (isocyanate crosslinker) (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) (G) component bis(trifluoromethanesulfonate) lithium imide, (meth) acrylate polymer and reactive (mercapto) acrylic acid having an ethylenic double bond in the side chain The weight average molecular weight (Mw) of vinegar polymer is determined by gel permeation chromatography (hereinafter referred to as gp) c method) determination. That is, a standard curve is first made using polystyrene. Thereafter, the weight average molecular weight (Mw) is represented by a polystyrene-converted value. Next, a tetrahydrofuran (THF) solution having a concentration of 1% by weight, such as a (mercapto) acrylate copolymer, is prepared, and is prepared by Tosoh Corporation.

GEL PER MEATION CHROMATOGRAPH HLC-8020 (3 series column consisting of TSKGEL GMHxl, TSKgel GMHxl, TSKgel G2000HXL) was used to measure the weight average molecular weight at 4 ° C, THF solvent, and 1 ml/min. In addition, as a guard column, it is manufactured by Tosoh Corporation; GUARD COLUMN. κ 2. Coating step of optical adhesive composition 201114866 The coating of the thickness of the benzoic acid stripping film 38_ was coated, and the system was coated. (10) The thickness of the film after the (10) is 25"m, and the drying process is carried out for 1 minute at the time of "9", and the optical layer is formed, and the obtained optical bonding & Adhesive layer structure 光学 optical adhesive composition layer / release film

3. Light irradiation step Next, the optical adhesive composition layer was formed into an optical 'mixture layer' from the side of the release film of the known structure by the following two-line (UV) to obtain an optical film. Polarization of the optical adhesive layer In addition, in Comparative Example 1, the light irradiation step was not performed. At this time, the thickness of the optical adhesive layer was 25 am. Lamp: manufactured by Fusion Co., Ltd., using an electrodeless lamp. Light volume: 600mJ/cm2 Illuminance: 150mW/cm2

In addition, the amount of ultraviolet light and the illuminance were measured using UVPF-36 manufactured by EYE GRAPHICS Co., Ltd. Evaluation (1) Evaluation of no aging treatment (1)-1 Evaluation of gelation rate to manufacture (more specifically, after active energy ray irradiation. In addition, in Comparative Example 1, it means coating adhesion to a release film After the composition of the composition, the optical adhesive layer after 1 day and after 7 days was the same. (The gelation rate of the film is measured.) The exposed surface of the structure 201114866 on the side of the optical adhesive composition layer/release film substrate obtained in the coating step of the optical adhesive composition described above (4) It is not manufactured by the other company, SP, PET3801). The light was irradiated under the same conditions as the above-described silking step, and the optical adhesive layer between the two lion's membranes was lost. The gel fraction of the silk secret agent layer at 23 C after 1 day after manufacture. That is, first, after curing the light, after the day and 7 , the obtained sample is made into a polyester mesh (mesh size _

In the state of the day, the weighing with a precision balance is only the weight of the sample. The weight at this time is Ml. The sample was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 5 %, and then dried in an oven at 80 degrees for 12 hours. Next, the weight of the dried sample is weighed using a precision balance. The weight at this time is M2.

Finally, the gel fraction (%) was calculated by the formula of (Μ2/Μ1)χ1〇〇. The results obtained are shown in Table 2. (1 > 2 Evaluation of Adhesive Strength The adhesion strength of the optical adhesive layer was measured 1 day after and 7 days after manufacture. - That is, except for the use of polyethylene terephthalate film (Dongli) Co., Ltd., Lumirror U426), in addition to the polarizing plate, the same operation as the above-mentioned polarizing plate with an optical adhesive layer to produce an optical film for measuring the adhesion strength. Then '1 day after manufacture and 7 After the sample on the optical film of the day was cut into a width of 25 mm and a length of 100 mm, the release film was peeled off, and the film was peeled off from the alkali-free glass (manufactured by Corning Co., Ltd., 1737), and the high pressure crucible (Chestnut made 32 201114866, shares The finite δ Ί ) 加压 加压 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 TENSIL〇N) The peeling and peeling angles are the conditions of the bonding strength of Zhejiang. The results obtained are shown in Table 2. (2) Evaluation of durability (2)-1 Evaluation of arching, peeling, etc. with optical The polarizer of the adhesive layer is evaluated with a dry adhesive under endurance conditions (5) Using a cutting device (manufactured by Takino Seiki Co., Ltd. = fnCTR PN1.) 'The resulting optical bonding is: 233mm x 309mm per 1 sheet and sheet 'After one day after manufacture, the m film' is attached to the non-test glass (manufactured by Corning Co., Ltd., and used high pressure dad (Kurihara Manufacturing Co., Ltd. • 5 MPa, 50 ° C, 20 minutes) Into the humidity 90_ and 8 (rc / dry each long-term article = use i. magnification magnifying glass to observe the 〇 durability. The results obtained are shown in Table 2. 丞竿, sub-estimated 〇: four-sided towel 'from the periphery End # G 6mm or more does not exist in any of the four sides of X. On the eve of the day. Arching, peeling, foaming, wave biting, etc. F „There are abnormalities. The skin, the specialist is more than 0.1 coffee. Appearance (2)-2 Evaluation of light leakage. Evaluation of the leakage under the specified conditions for the obtained polarizing plate with a binder layer, that is, using a cutting device (manufactured by Takino Seiki, SUPER CUTTER PN1 -_), Co., Ltd. The film is adjusted to the N-face (four) coffee mixture layer Griffin, which was placed on the unexamined 33 201114866 glass (manufactured by Corning Co., Ltd., 1737). Then, it was pressurized with a pressure of 5 MPa, 50 ° C, and 20 minutes using an autoclave (manufactured by Kurihara Seisakusho Co., Ltd.). In addition, the above-mentioned bonding is performed on the surface and the back surface of the glass-free glass in such a manner that the polarization axis of the polarizing plate is in a crossed Nicols state. Then, in this state, it is placed at 803⁄4 for 200 hours and then at 23°. C. The environment was allowed to stand for 2 hours under a relative humidity of 50%, and the light leakage was evaluated by the method shown below. That is, using the McpD_2〇〇〇 manufactured by Otsuka Electronics Co., Ltd., the brightness of each region shown in the second figure is measured, and the luminance difference ΔL* is obtained by the following equation. The results obtained are shown in Table 2. In addition, the smaller the value of 'Δί*' means less light leakage. △ L*=[(b+c+d+e)/4]-a (where 3,1), (:, (1 and 6 are eight regions, eight regions, (^ region, D region, and E, respectively) The brightness of the predetermined measurement point (one of each area) of the area.), 8 〇 °c placed 2 〇 M, and then placed at 23 ° C, relative humidity 0 after the brother placed for 2 hours The photographs of the light leakage from Example 1 and Comparative Example 1 are shown in Fig. 3 and Fig. 4. (3) Evaluation of haze value The blade coater applies the optical composition mixture to the first peel after drying (4). On the peeling layer of the film (Lindeke Co., Ltd., SP-PET3811). The agent group ΐ layer is implemented in 1 point, and the optical bonding adhesive is used to form the optical bonding adhesive. The exposed side of the adhesive composition layer is lighter peeling type _ 妓 SP, SP_PET38 () 1), and the 科 版 令 green ϊ 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以Zi Xi,······························································································· Then, the second peeling film was peeled off, and the haze value of the obtained measurement sample was measured using an integrating sphere type light transmittance measuring device 7105'. The obtained result column; (4) Evaluation of reworkability Polarizer with optical adhesive layer for evaluation of workability

That is, a sample having a width of 25 mm and a length of 10 mm was cut out from a polarizing plate with an optical adhesive layer after one day of manufacture, and then the release film was peeled off and attached to an alkali-free glass (Corning shares) Co., Ltd. manufactures, ι737). ‘Use high pressure dad (manufactured by Kurihara Seisakusho Co., Ltd.) to heat at 5 MPa, 50 ° C, and 20 minutes. Then, it was allowed to stand in an environment of 23 ° C and 50% RH for 7 days, and then a tensile tester (manufactured by 0RIENTEC Co., Ltd., TENSILON) was used at a peeling speed of 300 mm/min and a peeling angle of 180. The bonding strength was measured, and the reworkability was evaluated according to the following criteria. The results obtained are shown in Table 2.

〇: The bonding strength after 7 days after bonding is a value of less than 25 N/25 faces. X: The adhesive strength after 7 days after bonding is a value of 25 N/25 or more. (5) Evaluation of surface resistivity The surface resistivity of the optical adhesive layer obtained in Example 14 was measured in accordance with JIS K 6911. That is, the value of 3 sec after the start of the measurement was measured under the following conditions, and this was taken as the surface resistivity (Ω/port) of the optical adhesive layer. The results obtained are shown in Table 2. Determination of the shape of the sample: 50% x50 deleted sheet of polarizing plate with optical adhesive layer thickness of optical adhesive layer: 25

Measurement environment: 23±2t, 50±2% RH

Measuring machine: manufactured by Mitsubishi Chemical Corporation, HIRESTA-UP 35 201114866 MCP-HT450

Applied voltage: 100V Table 1 is formed in the η component β 4 c component Ρ 4 Ε _ component Ρ - component G 1 η m IV V VI W pass 100 a 40 10 0.6 0.2 — real M5»z 100 a 20 —- 10 0.5 0.2 — 一 — 100 — 10 — 10 — 0.2 0.2 — — — 宝 筠 4 100 10 10 10 10 0.6 —— 0.2 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — To a 10 a 0.5 a 0.2 — a capital » Example 7 100 a 5 a 10 — 0.5 0.2 — a one treasure 幡 8 100 — 10 a 40 a 0.5 0.2 — one treasure” «9 100 a 10 a 20 — 0.5 0.2 — — — — — — — — — — — — — — 9IR«i3 — 100 10 一 10一 0.5 0.2 一 — 耷 锊 14 a 100 10 a 10 a 0.5 0.2 a 2.S than a soft case 1 a 100 — a — a 0.2 — 1.5 a table 2 < 1 waist string (») Adhesive Feng (N/25ran) Durable Shin Hong Δ\Λ (-) S degree value reworkability surface electric η stroke 1 after 7 days after 1 husband 7 60°C after the day 90XRH 8〇 (3⁄4) (〇/□) Bao Shi Example 1 97 95 1.2 LS Ο ο 0.8 1.4 〇 _ 实 Μ 96 96 96 96 1.5 2 0 Ο ο 0.8 1.1 0 — ««3 87 85 11.7 4.S Ο ο 0.0 1.3 〇一耷幡例4 92 90 3.6 3.2 Ο 0 0.9 1.0 0 — 宝HS»s 95 93 2.8 2.7 Ο ο 0.8 0.8 〇一实谌》6 91 91 3.0 3.4 0 ο 0.9 0.9 0 一宝施»7 90 89 22.0 15.9 0 0 0·8 1.1 0 wmm 98 95 1.8 2.0 0 ο 0.7 ie 0 __ 宝»例9 96 94 2·0 2.3 ο ο 0.8 1·6 〇__ Real MS Example I» 92 91 3.2 2·β ο 0 Od 1.1 0 -- Bao Shi Example 11 95 94 1.8 1.5 ο ο 0.8 1.2 〇fflfiMu 94 94 3.2 2.9 ο ο 0.3 1.0 〇宝旖例13 93 90 14.6 6.3 0 0 0.8 1.0 〇宝施例η 90 89 2.1 1.8 0 ο 0 8 1 fr\ 1 Ον1Λ"*〇Comparative example 1 85 ο k— 34 «. σ v. 9 X 4.3 0.8 ο — [Industrial availability] As described above, according to the present invention, (A) a (meth) acrylate polymer having a molecular weight of 36 201114866 having a predetermined weight average, (B) a reactive (meth) acrylate having a predetermined weight average molecular weight is polymerized. The polyfunctional (meth) acrylate compound (C) and the (〇) photopolymerization initiator specified in (C) are mixed at a predetermined ratio to obtain a good adhesive property which is not affected by environmental changes even without aging treatment and It also improves transparency. As a result, it is possible to obtain an optical adhesive composition which is effective in suppressing the occurrence of light leakage and having excellent transparency even when exposed to environmental changes, and which is excellent in transparency. Therefore, the optical adhesive composition of the present invention can be expected to contribute significantly to the improvement of the quality and cost of optical films such as liquid crystal display devices, plasma display devices, organic electroluminescence devices, and inorganic electroluminescence devices. . * [Brief Description of the Drawings] Fig. 1 to Fig. 1 e are schematic views for explaining the use of the optical adhesive composition and the like and the method for producing the optical film. Figure 2 is a diagram for explaining the evaluation method of light leakage. Fig. 3 is a view for explaining the light leakage in the first embodiment. Fig. 4 is a view for explaining the light leakage in Comparative Example 1. [Main component symbol description] 1 Optical adhesive composition (layer) 2 Release film 10 Optical adhesive (layer) 101 Optical film substrate 100 Optical film 200 Adhesive 37

Claims (1)

201114866 VII. Patent application scope: 1. An optical adhesive composition comprising the following components (A) to (D): (A) a weight average molecular weight of 200,000 to 2.5 million (mercapto)acrylic acid 1 part by weight of the ester polymer, (B) 1 to 50 parts by weight of the reactive (meth) acrylate polymer having a vinyl double bond in the side chain, having a weight average molecular weight of 30,000 to 150,000 ( C) a polyfunctional (meth) acrylate compound 〇. 1 to 5 parts by weight, (D) a photopolymerization initiator 〇. 01 to 10 parts by weight. The optical adhesive composition according to claim 1, wherein the component (A) is a (fluorenyl) acrylate having a value of from 1 to 2 Å in a carbon atom of the group. And a monomer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and a decylamino group in the molecule as a structural unit, and the copolymerization ratio is set to be in the range of 99·9:0·1 to 8〇:20 The optical adhesive composition according to the first aspect of the invention, wherein the component (B) is in the range of 1 to 2 Å having an alkyl group having an alkyl group. The internal value of (indenyl) acrylic acid, and a monomer having an ethylenic double bond in a side chain as a structural unit, and the copolymerization ratio is set to a value in the range of 卯:1 to 50:50, the copolymerization It is based on weight. The optical adhesive composition according to claim 1, wherein the ethylenic double bond in the side chain of the component (B) is a (mercapto)acrylonitrile group introduced via an isocyanate group. Or (meth) propylene oxime. 5. The optical adhesive composition according to claim 1, wherein the component (c) is selected from the group consisting of tris(propylene oxyethyl) azide vinegar and bis (propylene) Ethyl) hydroxyethyl isocyanurate, isocyanuric acid ethylene oxide modified diacrylic acid, isocyanuric acid ethylene oxide modified triacrylate and ε-caprolactone modified three (c) At least one of the group consisting of oxy-ethyl)isocyanurate. 38 201114866 6. An optical adhesive composition comprising a decane coupling agent as described in the first step of the patent application, further comprising the component (A), the k component, and at the same time, relative to 1 part by weight The value inside. The content of the component is set to 0.001 to 1 〇 by weight. 7. The optical adhesive, the optical adhesive, characterized in that the step (1) of curing the optical adhesive composition is prepared to contain the step (1)~ (3) The step of forming the composition of the mixture, and the weight of the optically viscous ester polymer of the components (A) to (D) is 100? The amount of 200,000 to 2.5 million (mercapto) acrylic acid SS (meth) acryl oleic acid compound 0.1 to 50 parts by weight, (9) photopolymerization hair styling agent Ml ~ 1Q parts by weight; 垔 severe injury step (2 Applying the optical adhesive composition to the peeling 臈 步 县 县 县 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占 占step. An optical film comprising an adhesive layer comprising an optical adhesive according to claim 7 of the invention, wherein the thickness of the adhesive layer is Set to a value in the range of 1 to 100. 9. The optical film of claim 8, wherein the film substrate is a polarizing plate. 39