TW200903054A - Optical film with pressure-sensitive adhesive and optical laminate - Google Patents

Abstract

To provide an optical film with a pressure-sensitive adhesive excellent in reworkability, capable of suppressing not only whitening but also partial detachment or peeling between a glass substrate and the pressure-sensitive adhesive layer and foaming in the pressure-sensitive adhesive layer, and excellent also in durability, and to obtain an optical laminate by sticking the optical film on a glass substrate. The optical film with a pressure-sensitive adhesive is obtained by forming a pressure-sensitive adhesive layer on a surface of an optical film such as a polarizing film. The pressure-sensitive adhesive layer is formed of a composition comprising (A) an acrylic resin which is a copolymer of an alkyl (meth)acrylate and an unsaturated carboxylic acid, and has a weight average molecular weight (Mw) of 1,400,000-2,000,000 and an Mw to number average molecular weight (Mn) ratio (Mw/Mn) of <=5, wherein a content of units derived from the unsaturated carboxylic acid is 0.5-10 pts.wt. based on 100 pts.wt. of the entire resin, (B) an isocyanate compound, c an aziridine compound and (D) a silicone oligomer having a functional group such as a mercapto group and an alkoxy group within a molecule.

Description

200903054 IX. OBJECTS OF THE INVENTION [Technical Field] The present invention relates to an optical film having an adhesive attached thereto and an optical laminate obtained by bonding the same to a glass substrate, and the optical film to be used in the present invention includes, for example, Polarized film or retardation film. [Prior Art]

Liquid crystal cells (1 iquidcrysta 1 ce 11 ) used in liquid crystal display devices such as TN (Twisted Nematic) and STN (Super Twisted Nematic), which have liquid crystal components held in two The structure between the glass substrates of the sheet, and the optical film mainly comprising an acrylic resin as a main component, a polarizing film, a retardation film or the like laminated on the surface of each of the glass substrates, wherein the optical film is usually at least single The form of the optical film with the adhesive layer on the surface of the adhesive layer is formed in the form of a glass substrate at the stage of assembling the liquid crystal cell, and the adhesive side is bonded to the glass substrate. Such an optical film with an adhesive may have a large dimensional change due to expansion and contraction under heat or humid heat, so that it is prone to warpage and adheres to the optical laminate of the glass substrate, and there is an adhesive. In-layer foaming causes problems such as floating or peeling between the adhesive layer and the glass substrate. Moreover, recently, under the condition of heat or humidity, the distribution of residual stress acting on the optical film with the adhesive becomes uneven, and the stress concentration of the outer peripheral portion of the optical laminate bonded to the glass substrate results in 'TN liquid crystal cell. In the black display, a white-like 200903054 image called white v〇id appears in the outer periphery, and the S TN liquid crystal cell has a problem of color unevenness in the outer periphery. In addition, when the optical film with the adhesive is attached to the liquid crystal cell, when the film is incomplete, the optical film is peeled off and the optical film with the adhesive is reattached, and it is required to adhere to the cell glass. The optical film is peeled off together, and the so-called reworkability of the residue or the mist of the adhesive hardly occurs on the surface of the glass substrate connected to the adhesive layer. Thereby, even if the optical film with the adhesive adhered once from the glass substrate is peeled off, since the surface of the glass substrate after peeling is maintained in a favorable state, it can be used again as a glass substrate. Moreover, liquid crystal display devices have recently been used as vehicles for car navigation systems, etc., but in vehicle applications, it is also required to have appearance changes such as foaming or floating, peeling, and fogging even under high temperature and high humidity conditions. Persistence. In order to solve the related problems, for example, in the publication of Japanese Patent Publication No. 2000-1999, a high molecular weight acrylic resin having a weight average molecular weight of 800,000 or more is contained, and two or more of them can be reacted with the acrylic resin to form an intersection. A polyfunctional compound having a functional group of a linked structure, and an adhesive composition containing a decyl or alicyclic epoxy group-containing decane coupling agent. The inventors of the present invention reviewed the results of attaching an optical film with an adhesive attached to an optical film as disclosed in the above-mentioned publication to a glass substrate, and the result of heating from 70 ° C to cooling down to The process of -30 °C, followed by the temperature rise to 70 °C is called a cycle, and the cycle is repeated 10 times. This cycle applies thermal shock. It is obvious that peeling or fogging occurs on the surface of the glass substrate, and the durability is insufficient. . -5- 200903054 Therefore, the object of the present invention is to provide excellent reworkability, suppress whitening when bonded to a glass substrate, and suppress the adhesion between the glass substrate and the adhesive layer when bonded to a glass substrate. Floatment or peeling, and foaming in the adhesive layer, and even if heating and cooling are repeated, so-called durability such as whitening, floating, peeling, foaming, and fogging does not occur. An optical film with an adhesive attached thereto; an optical layer formed by laminating an optical film and a glass substrate with an adhesive layer interposed with an optical film to which the adhesive is attached. [Explanation] Φ #明者 and others have carefully studied the results, and found that by using the two types of acrylic resin which are the main components of the adhesive having the molecular weight and molecular weight distribution of the temple, The bonding agent, which is further blended with an oligomer having a special amount of an oligopolymer as a binder composition of a decane compound, is provided on the surface of the optical film to obtain excellent results. That is, according to the present invention, an adhesive layer is formed on at least one side of an optical film, and the adhesive layer is composed of a composition containing the following components (A), (B), (C) and (〇). An optical film with an adhesive attached. (A) the following formula ([)

Ri CH2=iG-〇^R2 (1) 〇200903054 (wherein R1 represents a hydrogen atom or a methyl group; and R2 each represents an alkyl group or an aralkyl group having 1 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms; The structural unit derived from the (meth) acrylate represented by the group is a main component, and the structural unit derived from an unsaturated carboxylic acid having one olefinic double bond and at least one carboxyl group in the molecule contains The first acrylic resin having a weight average molecular weight (Mw) of 1,400,000 to 2,000,000 and a molecular weight distribution of 5 or less represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (Mw/Mn), the above unsaturated The content of the structural unit derived from the carboxylic acid is 0.5 to 10 parts by weight based on 100 parts by weight of the total weight of the resin; (B) isocyanate compound 〇·〇 5 to 5 parts by weight; (C) nitrogen 0.01 to 0.1 parts by weight of a heterocyclopropane-based compound; and (D) a polyoxyalkylene oligomer having a functional group selected from a mercapto group, an epoxy group, and a (meth)acryloxy group and an alkoxy group in the molecule 0.05 to 〇-5 parts by weight. Further, according to the present invention, the above optical film with an adhesive attached thereto is provided, and the optical layer formed by bonding the adhesive layer side to the glass substrate is also provided. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the optical film with an adhesive according to the present invention will be described in detail. The adhesive film layer is contained on at least one surface of the optical film. A) an acrylic resin, 200903054 (B) an isocyanate compound, (C) an aziridine-based compound, and (D) a functional group selected from the group consisting of a mercapto group, an epoxy group, and a (meth)acryloxy group. The composition of the composition of the polyoxyalkylene oligomer of the alkoxy group is first described with respect to each component constituting the adhesive composition. [Acrylic Resin] The acrylic resin (A) which is a resin component of the adhesive, the structural unit derived from the (meth) acrylate represented by the above formula (I) as a main component and contains one olefinicity in the molecule. A structural unit derived from a double bond and at least one carboxyl group-containing unsaturated carboxylic acid, having a weight average molecular weight (1% by mass) of 1,400,000 to 2,000,000, a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (Mw /Mn) The first acrylic resin having a molecular weight distribution of 5 or less. The acrylic resin (A) may be composed only of the first acrylic resin specified herein, or may be composed of a mixture of a second acrylic resin different from the first acrylic resin. The structural unit derived from the above unsaturated carboxylic acid, the acrylic resin (A) is contained in the first acrylic resin in a ratio of 〇.5 to 1 〇 by weight in a total amount of 1 part by weight, and further, (A) The meaning of "acrylic acid" means "(meth)" of any of the "other" (meth) acrylates such as acrylic acid or methacrylic acid. In the above formula (I) which is the main structural unit of the first acrylic resin, R! is a hydrogen atom or a methyl group, R2 is an alkyl group having 1 to 14 carbon atoms or -8 - 200903054, and is preferably a hospital. base. The base or the aromatic base represented by R2 may be substituted with a hydrogen atom of 1 to 1 Å in each group. As the (meth) acrylate represented by the formula (I), specifically, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, η-octyl acrylate, and lauryl acrylate Chain alkyl acrylate; isobutyl acrylate '2-ethylhexyl acrylate, branched alkyl acrylate of isooctyl acrylate; such as methyl methacrylate, ethyl methacrylate, propyl methacrylate直-butyl methacrylate, η-octyl methacrylate, linear alkyl methacrylate of lauryl methacrylate; isobutyl methacrylate, 2-ethylhexyl methacrylate, A branched alkyl methacrylate such as isooctyl methacrylate. When R2 is an alkyl group substituted with an alkoxy group, that is, when R2 is an alkoxyalkyl group, the (meth) acrylate represented by the formula (I), specifically, 2-methoxy acrylate Ethyl ethyl ester, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, and the like. When the ruler 2 is an aralkyl group, the (meth) acrylate represented by the formula (I) is specifically benzyl acrylate or benzyl methacrylate. For the production of the first acryl resin, a certain compound may be used, or two or more kinds of compounds may be used as the (meth) acrylate represented by the formula (I). Among them, butyl acrylate is preferably used as the at least one monomer. Among them, the structural unit derived from the (meth) acrylate constituting the first acrylic resin contains a butyl acrylate-derived unit, which is a preferred embodiment. An unsaturated carboxy-9-200903054 acid which is another structural unit of the first acrylic resin, and a compound having an olefinic double bond and at least one carboxyl group in the molecule, and specific examples thereof include acrylic acid, methacrylic acid, and horse. Acid, itaconic acid, etc., of which acrylic acid or methacrylic acid is suitable. Further, the first acrylic resin may contain a structural unit derived from a monomer having a polar functional group other than a carboxyl group, and examples of the polar functional group other than the carboxyl group include a hydroxyl group, a decylamino group, an epoxy group, and an oxo group. Butanyl group, amine group, isocyanate group, aldehyde group and the like. Examples of the monomer having a polar functional group of a hydroxyl group include 2-hydroxyester (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like; as a polar functional group; Examples of the amide group-containing monomer include decyl acrylate, decyl methacrylate, N,N-dimethylaminopropyl decyl decylamine, hydrazine, hydrazine-dimethyl methacrylate, hydrazine, hydrazine. - diethyl methacrylate, hydrazine - hydroxymethyl methacrylate, etc.; as a monomer whose polar functional group is an ethoxy group, for example, glycidyl acrylate, glycidyl methacrylate, 3, 4- ring Oxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc.; as a monomer having a polar functional group of oxetanyl group, for example, oxetanyl group (Meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3-oxetanyl)methyl (indenyl) acrylate, (3 -ethyl-3-oxetanyl)methyl(methyl)propionate, etc.; as a monomer having a polar functional group as an amine group, For example, hydrazine, hydrazine-dimethylaminoethyl acrylate or allylamine; and examples of the monomer having a polar functional group of isocyanate group include, for example, 2 methacryloxyethyl isocyanate; Examples of the monomer having a polar functional group of an aldehyde group include acrylic acid aldehyde and the like. -10- 200903054 In the first acrylic resin, the (meth) acrylate derived by the formula (I) is usually from 60 to 99.5 by weight, preferably from 80 to 99. ί contains. Further, the structural unit derived from the unsaturated carboxylic acid is 1 part by weight based on the total amount of the resin (A), that is, when the acrylic resin is composed of the first acrylic resin, the first acrylic resin is used in relation to 100 parts by weight. In the case of the second acrylic tree different from the above, 100 parts by weight of the total amount is contained in a weight ratio of 0.5 to 10. The ratio of the structural unit derived from 100 parts by weight of the acid of the acrylic resin (A) is preferably from 1 to 6 parts by weight based on 100 parts by weight of the acrylic resin (A), by making the amount of the unsaturated structural unit When it is bonded to a glass substrate, it is effective in suppressing the floating or peeling of a glass substrate and adhesion, and it is made into the optical film by the temperature change etc. Since the dimensional change of the agent layer changes depending on the size thereof, there is no difference between the peripheral portion of the liquid crystal cell and the brightness of the central portion, and the effect of suppressing whitening is exhibited. The first acrylic resin may contain a unit of a monomer other than the above-mentioned formula (I) and a monomer other than the above-mentioned unsaturated carboxylic acid, and examples of the monomer which can be used arbitrarily are exemplified by one olefin. A double bond and at least one heterocyclic monomer having 5 or more members. Wherein, a 5-membered ring or more of a heterocyclic group, 5 or more, preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms, wherein the weight is a structural unit; the weight % of acrylic acid, (A) only, In addition, the proportion of the unsaturated carboxylic acid component of the fat component relative to the weight of the carboxylic acid-derived adhesive layer layer is not shown because of the brightness or color of the viscous (A-derived knot such as intramolecular heterocycle) The term "base" refers to a methyl group having a carbon number of at least one of -11 - 200903054, and a group substituted with a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. Specific examples of the heterocyclic monomer include propylene morpholine and ethylene. Base hexamethyleneamine, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone modified tetrahydrofurfuryl acrylate, etc. Further 'like 3,4- A hetero atom constituting a 3-membered ring and a 7-membered ring, such as an epoxycyclohexyl methacrylate or a 3,4-epoxycyclohexylmethyl methacrylate, is a heterocyclic ring having a 7-membered ring. The base can be used as a heterocyclic monomer, and an olefinic double bond such as 2,5-dihydrofuran or the like The heterocyclic group may be contained. As the heterocyclic monomer, two or more different monomers may be used as the heterocyclic monomer, and further, N-vinylpyrrolidone, vinyl caprolactam, and propylene may be used.醯 morpholine or a mixture of the above. When the structural unit derived from the heterocyclic monomer is contained in the first acrylic resin, the amount is preferably about 30% by weight based on the first acrylic resin, preferably Further, the structural unit derived from the heterocyclic monomer containing 0.1% by weight or more of the first acrylic resin is changed even if the size of the optical film changes, because the adhesive layer changes with this size. There is no difference between the brightness of the peripheral portion of the liquid crystal cell and the brightness of the central portion, and there is a tendency to suppress whitening or color unevenness. Further, as another monomer which can be used arbitrarily, it is exemplified that there is 1 in the molecule. An olefinic double bond and at least one alicyclic structure of an alicyclic monomer. The alicyclic structure is usually a cycloalkane structure or a cyclic olefin having a carbon number of 5 or more, preferably about 5 to 7 carbon atoms. Structure An olefinic double bond in the alicyclic structure. Specific examples of the acrylate-12-200903054 ester having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, and dicyclopentanyl acrylate. , Anodic acid ring 12-yard ester, Acetone methylcyclohexyl ester, Trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, α _ ethoxycyclohexyl acrylate, cyclohexyl acrylate Examples of the methacrylate having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, and methyl propylene storage acid cyclododecyl ester. Methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclopropyl phenyl methacrylate, and the like. Further, examples of the acrylic acid ester having a plurality of alicyclic structures in the molecule include dicyclohexylmethyl itaconate, bicyclooctyl itaconate, and dicyclododecylmethyl succinate. Further, ethylene vinyl ethyl hexyl acetate or the like may be an alicyclic monomer. Among them, isobornyl acrylate and cyclohexyl methacrylate, dicyclopentanyl acrylate, are preferred because they are easily available. Two or more different compounds may be used in combination as the alicyclic monomer. When the structural unit derived from the alicyclic monomer is contained in the first acrylic resin, the amount is usually about 30% by weight, preferably 15% by weight or less, based on the first acrylic resin. Further, the structural unit derived from the alicyclic monomer containing 0 to 1% by weight or more of the first acrylic resin has a glass substrate and an adhesive layer which are contained in an amount of 1% by weight or more. The tendency to float or peel off. Further, as the other monomer, an ethylenic monomer different from any of the (meth)propionic acid ester, the heterocyclic monomer, and the alicyclic monomer represented by the formula (n) can be used. Examples of the vinyl monomer include fatty acid-13-200903054 vinyl ester, vinyl halide, vinylidene halide, (meth) propylene compound, aromatic vinyl, etc. Among them, examples of the fatty acid vinyl ester include vinyl propionate. And vinyl butyrate and vinyl ethyl 2-ethylhexanoate; examples of the vinyl halide include vinyl chloride or vinyl bromide, and examples thereof include vinylidene chloride and (meth)acrylonitrile and methacrylonitrile; The conjugated diene compound is an olefin having a conjugated double bond, and specific examples thereof include an isoolefin and a chloroprene; and an aromatic vinyl means a compound having a vinyl group, and specific examples thereof include Such as styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, triethyl styrene, propyl styrene, butyl styrene, amyl styrene, octyl styrene, fluorobenzene Alkene, bromostyrene, dibromostyrene, iodobenzene , nitrostyrene, styrene monomer of methoxystyrene, nitrogen-containing aromatic vinyl of vinylcarbazole, etc. These two combinations of two or more compounds are used. In the structural monoenoic acid resin derived from the monomer, the amount is less than or equal to about 1% by weight based on the first acrylic resin, preferably 5% by weight, more preferably, or the like. When the structural unit derived from the structural unit derived from the body and the number of the number derived from the vinyl monomer, the total amount of these is the first acrylic resin nitrile, conjugated diene vinyl acetate, ester, lauric acid B. As the bismuth B, it can be exemplified that propylene has pentadiene in the molecule, an aromatic ring in the butyl group, ethylene, methyl styrene, diethyl styrene, hexylethylene, chlorophenethyl styrene, and b. The storage enthalpy of B is more than that of the urethane or olefinic monomer, which may be contained in the first propyl group, usually 5, which is substantially free of this, and the alicyclic meronomer is a reference, usually -14-200903054 is 3 0% by weight or less, preferably 20% by weight or less The method for producing the first acrylic resin described above may, for example, be a solution polymerization type emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or the like, in which a solution polymerization method is preferred as a specific example of the solution polymerization method. 'A monomer and an organic solvent which are mixed may be mentioned, and when the concentration of the monomer is adjusted to 50% by weight or more, preferably 50 to 60% by weight, the total amount of the monomers is 0.001 to 100 parts by weight. About 5 parts by weight of the polymerization initiator, about 4 to 90 ° C, preferably 45 to 70 ° C, more preferably 5 to 6 (about TC, stirring for 8 hours or more, preferably 8 to 12) For the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator may be used. As the photopolymerization initiator, for example, 4-(2-hydroxyethoxy)phenyl ( 2-hydroxy-2-propyl) ketone, etc.; as a thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) 1,1,-Azobis(cyclohexane-1-carbonitrile), 2,2'-azo (2,4-dimethylvaleronitrile), 2,2,-azo (2,4- two Even 4-methoxyvaleronitrile), dimethyl-2,2,-azo (2-methylpropionate), 2,2'-azo (2-hydroxymethylpropionitrile) Nitrogen compounds; such as barium peroxide, tert-butyl hydroperoxide, benzammonium peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate , bis-η·propyl peroxydicarbonate, tert-butyl peroxy neodecanoate, tert-butyl peroxytrimethyl acetate, (3,5,5-trimethylhexyl) An organic peroxide of a peroxide; an inorganic peroxide of potassium persulfate, ammonium persulfate or hydrogen peroxide. Further, a redox initiator such as a peroxide and a reducing agent may be used as a polymerization initiator. As the organic solvent used in the polymerization reaction, an aromatic hydrocarbon such as toluene or xylene; an ester such as ethyl acetate or butyl acetate; an aliphatic alcohol such as η-propanol or isopropanol; acetone , methyl ethyl ketone, ketones of methyl isobutyl ketone, and the like. The molecular weight of the first acrylic resin is a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of 1,400,000 to 2,000,000, and the weight average molecular weight (^\¥) is 1,400. In addition, since the adhesion under high temperature and high humidity is improved, the possibility of occurrence of floating or peeling between the glass substrate and the adhesive layer is lowered, and the reworkability tends to be improved. Preferably. Further, when the weight average molecular weight is 2, 〇〇〇 or 〇〇〇, the size of the optical film attached to the adhesive layer changes even if it changes due to temperature, since the dimensional change varies with the adhesive layer, The difference between the brightness of the peripheral portion of the liquid crystal cell and the brightness of the central portion disappears, and whitening or color unevenness tends to be suppressed. The molecular weight distribution represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (?n) is 5 or less, preferably 2 to 4, and Mw/Mn is 5 or less because of high temperature. The adhesiveness under high humidity tends to increase, and the possibility of occurrence of floating or peeling between the glass substrate and the adhesive layer tends to decrease, and the reworkability tends to be improved. The adhesive used in the present invention may contain, as the acrylic resin (A), a second acrylic resin different from the first acrylic resin, and as the second acrylic resin which may be additionally contained, for example, the above formula-16-200903054 The structural unit derived from the (meth) acrylate represented by (I) is a main component, and the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) is about 50,000 to 500,000. The range of low molecular weight people. When the second acrylic resin having a low molecular weight is used, the amount thereof is usually 5 parts by weight or less, preferably 30 parts by weight or less based on 100 parts by weight of the entire acrylic resin (A). The acrylic resin (A) used in the adhesive layer is only the acrylic acid resin (the acrylic resin is used only when the first acrylic resin is used, and when the first acrylic resin and the second acrylic resin are mixed, etc. Mixture) dissolved in ethyl acetate 'adjusted to a non-volatile concentration of 20% by weight solution' at a temperature of 25 ° C showed a temperature below 25 Pa. s, showing a viscosity below i ~ 15 Pa · s better 'this When the viscosity is 20 Pa·s or less, the adhesion under high temperature and high humidity is improved, and the possibility of occurrence of floating or peeling between the glass substrate and the adhesive layer is lowered, and the reworkability is improved. The tendency is better, and the viscosity can be measured by a B 〇stwick viscosity meter. In addition to the above-mentioned acrylic resin (A), the isocyanate compound (B) and the aziridine compound (C) which are further blended into a crosslinking agent, in addition to the adhesion of the adhesive layer to the glass substrate In combination, a polyoxyalkylene oligomer (D) having a functional group and an alkoxy group is further blended. [Isocyanate-based compound] The isocyanate-based compound (B) used as a crosslinking agent is a compound having at least two isocyanato groups (_NCO) in the molecule, and examples thereof include -17 to 200903054, for example, tolylene diisocyanate or hexamethylene Diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethyl diisocyanate, hydrogenated diphenylformamidine diisocyanate, naphthalene diisocyanate, triphenyl Methane triisocyanate and the like. Further, the isocyanate compound may be used in an adduct obtained by reacting a polyhydric alcohol such as glycerin or trimethylolpropane, or an isocyanate compound as a dimer or a trimer. A crosslinking agent for the adhesive composition. Further, two or more kinds of isocyanate compounds may be used in combination. In the isocyanate compound (B), xylene diisocyanate or tolylene diisocyanate or an isocyanate compound is reacted with a polyol such as glycerol or trimethylolpropane. The product or the mixture of the isocyanate compound or the like, or the isocyanate compound or the like is preferably used. The more suitable isocyanate-based compound is toluene diisocyanate, an adduct obtained by reacting tolylene diisocyanate with a polyhydric alcohol, a dimer of tolylene diisocyanate, and a terpolymer of tolylene diisocyanate. [Azacyclopropane-based compound] Another aziridine-based compound (C) used as a crosslinking agent has at least two nitrogen atoms and two carbons called methyleneimine in the molecule. Examples of the compound of the skeleton of the 3-membered ring formed by the atom include diphenylmethane-4,4'-bis(1-azetidincarbamide) and toluene-2,4-bis(1-nitrogen). Heterocyclopropanecarbamide, triethylene melamine, isophthalic acid bis-1-(2-methylaziridine) 'shen-azacyclopropane-18-200903054 phosphine oxide, Hexamethylene-1,6-bis(1-azacyclopropanecarbamide), trimethylolpropane-tri-/3-azanepropane propionate, tetramethylolmethane-tris-quinone-nitrogen Heterocyclopropane propionate, tetramethylolmethane-tetra-/3-azanepropane propionate, and the like. Among them, trimethylolpropane-tris-/3-azanepropane propionate and tetramethylolmethane-tris--3-azanepropane propionate are preferred because they are easily available. [Polysilicon oxide oligomer] Polyoxane oligomer (D), which is a decane compound having at least an alkoxy group, is condensed on average to form a -Si-0-Si- structure, on which a ruthenium atom is formed. A compound having at least one alkoxy group bonded to each other, and having a functional group selected from a mercapto group, an epoxy group, and a (meth)acryloxy group in the molecule. As described above, the polyoxyalkylene oligomer (D) is blended in order to improve the adhesion between the adhesive and the glass substrate, and further has a thiol group, an epoxy group, and a (meth) acryloxy group. The functional group has an effect of improving the adhesion to the resin constituting the optical film. These functional groups are preferably a mercapto group or an epoxy group, and particularly preferably a mercapto group. Adhesive agent obtained by blending such a polyoxymethane compound of such an oligomer type is bonded to an optical laminate of a glass substrate, and when subjected to heat shock, it can function in an optical laminate. The effect of lifting or peeling between the glass substrate and the adhesive layer is small, and the effect of improving the reworkability is also exhibited. Even a decane compound having a functional group such as a mercapto group or an epoxy group or a (meth) acryloxy group, when the monomer type is blended, as described above, the heat shock resistance or reworkability is improved -19-200903054 The effect may not be enough. The polyoxyalkylene oligomer (D)' is a dimer having two ruthenium atoms in one molecule, and the number of ruthenium atoms in one molecule is about 100', that is, the average degree of polymerization is about 2 to 100. However, when the average degree of polymerization is 2', since the monomer is present in a considerable amount, the purpose of using the oligomer type is not necessarily sufficient. Therefore, the average degree of polymerization is preferably 3 or more, and the higher the average degree of polymerization, the higher the viscosity of the oligomer, and in the extreme case, it becomes a paste or a solid, which makes it difficult to use. Wherein the average degree of polymerization is preferably 80 or less, more preferably 50 or less. a functional group selected from the group consisting of an anthracene, an epoxy group, and a (meth)acryloxy group in the polyoxyalkylene oligomer (D), usually bonded to a germanium atom via a linking group, and the related link Examples of the base include, for example, an alkylene group including a methyl group, an ethyl group, a propyl group, a hexyl group, a fluorenyl group, and the like, and a divalent hydrocarbon group having an aromatic ring in the middle of a methylphenylethyl group or the like. A divalent aliphatic group having an oxygen atom in the middle of a methoxymethyl group, a methoxyethyl group, a methoxypropyl group or the like. Further, an epoxy group may be formed between two adjacent carbon atoms constituting the carbon ring. In the polyoxyalkylene oligomer (D), a group in which a thiol group is bonded to a sand atom via a linking group is referred to as an "organic group having a fluorenyl group", and an epoxy group is bonded to a group of a ruthenium atom via a linking group. The term "organo group having an epoxy group" is also referred to as "an organic group having a (meth)acryloxy group" by a group in which a (meth)acryloxy group is bonded to a germanium atom via a linking group. The organic groups are collectively referred to as "organofunctional groups". As the organic group having a mercapto group, 'containing, for example, a mercaptomethyl group, 3_锍-20-200903054-propyl group, 6-fluorenylhexyl group, 1 fluorene-decyldodecyl group, 2 -(4-mercapto group) Methylphenyl)ethyl or the like; as an organic group having an epoxy group, for example, glycidoxymethyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl) Ethyl or the like; as an organic group having a (meth) propylene fluorenyloxy group, for example, an acryloxymethyl group, a 3-propenyloxypropyl group, a methacryloxymethyl group, a 3-methyl propylene group Alkoxypropyl and the like. The polyoxyalkylene oligomer (D) may be a co-oligomer obtained by partially co-hydrolyzing and condensing a functional group-containing decane compound represented by the following formula (Π) with a tetraalkoxy decane.

X I. (Π) R3O—Si—OR4 wherein R3 and r4 each independently represent an alkyl group or a phenyl group; X represents a functional group selected from the group consisting of a fluorenyl group, an epoxy group, and a (meth) acryloxy group. Organic group; Y represents an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, an aralkyl group or an aralkyloxy group. The adhesive obtained by using such a co-oligomer of a functional group-containing decane compound and a tetraalkoxy decane has excellent adhesion even under high temperature and high humidity, and the glass substrate and the adhesive layer are used. The tendency to float or peel off between them tends to be small, and the reworkability tends to be improved, which is preferable. In the formula (II), the alkyl group represented by R3 and r4 may be, for example, a carbon number of from 1 to 21 to 200903054 to about 10, wherein a compound in which r3 and a ruler 4 are each independently a methyl group or an ethyl group is suitably used. Specific examples of the organic functional group represented by X, as disclosed above, specific examples of the organic group having a mercapto group include mercaptomethyl group, 3-mercaptopropyl group, 6-fluorenylhexyl group, and 1 fluorene-fluorene group. A decyl group, a 2-(4-mercaptomethylphenyl)ethyl group, etc.; as a specific example of the organic group having an epoxy group, a glycidoxymethyl group and a 3-glycidoxy group are mentioned. a propyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, etc.; as a specific example of the organic group having a (meth) propylene fluorenyloxy group, a propylene methoxymethyl group, a 3- propylene hydrazine is mentioned. An oxypropyl group, a methacryloxymethyl group, a 3-methylpropenyloxypropyl group or the like. The alkyl group, the alkoxy group, the aralkyl group and the aralkyloxy group represented by Y may, for example, be about 1 to 10 carbon atoms. Specific examples of the functional group-containing decane compound represented by the formula (II) are disclosed below. Examples of the decane compound in which X is an organic group having a mercapto group include mercaptomethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, and 2- (4-mercaptomethylphenyl)ethyltrimethoxydecane, 6-decylhexyltrimethoxydecane, 10-mercaptodecyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane , 3-mercaptopropylmethyldiethoxydecane, and the like. Examples of the decane compound in which X is an organic group having an epoxy group include, for example, glycidoxymethyltrimethoxydecane, 3·glycidoxypropyltrimethoxydecane, and 2-(3,4-). Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane. As the decylation-22-200903054 compound wherein X is an organic group having a (meth) propylene fluorenyloxy group, for example, propylene methoxymethyltrimethoxy decane, 3-propylene methoxy propyltrimethoxy group can be mentioned. Decane, 3-propenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropene oxime Oxypropyl propyl triethoxy decane, 3-methyl propylene methoxy propyl tributoxy decane, 3 propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene decyloxy Propylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, and the like. In the tetraalkoxy decane which is partially co-hydrolyzed and polycondensed with the functional group-containing decane compound represented by the formula (Π), the alkoxy group bonded to the argon atom may be a carbon number of 1 to 10 about. In addition, the four alkoxy groups bonded to the ruthenium atom may be the same, or may be a compound of two, three or four different alkoxy groups bonded to a ruthenium atom, which is manufactured and easily obtained. From the viewpoint of the above, four compounds in which the same alkoxy group is bonded to a halogen atom are suitable, and specific examples thereof include tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, and tetrabutylene. Oxydecane, etc. When the functional group-containing decane compound represented by the above formula (11) is partially co-hydrolyzed and condensed with a tetraalkoxy decane to form a polyoxy siloxane oligo (D), a bond in the formula (Π) a stanol group formed by partial hydrolysis of an alkoxyalkyl group or a phenoxyalkyl group represented by 〇r3 and _〇R4, and an alkoxy fluorenyl group in a tetraalkoxy decane The stanol group formed by hydrolysis in part is condensed to form a polyoxyalkylene oligomer. In such an oligomer, in the coating and drying step of the adhesive, the polyoxyalkylene oligomer tends to be less likely to scatter, and is preferred. The polyoxyalkylene oligomer (D) is particularly preferably a compound having a methoxy group of -23-200903054 as an alkoxy group, more preferably a compound having both a methoxy group and an ethoxy group. Thereby, using a polyoxyalkylene oligomer having a methoxy group and/or an ethoxy group, even if a thermal impact is applied to the optical laminate to which the optical film is bonded to the glass substrate via the obtained adhesive, It is preferred to have a tendency to float or peel off between the glass substrate and the adhesive layer in the optical layer, and in particular, a polyoxyalkylene oligomer having both a methoxy group and an ethoxy group is used. This effect will become larger. Among them, a co-oligomer which is further used as a raw material of 3-mercaptopropyltrimethoxydecane and tetraethoxysilane is suitable. The polyoxyalkylene oligomer which can be used in the present invention is represented by a combination of monomers, and examples thereof include the following. Such as mercaptomethyltrimethoxydecane-tetramethoxydecane co-oligomer, mercaptomethyltrimethoxydecane-tetraethoxydecane co-oligomer, mercaptomethyltriethoxydecane-four a methoxymethyl alkene homopolymer, a mercaptomethyl-containing co-oligomer containing a mercaptomethyl group; such as 3-mercaptopropyltrimethoxy矽-tetramethoxydecane co-oligomer, 3-mercaptopropyltrimethoxydecane-tetraethoxydecane co-oligomer, 3-mercaptopropyltriethoxydecane-tetramethoxydecane Co-oligomer, 3-mercaptopropyltriethoxydecane-tetraethoxydecane co-oligomer mercaptopropyl-containing co-oligomer; glycidoxymethyltrimethoxydecane- Tetramethoxydecane co-oligomer, -24- 200903054 epoxy propoxymethyltrimethoxydecane-tetraethoxydecane co-oligomer, glycidoxymethyltriethoxydecane-four a methoxy methoxy alkane oligomer, a glycidoxymethyltriethoxy decane-tetraethoxy decane co-oligomer containing a glycidoxymethyl group-containing oligomer; such as 3-epoxy Propoxypropyl Methoxydecane-tetramethoxydecane co-oligomer, 3-glycidoxypropyltrimethoxydecane-tetraethoxydecane co-oligomer, 3-glycidoxypropyltriethyl a oxirane-tetramethoxydecane co-oligomer, a 3-glycidoxypropyltriethoxydecane-tetraethoxydecane co-oligomer containing a glycidoxypropyl group a polymer; such as 3-propenyloxypropyltrimethoxydecane-tetramethoxydecane co-oligomer, 3-propenyloxypropyltrimethoxynonane-tetraethoxydecane co-oligomer, 3-propenyloxypropyltriethoxydecane-tetramethoxydecane co-oligomer, 3-propenylmethoxypropyltriethoxydecane-tetraethoxydecane co-oligomer, '3 - propylene methoxy propyl methyl dimethoxy decane - tetramethoxy decane co-oligomer, -25- 200903054 3-propenyl methoxy propyl methyl dimethoxy decane - tetraethoxy decane Co-oligomer, 3-propenylmethoxypropylmethyldiethoxydecane-tetramethoxydecane co-oligomer, 3-propenyloxypropylmethyldiethoxydecane-tetraethoxy Base decane co-oligomer containing C a co-oligomer of a methoxy propyl group; such as a 3-methacryloxypropyltrimethoxydecane-tetramethoxydecane co-oligomer, 3-methylpropenyloxypropyltrimethoxy矽-tetraethoxy decane co-oligomer, 3-methacryloxypropyl triethoxy decane-tetramethoxy decane co-oligomer, 3-methyl propylene methoxy propyl triethyl Oxydecane-tetraethoxydecane co-oligomer, 3-methylpropenyloxypropylmethyldimethoxydecane-tetramethoxydecane co-oligomer, 3-methylpropenyloxy group Propylmethyldimethoxydecane-tetraethoxydecane co-oligomer, 3-methylpropenyloxypropylmethyldiethoxydecane-tetramethoxydecane co-oligomer, 3- A methacryloxypropyloxy group-containing co-oligomer of methacryloxypropylmethyldiethoxy decane-tetraethoxydecane co-oligomer. Commercially available polyoxyxane oligomers, all of which are sold by Shin-Etsu Chemical Co., Ltd., can be exemplified by fluorene- and methoxy-ethoxyl -26-200903054 polyoxyalkylene oligomerization. "X-4 〇 18〇5", "X-4 1-1 810" with a fluorenyl group and a methyl and methoxy polyoxyalkylene oligomer, having an epoxy group and a methyl group and a "X-4 1 - 1 0 5 3 " of the polyoxyalkylene oligomer of oxy group, "X-4 1 - 1" of a polyoxyalkylene oligomer having an epoxy group and a methyl group and a methoxy group 0 5 8 ” (all are trade names). These polyoxyalkylene oligomers are described in Silicone Review No. 57 "Polysilicon Oxygen Oligomers" on the same company's website &lt; URL : http : //www.silicone.jp/j /sil_news/90/images/review_90.pdf&gt; (Searched on January 19, 2007). [Adhesive Composition] In the present invention, as described above, the isocyanate compound (B) and the aziridine compound (C) which are blended as a crosslinking agent in the acrylic resin (A) are blended. The polyoxyalkylene oligomer (D) having a specific functional group becomes an adhesive composition. The blending amount of the isocyanate compound (B) is preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of the nonvolatile content of the acrylic resin (A) of the ruthenium-forming adhesive composition, and the amount is preferably 0.2. ~3 parts by weight. When the amount of the isocyanate compound (C) per 100 parts by weight of the acrylic resin (A) is 5 parts by weight or more, when the adhesive layer containing the adhesive layer is bonded to the glass substrate, the adhesive layer is applied. The effect of lifting or peeling between the glass substrate and the adhesive layer is suppressed, and further, by making the amount 5 parts by weight or less, the dimensional change of the optical film is caused even by temperature change or the like because the adhesive layer changes with the size thereof. Since there is no change between the brightness of the peripheral portion of the liquid crystal cell and the brightness of the central portion, the effect of suppressing whitening or color unevenness is exerted. The blending amount of the aziridine-based compound (C) is preferably from 0.01 to 0.1 part by weight, based on the weight of the non-volatile portion of the acrylic resin (A) constituting the adhesive composition, in an amount of from 0.01 to 0.1 part by weight. It is 0.02 to 0.08 parts by weight. When the amount of the azacyclopropane-based compound (C) per 100 parts by weight of the acrylic resin (A) is 0.01 part by weight or more, the adhesive layer containing the same is bonded to the glass substrate, thereby suppressing The effect of floating or peeling between the glass substrate and the adhesive layer, and by making the amount to be 0.1 part by weight or less, the dimensional change of the optical film is caused even by temperature change or the like because the adhesive layer varies with the change in size thereof. Therefore, there is no difference between the brightness of the peripheral portion of the liquid crystal cell and the brightness of the central portion, and the effect of suppressing whitening or color unevenness is exhibited. When the adhesive layer is bonded to the glass substrate by using the isocyanate compound (B) and the aziridine compound (C) as a crosslinking agent, the floating or peeling between the glass substrate and the adhesive layer is suppressed. Further, in addition, the adhesive layer is bonded to the liquid crystal cell of the glass substrate, and the effect of suppressing whitening or color unevenness due to temperature change becomes remarkable. The blending amount of the polyoxyalkylene oligomer (D) is from 5 to 0.5 parts by weight based on 1 part by weight of the nonvolatile portion of the acrylic resin (A), and the amount is preferably from 0.1 to 0.3. Parts by weight. When the amount of the polyoxyalkylene oligomer (D) is 100 parts by weight or more based on 100 parts by weight of the acrylic resin (A), the adhesion between the pressure-sensitive adhesive layer and the glass substrate is improved. Further, by making this amount 0 to 5 parts by weight or less, the polyoxyalkylene oligomer can be inhibited from the adhesive layer -28-200903054. The adhesive composition used in the present invention may further contain other crosslinking agents, cross-linking catalysts, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, etc., among them, In addition, when the cross-linking catalyst is mixed with the cross-linking agent in the adhesive, the adhesive layer can be prepared in a short time, and the obtained optical film with the adhesive adhered to the liquid crystal cell glass can suppress the optical Float or peeling occurs between the film and the adhesive layer, or foaming is caused in the adhesive layer, and the reworkability is also more excellent. Examples of the crosslinking catalyst include hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, and isophoronediamine. A diamine-polyamine resin, an amine compound of a melamine resin, or the like. The adhesive composition is usually prepared in a state in which the above components are dissolved in an organic solvent. Therefore, the organic solvent to be used may be any one which can dissolve the above components, and for example, an aromatic hydrocarbon such as toluene or xylene may be used. Esters such as ethyl acetate or butyl acetate, such as acetone or methyl ethyl, ketones of methyl isobutyl ketone, and the like. [Optical Film with Adhesive] The optical film with an adhesive according to the present invention is provided on at least the side of the optical film, and the adhesive layer formed of the above-mentioned adhesive composition is provided. The optical film used herein refers to a film having optical characteristics, and examples thereof include a polarizing film and a retardation film. The polarizing film is incident light of natural light or the like, and has a linearly polarized sound of a vibrating surface of a vibrating surface that emits a light -29-200903054 light, and a linear polarizing film. The iodine or the two-phase retardation may be, for example, a high-resolution film formed by, for example, an ester, a polyimide, a polyvinylidene-cellulose, or the like. Among them, one-axis stretching or axial phase difference thin film, etc., in addition, the refractive index is different to make it use light, such a phase, in addition, the film. The polarizing film includes a linear polarizing film having a linear polarized light and a linear polarizing film having a positive characteristic thereof; a polarizing film having a reflection line polarization and a polarizing film having a perpendicular thereto; and a laminated polarizing film circular polarizing film. As a polarizing film (also referred to as a photon or a photon thin, a dichroic dye such as a polyvinyl alcohol-based dendritic dye which is extended by a single axis is used. The film exhibits refractive index anisotropy. Polyvinyl alcohol, polycarbonate, poly, polyolefin, cyclic polyolefin, polystyrene fluoride / polymethyl methacrylate, ethylene-vinyl acetate copolymer saponified film, extending 1.01 ~ 6 times Further, a polymer film having a polycarbonate film or a cyclic polyaxial stretching is preferably used, and any of a film, a wide viewing angle retardation film, and low light can be applied. Coating and alignment of a liquid crystal compound The film of the nature, or the film which is anisotropically anisotropically formed by inorganic layering, can be used as a phase difference film, and is called a temperature-compensated type of Nippon Oil Co., Ltd., which absorbs vibration of a certain intersection with "LC film". A suitable thin film-up optical film having a surface having a vibrating surface in a certain direction and a phase described later, particularly as a film), an extended olefin obtained by ester, polyaromatic, polyfluorene, liquid crystal polyester, or polyvinyl chloride There is a film called a modulus of elasticity phase to make it appear as a coating film, and the film of the retardation film is a product of the phase difference film, which is sold by the Japanese brand of -30-200903054. A film in which a rod-shaped liquid crystal sold under the trade name "NH film" is obliquely aligned, and a disc-shaped liquid crystal which is sold under the trade name "WV film" by Fujifilm Co., Ltd., which is tilt-aligned, by Sumitomo Chemical Co., Ltd. (Complete) A completely biaxial alignment type film which is sold under the trade name "VAC film", and a biaxial alignment type film which is sold by Sumitomo Chemical Co., Ltd. under the trade name "new VAC film". Moreover, these optical film adhesive protective films can also be used as optical films. A transparent resin film is used as the protective film, and examples of the transparent resin include an acetaminocellulose resin typified by triethylene fluorene cellulose or diethyl fluorene cellulose, and polymethyl methacrylate. A methacrylic resin, a polyester resin, a polyolefin resin, a polycarbonate resin, a polyether ether resin, a polyfluorene resin, or the like. The resin constituting the protective film may be blended with a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a triazine-based compound, a cyanoacrylate-based compound, a nickel-salted salt-based compound, or the like. UV absorber. As the protective film, an acetaminocellulose-based resin film such as a triacetyl cellulose film is preferably used, and the above-mentioned retardation film can also be used as a direct protective film. Among the optical films described above, most of the linear polarizing films are used in a state in which a polarizing film is formed, for example, a polarizing film made of a polyvinyl alcohol-based resin is adhered to one side or both sides of a protective film. In addition, the above-mentioned circularly polarizing film 'is a laminated linear polarizing film and a retardation film, but the linear polarizing film is also mostly a single-sided or two-31 - 200903054 surface of the polarizing film. . In such a circularly polarizing film, when the adhesive layer of the invention is formed, an adhesive layer is usually formed on the side of the retardation film. A more preferable example of the optical film in which the pressure-sensitive adhesive layer of the present invention is provided includes polarized light composed of a composition of an acetaminophen-based protective film/polyvinyl alcohol-based polarizer/acetonitrile-based protective film. The optical film of a film includes an optical film of a polarizing film formed of a structure of an amorphous cyclic polyolefin resin film/polyvinyl alcohol-based polarizer/protective film. In the former, an adhesive layer is provided on the outer side of at least one of the outer layers, and the latter is preferably provided with an adhesive layer on the outer side of the amorphous cyclic polyolefin-based resin film. Here, the amorphous cyclic polyolefin resin refers to a resin in which a norbornene or a cyclic olefin such as polycyclic norbornene is a monomer, and the ring-opening polymer of the cyclic olefin can be hydrogenated. Then, the degree of hydrogenation is saturated, or a copolymer of a cyclic olefin and a chain olefin, and the like, and it is also effective to introduce a polar group. As a commercially available amorphous cyclic polyolefin resin, there are "ARTON" sold by JRS Co., Ltd., "ΖΕΟΝΕΧ" and "ZEONOR" sold by Nippon Co., Ltd., and Mitsui Chemicals Co., Ltd. "ΑΡΟ" and "APEL" (both are trade names) sold by the company. In the related amorphous cyclic polyolefin-based resin, since the photoelastic coefficient is small, it is difficult to change the phase difference with temperature change or the like, so that whitening when the liquid crystal display device is formed is effectively suppressed. In addition, when the adhesive layer is formed on the surface of the amorphous cyclic polyolefin resin-32-200903054 of the polarizing film formed of the amorphous cyclic polyolefin resin film/polarizer/protective film. On the bonding surface of the amorphous cyclic polyolefin resin film, in order to improve the adhesion to the adhesive layer, corona discharge treatment is preferably applied in advance. Corona discharge treatment means that a high voltage is applied between electrodes to discharge, and the treatment of the resin film disposed thereon is activated. It is preferable to set the output of the corona discharge treatment to about 200 to 1,000 W, and the effect of the treatment by the corona discharge treatment is 200 W or more, and the effect of the treatment becomes remarkable, and the adhesive layer and the amorphous layer are improved. Adhesion of a cyclic polyolefin resin film. Further, by making the output power of the corona discharge treatment to be 1,000 W or less, the dust which is likely to occur due to this treatment is alleviated. The effect of the corona discharge treatment differs depending on the type of electrode, the electrode interval, the voltage, the humidity, and the type of the resin film to be used. For example, the electrode interval is set to 1 to 5 mm, and the moving speed is set to about 3 to 20 m/min. Preferably. An optical film with an adhesive, for example, a method of forming an adhesive layer by applying the above-described adhesive composition on a release film, and laminating an optical film on the obtained adhesive layer The method of forming an adhesive layer on the optical film and then forming an adhesive layer is applied to the adhesive film to adhere the release film to form an optical film with an adhesive. In addition, as the peeling film, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate is used as a substrate. On the bonding surface of the substrate and the adhesive layer, a release treatment such as a polyoxyalkylene treatment is applied. The adhesive used in the present invention has a gel fraction of 70 to 90% by weight - 33 to 200903054. The gel fraction of the adhesive layer is preferably 70% by weight or more because the adhesive layer and the optical layer can be suppressed. The occurrence of floating or peeling between the films is likely to be low in the possibility of causing foaming in the adhesive layer. Further, the gel fraction is 90% by weight. /. The following 'is preferred because it is easy to manufacture. The gel fraction ' is determined by the following (1) to (IV). (I) A metal layer having an area of 8 cmx and an area of about 8 cm and a metal net made of SUS304 of about 10 cm x 10 cm (the weight of which is Wm) is attached. (II) Weighing the weight of the composition obtained in the above (I), the weight of which is set to W s, and then folded four times in a state of being wrapped in the adhesive layer, and then weighed by a stapler (binding machine). Its weight is set to Wb. (III) The above-mentioned (II) mesh fixed by a stapler was placed in a glass container, and after immersing in 60 ml of ethyl acetate, the glass container was stored at room temperature for 3 days. (IV) The net was taken out from the glass container and dried at 12 ° C for 24 hours, and the weight was determined to be Wa, and the gel fraction was calculated based on the following formula.

Gel fraction (% by weight) = [{Wa-(Wb-Ws)-Wm}/(Ws-Wm)] xlOO The thickness of the adhesive layer is not particularly limited, but is usually less than 30 // m Preferably, more than 10//m is better, and even more preferably 10 to 20//m. The thickness of the adhesive layer is 3 〇νπι or less, and there is a tendency that the adhesion under high temperature and high humidity is increased, and the possibility of occurrence of floating or peeling between the glass substrate and the adhesive layer is lowered, and there is a possibility of reprocessing. The tendency to improve is better than -34-200903054. In addition, the thickness is 1 〇# m or more, even if the size of the film attached to it changes, because the adhesive layer changes with the circumference of the liquid crystal cell. It is preferable that there is no difference between the brightness of the portion and the brightness of the center portion, which suppresses whitening or color unevenness. In the prior art, the thickness of the adhesive layer adhered to the liquid crystal cell glass is generally in the range of /zm, but in the present invention, even if the thickness is 20 &quot;m, it can also be sufficient as an adhesive layer. performance. The optical film with an adhesive of the present invention adheres to the glass substrate to form an optical laminate. After the optical is peeled off from the glass substrate due to some poor conditions, the adhesive layer is peeled off along with the optical film. On the surface of the glass substrate to be contacted, almost no fogging or slurry retention occurs, so that it is easy to reattach the optical film of the adhesive to the peeled glass substrate. That is, the so-called reworkability is excellent. [Optical Laminate] The optical film with an adhesive of the present invention can be an optical laminate by laminating an adhesive layer on a glass substrate. An optical layer formed by laminating an adhesive film to a glass substrate, for example, an adhesive layer obtained by peeling off an optical film with an adhesive obtained by the above-described method and attached to a glass substrate The surface is fine. In addition, examples of the glass substrate include a glass substrate for liquid crystal cells, and glass for glass for anti-glare. In addition, an optical film (upper film) on which the adhesive is attached to the glass substrate on the front side (side) of the liquid crystal cell is laminated on the glass substrate on the back side of the liquid crystal cell, and the other is attached. The optical layer is formed by an optical film (lower polarizing film) which is used as a glass and a light-adhesive film of -35-200903054. Used as a liquid crystal display device. Examples of the material of the glass substrate include alkali lime glass, low alkali glass, and alkali-free glass. The optical film with the adhesive is laminated on the glass substrate to form an optical laminate. The optical layered composition can be used as a liquid crystal cell for a liquid crystal display device, and a liquid crystal display device in which the liquid crystal cell is disposed can be used, for example, for a liquid crystal for personal computers including a notebook type, a desktop type, and a PDA (Personal Digital Assistance). Displays, televisions, car displays, electronic dictionaries, digital cameras, digital cameras, electronic computers, watches, etc. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to such examples. In the examples, the amounts and % of the amounts used and contents are used as weight basis for no particular reason. . In addition, the non-volatile content of the acrylic resin is the enthalpy measured by the method according to ΠSK 5 4 0, specifically, the adhesive solution is placed in the tray with an arbitrary weight, and the explosion-proof oven is used for 1 1 5 X: The residual non-volatile weight after drying for 2 hours is expressed relative to the ratio of the weight of the initially measured solution. The viscosity is measured at 25 ° C by a Bostwick viscometer. The weight average molecular weight and the number average molecular weight are arranged in series in a GPC apparatus, and two columns of "TSK gel GMHHR-H(S)" manufactured by Tosoh Corporation as a column are arranged in series, using tetranitrofuran as ί. The chaotropic liquid was measured by the standard polystyrene-36-200903054 olefin conversion under the conditions of a sample concentration of 5 mg/ml, a sample introduction amount of 1 〇〇#1, a temperature of 40 ° C, and a flow rate of iml /min. First, an acrylic resin having a high molecular weight and a small molecular weight distribution prescribed in the present invention and an acrylic resin in a range other than those specified in the present invention are listed. [Polymerization Example 1] A reactor containing a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer was charged with a mixed solution of 81.8 parts of propylene, 98.9 parts of butyl acrylate, and 1_1 parts of acrylic acid, and the air in the apparatus was replaced with nitrogen. It is oxygen-free and increases the internal temperature to 55 °C. Then, a solution of azobisisobutyronitrile (polymerization initiator) 0.12 parts was dissolved in 10 parts of acetone to be added in a total amount. After the addition of the initiator for 1 hour, ethyl acetate was continuously added to the reactor at an addition rate of 17.3 parts/hr, so that the concentration of the acrylic resin other than the monomer was 35%, and the internal temperature was 54 to 56 °C. The temperature was maintained for 12 hours. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The viscosity of the obtained acrylic resin was 1 2 P a · s. The weight average molecular weight Mw of the acrylic resin was 1,670,000, and Mw/Μη was 4.4' This was designated as acrylic resin A1. [Polymerization Example 2] The polymerization example was changed except that the monomer composition was changed to 78.9 parts of butyl acrylate, 2 parts of methyl acrylate, and 1 part of acrylic acid, and the amount of azobisisobutyronitrile was changed to 0.2 part. 1 The same method is used to obtain a 20% strength acrylic resin solution, and the obtained acrylic resin has a viscosity of 12.3 - 37 - 200903054

Pa. s, this acrylic resin had a weight average molecular weight Mw of 1,440,000 and M w / Μη of 4.2, which was designated as acrylic resin A2. [Polymerization Example 3] A reaction solution containing a cooling tube, a nitrogen gas introduction tube, a thermometer, and a scrambler was charged with a mixed solution of 100 parts of ethyl acetate, 98 parts of butyl acrylate, and 1.1 parts of acrylic acid, and was replaced with nitrogen. After the air in the apparatus became oxygen-free, a solution in which 0.2 parts of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added in a total amount, and the internal temperature was raised to 65 ° C, and then reacted for 6 hours. The temperature was raised to 70 ° C and allowed to react for 2 hours. Then, the solution of 4 parts of azobisisobutyronitrile was dissolved in 20 parts of ethyl acetate for 1 hour, and the concentration of the acrylic resin was further added with ethyl acetate. The viscosity was adjusted to 20%, and the obtained acrylic resin had a viscosity of 9.8 P a · s. The acrylic resin had a weight average molecular weight Mw of 1,370,000 and M w/Mn of 14.0, which was designated as acrylic resin A3. [Polymerization Example 4] The same procedure as in Polymerization Example 3 except that the initial reaction temperature was changed to 70 ° C and the amount of the initial azobisisobutyronitrile was changed to 2 · 5 parts. The method of obtaining a 20% strength acrylic resin solution, the viscosity of the obtained acrylic resin is 9 · 0 P a · s, the acrylic resin weight average molecular weight Mw is 1,360,000, Mw / Mn is 18_0, which is defined as acrylic resin A4. -38-200903054 [Polymerization Example 5] The same procedure as in Polymerization Example 3 except that the initial reaction temperature was changed from 65 °C to 7 Torr and the initial amount of azobisisobutyronitrile was changed to 0.25 parts. A 20% strength acrylic resin solution was obtained, and the obtained acrylic resin had a viscosity of 9.8 Pa·s. The acrylic resin had a weight average molecular weight Mw of 710,000 and Mw/Mn of 12.0. This was designated as acrylic resin A5. Next, an adhesive made of the above acrylic resin is used, and examples and comparative examples suitable for the optical film are listed. In the following examples, the isocyanate compound of the component (B), the aziridine compound of the component (C), and the decane compound of the component (D) are used as an isocyanate compound or an aziridine compound. For each of the crosslinking agents, the following is used (the name of the symbol " " is the trade name). (B) Isocyanate-based compound "CORONATE L": Ethyl acetate solution of toluene diisocyanate in trimethylol propyl acetate (solid content concentration of 7 5 %), taken from Japan Polyglycolic Acid Ethyl Acetate Industry (Shares), in Table 1 which is not disclosed below, this compound is simply referred to as "Cor-L". (C) Azacyclopropane-based compound "TAZM": tris-methylpropane tri-/5-oxacyclopropionate (liquid), obtained from mutual pharmaceuticals. "TAZO": a compound containing tetramethylol methane tri-/3-oxalylpropionate as a main component of tetramethylolethane tri-cold-oxopropyl propionate-39-200903054 (Liquid), obtained from mutual pharmaceuticals (shares). Other crosslinkers (epoxy crosslinkers) "TETRAD-C" : 1,3-bis(indole, fluorene-diepoxypropylaminomethyl) cyclohexane (liquid) from Mitsubishi Gas Chemical (share) obtained. (D) a decane-based compound "Χ-41-1805": an oligomer (liquid) of 3-mercaptopropyltrimethoxydecane and tetraethoxydecane having a weight average molecular weight of 2,000 and an anthracene equivalent of 8 〇〇g / Moer's obtained from Shin-Etsu Chemical Industry Co., Ltd. "S-810": 3-mercaptopropyltrimethoxydecane (liquid) obtained from CHISSO (stock). [Examples 1 and 2 and Comparative Examples 1 to 1] (a) The adhesive was produced by using acrylic resins A1 to A5 obtained in a polymerization example of 5% by weight in a nonvolatile content, and mixed therein. The adhesive solution was obtained according to the amount of the cross-linking agent (isocyanate-based or cyanide-based, azathiophene-based or epoxy-based) and the samarium compound represented by each of Table 1, and the adhesive solution was obtained. The amount (parts) of the isocyanate-based compound "CORONATE L" is the amount of the solid portion. Each adhesive solution was applied to a release-treated polyethylene terephthalate film ("PET 3 81 1", obtained from Lintec" as a separator) using a coater. Release treatment -40,030,040,54 The thickness after drying was 15#m or 25wm, and it was dried at 10CC for 1 minute to obtain a sheet-like adhesive. In Table 1, the coating film thickness and the gel fraction of each of the adhesives are also indicated by 倂. Table 1 Example No. Acrylic acid isocyanate-based crosslinking agent Aziridine-based epoxy decane compound Coating film Thick gel fraction Cor-L TAZM TAZO TETRAD-C Example 1 A1 2.0 parts 0.02 parts - 0.15 Part 1 15 80% 2 A2 2.0 parts 0.02 parts - 0.15 parts _ 15/zm 75% Comparative Example 1 A1 1.5 parts - 0.02 parts one - 0.3 parts 15 / / m 67% 2 A1 1-5 parts - 〇.〇 2 parts - 0.3 parts 25 jum 67% 3 A1 1_5 parts - 0.02 parts 0.3 parts 25 μ m 70% 4 A3 2.0 parts 0.02 parts - 0.15 parts \5 βΐΆ 75% 5 A3 2.25 parts - — — — 0.3 parts 25 /zm 63% 6 A3 1.5 parts - ~ 0.02 parts 0.3 parts 25/zm 72% 7 A3 1.5 parts - 0.02 parts - 0.3 parts 15 / m 71% 8 A3 1.5 parts - 0.02 parts - 0.3 parts 25 jim 71% 9 A4 2.0 parts 0.02 parts - 0.15 parts 15/zm 71% 10 A5 1.5 parts - 0.02 parts - 0.3 parts 25 βχη. 50% (b) Preparation of optical film with adhesive Preparation of norbornene-based resin film /Polyvinyl alcohol-based polarizing element / triacetyl cellulose protective film composed of a polarizing film 'hereene base tree On the surface of the lipid film, after the corona discharge treatment was applied under the conditions of an output power of 600 W and a moving speed of 1 (m/min), 'on the corona discharge treated surface, the laminator was used to adhere to the adhesive side. The adhesive of the separator sheet of the sheet-like type -41 - 200903054 obtained in the above (a) was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain a polarizing film with an adhesive. (c) Preparation of Optical Laminate The separator was peeled off from the polarizing film with an adhesive prepared in the above (b), and the adhesive layer side was adhered to the liquid crystal cell substrate [CORING Co., Ltd." 1 73 7 An optical laminate was produced by direct-polarization on both sides of "(trade name)]. (d) Evaluation of durability, etc. Each of the optical laminates obtained in the above (c) was subjected to a heat resistance test under a drying condition of 8 ° C for 300 hours to visually observe the whitening after each test. Performance status. In addition, when performing the above heat resistance test, when it is stored at a temperature of 60 ° C and a relative humidity of 90% for 300 hours, the temperature is lowered to -30 ° C from the state of heating to 70 ° C, and then the temperature is raised to 7 ° °. The process of C is called one cycle (1 hour), and when the thermal shock test of this cycle is repeated 100 times, the results of visual observation of the optical laminate after the test are classified according to the following criteria, and are collectively shown in Table 2. (Evaluation of the whitening performance state) The whitening performance state when light is incident from one of the polarizing film sides is evaluated in the following three stages. 〇: Whitening is almost inconspicuous. △: Whitening is slightly noticeable. -42 - 200903054 X: Whitening is obvious. (Evaluation of heat resistance, moist heat resistance, and thermal shock resistance (described as "HS resistance" in Table 2)) The optical laminates after each of the heat resistance test, the damp heat resistance test, and the thermal shock resistance test were subjected to the following three stages. Evaluation. 〇: The appearance change of floating, peeling, foaming, etc. is hardly seen. △: The appearance change of floating, peeling, foaming, etc. is slightly noticeable. X: The appearance of floating, peeling, foaming, etc. changes significantly. (e) Reworkability evaluation A polarizing film with an adhesive prepared in (b) was cut into a test piece of 25 mm x 150 mm in size, and the test piece was subjected to an adhesive device ["FIIPIPER" manufactured by FIjIPLA Co., Ltd. (trade name) )] adhered to a glass substrate for liquid crystal cell, and subjected to a pressure cooker treatment at a temperature of 50 ° C and a pressure of 5 kgf / cm 2 ( 490.3 kPa) for 20 minutes, followed by storage in an oven at 50 ° C for 48 hours - at a temperature of 23 ° C. In a gas atmosphere having a relative humidity of 50%, the adhesive test piece was peeled off at a speed of 300 mm/min in a 180° direction to observe the state of the surface of each glass substrate, and the results were evaluated according to the following criteria, and the results are shown together in the table. 2. 〇: There are almost no fog points on the surface of the glass plate. △: A fog point or the like was confirmed on the surface of the glass plate. X: Adhesive residue was confirmed on the surface of the glass plate. -43- 200903054 [Table 2] Example No. Composition Summary * Whitening heat resistance, heat resistance, HS resistance, reworkability Example 1 A1/aziridine/oligomer〇〇〇〇〇&quot;2 A2 /Azacyclopropane/oligomer 〇〇〇〇〇Comparative Example 1 A1/Aziridine/Monomer 〇〇〇Δ Δ 2 A1/Aziridine 浑Δ 〇Δ X &quot;3 A1 /epoxy steroid △ Δ Δ X &quot;4 A3/azetane/oligomer 〇Δ 〇Δ 〇〃 5 A painful 〇X 〇Δ X ” 6 A3/epoxy steroid 〇Δ 〇Δ X 7 A3/aziridine/monomer 〇Δ 〇Δ X v 8 A3/aziridine/monomer 〇Δ 〇Δ X &quot;9 A4/azetane/oligomer 〇Δ Δ X 〇 10 A5/aziridine/monomer 〇〇X Δ Δ Composition summary: It is represented by the type of acrylic resin/the type of crosslinking agent/sandane compound used for the isocyanate crosslinking agent. [Industrial Applicability] The optical film with an adhesive of the present invention is adhered to an optical laminate of a liquid crystal cell glass substrate, for example, even under high temperature conditions or under moist heat conditions, because of adhesion. The agent layer absorbs the stress caused by the dimensional change of the optical film and the glass substrate, and the local stress concentration is reduced, and the occurrence of floating or peeling of the adhesive layer on the glass substrate is suppressed, and since The optical defects caused by the uniform stress distribution, when the glass substrate is a TN liquid crystal cell, the whitening is suppressed, and when the STN liquid crystal cell is used, the color unevenness is suppressed. Further, since the optical film to which the adhesive is attached is excellent in reworkability, the optical film with the adhesive once attached to the glass substrate is peeled off from the glass substrate, and the glass substrate of the peeled glass-44-200903054 is removed. The generation of residual adhesive or fogging on the surface is suppressed, and it can be used as a glass substrate. Therefore, the optical film with an adhesive attached to the present invention or the optical laminate bonded to the glass substrate can be used to have a TN liquid crystal cell because it can suppress whitening even if it is enlarged in size, and is excellent in durability. Or a liquid crystal display device such as an STN liquid crystal cell. -45-

Claims (1)

200903054 X. Patent application scope 1. An optical film with an adhesive, which is formed by forming an adhesive layer on one side with an adhesive agent. The adhesive layer contains (A) the following formula (I) CH2= CC-〇-R2 II 〇 (wherein Ri represents a hydrogen atom or a methyl group; R 2 is independently substituted by an alkoxy group of 1 〇, and a structural unit derived from an alkyl group having 1 to 14 carbon atoms or a (meth) acrylate. It has a olefinic double bond having one molecule and at least a structural unit derived from a carboxylic acid, and has a weight ratio of 2F of 1,400,000 to 2,000,000, and a weight average molecular weight (?η) ratio (Mw/Mn) expressed as follows. The content of the first acrylic resin' unsaturated carboxylic acid is 100 parts by weight based on 1 part by weight of the total resin: (B) isocyanate compound 〇. 〇 5 to 5 weight (C) nitrogen heterocycle Propane-based compound 0 · 0 1 to 0 (D) at least an optical film having a polysiloxane-weighted optical film selected from the group consisting of a functional group such as a fluorenyl group and an epoxy oxy group; The special table can not be represented by the carbon number 1~ aralkyl group as the main component And the molecular weight distribution (Mw) of the carboxyl group containing one carboxyl group (Mw) and the molecular weight distribution of the number of squares are 0.5 to 10 parts by weight based on the structure of the acid derived from the acid; The composition of the group and the (meth) propylene oligomer 0 · 0 5~0.5 -46 - 200903054 is formed. 2. The optical film with an adhesive attached to the ninth aspect of the patent application, wherein the polyoxyalkylene oligomer (D) is a functional group-containing decane compound and a tetraalkoxy group represented by the following formula (Π) a co-oligomer of decane 'X (Π) R3O—Si—OR4 (wherein r3 and 114 each independently represent an alkyl group or a phenyl group; and X represents an alkyl group selected from the group consisting of an anthracenyl group, an epoxy group, and a (meth) propylene group. An organic group of a functional group of a decyloxy group; Y represents an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, an aralkyl group or a aryloxy group). 3. An optical film with an adhesive attached to claim 1, wherein the polyoxyalkylene oligomer (D) has at least an epoxy group in the molecule. 4) An optical film with an adhesive attached to the scope of the patent application, wherein the polyoxyalkylene oligomer (D) has at least a methoxy group and an ethoxy group in the molecule. The optical film with an adhesive according to any one of claims 1 to 4, wherein the functional group constituting the polyoxyalkylene oligomer (D) is a sulfhydryl group. The optical film with an adhesive according to any one of claims 1 to 4, wherein the optical film is protected by an acetaminocellulose-based protective film/polyvinyl alcohol-based polarizer/acetamethylene cellulose. The polarizing film formed by the constitution of the film forms the adhesive layer on the outer side thereof. -47-200903054 7 The optical film with an adhesive according to any one of claims 1 to 4 wherein the optical film comprises an amorphous cyclic polyolefin resin film/polyvinyl alcohol-based photon The polarizing film formed of the protective film is formed on the outer side of the amorphous cyclic polyolefin resin film. The optical film with an adhesive according to any one of claims 1 to 4, wherein the adhesive layer has a thickness of 10 to 20/zm. 9. An optical film with an adhesive attached to the first application of the patent scope, wherein a surface of the adhesive layer is adhered to the release film. An optical film comprising an adhesive according to any one of claims 1 to 4, which is attached to the glass substrate with the adhesive layer side. -48- 200903054 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the feature: none