JP5250307B2 - Adhesive optical film and image display device - Google Patents

Description

The present invention relates to an adhesive optical film and an image display device .

  Conventionally, optical films such as polarizing films, retardation films, brightness enhancement films, and viewing angle widening films have been used in various industrial applications, such as liquid crystal displays, organic electroluminescence devices (organic EL display devices), It is used by being attached to an image display device such as a plasma display panel (PDP).

  As such an optical film, an adhesive optical film in which an adhesive is laminated on an optical film is known. In the adhesive optical film, a solvent-type adhesive that uses an organic solvent as a solvent is usually used.

  On the other hand, in recent years, from the viewpoint of environmental impact, it is desired to reduce the use of organic solvents, and the conversion from a solvent-type adhesive to a water-dispersed adhesive that uses water as a dispersion medium is desired. .

  As such a water-dispersed pressure-sensitive adhesive, for example, a pressure-sensitive adhesive composition containing a copolymer emulsion, wherein the copolymer is 10 to 50% by weight of methacrylic acid 2- A pressure-sensitive adhesive composition in which ethylhexyl is copolymerized and the glass transition temperature of the copolymer is −25 ° C. or lower has been proposed (for example, see Patent Document 1).

  However, the conventional water-dispersed pressure-sensitive adhesives including Patent Document 1 as described above have improved adhesion to hydrophobic adherends such as polyolefins, but have particularly good adhesion to hydrophilic adherends such as glass. There is a problem that it is difficult to firmly adhere to a glass substrate such as an image display device.

Accordingly, an aqueous dispersion of an acrylic copolymer obtained by emulsion polymerization of butyl acrylate, acrylic acid and 3-methacryloyloxypropyltrimethoxysilane as a water-dispersible pressure-sensitive adhesive having transparency and applicable to glass A water-dispersed acrylic pressure-sensitive adhesive composition obtained by mixing a smectite-based layered clay mineral aqueous dispersion has been proposed (see, for example, Patent Document 2).
JP 2001-254063 A JP 2006-316085 A

  However, although the water-dispersed acrylic pressure-sensitive adhesive composition described in Patent Document 2 can ensure adhesion to glass, it has slightly low adhesion (heat-resistant adhesion) in a high-temperature atmosphere, and is therefore applicable to optical films. There is a limit to it.

  An object of the present invention is a pressure-sensitive adhesive composition having a high adhesiveness to an optical film, having heat resistance and moisture resistance, and excellent in transparency, and a pressure-sensitive adhesive type comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition An object is to provide an optical film and an image display device using the same.

  In order to achieve the above object, the pressure-sensitive adhesive composition of the present invention comprises a (meth) acrylic acid alkyl ester having a C 4-18 alkyl group, a carboxyl group-containing vinyl monomer, and a phosphate group-containing vinyl monomer. A monomer component containing as an optional component a copolymerizable vinyl monomer that is copolymerizable with the essential component and contained as an essential component, the (meth) acrylic acid alkyl ester is 60 to 100 parts by weight of the monomer component. 99 parts by weight, and the total amount of the carboxyl group-containing vinyl monomer, the phosphate group-containing vinyl monomer, and the copolymerizable vinyl monomer is 1 to 40 parts by weight, and the carboxyl group concentration in the monomer component is 0.05. ˜1.50 mmol / g and the phosphate group concentration is 0.01 to 0.45 mmol / g A copolymer obtained by producing and polymerizing, and a clay mineral are contained so that the clay mineral is 0.5 to 10 parts by weight with respect to 100 parts by weight of the copolymer. It is said.

  In addition, the pressure-sensitive adhesive composition of the present invention further comprises 0.1 to 5 parts by weight of a phosphate dispersant and / or 0.1 of a polycarboxylate dispersant with respect to 100 parts by weight of the copolymer. It is preferable to contain -5 weight part.

  In the pressure-sensitive adhesive composition of the present invention, the carboxyl group-containing vinyl monomer is 0.5 to 15 parts by weight and the phosphate group-containing vinyl monomer is 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer component. Part of the copolymerizable vinyl monomer is preferably 39 parts by weight or less.

  Moreover, in the adhesive composition of this invention, it is suitable to contain 0.001-1 weight part of alkoxy silyl group containing vinyl monomers as said copolymerizable vinyl monomer with respect to 100 weight parts of said monomer components. is there.

  The pressure-sensitive adhesive composition of the present invention is preferably water-dispersed.

  In the pressure-sensitive adhesive composition of the present invention, it is preferable that the clay mineral is smectite.

  In the pressure-sensitive adhesive composition of the present invention, it is preferable that the clay mineral includes an organically treated clay mineral.

  In the pressure-sensitive adhesive composition of the present invention, it is preferable that the organically treated clay mineral is organically treated with an organic cation having a hydrophilic functional group.

  In the pressure-sensitive adhesive composition of the present invention, it is preferable that the organic cation having the hydrophilic functional group is a quaternary ammonium salt having a hydroxyl group.

  The pressure-sensitive adhesive composition of the present invention includes an aqueous dispersion obtained by dispersing the clay mineral in water in which the phosphate dispersant and / or the polycarboxylate dispersant is blended. It is preferably obtained by blending with an aqueous dispersion of the copolymer.

  The pressure-sensitive adhesive optical film of the present invention comprises an optical film, a pressure-sensitive adhesive layer laminated on at least one surface of the optical film, and an undercoat layer interposed between the optical film and the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer is characterized by comprising the above-mentioned pressure-sensitive adhesive composition.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the undercoat layer contains an oxazoline group-containing polymer.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the undercoat layer contains a water-soluble or water-dispersible conductive material.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the undercoat layer contains a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the undercoat layer contains a mixture of an oxazoline group-containing polymer and a water-soluble or water-dispersible conductive material.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the undercoat layer contains a mixture of an oxazoline group-containing polymer and a polyamine polymer.

  In the pressure-sensitive adhesive optical film of the present invention, the undercoat layer preferably contains a mixture of an oxazoline group-containing polymer, a compound containing a plurality of carboxyl groups, and a water-soluble or water-dispersible conductive material. It is.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the water-soluble or water-dispersible conductive material is a conductive polymer.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the conductive polymer is polyaniline and / or polythiophene.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the water-soluble or water-dispersible conductive material is an organometallic compound.

  In the pressure-sensitive adhesive optical film of the present invention, it is preferable that the organometallic compound is at least one selected from the group consisting of an organozirconium compound, an organotitanium compound, and an organoaluminum compound.

  The image display device of the present invention is characterized by using at least one of the above-mentioned adhesive optical films.

  Since the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has high adhesion to the optical film, in the pressure-sensitive adhesive optical film of the present invention having the pressure-sensitive adhesive layer, the optical film and the substrate are firmly bonded. Can be achieved.

  Moreover, the pressure-sensitive adhesive optical film of the present invention is excellent in transparency. Furthermore, since it has high heat resistance and moisture resistance, it is possible to obtain an excellent adhesive force with a substrate in a high temperature atmosphere or a high humidity atmosphere.

  Therefore, the image display device of the present invention in which the pressure-sensitive adhesive optical film of the present invention is used can obtain a good appearance, and can realize high heat resistance and moisture resistance.

  The pressure-sensitive adhesive composition of the present invention contains a copolymer obtained by preparing and polymerizing monomer components and a clay mineral.

  The monomer component contains a (meth) acrylic acid alkyl ester, a carboxyl group-containing vinyl monomer and a phosphate group-containing vinyl monomer as essential components, and a copolymerizable vinyl monomer copolymerizable with the essential component as an optional component. Yes.

  The (meth) acrylic acid alkyl ester is, for example, a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms and having a linear or branched alkyl group (methacrylic acid alkyl ester and / or acrylic acid alkyl ester), Preferably, it is a (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms and having a linear or branched alkyl group. Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 4 to 18 carbon atoms include, for example, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and (meth) acrylic. T-butyl acid, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meta ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate , Dodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) acrylic Acid tetradecyl, (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl and the like (meth) octadecyl acrylate. Preferably, butyl acrylate is used. These alkyl (meth) acrylates can be used alone or in combination of two or more.

  The compounding ratio of the (meth) acrylic acid alkyl ester is 60 to 99 parts by weight, preferably 70 to 99 parts by weight, and more preferably 80 to 99 parts by weight with respect to 100 parts by weight of the monomer component.

  The carboxyl group-containing vinyl monomer is a vinyl monomer for introducing a crosslinking point (carboxyl group) for thermal crosslinking to improve the adhesion of the pressure-sensitive adhesive layer (described later) to the substrate. Vinyl monomer having a group. Examples of the carboxyl group-containing vinyl monomer include unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid and cinnamic acid, such as monomethyl itaconate, monobutyl itaconate, 2- Unsaturated dicarboxylic acid monoesters such as acryloyloxyethylphthalic acid, for example, unsaturated tricarboxylic acid monoesters such as 2-methacryloyloxyethyl trimellitic acid, 2-methacryloyloxyethyl pyromellitic acid, such as carboxyethyl acrylate (β- And carboxyalkyl acrylates such as carboxypentyl acrylate.

  Examples of the carboxyl group-containing vinyl monomer also include unsaturated dicarboxylic acid anhydrides such as itaconic anhydride, maleic anhydride, and fumaric anhydride.

  These carboxyl group-containing vinyl monomers can be used alone or in combination of two or more.

  Of these carboxyl group-containing vinyl monomers, acrylic acid and carboxyethyl acrylate are preferable.

  The carboxyl group concentration of the carboxyl group-containing vinyl monomer is 0.05 to 1.50 mmol / g, preferably 0.20 to 0.90 mmol / g in the monomer component. To bring the carboxyl group concentration of the carboxyl group-containing vinyl monomer into the above-mentioned range, although depending on the molecular weight of the carboxyl group-containing vinyl monomer, the blending ratio of the carboxyl group-containing vinyl monomer is based on 100 parts by weight of the monomer component. For example, it is set to 0.4 to 41 parts by weight, preferably 1.4 to 25 parts by weight. The mixing ratio of the carboxyl group-containing vinyl monomer is, for example, 0.5 to 15 parts by weight, preferably 0.5 to 10 parts by weight, within the above-mentioned range of the carboxyl group concentration with respect to 100 parts by weight of the monomer component. It can also be set to a part. When the amount is less than the above range, the stability during polymerization and the cohesive force of the pressure-sensitive adhesive composition are lowered, and when it is larger than the above range, the water resistance of the pressure-sensitive adhesive composition may be lowered.

  The carboxyl group concentration of the carboxyl group-containing vinyl monomer is calculated by the following formula.

Carboxyl group concentration [mmole / g] = 1000 × {(blended weight of carboxyl group-containing vinyl monomer [g]) / (molecular weight of carboxyl group-containing vinyl monomer [g / mol])} / (monomer component weight [g])
Since such a carboxyl group-containing vinyl monomer is contained in the monomer component, when the undercoat layer contains an oxazoline group-containing polymer or polyamine polymer, it reacts efficiently with these oxazoline groups or amino groups, The adhesive force between the pressure-sensitive adhesive layer and the optical film can be increased.

  The phosphoric acid group-containing vinyl monomer is, for example, a polyalkylene oxide (meth) acrylate phosphate ester represented by the following general formula (1):

(In general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a polyoxyalkylene group, and X represents a phosphoric acid group or a salt thereof.)
The polyoxyalkylene group represented by R ² is represented by the following general formula (2),

(In general formula (2), n represents an integer of 1 to 4, and m represents an integer of 2 or more.)
For example, a polyoxyethylene group (corresponding to n = 2 in the general formula (2)), a polyoxypropylene group (corresponding to n = 3 in the general formula (2)) and a random, block or graft unit thereof. The degree of polymerization of these oxyalkylene groups, that is, in the general formula (2), m is preferably 4 or more and usually 40 or less.

  Further, the phosphate group represented by X or a salt thereof is represented by the following general formula (3),

(In General Formula (3), M ¹ and M ² each independently represent a hydrogen atom or a cation.)
The cation is not particularly limited, and examples thereof include inorganic cations such as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and organic cations such as quaternary amines.

  Moreover, what is generally marketed can be used for the phosphoric acid group containing vinyl monomer, for example, Sipomer PAM-100 (made by Rhodia Nikka), Phosmer PE (made by Unichemical), Phosmer PEH (Unichemical) Mono [poly (ethylene oxide) methacrylate] phosphate esters such as Phosmer PEDM (Unichemical), for example, Sipomer PAM-200 (Rhodia Nikka), Phosmer PP (Unichemical), Phosmer Examples include mono [poly (propylene oxide) methacrylate] phosphoric acid esters such as PPH (manufactured by Unichemical) and Phosmer PPDM (manufactured by Unichemical).

  These phosphate group-containing vinyl monomers can be used alone or in combination of two or more.

  The phosphate group concentration of the phosphate group-containing vinyl monomer is 0.01 to 0.45 mmol / g, preferably 0.02 to 0.20 mmol / g in the monomer component. In order to make the phosphoric acid group concentration of the phosphoric acid group-containing vinyl monomer within the above-mentioned range, although depending on the molecular weight of the phosphoric acid group-containing vinyl monomer, the proportion of the phosphoric acid group-containing vinyl monomer is 100 parts by weight of the monomer component. For example, 0.4 to 22 parts by weight, preferably 0.8 to 10 parts by weight is set. The blending ratio of the phosphate group-containing vinyl monomer is, for example, 0.5 to 20 parts by weight, preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the monomer component. It can also be set to 10 parts by weight. When the amount is less than the above range, the heat resistant adhesiveness (adhesiveness in a high temperature atmosphere) is lowered. When the amount is more than the above range, the stability during polymerization is lowered, or the elastic modulus of the pressure-sensitive adhesive composition is excessively high. As a result, the adhesiveness may decrease.

  The phosphate group concentration of the phosphate group-containing vinyl monomer is calculated by the following formula.

Phosphate group concentration [mmol / g] = 1000 × {(Blend weight of phosphate group-containing vinyl monomer [g]) / (Molecular weight of phosphate group-containing vinyl monomer [g / mol])} / (Monomer component weight [ g])
Examples of the copolymerizable vinyl monomer include functional group-containing vinyl monomers other than carboxyl group-containing vinyl monomers.

  Examples of such functional group-containing vinyl monomers include vinyl acetate, vinyl propionate and other carboxylic acid vinyl esters, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, and the like. Hydroxyl group-containing vinyl monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N- Amide group-containing unsaturated monomers such as methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-vinylcarboxylic acid amide, for example, aminoethyl (meth) acrylate, ( Me ) Amino group-containing unsaturated monomers such as N, N-dimethylaminoethyl acrylate and (meth) acrylic t-butylaminoethyl, for example, glycidyl groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate Unsaturated monomers, for example, cyano group-containing unsaturated monomers such as acrylonitrile and methacrylonitrile, for example, isocyanate group-containing unsaturated monomers such as 2-methacryloyloxyethyl isocyanate, such as styrene sulfonic acid, allyl sulfonic acid, 2- ( Sulfonic acid group-containing unsaturated monomers such as (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid, examples For example, maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octyl Itaconimide monomers such as itaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxy Succinimide monomers such as hexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide, such as polyethylene glycol (meth) acrylate, (meth) acrylic acid Examples include glycol-based acrylic ester monomers such as polypropylene glycol silylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate.

  Furthermore, a polyfunctional monomer is mentioned as an above-described functional group containing vinyl monomer.

Examples of the multifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetraethylene glycol di (meth) acrylate. (Mono or poly) alkylene glycol di (meth) such as (mono or poly) ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate In addition to acrylate, neopentyl glycol di (meth) acrylate, 1,
Of polyhydric alcohols such as 6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate ( Examples include (meth) acrylic acid ester monomers such as divinylbenzene. Examples of the polyfunctional monomer include epoxy acrylate, polyester acrylate, and urethane acrylate.

  In addition to the above functional group-containing vinyl monomers, examples of the copolymerizable vinyl monomer include aromatic vinyl monomers such as styrene and vinyltoluene, such as cyclopentyl di (meth) acrylate and cyclohexyl (meth) acrylate. (Meth) acrylic acid alicyclic hydrocarbon esters such as (meth) acrylic acid bornyl, isobornyl (meth) acrylic acid, for example, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, for example (meta ) Alkoxy group-containing unsaturated monomers such as methoxyethyl acrylate and ethoxyethyl (meth) acrylate, for example, olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene, for example, vinyl ether monomers such as vinyl ether, Halogen-containing unsaturated monomers such as vinyl chloride, and others such as N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, Vinyl group-containing heterocyclic compounds such as N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, tetrahydrofurfuryl (meth) acrylate, such as fluorine (meth) acrylate And acrylate monomers containing halogen atoms such as fluorine atoms.

  Furthermore, examples of the copolymerizable vinyl monomer include alkoxysilyl group-containing vinyl monomers. Examples of the alkoxysilyl group-containing vinyl monomer include silicone-based (meth) acrylate monomers and silicone-based vinyl monomers.

  Examples of the silicone-based (meth) acrylate monomer include (meth) acryloyloxymethyl-trimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-trimethoxysilane, 2- ( (Meth) acryloyloxyethyl-triethoxysilane, 3- (meth) acryloyloxypropyl-trimethoxysilane, 3- (meth) acryloyloxypropyl-triethoxysilane, 3- (meth) acryloyloxypropyl-tripropoxysilane, 3 -(Meth) acryloyloxypropyl-trialkoxysilane, such as (meth) acryloyloxypropyl-triisopropoxysilane, 3- (meth) acryloyloxypropyl-tributoxysilane, Acryloyloxymethyl-methyldimethoxysilane, (meth) acryloyloxymethyl-methyldiethoxysilane, 2- (meth) acryloyloxyethyl-methyldimethoxysilane, 2- (meth) acryloyloxyethyl-methyldiethoxysilane, 3- ( (Meth) acryloyloxypropyl-methyldimethoxysilane, 3- (meth) acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyloxypropyl-methyldipropoxysilane, 3- (meth) acryloyloxypropyl-methyldiiso Propoxysilane, 3- (meth) acryloyloxypropyl-methyldibutoxysilane, 3- (meth) acryloyloxypropyl-ethyldimethoxysilane, 3- (meth) acryloyloxypropyl- Tildiethoxysilane, 3- (meth) acryloyloxypropyl-ethyldipropoxysilane, 3- (meth) acryloyloxypropyl-ethyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-ethyldibutoxysilane, 3- (Meth) acryloyloxypropyl-propyldimethoxysilane, (meth) acryloyloxyalkyl-alkyldialkoxysilane such as 3- (meth) acryloyloxypropyl-propyldiethoxysilane, and (meth) acryloyloxyalkyl- corresponding to these Examples thereof include dialkyl (mono) alkoxysilane.

  Examples of the silicone-based vinyl monomer include vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, and vinyl corresponding to these. Alkyldialkoxysilanes and vinyldialkylalkoxysilanes such as vinylmethyltrimethoxysilane, vinylmethyltriethoxysilane, β-vinylethyltrimethoxysilane, β-vinylethyltriethoxysilane, γ-vinylpropyltrimethoxysilane, γ -Vinylalkyl such as vinylpropyltriethoxysilane, γ-vinylpropyltripropoxysilane, γ-vinylpropyltriisopropoxysilane, γ-vinylpropyltributoxysilane Another trialkoxysilane, these correspond and (vinyl) alkyl dialkoxy silanes, and the like (vinyl alkyl) dialkyl (mono) alkoxysilanes.

  These copolymerizable vinyl monomers can be used alone or in combination of two or more.

  Of these copolymerizable vinyl monomers, an alkoxysilyl group-containing vinyl monomer is preferable.

  By using an alkoxysilyl group-containing vinyl monomer as the copolymerizable vinyl monomer, an alkoxysilyl group is introduced into the polymer chain, and a cross-linked structure can be formed by a reaction between them. In particular, in a water-dispersed pressure-sensitive adhesive composition, the cross-linking agent described later has a non-uniform cross-linking structure, and terminal peeling is likely to occur. However, when an alkoxysilyl group-containing monomer is used, a uniform cross-linked structure can be formed, so that adhesion and fixation to a substrate can be improved. In addition, the alkoxysilyl group can interact with the glass substrate to enhance the adhesion to the glass substrate.

  The copolymerizable vinyl monomer is optionally blended as necessary, and the blending ratio is, for example, 39 parts by weight or less, preferably 30 parts by weight or less, and more preferably 20 parts by weight with respect to 100 parts by weight of the monomer component. Or less. Moreover, when a copolymerizable vinyl monomer is a functional group containing vinyl monomer, the compounding ratio is 0.5-12 weight part with respect to 100 weight part of monomer components, Preferably, it is 1-8. Parts by weight. Further, when the copolymerizable vinyl monomer is an alkoxysilyl group-containing vinyl monomer, the blending ratio is, for example, 0.001 to 1 part by weight, preferably 0.01 to 100 parts by weight of the monomer component. -0.1 parts by weight. If the amount of the alkoxysilyl group-containing vinyl monomer is less than the above range, crosslinking by the alkoxysilyl group is insufficient, leading to a decrease in the cohesive force of the adhesive composition, or an improvement in the adhesion between the adhesive composition and the substrate. If the amount is more than the above range, stability during polymerization and adhesion may be reduced.

  In addition, among the monomer components described above, the total amount of the carboxyl group-containing vinyl monomer, the phosphate group-containing vinyl monomer, and the copolymerizable vinyl monomer is 1 to 40 with respect to 100 parts by weight of the monomer component. Part by weight, preferably 1 to 30 parts by weight.

  And in order to polymerize a monomer component and to obtain a copolymer, the monomer component prepared by said mixing | blending ratio is copolymerized by polymerization methods, such as emulsion polymerization, for example.

  In emulsion polymerization, for example, a polymerization initiator, an emulsifier, and, if necessary, a chain transfer agent are blended in water together with the above-described monomer components for copolymerization. More specifically, for example, known emulsion polymerization methods such as a batch charging method (batch polymerization method), a monomer dropping method, and a monomer emulsion dropping method can be employed. In the monomer dropping method, continuous dropping or divided dropping is selected. Although reaction conditions etc. are selected, polymerization temperature is 20-100 degreeC, for example.

  The dissolved oxygen concentration in the monomer component solution can also be reduced by nitrogen substitution before, while or after the polymerization initiator is mixed with the monomer component.

  The polymerization initiator is not particularly limited, and a polymerization initiator usually used for emulsion polymerization is used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2, 2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis (N, N Azo initiators such as' -dimethyleneisobutylamidine), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, for example, persulfate such as potassium persulfate and ammonium persulfate Salt-based initiators, for example, peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide, for example, substituted ethers such as phenyl-substituted ethane. For example, carbonyl initiators such as aromatic carbonyl compounds, redox initiators such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc. It is done.

  These polymerization initiators can be used alone or in combination of two or more. Of these polymerization initiators, an azo initiator is preferably used.

  The blending ratio of the polymerization initiator is selected, and is, for example, 0.05 to 1 part by weight with respect to 100 parts by weight of the monomer component.

  The emulsifier is not particularly limited, and a known emulsifier usually used for emulsion polymerization is used. For example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene Anionic emulsifiers such as sodium alkylsulfosuccinate, for example, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene polyoxypropylene block polymer.

  In addition, radically polymerizable (reactive) emulsifiers (for example, HS-10 (No. 1), in which radically polymerizable functional groups (reactive groups) such as propenyl groups and allyl ether groups are introduced into these anionic and nonionic emulsifiers. Ichikogaku Pharmaceutical Co., Ltd.)).

  These emulsifiers can be used alone or in combination of two or more. Moreover, the mixture ratio of an emulsifier is 0.2-10 weight part with respect to 100 weight part of monomer components, Preferably, it is 0.5-5 weight part.

  The chain transfer agent is blended as necessary to adjust the molecular weight of the copolymer, and a chain transfer agent usually used for emulsion polymerization is used. Examples thereof include mercaptans such as 1-dodecanethiol, mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl thioglycolate, and 2,3-dimethylcapto-1-propanol.

  These chain transfer agents can be used alone or in combination of two or more. Moreover, the mixture ratio of a chain transfer agent is 0.001-0.5 weight part with respect to 100 weight part of monomer components, for example.

  And the copolymer obtained by such emulsion polymerization can be prepared as an emulsion, ie, the aqueous dispersion of a copolymer.

  The aqueous dispersion of the copolymer may be prepared, for example, by polymerizing the above-described monomer component by a method that does not use an organic solvent other than emulsion polymerization and then dispersing it in water using the above-described emulsifier. it can.

  Such a copolymer has a gel fraction (gel fraction of the solid content of the emulsion) of, for example, 50 to 100% by weight, preferably 70 to 100% by weight. When the gel fraction is lower than the above value, when an aqueous dispersion type adhesive composition comprising an aqueous dispersion of a copolymer is applied to an adhesive type optical film and used in a high temperature and high humidity atmosphere, foaming occurs. May cause peeling.

  Examples of the clay mineral include smectite, that is, a phyllosilicate mineral that is a montmorillonite group mineral and has a layered structure. Examples of smectites include montmorillonite, magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite (saponite), and aluminian support. Stones, hectorites, soconites, steven sites, etc. These clay minerals can be used alone or in combination of two or more.

  The clay mineral is preferably organically treated and has an organically treated portion. The organically treated portion is a portion in the crystal structure, that is, a cation between layers is hydrophobized (lipophilicized) with a cationic dispersant or the like.

  The cation of the clay mineral is an exchangeable cation, for example, a metal cation such as sodium ion or calcium ion present on the surface of the crystal layer of the layered clay mineral.

Examples of the cationic dispersant include quaternary ammonium salts and quaternary phosnium salts, and preferably quaternary ammonium salts. The quaternary ammonium salt includes a cation in which a hydrogen atom of an ammonium ion (NH ⁴⁺ ) is substituted with a propylene oxide skeleton, an ethylene oxide skeleton, an alkyl skeleton, or the like, and an anion such as a halide ion (for example, a chloride ion). And the salt. The cation preferably has a hydrophilic functional group such as a hydroxyl group at the terminal. More specifically, examples of the cationic dispersant include quaternary ammonium salts having a propylene oxide skeleton having a hydroxyl group at the terminal. The cationic dispersants can be used alone or in combination of two or more.

  As the clay mineral having such an organically treated portion, a general commercially available product is usually used, for example, Lucentite series (manufactured by Co-op Chemical Co.), and more specifically, Lucentite SPN, Examples include Lucentite SAN, Lucentite SEN, and Lucentite STN.

  The ratio of the organically treated portion in the clay mineral is not particularly limited, and for example, 80 to 240 mol eq. / 100g.

  Since the cation of clay mineral is usually hydrophilic, it has hydrophobicity (lipophilicity) between clay mineral layers by having an organic (hydrophobic) treatment part, and swells the clay mineral. It is possible to prevent gelation in water and ensure dispersion in the emulsion.

  As for the size of the clay mineral, the thickness is, for example, 1 to 100 nm, and the length (maximum length) is 500 nm or less, preferably 100 nm or less. When the maximum length of the clay mineral exceeds the above range, the transparency may be lowered.

  The blending ratio of the clay mineral (clay component, that is, the part other than the part subjected to the organic treatment in the clay mineral) is 0.5 to 10% by weight with respect to 100 parts by weight of the copolymer (that is, the solid content of the emulsion). Parts, preferably 1 to 8 parts by weight, more preferably 1 to 5 parts by weight. When the blending ratio of the clay mineral exceeds the above range, the transparency is lowered and a good appearance cannot be obtained. On the other hand, when the blending ratio of the clay mineral is less than the above-described range, it is impossible to improve the adhesiveness of the pressure-sensitive adhesive layer to the substrate, particularly, the adhesiveness in a high-temperature and high-humidity atmosphere.

  By adding clay mineral to the pressure-sensitive adhesive composition, it is possible to improve the adhesiveness of the pressure-sensitive adhesive layer to the substrate, in particular, the adhesiveness in a high-temperature and high-humidity atmosphere.

  And in order to prepare the adhesive composition of this invention, a copolymer and a clay mineral are mix | blended. For example, an aqueous dispersion of clay mineral is prepared, and the aqueous dispersion of clay mineral and the aqueous dispersion of copolymer are mixed.

  In order to prepare an aqueous dispersion of clay mineral, for example, the clay mineral is blended in water or water containing a dispersant if necessary. Thereafter, the clay mineral is dispersed in water using a disperser.

  The dispersant is blended in order to efficiently disperse the clay mineral in water, and examples thereof include a polymer dispersant or a low molecular dispersant, and preferably a low molecular dispersant. If it is a low molecular weight dispersing agent, it will easily enter between the particles of the agglomerated (secondary agglomerated) clay mineral, and the particles can be crushed and efficiently dispersed. Moreover, since it is easy to adsorb | suck also to the clay mineral particle | grains (primary particle) if it is a low molecular dispersant, aggregation of the clay mineral particle | grains can be suppressed by the repulsive force between the low molecular dispersants adsorb | sucked to particle | grains.

  Examples of the low molecular weight dispersant include an anionic dispersant, and preferably a phosphate dispersant and a polycarboxylate dispersant.

  Examples of phosphate dispersants include phosphates of metal cations such as sodium and phosphoric acid, and more specifically, sodium orthophosphate, sodium pyrophosphate (sodium diphosphate), tripolyphosphorus Examples thereof include sodium phosphate (sodium triphosphate), sodium tetraphosphate, sodium hexametaphosphate, sodium polyphosphate, trisodium phosphate, and sodium dihydrogen phosphate. Preferably, sodium hexametaphosphate is mentioned. These phosphate dispersants can be used alone or in combination of two or more.

  As the polycarboxylate-based dispersant, for example, an inorganic cation (metal cation) such as sodium, an organic cation such as ammonium, and a carboxylate polymer of carboxylic acid, more specifically, Examples thereof include sodium poly (meth) acrylate, ammonium poly (meth) acrylate, sodium acrylate / sodium maleate copolymer, ammonium acrylate / ammonium maleate copolymer, and the like. These polycarboxylate-based dispersants can be used alone or in combination of two or more.

  When the polycarboxylate-based dispersant is prepared in an aqueous dispersion or an aqueous solution, the content of the carboxyl anion is, for example, 4 to 10 mmol / g (weight of the polycarboxylate-based dispersant). In addition, content of the carboxyl anion of a polycarboxylate-type dispersing agent is calculated | required by neutralization titration.

  Further, the surface tension of a 1% aqueous solution of the polycarboxylate-based dispersant at 20 ° C. is, for example, 70 mN / m or more, and usually 73 mN / m or less.

  These dispersants can be used alone or in combination of two or more.

  If a phosphate dispersant and / or a polycarboxylate dispersant is used as the dispersant, it is possible to prevent re-aggregation of the clay mineral dispersed by the dispersing device.

  When the dispersant is a phosphate-based dispersant, the blending ratio of the dispersant is, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (solid content of the emulsion). The amount is preferably 0.3 to 3 parts by weight, more preferably 0.4 to 2 parts by weight, and particularly preferably 0.5 to 2 parts by weight. Moreover, the blending ratio of the phosphate dispersant is set to, for example, 1 to 200 parts by weight, preferably 2 to 100 parts by weight, and more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the clay mineral. You can also When the blending ratio of the phosphate dispersant exceeds the above range, the dispersibility of the clay mineral may be lowered. On the other hand, when the blending ratio of the phosphate-based dispersant is less than the above range, the effect of dispersion stability may be reduced and aggregates may be generated.

  Moreover, when a dispersing agent is a polycarboxylate-type dispersing agent, the mixture ratio is 0.1-5 weight part with respect to 100 weight part of copolymers (solid content of an emulsion), for example, Preferably Is 0.3 to 3 parts by weight, more preferably 0.4 to 2 parts by weight, and particularly preferably 0.5 to 2 parts by weight. The blending ratio of the polycarboxylate-based dispersant is, for example, 1 to 200 parts by weight, preferably 2 to 100 parts by weight, and more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the clay mineral. It can also be set. If the blending ratio of the polycarboxylate dispersant exceeds the above range, the dispersibility of the clay mineral may be lowered. On the other hand, when the blending ratio of the polycarboxylate-based dispersant is less than the above-described range, the effect of dispersion stability may be reduced and aggregates may be generated.

  As the disperser, for example, a disperser such as an ultrasonic disperser, a homomixer, or a high-pressure homogenizer is used.

  Then, as described above, by mixing the clay mineral aqueous dispersion and the copolymer aqueous dispersion, the pressure-sensitive adhesive composition of the present invention is converted into an emulsion, that is, a water-dispersed pressure-sensitive adhesive composition. Can be obtained.

  The pressure-sensitive adhesive composition includes, for example, a viscosity modifier, a cross-linking agent, and if necessary, a release modifier, a plasticizer, a softener, a filler, a colorant (pigment, dye, etc.), an anti-aging agent, an interface Additives such as activators can be added. The mixing ratio of these additives is not particularly limited and can be selected.

  The viscosity modifier is not particularly limited, and examples thereof include an acrylic thickener.

  Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents are not particularly limited, and oil-soluble or water-soluble crosslinking agents are used. These crosslinking agents are suitably used alone or in combination, and the blending ratio thereof is, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the emulsion.

  Hereinafter, with reference to FIG. 1, the manufacturing method of the adhesive optical film which is one Embodiment of the adhesive optical film of this invention is demonstrated.

  The pressure-sensitive adhesive optical film of the present invention comprises an optical film 1, a pressure-sensitive adhesive layer 3 laminated on at least one surface of the optical film 1, and an undercoat layer 2 interposed between the optical film 1 and the pressure-sensitive adhesive layer 3. I have.

  The optical film 1 is not particularly limited as long as it has optical characteristics and is attached to a liquid crystal display, and examples thereof include a polarizing film, a retardation film, a brightness enhancement film, and a viewing angle widening film. .

  As a polarizing film, what provided the transparent protective film on the single side | surface or both surfaces of a polarizer is used.

  The polarizer is not particularly limited, and examples thereof include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, ethylene / vinyl acetate copolymer partially saponified films, iodine and dichroism. Examples thereof include uniaxially stretched films dyed with dichroic substances such as dyes, and polyene-based oriented films such as polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Preferably, a polarizer obtained by uniaxially stretching a polyvinyl alcohol film with iodine is used.

  Examples of the transparent protective film include polyester polymer films such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymer films such as diacetyl cellulose and triacetyl cellulose, acrylic polymer films such as polymethyl methacrylate, polystyrene, acrylonitrile and styrene. Examples thereof include a styrene polymer film such as a polymer (AS resin), and a polycarbonate polymer film. In addition, polyethylene, polypropylene, polyolefin having a cyclo or norbornene structure, polyolefin polymer film such as ethylene / propylene copolymer, vinyl chloride polymer film, nylon, amide polymer film such as aromatic polyamide, imide polymer film, Sulfone polymer film, polyether sulfone polymer film, polyether ether ketone polymer film, polyphenylene sulfide polymer film, vinyl alcohol polymer film, vinylidene chloride polymer film, vinyl butyral polymer film, arylate polymer film, poly Of oxymethylene-based polymer film, epoxy-based polymer film, or blends of the above-mentioned polymers Irumu also include such.

  The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

  As a transparent protective film, Preferably, a cellulose polymer is mentioned. The thickness in particular of a transparent protective film is not restrict | limited, For example, it is 500 micrometers or less, Preferably, it is 1-300 micrometers, More preferably, it is 5-200 micrometers.

  In order to bond the polarizer and the transparent protective film, for example, an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based adhesive, a latex-based adhesive, a water-based polyester adhesive, or the like is used. Glue.

  Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer supported by the film. The thickness of the retardation film is not particularly limited and is, for example, 20 to 150 μm.

  Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyarylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Polyphenylene sulfide, polyphenylene oxide, polyallylsulfone, polyvinyl alcohol, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose polymer, or binary, ternary copolymers, graft copolymers, blends Such as things. These polymer materials become an oriented product (stretched film) by stretching or the like.

  Examples of the liquid crystalline polymer include various main chain types and side chain types in which a conjugated linear atomic group (mesogen) imparting liquid crystal orientation is introduced into the main chain or side chain of the polymer. It is done. As the main chain type liquid crystalline polymer, for example, a structure in which a mesogenic group is bonded at a spacer portion imparting flexibility, specifically, a nematic orientation polyester-based liquid crystalline polymer, a discotic polymer or a cholesteric polymer. Etc. As the side chain type liquid crystalline polymer, for example, polysiloxane, polyacrylate, polymethacrylate or polymalonate is used as the main chain skeleton, and the side chain is substituted by a nematic orientation-imparting para-substitution through a spacer portion composed of a conjugated atomic group. Examples thereof include those having a mesogenic part composed of a cyclic compound unit. These liquid crystalline polymers are prepared by, for example, applying a solution of a liquid crystalline polymer on an alignment-treated surface such as a surface of a thin film such as polyimide or polyvinyl alcohol formed on a glass plate, or an oblique deposition of silicon oxide. It is obtained by developing and heat treatment.

  In addition, the retardation film may be, for example, a film for the purpose of expanding coloring or viewing angle due to birefringence of various wavelength films or liquid crystal layers, or may have a retardation depending on the purpose of use. What laminated | stacked the retardation film of the seed | species or more and controlled optical characteristics, such as retardation, may be used.

  Examples of brightness enhancement films are those that transmit linearly polarized light with a predetermined polarization axis and reflect other light, such as dielectric multilayer thin films and multilayer laminates of thin film films with different refractive index anisotropies. , Cholesteric liquid crystal polymer alignment films and those whose alignment liquid crystal layer is supported on a film substrate, such as those that reflect either left-handed or right-handed circularly polarized light and transmit other light, etc. Is mentioned.

  The viewing angle widening film is a film that widens the viewing angle so that the image can be seen relatively clearly even when the screen of the liquid crystal display is viewed from a slightly oblique direction rather than perpendicular to the screen. Examples thereof include an alignment film such as a film and a liquid crystal polymer, and a support in which an alignment layer such as a liquid crystal polymer is supported on a transparent substrate. Retardation films used as viewing angle widening films include birefringent polymer films stretched biaxially in the plane direction and thickness direction refractions stretched uniaxially in the plane direction and stretched in the thickness direction. A birefringent film such as a polymer having birefringence with a controlled rate or a tilted orientation film is used.

  Then, the undercoat layer 2 is provided on one side of the optical film 1. In this description, the undercoat layer 2 is provided on one side of the optical film 1. For example, although not illustrated in FIG. 1, the undercoat layer 2 may be provided on both sides of the optical film 1 as necessary.

  Undercoat layer 2 contains, for example, at least one selected from the group consisting of an oxazoline group-containing polymer, a compound containing a plurality of carboxyl groups, a water-soluble or water-dispersible conductive material, and a polyamine polymer. .

  The oxazoline group-containing polymer includes, for example, a main chain composed of an acrylic skeleton or a styrene skeleton, and has an oxazoline group in the side chain of the main chain, and preferably includes a main chain composed of an acrylic skeleton. And an oxazoline group-containing acrylic polymer having an oxazoline group in the side chain of the main chain.

  Examples of the oxazoline group include 2-oxazoline group, 3-oxazoline group, 4-oxazoline group, and preferably 2-oxazoline group.

  The 2-oxazoline group is generally represented by the following general formula (4).

(In the general formula (4), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group or a substituted phenyl group.)
The number average molecular weight of the oxazoline group-containing polymer is, for example, 5000 or more, preferably 10,000 or more, and usually 1000000 or less. If the number average molecular weight is lower than 5000, the strength of the undercoat layer 2 is insufficient, causing cohesive failure, and the anchoring force may not be improved. When the number average molecular weight is higher than 1,000,000, workability may be inferior. The oxazoline group-containing polymer has an oxazoline value of, for example, 1500 g solid / eq. Hereinafter, preferably, 1200 g solid / eq. It is as follows. The oxazoline value is 1500 g solid / eq. If it is larger, the amount of the oxazoline group contained in the molecule decreases, and the anchoring force may not be improved.

  As the oxazoline group-containing polymer, a general commercial product is usually used. Specifically, Epocros WS-500 (aqueous solution type, solid content 40%, main chain: acrylic, pH 7-9, oxazoline value 220 g solid / eq , Manufactured by Nippon Shokubai Co., Ltd.), Epocros WS-700 (aqueous solution type, solid content 25%, main chain: acrylic, pH 7-9, oxazoline number 220 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) Polymers such as Epocross K-1000 series (emulsion type, solid content 40%, main chain: styrene / acrylic, oxazoline number 1100 g solid / eq., PH 7-9, manufactured by Nippon Shokubai Co., Ltd.), Epocross K-2000 series (Emulsion type, solid content 40%, main chain: styrene / acrylic, H7～9, oxazoline value 550 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) oxazoline group-containing acrylic / styrene polymers and the like. From the viewpoint of improving adhesion, an aqueous solution type is preferable to an emulsion type containing an emulsifier.

  These oxazoline group-containing polymers can be used alone or in combination of two or more.

  The oxazoline group-containing polymer reacts with a functional group (such as a carboxyl group) contained in the pressure-sensitive adhesive composition at a relatively low temperature. Therefore, when the oxazoline group-containing polymer is included in the undercoat layer 2, It reacts with a functional group or the like in the pressure-sensitive adhesive layer 3 and can adhere firmly.

  Examples of the compound containing a plurality of carboxyl groups include saturated low molecular weight compounds containing a plurality of carboxyl groups such as dicarboxylic acid compounds such as succinic acid, adipic acid, and phthalic acid, for example, tricarboxylic acid compounds such as citric acid. Is mentioned.

  The compound containing a plurality of carboxyl groups is a high molecular compound, for example, a polymer of an unsaturated compound such as acrylic acid or methacrylic acid (polyacrylic acid, polymethacrylic acid, etc.), Copolymers of saturated compounds, specifically copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and maleic acid, copolymers of methacrylic acid and maleic acid, acrylic acid, methacrylic acid and maleic acid And the like. Preferably, a copolymer of acrylic acid and maleic acid is used.

  The compound containing a plurality of carboxyl groups has a number average molecular weight (GPC measurement, standard polyethylene glycol equivalent) of, for example, 1000 or more, preferably 3000 to 200000.

  As the compound containing a plurality of carboxyl groups, generally commercially available products are used. Specifically, Poise 532A (acrylic acid / maleic acid copolymer ammonium salt, number average molecular weight of about 10,000, manufactured by Kao Corporation), etc. Is mentioned.

  These compounds containing a plurality of carboxyl groups can be used alone or in combination of two or more.

  The water-soluble conductive material is not particularly limited as long as it is a conductive material exhibiting water solubility, and the solubility in 100 g of water is, for example, 5 g or more, preferably 20 to 30 g. If the solubility in 100 g of water is less than 5 g, it may hinder industrially forming a coating film.

  The water-dispersible conductive material is not particularly limited as long as it is a fine-particle conductive material that can be dispersed in water, and the average particle diameter (size) of the fine particles is, for example, from the viewpoint of uniformity of the undercoat layer 2, 1 μm or less. The water-dispersible conductive material has a small liquid viscosity of its aqueous dispersion (corresponding to a coating liquid described later), and can be easily applied to form the undercoat layer 2 (thin film coating). Furthermore, the uniformity of the water-dispersible conductive material in the undercoat layer 2 is excellent.

  Examples of the water-soluble or water-dispersible conductive material include conductive polymers and organometallic compounds.

  Examples of the conductive polymer include polyaniline, polythiophene, polypyrrole, and polyquinoxaline. Of these, polyaniline or polythiophene is preferable from the viewpoint of coatability.

  Polyaniline has a polystyrene-reduced weight average molecular weight by GPC measurement of, for example, 500,000 or less, and preferably 300,000 or less. Polythiophene has a polystyrene-reduced weight average molecular weight of, for example, 400000 or less, preferably 300000 or less as measured by GPC.

  When the weight average molecular weight of the above polyaniline or polythiophene exceeds the above value, the polyaniline or polythiophene does not exhibit any of the above water-soluble or water-dispersible properties, and contains such polyaniline or polythiophene. When the coating solution is prepared, the solid content of the polyaniline or polythiophene in the coating solution remains, or a part of the polyaniline or polythiophene increases in viscosity to form the undercoat layer 2 having a uniform thickness. Tend to be difficult.

  Such polyaniline or polythiophene preferably has a hydrophilic functional group in the molecule.

Examples of the hydrophilic functional group include a sulfo group, amino group, amide group, imino group, quaternary ammonium base, hydroxyl group, mercapto group, hydrazino group, carboxyl group, sulfate ester group (—O—SO ₃ H), A phosphate ester group (—O—PO (OH) ₂ ) or a salt thereof (excluding a quaternary ammonium base) is included. By having such a hydrophilic functional group in the molecule, it is easy to dissolve or disperse in water, and a polyaniline or polythiophene coating solution can be easily prepared.

  As such a water-soluble or water-dispersible conductive polymer, commercially available ones can be used. Among these, examples of the water-soluble conductive polymer include polyaniline sulfonic acid (Mitsubishi Rayon Co., Ltd.). Examples of the water-dispersible conductive polymer include polythiophene-based conductive polymers (manufactured by Nagase Chemtech, trade name “Denatron” (Denatron series)).

  Examples of organometallic compounds include metal alkoxides, metal chelates, organometallic salts, organometallic oxides, etc. used as polymer crosslinking agents. Depending on the type of metal, for example, organozirconium compounds, organotitanium compounds, organoaluminum compounds Etc.

  Examples of the organic zirconium compound include zirconium alkoxide, zirconium chelate, zirconium acylate and the like.

  Examples of the organic titanium compound include titanium alkoxide, titanium chelate, and titanium acylate.

  Examples of the organoaluminum compound include aluminum alkoxide, aluminum chelate, and aluminum acylate.

  These conductive materials can be used alone or in combination of two or more.

  The polyamine-based polymer is a polymer having a plurality of primary or secondary amino groups in the molecule, and includes, for example, polyethyleneimine, polyallylamine, and a main chain composed of an acrylic skeleton, and a side chain of the main chain. Examples thereof include ethyleneimine-modified acrylic polymers and allylamine-modified acrylic polymers in which a polyethyleneimine chain represented by the following general formula (5) and a polyallylamine chain represented by the following general formula (6) are modified. . Preferably, an ethyleneimine modified acrylic polymer is used.

(In general formula (5), x and y indicate the degree of polymerization of the polyethyleneimine chain.)

(In general formula (6), z represents the degree of polymerization of the polyallylamine chain.)
The number average molecular weight of the polyamine polymer is, for example, 200 or more, preferably 1000 or more, more preferably 8000 or more, and usually 1000000 or less. When the number average molecular weight is smaller than 200, the strength of the undercoat layer 2 is insufficient, causing cohesive failure, and the anchoring force may not be improved. When the number average molecular weight is larger than 1,000,000, workability may be inferior. The polyamine polymer has an amine hydrogen equivalent of, for example, 1500 g solid / eq. Hereinafter, preferably, 1200 g solid / eq. It is as follows. The amine hydrogen equivalent weight is 1500 g solid / eq. If it is larger, the amount of amino groups contained in the molecule decreases, and the anchoring power may not be improved.

  As the polyamine polymer, a general commercial product is usually used. Specifically, Epomin SP-003 (water-soluble type, amine hydrogen equivalent 47.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP-006 (Water-soluble type, amine hydrogen equivalent 50.0 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP-012 (Water-soluble type, amine hydrogen equivalent 52.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP -018 (water-soluble type, amine hydrogen equivalent 52.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP-103 (water-soluble type, amine hydrogen equivalent 52.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP-110 (water-soluble type, amine hydrogen equivalent 55.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin SP-2 0 (water-soluble type, amine hydrogen equivalent 55.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Epomin P-1000 (water-soluble type, amine hydrogen equivalent 52.6 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), etc. Polyethyleneimine, for example, Polyment SK-1000 (emulsion type, amine hydrogen equivalent 650 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Polyment NK-350 (Solvent type, amine hydrogen equivalent 1100 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) , Poliment NK-380 (solvent type, amine hydrogen equivalent 1100 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Poliment NK-100PM (water-soluble type, amine hydrogen equivalent 350-450 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.), Poliment NK-200PM (water-soluble type, amino Hydrogen equivalent 350~450g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) ethyleneimine-modified acrylic polymer, such as.

  These polyamine polymers can be used alone or in combination of two or more.

  The undercoat layer 2 is preferably composed only of an oxazoline group-containing polymer, composed of only a conductive material, composed of a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, an oxazoline group-containing polymer, and a conductive layer. Examples thereof include those composed of a mixture of materials, oxazoline group-containing polymers, compounds composed of a compound containing a plurality of carboxyl groups and a conductive material, and materials composed of a mixture of an oxazoline group-containing polymer and a polyamine-based polymer.

  If the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, the oxazoline group of the oxazoline group-containing polymer reacts with the carboxyl groups of the compound containing a plurality of carboxyl groups. As a result, the undercoat layer 2 is cross-linked to form a stronger undercoat layer 2, whereby the heat resistance and moist heat resistance are increased, and the adhesion can be increased.

  If the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a conductive material, the undercoat layer 2 can be formed as an antistatic layer, while having good affinity with the water-dispersed pressure-sensitive adhesive composition, By increasing the adhesion between the optical film and the water-dispersed pressure-sensitive adhesive composition, a pressure-sensitive adhesive optical film having high heat resistance can be obtained. Therefore, it is possible to obtain a pressure-sensitive adhesive optical film having good reworkability and having high heat resistance and antistatic function.

  If the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer, a compound containing a plurality of carboxyl groups and a conductive material, the undercoat layer 2 can be formed as an antistatic layer, while the oxazoline group of the oxazoline group-containing polymer And the carboxyl group of the compound containing a plurality of carboxyl groups reacts to crosslink the undercoat layer 2 to form a stronger undercoat layer 2, thereby increasing the heat resistance and heat-and-moisture resistance. The power can be increased.

  If the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a polyamine-based polymer, the adhesive optical film has high moisture and heat resistance while maintaining high adhesion and heat resistance when only the oxazoline group-containing polymer is used. A pressure-sensitive adhesive optical film having high adhesion, heat resistance, and heat and humidity resistance can be obtained.

  When the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, the blending ratio of the compound containing a plurality of carboxyl groups is, for example, 1 to 100 parts by weight based on the total amount of the mixture. 30 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 10 parts by weight. When the compound containing a plurality of carboxyl groups is less than 1 part by weight, the effect of crosslinking the undercoat layer 2 may be reduced. If the compound containing a plurality of carboxyl groups is more than 30 parts by weight, the undercoat layer 2 may become cloudy and optical properties may be deteriorated.

  When the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a conductive material, the blending ratio of the oxazoline group-containing polymer is, for example, 10 to 500 parts by weight, preferably 20 to 20 parts by weight with respect to 100 parts by weight of the conductive material. 400 parts by weight.

  When the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer, a compound containing a plurality of carboxyl groups and a conductive material, the blending ratio of the compound containing a plurality of carboxyl groups with respect to 100 parts by weight of the total mixture is, for example, 1 to 30 parts by weight, preferably 2 to 20 parts by weight, and more preferably 3 to 10 parts by weight. The blending ratio of the oxazoline group-containing polymer and the blending ratio of the conductive material are the same as the blending ratio of each component when the undercoat layer 2 is made of a mixture of the oxazoline group-containing polymer and the conductive material.

  When the undercoat layer 2 is composed of a mixture of an oxazoline group-containing polymer and a polyamine polymer, the blending ratio of the polyamine polymer is 50 to 98 parts by weight, preferably 70 to 97 parts by weight with respect to 100 parts by weight of the total amount of the mixture. More preferably, it is 80 to 95 parts by weight. If the polyamine polymer is less than 50 parts by weight, the heat and moisture resistance may be poor. When the amount of the polyamine polymer is more than 98 parts by weight, the heat resistance may be inferior.

  Each of the above components (oxazoline group-containing polymer, compound containing a plurality of carboxyl groups, conductive material or polyamine polymer, or a mixture thereof) is dissolved or dispersed in a solvent. It is prepared as a liquid.

  Preferably, from the viewpoint of preventing deterioration of the optical film, each component is prepared as an aqueous solution or aqueous dispersion (hereinafter, simply referred to as “coating liquid”) in which each component is dissolved or dispersed in water. ing. In such a coating liquid, it is not necessary to use a non-aqueous organic solvent, and therefore, the alteration of the optical film 1 due to the organic solvent can be suppressed.

  In the coating solution, in addition to water, alcohols can be further contained as an aqueous solvent.

  Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, Examples include 1-ethyl-1-propanol, 2-ethyl-1-butanol, n-hexanol, and cyclohexanol.

  In the coating solution, the blending ratio of each component is, for example, 0.05 to 80% by weight, preferably 0.1 to 50% by weight.

  In order to provide the undercoat layer 2, for example, the optical film 1 is directly coated with the above-described undercoat layer coating solution by a known coating method such as a knife coating method and then dried.

  The undercoat layer 2 has a thickness (thickness after drying) of, for example, 10 to 1000 nm, preferably 20 to 500 nm, and more preferably 30 to 200 nm.

When the undercoat layer 2 contains a conductive material, that is, when the undercoat layer 2 is formed as an antistatic layer, the surface resistance is usually preferably 1 × 10 ¹² Ω / □ or less, Preferably, it is 1 × 10 ¹¹ Ω / □ or less, particularly preferably 1 × 10 ¹⁰ Ω / □ or less. When the surface resistance exceeds 1 × 10 ¹² Ω / □, the antistatic function may not be sufficient.

  Next, the pressure-sensitive adhesive layer 3 is provided on at least one surface of the optical film 1 via the undercoat layer 2.

  In order to provide the pressure-sensitive adhesive layer 3, for example, the pressure-sensitive adhesive layer 3 is transferred from the release sheet 4 on which the pressure-sensitive adhesive layer 3 is formed to the above-described undercoat layer 2. The release sheet 4 having the pressure-sensitive adhesive layer 3 formed thereon is directly coated with the above-mentioned pressure-sensitive adhesive composition by a known coating method such as a knife coating method. Thereafter, the pressure-sensitive adhesive layer 3 is provided on the release sheet 4 by heating and drying at 80 to 150 ° C. for 1 to 10 minutes, for example. To transfer the pressure-sensitive adhesive layer 3, the release sheet 4 on which the pressure-sensitive adhesive layer 3 is formed is bonded to the undercoat layer 2, and then the release sheet 4 is peeled off from the pressure-sensitive adhesive layer 3.

  In order to provide the pressure-sensitive adhesive layer 3, for example, the above-described pressure-sensitive adhesive composition is directly coated on the above-described undercoat layer 2 by a known coating method such as a knife coating method. It can also be dried by heating at ˜150 ° C. for 1 to 10 minutes.

  Examples of the release sheet 4 include synthetic resin films such as paper, polyethylene, polypropylene, and polyethylene terephthalate, such as rubber sheets, cloths, nonwoven fabrics, nets, foam sheets, metal foils, and laminated sheet bodies thereof. The surface of the release sheet 4 may be subjected to treatment (peeling treatment) such as silicone treatment, long-chain alkyl treatment, and fluorine treatment as necessary in order to enhance the peelability from the pressure-sensitive adhesive layer 3.

  The thickness (thickness after drying) of the pressure-sensitive adhesive layer 3 is set in the range of, for example, 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 30 μm.

  Thus, by providing the pressure-sensitive adhesive layer 3 formed from the above-described pressure-sensitive adhesive composition on at least one surface of the optical film 1 via the undercoat layer 2, a pressure-sensitive adhesive optical film can be obtained.

  The adhesive optical film thus obtained is suitably used for various industrial applications as an adhesive optical film such as a polarizing film, a retardation film, a brightness enhancement film, and a viewing angle widening film.

  And in this adhesive optical film, the adhesive force of the adhesive layer 3 and the glass substrate of a liquid crystal display is high, and also the adhesive force of the adhesive layer 3 and optical film 1 which are formed from an above-mentioned adhesive composition. Therefore, strong adhesion between the optical film 1 and the substrate can be achieved. Therefore, it is possible to effectively suppress pressure-sensitive adhesive chipping and pressure-sensitive adhesive residue when handling a pressure-sensitive adhesive optical film.

  Moreover, since it has high adhesiveness also when adhere | attaching on the glass substrate of a liquid crystal display, an adhesive optical film can be firmly adhere | attached on a glass substrate.

  Moreover, this adhesive optical film is excellent in transparency. Furthermore, since this pressure-sensitive optical film has high heat resistance and moisture resistance, it is possible to obtain an excellent adhesive force with a glass substrate in a high temperature atmosphere or a high humidity atmosphere. In particular, even when a relatively thick optical film that applies a large load to the pressure-sensitive adhesive layer is used, it is possible to maintain an excellent adhesive force with a glass substrate in a high-temperature atmosphere.

  For this reason, the adhesive optical film is applied to the surface of a substrate of an image display device such as a liquid crystal display, an organic electroluminescence device (organic EL display device), a plasma display panel (PDP), and the undercoat layer 2 and the adhesive layer 3. By sticking through, an excellent appearance can be secured, and an image display device having high heat resistance and moisture resistance can be obtained.

Hereinafter, the present invention will be described more specifically with reference to Examples , Reference Examples and Comparative Examples. However, the present invention is not limited to the following examples , reference examples and comparative examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.

Reference example 1
(Preparation of monomer pre-emulsion)
In a container, 100 parts of butyl acrylate, 5 parts of acrylic acid, 2 parts of mono [poly (propylene oxide) methacrylate] phosphate ester (PAM-200, average degree of polymerization of propylene oxide of about 5.0, manufactured by Rhodia Nikka Co., Ltd.) Then, 0.01 part of 3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed to prepare a monomer component.

Next, 13 g of reactive emulsifier Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and 360 g of ion-exchanged water were added to 627 g of the prepared monomer component, and 5000 (1) for 5 minutes using a homogenizer (manufactured by Tokushu Kika Co., Ltd.). / Min) and stirring and forced emulsification to prepare a monomer pre-emulsion.
(Preparation of emulsion)
200 g of the monomer pre-emulsion prepared above and 300 g of ion-exchanged water were charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and then the reaction vessel was purged with nitrogen and 2,2 ′ -0.2 g of azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) was added and polymerized at 60 ° C for 1 hour. Next, 800 g of the remaining monomer pre-emulsion was dropped into the reaction vessel over 3 hours, and then polymerized for 3 hours. Thereafter, polymerization was further carried out at 60 ° C. for 3 hours while purging with nitrogen to obtain an emulsion (copolymer aqueous dispersion) having a solid content of 48%.

Thereafter, the emulsion is cooled to room temperature, then 10% aqueous ammonia is added to adjust the pH to 8, and 3.0 g acrylic thickener (Aron B-500, manufactured by Toagosei Co., Ltd.) is added. did.
(Preparation of aqueous dispersion of clay mineral)
After adding 0.5 parts of sodium hexametaphosphate (phosphate dispersant, manufactured by Kishida Chemical Co., Ltd.) to 90 parts of ion-exchanged water and dissolving it, Lucentite SPN (propylene oxide having a hydroxyl group at the terminal) was added thereto. Smectite with a quaternary ammonium salt (cationic dispersant) having a skeleton and hydrophobized between layers at a ratio of 120 mol eq./100 g Maximum theoretical length of each layer 50 nm Clay component / cationic dispersant content = 40 parts / 60 parts, manufactured by Co-op Chemical Co., Ltd.) was added and left for 48 hours to swell the Lucentite SPN by immersing it in ion-exchanged water. Then, the clay mineral aqueous dispersion was prepared by stirring and disperse | distributing for 15 minutes with 7000 (1 / min) using the homogenizer (made by a special machine company).
(Preparation of water-dispersed pressure-sensitive adhesive composition)
10 parts of clay mineral (Lucentite SPN) in an aqueous dispersion of clay mineral with respect to 100 parts of emulsion solids (copolymer) in emulsion (emulsion added with pH adjustment and additives) (clay component) The water-dispersed pressure-sensitive adhesive composition was prepared by mixing an aqueous dispersion of clay mineral so that the content of
(Preparation of optical film)
A polyvinyl alcohol film having a thickness of 80 μm is stretched 5 times the original length in an aqueous iodine solution at 40 ° C., and then the polyvinyl alcohol film is pulled up from the aqueous iodine solution and dried at 50 ° C. for 4 minutes to obtain a polarized light having a thickness of 20 μm. I got a child. Using a polyvinyl alcohol adhesive on both sides of this polarizer, a triacetyl cellulose film with a thickness of 40 μm and a thickness of 80 μm is adhered as a transparent protective film, respectively, and a thin polarizing film with a thickness of 100 μm and a standard type with a thickness of 180 μm Two types of optical films with a polarizing film were obtained.
(Formation of undercoat layer)
Epocross WS-700 (oxazoline group-containing acrylic polymer, manufactured by Nippon Shokubai Co., Ltd.) is diluted with a mixed solution of water / ethanol (1: 1 by weight) to a solid content of 0.25%, and an undercoat layer A coating solution was prepared. This coating solution was coated on one side of two types of optical films using wire bar # 5 and dried at 40 ° C. for 2 minutes to form an undercoat layer.
(Preparation of adhesive optical film)
The water-dispersed pressure-sensitive adhesive composition was coated on a release film (polyethylene terephthalate base material, Diafoil MRF38, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) so that the thickness after drying was 23 μm. Then, it was made to dry at 100 degreeC for 2 minute (s) with a hot-air circulation type oven, and the adhesive layer was formed on the release film. This was stuck to the treated surface (surface on the undercoat layer side) of two types of optical films provided with an undercoat layer in advance to produce an adhesive optical film.

Reference example 2
In the preparation of the aqueous dispersion adhesive composition of Reference Example 1, except that the 5 parts of the clay mineral (Lucentite SPN) in the aqueous dispersion of the clay mineral (the weight content of 2 parts of clay component.) Are reference A water-dispersed pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, and subsequently a pressure-sensitive adhesive optical film was produced.

Reference example 3
In the preparation of the aqueous dispersion of the clay mineral of Example 1, except for changing the 1 part of sodium hexametaphosphate, in the same manner as in Reference Example 1 to prepare an aqueous dispersion of the clay mineral, then water-dispersed PSA composition Then, an adhesive optical film was prepared.

Reference example 4
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocros WS-700, Epocros WS-700, and Poise 532A (acrylic acid / maleic acid copolymer ammonium salt, number average molecular weight of about 10,000, manufactured by Kao Corporation ) And the mixture of Epocross WS-700 and Poise 532A was changed to 95: 5, and the same treatment as in Reference Example 1 was performed except that the solid content of the coating solution was changed to 2%. An undercoat layer was formed, and then an adhesive optical film was produced.

Reference Example 5
In preparation of the coating liquid in the formation of the undercoat layer of Reference Example 1, Epocros WS-700 was changed to Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation), and the solid content of the coating liquid was changed to 0.5%. Except having changed, it processed like the reference example 1, the undercoat layer was formed, and then the adhesion type optical film was produced.

Example 6
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocros WS-700 is mixed with Epocros WS-700 and Denatron P502RG, and the mixing ratio of Epocros WS-700 and Denatron P502RG is 1: 2. In the same manner as in Reference Example 1 except that the solid content of the coating solution was changed to 0.75%, an undercoat layer was formed, and then an adhesive optical film was produced.

Example 7
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocross WS-700 was mixed with Epocross WS-700, Poise 532A, and Denatron P502RG, and Epocross WS-700, Poise 532A, and Denatron P502RG were mixed. The ratio was changed to 190: 10: 25, and the undercoat layer was formed in the same manner as in Reference Example 1 except that the solid content of the coating solution was changed to 2.25%. An optical film was produced.

Example 8
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocros WS-700 was replaced with Epocros WS-700 and Olgatrix ZB-125 (zirconium chloride compound, ZrO ₂ content 15%, manufactured by Matsumoto Pharmaceutical Co., Ltd.) In the same manner as in Reference Example 1, except that the mixture ratio of Epocros WS-700 and Olgatics ZB-125 was changed to 1: 2, and the solid content of the coating solution was changed to 0.75%. Then, an undercoat layer was formed, and then an adhesive optical film was produced.

Example 9
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocros WS-700 was changed to Epocros WS-700, Olgatrix TC-400 (diisopropoxytitanium bis (triethanolaminate), (C ₃ H ₇ O ) ₂ Ti (C ₆ H ₁₄ O ₃ N) ₂ , Ti content ratio 8%, manufactured by Matsumoto Pharmaceutical Co., Ltd.), the mixing ratio of Epocross WS-700 and Olgatics TC-400 is 1: 2. In the same manner as in Reference Example 1 except that the solid content of the coating solution was changed to 0.75%, an undercoat layer was formed, and then an adhesive optical film was produced.

Reference Example 10
In the preparation of the coating solution in the formation of the undercoat layer of Reference Example 1, Epocros WS-700 was changed to Epocros WS-700 and Poliment SK-1000 (emulsion type, amine hydrogen equivalent 650 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) The same procedure as in Reference Example 1 was conducted except that the mixing ratio of Epocross WS-700 and Poliment SK-1000 was changed to 1: 1 and the solid content of the coating solution was changed to 0.50%. An undercoat layer was formed, and then an adhesive optical film was produced.

Reference Example 11
In the preparation of the water-dispersed pressure-sensitive adhesive composition of Reference Example 1, except that the clay mineral (Lucentite SPN) in the clay mineral aqueous dispersion was changed to 2 parts (the content of the clay component was 0.8 parts). In the same manner as in Reference Example 1, a water-dispersed pressure-sensitive adhesive composition was prepared, and then a pressure-sensitive adhesive optical film was produced.

Reference Example 12
In the preparation of the aqueous dispersion adhesive composition of Reference Example 1, except for changing the clay minerals in aqueous dispersion of the clay mineral (Lucentite SPN) to 20 parts (containing weight 8 parts of clay component.) Are reference In the same manner as in Example 1, a water-dispersed pressure-sensitive adhesive composition was prepared, and then a pressure-sensitive adhesive optical film was produced.

Reference Example 13
(Preparation of aqueous dispersion of clay mineral)
To 95 parts of ion-exchanged water, 5 parts of Kunipia F (smectite, non-hydrophobized product, manufactured by Kunimine Kogyo Co., Ltd.) was added, and then 7000 (1 / Min) and stirring and dispersing to prepare an aqueous dispersion of clay mineral.
(Preparation of water-dispersed pressure-sensitive adhesive composition)
In the preparation of the water-dispersed pressure-sensitive adhesive composition of Reference Example 1, the clay mineral was adjusted so that the clay mineral (Kunipia F) in the aqueous dispersion of clay mineral was 0.5 part with respect to 100 parts of the solid content of the emulsion. A water-dispersed pressure-sensitive adhesive composition was prepared in the same manner as in Reference Example 1 except that the aqueous dispersion was mixed, and then a pressure-sensitive adhesive optical film was produced.

Reference Example 14
In the preparation of the water-dispersed pressure-sensitive adhesive composition of Reference Example 13, the water-dispersed pressure-sensitive adhesive composition was the same as in Reference Example 13, except that the clay mineral (Kunipia F) in the clay mineral aqueous dispersion was changed to 1 part. Then, an adhesive optical film was prepared.

Reference Example 15
In the preparation of the water-dispersed pressure-sensitive adhesive composition of Reference Example 13, the water-dispersed pressure-sensitive adhesive composition was the same as in Reference Example 13, except that the clay mineral (Kunipia F) in the clay mineral aqueous dispersion was changed to 2 parts. Then, an adhesive optical film was prepared.

Reference Example 16
In the preparation of the water-dispersed pressure-sensitive adhesive composition of Reference Example 13, the water-dispersed pressure-sensitive adhesive composition was the same as in Reference Example 13, except that the clay mineral (Kunipia F) in the clay mineral aqueous dispersion was changed to 4 parts. Then, an adhesive optical film was prepared.

Reference Example 17
0.5 parts of sodium hexametaphosphate in Reference Example 1 was changed to 1 part (solid content) of Aron A-208 (polyacrylic acid sodium salt, carboxyl anion content 6.5 mmol / g, manufactured by Toagosei Co., Ltd.). Except for the above, an aqueous dispersion of clay mineral was prepared in the same manner as in Reference Example 1, and then a water-dispersed pressure-sensitive adhesive composition was prepared to produce a pressure-sensitive optical film.

Reference Example 18
0.5 parts of sodium hexametaphosphate in Reference Example 1 was replaced with 1 part of Aqualic TL-37 (sodium acrylate / sodium maleate copolymer, carboxyl anion content 6.4 mmol / g, manufactured by Nippon Shokubai Co., Ltd.) A clay mineral aqueous dispersion was prepared in the same manner as in Reference Example 1 except that the solid content was changed to a solid content, and then a water-dispersed pressure-sensitive adhesive composition was prepared to produce a pressure-sensitive adhesive optical film.

Reference Example 19
0.5 part of sodium hexametaphosphate in Reference Example 1 was added to 1 part (solid content) of Charol AN-103P (polyacrylic acid ammonium salt, carboxyl anion content 7.9 mmol / g, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Except for the change, an aqueous dispersion of clay mineral was prepared in the same manner as in Reference Example 1, and then a water-dispersed pressure-sensitive adhesive composition was prepared to produce a pressure-sensitive adhesive optical film.

Reference Example 20
0.5 g of sodium hexametaphosphate in Reference Example 1 was changed to 1 part (solid content) of SN Dispersant 5034 (poly (meth) acrylate sodium, carboxyl anion content 7.0 mmol / g, manufactured by San Nopco). Except for the above, an aqueous dispersion of clay mineral was prepared in the same manner as in Reference Example 1, and then a water-dispersed pressure-sensitive adhesive composition was prepared to produce a pressure-sensitive optical film.

Comparative Example 1
In the preparation of the monomer pre-emulsion of Reference Example 1, a monomer pre-emulsion was prepared in the same manner as in Reference Example 1 except that mono [poly (propylene oxide) methacrylate] phosphate was not added. An aqueous dispersion of clay mineral was prepared in the same manner as in Reference Example 1 except that sodium hexametaphosphate was not added in the preparation of the aqueous dispersion. Subsequently, a water-dispersed pressure-sensitive adhesive composition was prepared in the same manner as in Reference Example 1, and then a pressure-sensitive adhesive optical film was produced.

Comparative Example 2
In the preparation of the clay mineral aqueous dispersion of Reference Example 1, a clay mineral aqueous dispersion was prepared in the same manner as in Reference Example 1 except that sodium hexametaphosphate and Lucentite SPN were not added. A pressure-sensitive adhesive composition was prepared, and then a pressure-sensitive adhesive optical film was prepared.

Comparative Example 3
In the preparation of the aqueous dispersion adhesive composition of Reference Example 1, except that 30 parts of clay mineral (Lucentite SPN) in the aqueous dispersion of the clay mineral (the weight content of the clay component is 12 parts.) Was changed to the reference A water-dispersed pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, and subsequently a pressure-sensitive adhesive optical film was produced.

Tables 1 and 2 show the formulation of the water-dispersed pressure-sensitive adhesive composition and the coating solution for the undercoat layer in Reference Examples 1 to 5, Examples 6 to 9, Reference Examples 10 to 20, and Comparative Examples 1 to 3. In addition, the numerical value of the column of the mixing | blending prescription of the water dispersion type adhesive composition in Table 1 and Table 2 shows the number of compounding parts except the case where a unit is specified clearly.

In addition, the symbol in Table 1 and Table 2 is shown below.
PAM-200: Sipomer PAM-200 (mono [poly (propylene oxide) methacrylate) phosphate ester (average degree of polymerization of propylene oxide of about 5.0), manufactured by Rhodia Nikka Co., Ltd.)
KBM-503: 3-methacryloyloxypropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Lucentite SPN: Smectite partially hydrophobized (Coop Chemical) Kunipia F: Smectite (Non-hydrophobic product, Kunimine Industries)
Epocros WS-700: Oxazoline group-containing acrylic polymer (aqueous solution, solid content 25%, main chain: acrylic, pH 7-9, oxazoline number 220 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.)
Poise 532A: Acrylic acid / maleic acid copolymer ammonium salt (number average molecular weight about 10,000, manufactured by Kao Corporation)
Denatron P502RG: Polythiophene-based conductive polymer (manufactured by Nagase ChemteX Corporation)
ZB-125: ORGATICS ZB-125 (zirconium chloride compound, ZrO ₂ content ratio 15%, manufactured by Matsumoto Pharmaceutical Co., Ltd.)
TC-400: ORGATICS TC-400 (diisopropoxytitanium bis (triethanolamate), (C ₃ H ₇ O) ₂ Ti (C ₆ H ₁₄ O ₃ N) ₂ , Ti content 8%, Matsumoto Pharmaceutical (Made by company)
Poliment SK-1000: polyamine polymer (emulsion type, amine hydrogen equivalent 650 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.)
Aron A-208: (polyacrylic acid sodium salt, polycarboxylate-based dispersant, carboxyl anion content 6.5 mmol / g, manufactured by Toagosei Co., Ltd. hexametaphosphate Na: sodium hexametaphosphate, phosphate-based dispersant, Aquaric TL-37 manufactured by Kishida Chemical Co., Ltd .: sodium acrylate / maleic acid sodium copolymer, polycarboxylate-based dispersant, carboxyl anion content 6.4 mmol / g, Nippon Shokubai Co., Ltd. Charol AN-103P: poly Ammonium acrylate salt, polycarboxylate-based dispersant, carboxyl anion content 7.9 mmol / g, SN Dispersant 5034 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: poly (meth) acrylate sodium (polycarboxylate-based dispersant ), Carboxyl anion content 7.0 mmol / g, San Nopco Made (Evaluation)
1) Haze The adhesive optical film (adhesive optical film using a thin polarizing film) obtained in each example , each reference example and comparative example was cut into 50 × 50 mm, and haze computer HZ-1 (Suga test) The haze was measured by a machine company). The results are shown in Tables 3 and 4.

2) Initial adhesive force between adhesive layer and optical film The adhesive optical film (adhesive optical film using a thin polarizing film) of each example , each reference example and each comparative example was cut into a size of 25 × 120 mm. This was used as a sample. The release film of this sample was peeled off, and a polypropylene porous film was attached to the pressure-sensitive adhesive surface of the sample (the surface of the pressure-sensitive adhesive layer), and an adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) was adhered to the polypropylene porous film. After being stuck and reinforced, it was left in an atmosphere of 23 ° C. and 60% RH for 24 hours. Then, SUS304 steel plate was attached to the back surface of the adhesive optical film after standing (surface on the optical film side of the adhesive optical film) using a double-sided tape, and at a speed of 300 mm / min in the 180 ° direction by a tensile tester. The film was peeled at the interface between the polypropylene porous membrane and the sample, and the peel stress was measured. After the measurement, it was confirmed whether or not the pressure-sensitive adhesive layer adhered to the polypropylene porous membrane side, that is, whether or not the optical film was broken. The results are shown in Tables 3 and 4.

3) Adhesive strength with time of adhesive layer and optical film Adhesive optical film (adhesive optical film using a thin polarizing film) of each example , each reference example and each comparative example is 25 × 120 mm in size. This was cut and used as a sample. This sample was aged for 7 days in an atmosphere of 50 ° C. and 60 ° C./90% RH, respectively. After the aging, the release film of the sample was peeled off, and a polypropylene porous film was stuck on the pressure-sensitive adhesive surface of the sample (the surface of the pressure-sensitive adhesive layer), and an adhesive tape (No. 31B, Nitto Denko Corporation) was adhered on the polypropylene porous film. The product was affixed and reinforced for 1 day in an atmosphere of 23 ° C. and 60% RH. Then, SUS304 steel plate was attached to the back surface of the adhesive optical film after standing (surface on the optical film side of the adhesive optical film) using a double-sided tape, and at a speed of 300 mm / min in the 180 ° direction by a tensile tester. The film was peeled at the interface between the polypropylene porous membrane and the sample, and the peel stress was measured. After the measurement, it was confirmed whether or not the pressure-sensitive adhesive layer adhered to the polypropylene porous membrane side, that is, whether or not the optical film was broken. The results are shown in Tables 3 and 4.

4) Adhesive fixing property of adhesive optical film After cutting two types of adhesive optical films (thin polarizing film and standard polarizing film) of each example , each reference example and comparative example into a size of 230 × 310 mm The release film was peeled off, and this was attached to a glass plate having a thickness of 0.7 mm (Corning # 1737, manufactured by Corning) and left in an autoclave at 50 ° C. and 0.5 MPa for 15 minutes. It was heated for 500 hours in an atmosphere of 0 ° C. and in an atmosphere of 60 ° C./90% RH, and the presence or absence of peeling of the adhesive optical film was confirmed by visual observation. The results are shown in Tables 3 and 4.

  In addition, about the presence or absence of peeling of an adhesive optical film, it confirmed on the following reference | standard.

A: No change such as peeling was observed. ○: Peeling of less than 0.5 mm was observed at the edge of the adhesive optical film. Δ: Peeling of 0.5 mm or more and less than 1 mm was observed at the edge of the adhesive optical film. X: Peeling of 1 mm or more was observed at the edge of the adhesive optical film 5) Surface resistance of the optical film In each example , each reference example and comparative example, an optical film (thin film) provided with only an undercoat layer The pressure-sensitive adhesive thin polarizing film before forming the pressure-sensitive adhesive layer was allowed to stand in an atmosphere of 23 ° C. and 60% RH. Then, the optical film after 1 minute at an applied voltage of 500 V using a USR probe with a resistivity meter (Hiresta-Up MCP-HT450, manufactured by Dia Instruments Co., Ltd.) in an atmosphere of 23 ° C. and 60% RH. The surface resistance of the surface on which the undercoat layer was formed was measured. The results are shown in Tables 3 and 4.

It is an expanded sectional view of one embodiment of the adhesion type optical film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical film 2 Undercoat layer 3 Adhesive layer 4 Release sheet

Claims (15)

An optical film, an adhesive layer laminated on at least one surface of the optical film, and an undercoat layer interposed between the optical film and the adhesive layer,
The pressure-sensitive adhesive layer is
Copolymerizable vinyl containing (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms, carboxyl group-containing vinyl monomer and phosphate group-containing vinyl monomer as essential components, and copolymerizable with the essential components The monomer component containing a monomer as an optional component is 60 to 99 parts by weight of the (meth) acrylic acid alkyl ester with respect to 100 parts by weight of the monomer component, and includes the carboxyl group-containing vinyl monomer and the phosphate group. The total amount of the vinyl monomer and the copolymerizable vinyl monomer is 1 to 40 parts by weight, and in the monomer component, the carboxyl group concentration is 0.05 to 1.50 mmol / g, and the phosphate group concentration is 0.01. A copolymer obtained by preparing and polymerizing to be ~ 0.45 mmol / g;
With clay minerals,
It consists of an adhesive composition containing the clay mineral in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the copolymer ,
The undercoat layer contains a mixture of an oxazoline group-containing polymer and a water-soluble or water-dispersible conductive material, or contains an organometallic compound that is a water-soluble or water-dispersible conductive material. An adhesive optical film. The pressure-sensitive adhesive composition further comprises 0.1 to 5 parts by weight of a phosphate dispersant and / or 0.1 to 5 parts by weight of a polycarboxylate dispersant with respect to 100 parts by weight of the copolymer. The pressure-sensitive adhesive optical film according to claim 1, comprising: The pressure-sensitive adhesive composition comprises an aqueous dispersion obtained by dispersing the clay mineral in water mixed with the phosphate dispersant and / or the polycarboxylate dispersant, The pressure-sensitive adhesive optical film according to claim 2 , wherein the pressure-sensitive adhesive optical film is obtained by blending with a combined aqueous dispersion. The carboxyl group-containing vinyl monomer is 0.5 to 15 parts by weight, the phosphate group-containing vinyl monomer is 0.5 to 20 parts by weight, and the copolymerizable vinyl monomer is 39 parts by weight with respect to 100 parts by weight of the monomer component. The pressure-sensitive adhesive optical film according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive optical film is not more than part . The pressure-sensitive adhesive composition contains 0.001 to 1 part by weight of an alkoxysilyl group-containing vinyl monomer as the copolymerizable vinyl monomer with respect to 100 parts by weight of the monomer component. The pressure-sensitive adhesive optical film according to any one of 1 to 4 . The pressure-sensitive adhesive composition, characterized in that it is a water-dispersible, pressure-sensitive adhesive optical film according to any one of claims 1-5. The clay mineral, characterized in that it is a smectite, adhesive optical film according to any one of claims 1-6. The clay mineral, characterized in that it comprises a clay mineral which has been organically treated, adhesive optical film according to any one of claims 1-7. 9. The pressure-sensitive adhesive optical film according to claim 8 , wherein the organically treated clay mineral is organically treated with an organic cation having a hydrophilic functional group. The pressure-sensitive adhesive optical film according to claim 9 , wherein the organic cation having the hydrophilic functional group is a quaternary ammonium salt having a hydroxyl group. 11. The undercoat layer according to any one of claims 1 to 10, wherein the undercoat layer contains a mixture of an oxazoline group-containing polymer, a compound containing a plurality of carboxyl groups, and a water-soluble or water-dispersible conductive material . 2. The pressure-sensitive adhesive optical film described in 1. The water-soluble or water-dispersible conductive material, characterized in that it is a conductive polymer, pressure-sensitive adhesive optical film according to any one of claims 1 to 11. The pressure-sensitive adhesive optical film according to claim 12 , wherein the conductive polymer is polyaniline and / or polythiophene. The organometallic compound is an organic zirconium compound, and wherein the at least one selected from the group consisting of organic titanium compound and an organoaluminum compound, adhesive optical film according to any one of claims 1 to 13. Characterized in that at least one piece of the pressure-sensitive adhesive optical film according to any one of claims 1 to 14, the image display device.

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