JP5000171B2 - Adhesive film and image display device - Google Patents

Description

  The present invention relates to an adhesive film and an image display device, and more particularly to an adhesive film used in various industrial fields such as electrical machinery / electronics or optics, and an image display device using the adhesive film.

Conventionally, optical films such as a polarizing film, a retardation film, a brightness enhancement film, and a viewing angle widening film have been used for various industrial applications. For example, a liquid crystal display (LCD), an organic electroluminescence device (organic EL display). Device) and an image display device such as a plasma display panel (PDP).
As an optical film attached to these image display devices, an adhesive optical film in which an adhesive is laminated on an optical film is known.

In recent years, from the viewpoint of environmental impact, it has been desired to reduce the use of organic solvents. From solvent-based adhesives that use organic solvents as solvents, to water-dispersed adhesives that use water as a dispersion medium. Conversion 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).

  In addition, the adhesive optical film has a surface protective film attached to the surface of the adhesive optical film so that the surface of the adhesive optical film is not scratched or soiled in the manufacturing process or the transport process after manufacture. The adhesive optical film is attached to the image display device. And if the transport process of an image display apparatus is complete | finished, the surface protection film will usually be peeled from the adhesive optical film.

However, when the surface protective film is peeled from the adhesive optical film, static electricity (so-called peeling charge) is generated between the adhesive optical film and the surface protective film, and the liquid crystal alignment of the adhesive optical film is disturbed. If the circuit of the attached image display device is destroyed, the image is disturbed.
Therefore, as the pressure-sensitive adhesive film including the pressure-sensitive adhesive optical film that can prevent the above-described peeling charge, for example, a base film and a base film formed on one main surface of the base film are tin oxide-based and indium oxide-based. An antistatic pressure-sensitive adhesive sheet having an antistatic layer comprising a conductive filler such as zinc oxide and an organic binder and an adhesive layer formed on the surface of the antistatic layer has been proposed (for example, Patent Documents) 2).
JP 2001-254063 A JP-A-8-245932

However, although the adhesive film using the conventional water-dispersed adhesive including Patent Document 1 has improved adhesion to hydrophobic adherends such as polyolefin, it has adhesion to hydrophilic adherends such as glass. There is a problem that it is particularly low and it is difficult to firmly adhere to the glass substrate of the image display device.
In addition, the water-dispersed pressure-sensitive adhesive layered on the pressure-sensitive adhesive film is required to have high heat resistance and heat-and-moisture resistance that do not deteriorate the adhesiveness due to severe heating or humidification.

Furthermore, in the antistatic pressure-sensitive adhesive sheet proposed in Patent Document 2, it is difficult to ensure sufficient adhesion between the base film and the pressure-sensitive adhesive layer.
The object of the present invention is to have high adhesion to a glass substrate, high heat resistance and moist heat resistance, and to prevent the charging of the adhesive film and effectively remove the charge when peeling the surface protective film. The present invention provides an adhesive film having an antistatic layer capable of preventing adhesion and improving the adhesion between a substrate and an adhesive layer, and an image display device using the adhesive film. .

（一般式（１）中、Ｒ^１は、水素原子またはメチル基を、Ｒ^２は、下記一般式（２）で表されるポリオキシアルキレン基を、Ｘは、下記一般式（３）で表されるリン酸基またはその塩を示す。）

（一般式（２）中、ｎは１〜４の整数、ｍは２以上の整数を示す。）

（一般式（３）中、Ｍ^１およびＭ^２は、それぞれ独立に、水素原子またはカチオンを示す。）
前記カルボキシル基含有ビニルモノマー濃度［ミリモル／ｇ］＝１０００×｛（前記カルボキシル基含有ビニルモノマーの配合重量［ｇ］）／（前記カルボキシル基含有ビニルモノマーの分子量［ｇ／モル］）｝／（前記原料モノマーの総重量［ｇ］ （４）
前記リン酸基含有ビニルモノマー濃度［ミリモル／ｇ］＝１０００×｛（前記リン酸基含有ビニルモノマーの配合重量［ｇ］）／（前記リン酸基含有ビニルモノマーの分子量［ｇ／モル］）｝／（前記原料モノマーの総重量［ｇ］ （５） In order to achieve the above object, the pressure-sensitive adhesive film of the present invention is interposed between a base material, a pressure-sensitive adhesive layer laminated on at least one surface of the base material, and the base material and the pressure-sensitive adhesive layer. An antistatic layer, and the pressure-sensitive adhesive layer is a (meth) acrylic acid alkyl ester having a C 4-18 alkyl group, a carboxyl group-containing vinyl monomer, and a phosphate group represented by the following general formula (1) A pressure-sensitive adhesive composition obtained by polymerizing a raw material monomer containing a vinyl monomer and optionally a copolymerizable vinyl monomer copolymerizable with the monomer, and the mixing ratio of the raw material monomer is 100 The (meth) acrylic acid alkyl ester is 60 to 99 parts by weight with respect to parts by weight, and the carboxyl group-containing vinyl monomer and the phosphate group-containing vinyl monomer. The total amount of the pre-said copolymerizable vinyl monomer is 1 to 40 parts by weight, the raw material monomer, carboxyl group-containing vinyl monomer concentration represented by the following formula (4) is 0.05 to 1.50 mmol / g, And the phosphoric acid group containing vinyl monomer density | concentration shown by following formula (5) is 0.01-0.45 mmol / g, and the said antistatic layer contains water-soluble or water-dispersible electrically-conductive material. It is characterized by.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a polyoxyalkylene group represented by the following general formula (2), and X represents the following general formula (3). A phosphoric acid group or a salt thereof.

(In general formula (2), n represents an integer of 1 to 4, and m represents an integer of 2 or more.)

(In General Formula (3), M ¹ and M ² each independently represent a hydrogen atom or a cation.)
The carboxyl group-containing vinyl monomer concentration [mmol / g] = 1000 × {(the blending weight of the carboxyl group-containing vinyl monomer [g]) / (the molecular weight of the carboxyl group-containing vinyl monomer [g / mol])} / (the above Total weight of raw material monomer [g] (4)
Concentration of the phosphate group-containing vinyl monomer [mmol / g] = 1000 × {(Blend weight of the phosphate group-containing vinyl monomer [g]) / (Molecular weight of the phosphate group-containing vinyl monomer [g / mol])} / (Total weight of raw material monomers [g] (5)

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a polyoxyalkylene group represented by the following general formula (2), and X represents the following general formula (3). A phosphoric acid group or a salt thereof.

  (In general formula (2), n represents an integer of 1 to 4, and m represents an integer of 2 or more.)

(In General Formula (3), M ¹ and M ² each independently represent a hydrogen atom or a cation.)
In the pressure-sensitive adhesive film of the present invention, the pressure-sensitive adhesive composition further contains an alkoxysilyl group-containing vinyl monomer as the copolymerizable vinyl monomer, and the blending ratio thereof is 100 parts by weight based on the total amount of raw material monomers. And 0.001 to 1 part by weight is preferable.

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

In the pressure-sensitive adhesive 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 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.

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

In the pressure-sensitive adhesive film of the present invention, it is preferable that the antistatic layer further contains a polyamine polymer.
In the pressure-sensitive adhesive film of the present invention, it is preferable that the substrate is an optical film.
The image display device of the present invention is characterized by using at least one adhesive film described above.

The pressure-sensitive adhesive film of the present invention has high adhesive strength with a glass substrate and can achieve strong adhesion. Furthermore, since it has high heat resistance and heat-and-moisture resistance, excellent durability under a high-temperature atmosphere or a high-temperature and high-humidity atmosphere can be obtained. Therefore, the image display device of the present invention in which the pressure-sensitive adhesive film of the present invention is used can achieve high heat resistance and moist heat resistance.
In the pressure-sensitive adhesive film of the present invention, since the antistatic layer contains a water-soluble or water-dispersible conductive material, it is difficult to be charged and the adhesion between the substrate and the pressure-sensitive adhesive layer can be increased. Therefore, the pressure-sensitive adhesive film of the present invention can effectively prevent the peeling charge when peeling the surface protective film, and can be used in various industrial fields as a pressure-sensitive adhesive film having high adhesion between the substrate and the pressure-sensitive adhesive layer. it can.

  The image display device using the pressure-sensitive adhesive film of the present invention can achieve a high antistatic effect and a high adhesion between the substrate and the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive film of the present invention includes a base material, a pressure-sensitive adhesive layer laminated on at least one surface of the base material, and an antistatic layer interposed between the base material and the pressure-sensitive adhesive layer.
In the pressure-sensitive adhesive film of the present invention, the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive composition, and this pressure-sensitive adhesive composition is a water-dispersed pressure-sensitive adhesive composition, and has 4 to 18 carbon atoms of an alkyl group as a raw material monomer. (Meth) acrylic acid alkyl ester, carboxyl group-containing vinyl monomer, phosphoric acid group-containing vinyl monomer represented by the following general formula (1), and optionally a copolymerizable vinyl monomer copolymerizable with the above-mentioned monomer The mixing ratio of the raw material monomers is 60 to 99 parts by weight of the (meth) acrylic acid alkyl ester with respect to 100 parts by weight of the total amount of raw material monomers, and the carboxyl group-containing vinyl monomer, phosphate group-containing vinyl monomer and the total amount of the polymerizable vinyl monomer is 1 to 40 parts by weight, the raw material monomer, 0.05 carboxyl group-containing vinyl monomer concentration It was .50 mmol / g, and phosphoric acid group-containing vinyl monomer concentration is 0.01 to 0.45 mmol / g.

(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.)
Examples of the (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group include a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester, and examples thereof include butyl (meth) acrylate and isobutyl (meth) acrylate. , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (meth) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate, (Meth) dodecyl acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate ( Examples include (meth) acrylic acid alkyl (linear or branched alkyl having 4 to 18 carbon atoms) ester. These alkyl (meth) acrylates are used alone or in combination as appropriate.

The compounding ratio of the (meth) acrylic acid alkyl ester is, for example, 60 to 99 parts by weight, or preferably 70 to 99 parts by weight with respect to 100 parts by weight of the total amount of raw material monomers.
As the carboxyl group-containing vinyl monomer, any vinyl monomer having a carboxyl group in the molecule may be used. For example, unsaturated carboxylic acid such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, etc. Acids such as monomethyl itaconate, monobutyl itaconate, 2-acryloyloxyethylphthalic acid and other unsaturated dicarboxylic acid monoesters such as 2-methacryloyloxyethyl trimellitic acid, 2-methacryloyloxyethyl pyromellitic acid, etc. Saturated tricarboxylic acid monoesters, for example, carboxyalkyl acrylates such as β-carboxyethyl acrylate, carboxypentyl acrylate, ω-carboxy-polycaprolactone monoacrylate and the like.

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 are used alone or in combination as appropriate.
The carboxyl group-containing vinyl monomer concentration of the carboxyl group- containing vinyl monomer is, for example, 0.05 to 1.50 mmol / g, preferably 0.20 to 0.90 mmol / g in the raw material monomer. In order to set the carboxyl group- containing vinyl monomer concentration of the carboxyl group- containing vinyl monomer within 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 set to 100 wt. For example, 0.4 to 41 parts by weight, preferably 1.4 to 25 parts by weight with respect to parts. When the amount is less than the above range, the cohesive force of the water-dispersed pressure-sensitive adhesive composition is lowered, and when it is more than the above-mentioned range, stability during emulsion polymerization and water resistance of the water-dispersed pressure-sensitive adhesive composition are lowered.

In addition, the carboxyl group- containing vinyl monomer concentration in the raw material monomer is calculated by the following formula.
Concentration of carboxyl group- containing vinyl monomer [mmol / g] = 1000 × {(Blend weight of carboxyl group-containing vinyl monomer [g]) / (Molecular weight of carboxyl group-containing vinyl monomer [g / mol])} / (Total weight of raw material monomers) [G])
In the above formula, the total weight of raw material monomers is a weight that does not include water and additives such as an initiator, an emulsifier, a chain transfer agent, a crosslinking agent, and a viscosity modifier, which will be described later.

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

(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.

The higher the degree of polymerization of the oxyalkylene group, the higher the mobility of the side chain having the phosphate group, and the quicker interaction with the glass improves the adhesion of the water-dispersed pressure-sensitive adhesive composition to the glass substrate. To do.
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 a phosphoric acid group containing vinyl monomer, for example, Sipomer PAM-100 (made by Rhodia Nikka Co., Ltd.), Phosmer PE (made by Unichemical Co., Ltd.), Phosmer. Mono [poly (ethylene oxide) methacrylate] phosphate esters such as PEH (Unichemical Co., Ltd.) and Phosmer PEDM (Unichemical Co., Ltd.), for example, Sipomer PAM-200 (Rodia Nikka Co., Ltd.), Mono [poly (propylene oxide) methacrylate] phosphates such as Phosmer PP (manufactured by Unichemical Co., Ltd.), Phosmer PPH (manufactured by Unichemical Co., Ltd.), and Phosmer PPDM (manufactured by Unichemical Co., Ltd.). .

These phosphate group-containing vinyl monomers are used alone or in combination as appropriate.
The phosphoric acid group- containing vinyl monomer concentration of the phosphoric acid group- containing vinyl monomer is, for example, 0.01 to 0.45 mmol / g, preferably 0.02 to 0.20 mmol / g in the raw material monomer. In order to set the phosphoric acid group- containing vinyl monomer concentration of the phosphoric acid group- containing vinyl monomer within the above-mentioned range, the mixing ratio of the phosphoric acid group-containing vinyl monomer is determined depending on the molecular weight of the phosphoric acid group-containing vinyl monomer. For example, 0.4 to 22 parts by weight, preferably 0.8 to 10 parts by weight is set with respect to 100 parts by weight of the total amount. If the amount is less than the above range, the effect of improving the adhesion to the glass substrate cannot be obtained sufficiently. If the amount is more than the above range, the stability during emulsion polymerization is lowered, or the elastic modulus of the water-dispersed pressure-sensitive adhesive composition is reduced. The adhesiveness may decrease due to the increase in the thickness.

Incidentally, phosphoric acid group-containing vinyl monomer concentration in the raw material monomer is calculated by the following equation.
Phosphoric group- containing vinyl monomer concentration [mmol / g] = 1000 × {(Blend weight of phosphate group-containing vinyl monomer [g]) / (Molecular weight of phosphate group-containing vinyl monomer [g / mol])} / (Raw material Total monomer weight [g])
In the above formula, the total weight of raw material monomers is a weight that does not include water and additives such as an initiator, an emulsifier, a chain transfer agent, a crosslinking agent, and a viscosity modifier.

Examples of the copolymerizable vinyl monomer copolymerizable with the above-described monomer include functional group-containing vinyl monomers other than carboxylic acid.
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, glycidyl (meth) acrylate, (meta ) Methyl glycy acrylate Glycidyl group-containing unsaturated monomers such as styrene, 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 group-containing unsaturated monomers such as sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, For example, maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, such as N-methylitaconimide, N-ethylitaconimide N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl leuconconimide, N-lauryl itaconimide and other itaconimide monomers such as N- (meth) acryloyloxymethylene succinimide, Succinimide monomers such as N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate And glycol-based acrylic ester monomers such as (meth) acrylic acid methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol.

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, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Examples include tall tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and divinylbenzene. Examples of the polyfunctional monomer include epoxy acrylate, polyester acrylate, and urethane acrylate.

  As the copolymerizable vinyl monomer, in addition to the above functional group-containing vinyl monomer, for example, aromatic vinyl monomers such as styrene, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Alkyl (meth) acrylate (linear or branched alkyl having 1 to 3 carbon atoms) such as propyl acrylate and isopropyl (meth) acrylate, such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, (Meth) acrylic acid alicyclic hydrocarbon esters such as isobornyl (meth) acrylate, for example, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, for example, methoxyethyl (meth) acrylate, (meth ) Alkoxy group-containing unsaturated monomers such as ethoxyethyl acrylate, for example, ethylene, propylene Olefin monomers such as isoprene, butadiene and isobutylene, vinyl ether monomers such as vinyl ether, halogen atom-containing unsaturated monomers such as vinyl chloride, and others such as N-vinylpyrrolidone and N- (1-methylvinyl). ) Pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, (meth) Examples thereof include vinyl group-containing heterocyclic compounds such as tetrahydrofurfuryl acrylate, and acrylic ester monomers containing halogen atoms such as fluorine atoms such as fluorine (meth) acrylate.

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-triisopropoxysilane, (meth) acryloyloxyalkyl-trialkoxysilane such as 3- (meth) acryloyloxypropyl-tributoxysilane, for example, (meth) acryloyloxymethyl-methyl Dimethoxysilane, (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-methyldiisopropoxysilane, 3- (Meth) acryloyloxypropyl-methyldibutoxysilane, 3- (meth) acryloyloxypropyl-ethyldimethoxysilane, 3- (meth) acryloyloxypropyl-ethyldiethoxysilane, 3- (meth) acryloyloxypropyl Ethyl dipropoxysilane, 3- (meth) acryloyloxypropyl-ethyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-ethyldibutoxysilane, 3- (meth) acryloyloxypropyl-propyldimethoxysilane, 3- ( Examples include (meth) acryloyloxyalkyl-alkyl dialkoxysilanes such as (meth) acryloyloxypropyl-propyldiethoxysilane, and (meth) acryloyloxyalkyl-dialkyl (mono) alkoxysilanes corresponding to these.

  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 are used alone or in combination as appropriate.
Of these copolymerizable vinyl monomers, an alkoxysilyl group-containing vinyl monomer is preferable.
By using an alkoxysilyl group-containing vinyl monomer as a 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 glass 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 19 parts by weight or less, with respect to 100 parts by weight of the total amount of raw material monomers. 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 with respect to 100 parts by weight of the total amount of raw material monomers. 0.005 to 0.1 part by weight. If the alkoxysilyl group-containing vinyl monomer is less than the above range, crosslinking by the alkoxysilyl group is insufficient, resulting in a decrease in cohesive strength of the pressure-sensitive adhesive, or adhesion between the water-dispersed adhesive composition and the glass substrate. If the improvement is not obtained and the amount is larger than the above range, stability may be lowered during emulsion polymerization or adhesion may be lowered.

Moreover, among the above-mentioned raw material monomers, the total amount of the above-mentioned carboxyl group-containing vinyl monomer, phosphoric acid group-containing vinyl monomer and copolymerizable vinyl monomer is such that the blending ratio is, for example, 100 parts by weight of the total amount of raw material monomers. 1 to 40 parts by weight, preferably 1 to 30 parts by weight.
And in order to prepare a water dispersion-type adhesive composition, the above-mentioned raw material monomer 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 appropriately blended in water together with the above-described raw material monomers 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 appropriately selected. Although reaction conditions etc. are selected suitably, superposition | polymerization temperature is 20-90 degreeC, for example.

  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 are suitably used alone or in combination.
Of these polymerization initiators, azo initiators are preferably used.
The mixing ratio of the polymerization initiator is appropriately selected, and is, for example, 0.005 to 1 part by weight with respect to 100 parts by weight of the total amount of raw material monomers.
Note that the dissolved oxygen concentration in the monomer solution may be reduced by nitrogen substitution before or while blending the above-described raw material monomer with the polymerization initiator.

  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. Ichi Kogyo Seiyaku Co., Ltd.)).
These emulsifiers are used alone or in combination as appropriate. Moreover, the mixture ratio of an emulsifier is 0.2-10 weight part with respect to 100 weight part of total amounts of a raw material monomer, Preferably, it is 0.5-5 weight part.

The chain transfer agent adjusts the molecular weight of the water-dispersed pressure-sensitive adhesive composition as necessary, 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 are appropriately used alone or in combination. Moreover, the mixture ratio of a chain transfer agent is 0.001-0.5 weight part with respect to 100 weight part of total amounts of a raw material monomer, for example.

And the copolymer obtained by such emulsion polymerization can be prepared as an emulsion (water dispersion) of a water-dispersed pressure-sensitive adhesive composition.
The water-dispersed pressure-sensitive adhesive composition may be prepared, for example, by polymerizing the above-described raw material monomers by a method that does not use an organic solvent other than emulsion polymerization, and then dispersing in water using the above-described emulsifier. it can.

  Moreover, you may mix | blend a crosslinking agent with a water dispersion-type adhesive composition as needed according to the objective and use. 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 total amount of raw material monomers.

The water-dispersed pressure-sensitive adhesive composition is adjusted to, for example, pH 7-9, preferably pH 7-8, for example, with ammonia water for the purpose of improving the stability of the emulsion.
Furthermore, the water-dispersed pressure-sensitive adhesive composition includes a viscosity modifier, and if necessary, a release modifier, a plasticizer, a softener, a filler, a colorant (pigment, dye, etc.), an anti-aging agent, and a surfactant. For example, additives that are usually added to the water-dispersed pressure-sensitive adhesive composition may be appropriately added. The mixing ratio of these additives is not particularly limited, and can be appropriately selected.

The viscosity modifier is not particularly limited, and examples thereof include an acrylic thickener.
The gel fraction of the water-dispersed pressure-sensitive adhesive composition (solid content) thus prepared is, for example, 50 to 100% by weight, and preferably 70 to 100% by weight. When the gel fraction is lower than the above-mentioned value, this water-dispersed pressure-sensitive adhesive composition is applied to a pressure-sensitive adhesive film whose base material is an optical film (that is, pressure-sensitive adhesive optical film), and in a high-temperature and high-humidity atmosphere. When used, foaming or peeling may occur.

The gel fraction can be calculated by the following formula when the water-dispersed pressure-sensitive adhesive composition is covered with a Teflon sheet and immersed in ethyl acetate for 7 days.
Gel fraction (% by weight) = (weight of water-dispersed pressure-sensitive adhesive composition adhering to the Teflon sheet after immersion) / weight of water-dispersed pressure-sensitive adhesive composition before immersion) × 100
In the pressure-sensitive adhesive film of the present invention, the antistatic layer contains a water-soluble or water-dispersible conductive material.

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 size (size) of the fine particles is, for example, from the viewpoint of uniformity of the antistatic layer, 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 is easy to apply for forming an antistatic layer (thin film coating). Furthermore, the uniformity of the water-dispersible conductive material in the antistatic layer is excellent.

Examples of the water-soluble or water-dispersible conductive material include conductive polymers, organometallic compounds, metal oxides, and carbon nanomaterials.
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 remains in the coating solution, or a part of the polyaniline or polythiophene has a high viscosity to form an antistatic layer 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 Co., Ltd., trade name “Denatron” (Denatron series)).

These conductive polymers are suitably used alone or in combination.
Further, for example, a doping agent, a crosslinking agent, a radical initiator, and a crosslinking reaction type compound can be added to the conductive polymer.
The doping agent functions as a dopant and more reliably imparts (doping) conductivity to the conductive polymer, and examples thereof include sulfonic acid compounds.

  The sulfonic acid compound is water-soluble, for example, p-toluenesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, m-xylenesulfonic acid, polystyrenesulfone. An acid, polyvinyl sulfonic acid, etc. are mentioned. Preferably, polystyrene sulfonic acid and polyvinyl sulfonic acid are used in order to improve the solubility and water dispersibility of the conductive polymer. These sulfonic acid compounds are appropriately used alone or in combination.

By adding such a doping agent, the conductive polymer and the sulfonic acid compound partially react to form a sulfonate, and it is estimated that the antistatic function of the antistatic layer is improved by the action of the sulfonate. The
The blending ratio of the doping agent is, for example, 100 to 300 parts by weight, preferably 150 to 250 parts by weight with respect to 100 parts by weight of the conductive polymer. When the blending ratio of the doping agent is less than 100 parts by weight, a sufficient antistatic function may not be obtained because the amount of sulfonate formed by the reaction between the conductive polymer and the sulfonic acid compound decreases. . On the other hand, when the compounding ratio of the doping agent is more than 300 parts by weight, the antistatic function tends not to be improved by increasing the doping agent from the above-described mixing ratio.

Although it does not specifically limit as a crosslinking agent, For example, a melamine type crosslinking agent, a polycarbodiimide type crosslinking agent, a polyoxazolidine type crosslinking agent, a polyepoxy type crosslinking agent, a polyisocyanate type crosslinking agent etc. are mentioned, Preferably, a melamine type is mentioned. A crosslinking agent is mentioned. These crosslinking agents are suitably used alone or in combination.
By adding such a crosslinking agent, the conductive polymer is crosslinked and cured, so that an antistatic layer having excellent water resistance and durability can be formed.

The blending ratio of the crosslinking agent is, for example, 0.001 to 5 parts by weight, preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the conductive polymer.
A radical initiator is a compound that generates radicals by irradiation with heat, light (for example, ultraviolet (UV), electron beam (EB), etc.), and is used for the above-described emulsion polymerization, for example. The thing similar to an initiator is mentioned. Preferably, peroxide initiators (such as benzoyl peroxide), sulfate initiators (such as potassium persulfate), and azo initiators (such as 2,2′-azobisisobutyronitrile) are used. These radical initiators are suitably used alone or in combination.

By adding such a radical initiator, hydrogen atoms of the conductive polymer are extracted by the generated radicals, and radicals are generated on the conductive polymer. Subsequently, these radicals react with each other, crosslink and cure, so that an antistatic layer having excellent water resistance and durability can be formed.
The blending ratio of the radical initiator is, for example, 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the conductive polymer. is there.

The crosslinking reaction type compound is a binder component, and is a monomer, oligomer or polymer that is soluble in water before the crosslinking reaction, and is a compound that forms a three-dimensional network structure and is insoluble in water after the crosslinking reaction. is there. For example, a two-component reaction type epoxy resin, urea resin, melamine resin and the like can be mentioned.
A two-component reaction type epoxy resin is composed of a main agent and a curing agent, and by blending both, an irreversible crosslinking reaction is performed to form a three-dimensional polymer network structure.

  The main agent is a water-soluble polyfunctional epoxy resin. Examples of such water-soluble polyfunctional epoxy resins include triglycidyl isocyanurate, sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, polyethylene glycol diester. Examples thereof include aliphatic glycidyl ethers such as glycidyl ether and (poly) propylene glycol diglycidyl ether, and alicyclic glycidyl ethers such as sorbitan polyglycidyl ether.

  The curing agent is a water-soluble curing agent. Examples of such a water-soluble curing agent include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and polyamidoamine, such as 2-methylimidazole, Imidazoles such as 2-ethyl-4-methylimidazole, for example, tertiary amines such as benzyldimethylamine, such as phthalic anhydride, methyl hymic anhydride (eg, 3-methyl-1,2,3 , 6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, etc.), for example, Lewis acids such as boron trifluoride.

The urea resin is obtained by subjecting an initial prepolymer (monomethylol urea) obtained by addition reaction of urea and formaldehyde to a dehydration condensation reaction. The initial prepolymer of urea resin may be modified with phenols or benzoguanamine.
The melamine resin is obtained by subjecting an initial prepolymer (methylol melamine and dimethylol melamine) obtained by addition reaction of melamine and formaldehyde to a dehydration condensation reaction. The initial prepolymer of melamine resin may be modified with phenols or benzoguanamine.

As the above-mentioned initial prepolymer of urea resin and initial prepolymer of melamine resin, commercially available products can be used. For example, the Euramin series (manufactured by Mitsui Chemicals), the Nicarac series (Sanwa Chemical) Etc.).
These crosslinking reaction type compounds are used alone or in combination as appropriate.
By adding such a crosslinking reaction type compound, a three-dimensional network structure is formed and cured, so that an antistatic layer excellent in water resistance and durability can be formed without impairing optical properties and antistatic effects. Can do.

The blending ratio of the crosslinking reaction type compound is, for example, 10 to 250 parts by weight, and preferably 30 to 200 parts by weight with respect to 100 parts by weight of the conductive polymer.
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 organometallic compounds are suitably used alone or in combination.
Examples of the metal oxide include a tin oxide system, an antimony oxide system, an indium oxide system, and a zinc oxide system, and a tin oxide system is preferable.
As the tin oxide system, for example, tin oxide, in addition to tin oxide, for example, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide Examples of the composite include a composite of titanium oxide and tin oxide.

The shape of the metal oxide is, for example, in the form of particles or needles, and the maximum length (in the case of particles, the average particle diameter) is, for example, 1 to 100 nm, preferably 2 to 50 nm. .
These metal oxides are appropriately used alone or in combination.
Examples of the carbon nanomaterial include carbon nanotubes, carbon nanohorns, carbon nanowalls, fullerenes, and preferably carbon nanotubes.

The carbon nanotube is generally a carbon fiber formed in a hollow fiber shape, and its diameter is, for example, 0.5 nm to 5 μm, preferably 0.5 nm to 1 μm, and its maximum length is, for example, 10 nm. ˜1000 μm, preferably 10 nm to 100 μm.
These carbon nanomaterials are appropriately used alone or in combination.
Of these water-soluble or water-dispersible conductive materials, conductive polymers and organometallic compounds are preferable.

In the pressure-sensitive adhesive film of the present invention, the antistatic layer preferably further contains an oxazoline group-containing polymer, a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, or 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 general formula (4), R ³ , R ⁴ , R ⁵ and R ⁶ 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 5,000, the strength of the antistatic layer 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.

The oxazoline group-containing polymer contains an oxazoline group-containing polymer in the antistatic layer because the oxazoline group reacts with a functional group (such as a carboxyl group or a hydroxyl group) contained in the water-dispersed pressure-sensitive adhesive composition at a relatively low temperature. If it does, it reacts with the functional group etc. in an adhesive layer, and can adhere | attach firmly.
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.), Epocross WS-700 (aqueous solution type, solid content 25%, main chain: acrylic, pH 7-9, oxazoline value 220 g solid / eq., Manufactured by Nippon Shokubai Co., Ltd.) Oxazoline group-containing acrylic polymer, for example, Epocross K-1000 series (emulsion type, solid content 40%, main chain: styrene / acrylic, oxazoline value 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 / a Lil system, pH 7-9, oxazoline value 550 g solid / eq., And the like oxazoline group-containing acrylic / styrene polymers, such as KK Nippon Shokubai). From the viewpoint of improving adhesion, an aqueous solution type is preferable to an emulsion type containing an emulsifier.

These oxazoline group-containing polymers are appropriately used alone or in combination.
In general, when a substrate such as an optical film is attached to an image display device, the optical film is attached to the image display device, and then peeled off for position adjustment as necessary, and then reattached (rework) However, with such an adhesive, the adhesive remains on the surface of the image display device at the time of peeling (hereinafter referred to as “adhesive residue”), and there is a problem that the reworkability is not sufficient.

  However, if the antistatic layer contains the above-mentioned oxazoline group-containing polymer, the affinity with the water-dispersed pressure-sensitive adhesive composition is good, and the adhesion between the optical film and the water-dispersed pressure-sensitive adhesive composition is increased. An adhesive film having high heat resistance can be obtained. As a result, it is possible to obtain a pressure-sensitive adhesive optical film having an antistatic function with good reworkability and high heat resistance.

In a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, examples of the compound containing a plurality of carboxyl groups include dicarboxylic acid compounds such as succinic acid, adipic acid, and phthalic acid, such as citric acid. And saturated low molecular weight compounds containing a plurality of carboxyl groups, such as tricarboxylic acid compounds.
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.
Moreover, the carboxyl group which the compound containing a some carboxyl group has may form the salt with the cation all or one part.

Examples of the cation include inorganic cations such as potassium ion and sodium ion, for example, ammonium cations, and organic cations such as primary amine, secondary amine, and tertiary amine cations.
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) ) And the like.

These compounds containing a plurality of carboxyl groups are appropriately used alone or in combination.
In general, when a water-soluble material is used as the antistatic layer, if the antistatic layer is thick, the antistatic layer is reduced in strength when used in a high-humidity atmosphere, resulting in interlayer breakdown. There is a case. However, when the antistatic layer includes 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 and a compound containing a plurality of carboxyl groups By reacting with a carboxyl group, the antistatic layer is cross-linked and becomes a stronger antistatic layer, so that it is presumed that heat resistance and moist heat resistance are increased and adhesion is increased.

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

  The polyamine 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. An ethyleneimine-modified acrylic polymer or an allylamine-modified acrylic polymer in which a polyethyleneimine chain represented by the following general formula (5) or a polyallylamine chain represented by the following general formula (6) is modified on the side chain Can be mentioned. 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. If the number average molecular weight is less than 200, the strength of the antistatic layer may be 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., Japan) Catalyst), Epomin SP-018 (water-soluble type, amine hydrogen equivalent 52.6 g solid / eq., Nippon Shokubai Co., Ltd.), Epomin SP-103 (water-soluble type, amine hydrogen equivalent 52.6 g solid / eq) Epomin SP-110 (water-soluble type, amine hydrogen equivalent 55.6 g solid / eq., Nippon Touch Co., Ltd.) Epomin SP-200 (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. , Polyimine 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. (Made by Nippon Shokubai Co., Ltd.) POLYMENT NK-200 pM (soluble type, amine hydrogen equivalent 350~450g solid / eq., (Ltd.) manufactured by Nippon Shokubai Co., Ltd.) and the like ethyleneimine-modified acrylic polymer, such as.

These polyamine polymers are used alone or in combination as appropriate.
In addition to the water-soluble or water-dispersible conductive material, the oxazoline group-containing polymer, the mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups, or a component such as a polyamine polymer, Furthermore, a binder may be included.

  The binder is optionally used in combination with each of the above-described components for the purpose of improving the adhesion of the water-soluble or water-dispersible conductive material to a thin film coating property, a substrate such as an optical film, For example, polymer compounds such as polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, polystyrene resins, polyethylene glycol resins, for example, penta And low molecular weight compounds such as erythritol. Preferably, polyurethane resin, polyester resin, and acrylic resin are used.

These binders are suitably used alone or in combination depending on the application.
Each component (water-soluble or water-dispersible conductive material, oxazoline group-containing polymer, mixture of oxazoline group-containing polymer and compound containing a plurality of carboxyl groups, polyamine polymer, binder) is dissolved or dispersed in a solvent. It is prepared as a solution or dispersion of each component.

  Preferably, from the viewpoint of preventing alteration of the optical film, an aqueous solution or an aqueous dispersion in which each component is dissolved or dispersed in water (hereinafter, these may be simply referred to as “coating liquid” in some cases). It has been prepared as. More preferably, a water-dispersible conductive material coating solution, a water-dispersible conductive material and an oxazoline group-containing polymer coating solution, a water-dispersible conductive material and an oxazoline group-containing polymer and a plurality of these components are dispersed in water. It is prepared as a coating solution of a mixture with a compound containing a carboxyl group, or a coating solution of a dispersible conductive material and a polyamine polymer.

In such a coating liquid, it is not necessary to use a non-aqueous organic solvent, and therefore, alteration of the substrate (such as an optical film) due to the organic solvent can be suppressed.
In such a 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 described above, the blending ratio of the water-soluble or water-dispersible conductive material is, for example, 0.05 to 80% by weight, preferably 0.1 to 50% by weight. In particular, when the water-soluble or water-dispersible conductive material is an organometallic compound, the blending ratio of the organometallic compound is, for example, 0.1 to 80% by weight, preferably 1 to 50% by weight. If the compounding ratio of the organometallic compound is within the above range, the metal content of the organometallic compound in the coating solution is 0.1 to 20% by weight, preferably 1 to 15 depending on the composition of the organometallic compound. % By weight.

  The blending ratio of the oxazoline group-containing polymer is, for example, 0.01 to 20% by weight, preferably 0.05 to 10% by weight in the coating solution. The blending ratio of the mixture of the oxazoline group-containing polymer and the compound containing a plurality of carboxyl groups is, for example, 0.01 to 25% by weight, preferably 0.05 to 15% by weight in the coating solution. The mixing ratio of the polyamine polymer is, for example, 0.01 to 20% by weight, preferably 0.05 to 10% by weight in the coating solution.

The blending ratio of the binder is, for example, 0.01 to 10% by weight, preferably 0.05 to 5% by weight in the coating solution.
The above-described coating solution forms an antistatic layer by coating and drying described later.
In the antistatic layer formed in this way, the blending ratio of the water-soluble or water-dispersible conductive material is, for example, 10 to 100 parts by weight, preferably 20 to 20 parts by weight with respect to 100 parts by weight of the total amount of each component described above. 90 parts by weight.

  The blending ratio of the oxazoline group-containing polymer is, for example, 10 to 500 parts by weight, preferably 20 to 400 parts by weight with respect to 100 parts by weight of the water-soluble or water-dispersible conductive material. The blending ratio of the mixture of the oxazoline group-containing polymer and the compound containing a plurality of carboxyl groups is, for example, 20 to 800 parts by weight, preferably 30 to 500 parts per 100 parts by weight of the water-soluble or water-dispersible conductive material. Parts by weight. The compounding ratio of the polyamine polymer is, for example, 10 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the water-soluble or water-dispersible conductive material.

The blending ratio of the binder is, for example, 5 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the water-soluble or water-dispersible conductive material.
The substrate is not particularly limited, and examples thereof include an optical film. Such an optical film is not particularly limited as long as it has optical characteristics and is a film attached to an image display device or the like. 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 phase difference as appropriate depending on the purpose of use. Two or more retardation films may be laminated to control optical characteristics such as retardation.
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.

Hereinafter, with reference to FIG. 1, one Embodiment of the manufacturing method of the adhesive film of this invention is described.
In order to obtain the adhesive film shown in FIG. 1, first, a base material 1 is prepared, and an antistatic layer 2 is laminated on one side of the base material 1.
The thickness of the base material 1 is 10-1000 micrometers, for example, Preferably, it is 50-500 micrometers.

In order to provide the antistatic layer 2, for example, a coating solution containing the above water-soluble or moisture conductive material is directly applied to the substrate 1 by a known coating method such as a coating method, a dipping method, or a spray method. The method of drying is mentioned.
Thus, by providing the antistatic layer 2, the adhesive force (throwing force) with the adhesive layer 3 can be improved.

  The thickness of the antistatic layer 2 is, for example, 1 to 500 μm, preferably 10 to 100 μm, more preferably 20 to 50 μm before drying, and the thickness after drying is, for example, 1 to 1000 nm, preferably , 10 to 500 nm, more preferably 20 to 400 nm. If it is in the above-mentioned thickness range, charging of the adhesive film and the adherend can be effectively prevented.

In addition, the surface resistance of the antistatic layer 2 is preferably 1 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less, when the antistatic layer 2 is provided on the substrate 1. Particularly preferably, it is 1 × 10 ¹⁰ Ω / □ or less. When the surface resistance exceeds 1 × 10 ¹² Ω / □, the antistatic function is not sufficient, and static electricity is generated and charged when the surface protective film shown in Examples described later is peeled off. There may be a problem that a circuit of the display device is broken or an image of the image display device is disturbed.

Next, the pressure-sensitive adhesive layer 3 is provided on one side of the substrate 1 with the antistatic layer 2 interposed therebetween.
In order to provide the pressure-sensitive adhesive layer 3, for example, a method of transferring the pressure-sensitive adhesive layer 3 from the release film having the pressure-sensitive adhesive layer 3 formed on the above-described antistatic layer 2 can be mentioned.
Examples of the release film include paper, synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate, rubber films, cloths, nonwoven fabrics, nets, foamed films and metal foils, and laminated films thereof. The surface of the release film may be subjected to treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment as necessary in order to enhance the release property from the pressure-sensitive adhesive layer 3.

  The release film on which the pressure-sensitive adhesive layer 3 is formed is directly applied to the release film with a coater such as a roll, a gravure, a bar, a knife, a comma, or a die, and then dried. Thus, it can be formed by forming the pressure-sensitive adhesive layer 3. In order to transfer the pressure-sensitive adhesive layer 3, the release film on which the pressure-sensitive adhesive layer 3 is formed is brought into contact with the base material 1 on which the antistatic layer 2 is provided, and the antistatic layer 2 and the pressure-sensitive adhesive layer 3 are in contact with each other. Thus, after bonding, the release film is peeled off from the pressure-sensitive adhesive layer 3.

In order to provide the pressure-sensitive adhesive layer 3, for example, the water-dispersed pressure-sensitive adhesive composition is directly applied to the antistatic layer 2 by a coater such as a roll, a gravure, a bar, a knife, a comma, or a die. It can also be formed by drying.
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, a pressure-sensitive adhesive film comprising the base material 1, the pressure-sensitive adhesive layer 3 laminated on one side of the base material 1, and the antistatic layer 2 interposed between the base material 1 and the pressure-sensitive adhesive layer 3 Can be obtained.
The pressure-sensitive adhesive film thus obtained is used for various industrial applications as a pressure-sensitive adhesive film such as a polarizing film, a retardation film, a brightness enhancement film, and a viewing angle widening film.

  This pressure-sensitive adhesive film is interposed between the base material 1 and the pressure-sensitive adhesive layer 3 and includes an antistatic layer 2 containing a water-soluble or water-dispersible conductive material. The adhesive force with the agent layer 3 can be increased. Therefore, the adhesive film can effectively prevent peeling electrification when the surface protective film is peeled off, and as an adhesive film having a high adhesive force between the base material 1 and the adhesive layer 3, electric / electronic, semiconductor, optical, etc. It can be used in various industrial fields. Preferably, the pressure-sensitive adhesive film is used as a pressure-sensitive adhesive optical film using an optical film as the substrate 1.

If this pressure-sensitive adhesive film is used as a pressure-sensitive adhesive optical film, the adhesive strength with the glass substrate of the image display device is high, and strong adhesion can be achieved.
Furthermore, since the above-mentioned adhesive film has high heat resistance and wet heat resistance, if this adhesive film is used as an adhesive optical film, a liquid crystal display (LCD), an organic electroluminescence device (organic EL display) Device) and a glass substrate surface of an image display device such as a plasma display panel (PDP), excellent durability can be obtained even in a high temperature atmosphere and a high temperature and high humidity atmosphere. Therefore, such an image display device can realize high heat resistance and moisture heat resistance.

In the above description, the antistatic layer 2 and the pressure-sensitive adhesive layer 3 are provided on one side of the substrate 1, but can also be provided on both sides of the substrate 1.
In addition, in a normal water-dispersed pressure-sensitive adhesive composition, a rosin resin, a tackifying resin such as an elastomer, and the like are added in order to increase the adhesion to an adherend, but it is used for the pressure-sensitive adhesive film of the present invention. Although the water-dispersed pressure-sensitive adhesive composition is water-dispersed, it can increase the adhesion without adding such a tackifying resin, so that the water-dispersed pressure-sensitive adhesive composition has high adhesion at low cost. An adhesive film having an adhesive layer made of a product, and an image display device using such an adhesive film can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.
(Preparation of monomer pre-emulsion)
In the container, as raw material monomers, 100 parts of butyl acrylate, 5 parts of acrylic acid, 2 parts of mono [poly (propylene oxide) methacrylate] phosphate ester (average degree of polymerization of propylene oxide of about 5.0), 3-methacryloyloxypropyl -A trimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 0.01 part was added and mixed, and the monomer mixture was prepared. Next, 13 g of reactive emulsifier Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and 360 g of ion-exchanged water are added to 627 g of the prepared monomer mixture, and 5 minutes using a homogenizer (manufactured by Tokushu Kika Co., Ltd.). A monomer pre-emulsion was prepared by stirring and forcibly emulsifying at 5000 (1 / min).
(Preparation of water-dispersed pressure-sensitive adhesive composition)
200 g of the monomer pre-emulsion prepared above and 330 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. did. 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 performed at 60 ° C. for 3 hours while purging with nitrogen to obtain an emulsion solution of a water-dispersed pressure-sensitive adhesive composition having a solid content of 48%. Next, this was cooled to room temperature, 10% aqueous ammonia was added to adjust the pH to 8, and 3.0 g of acrylic thickener Aron B-500 (manufactured by Toagosei Co., Ltd.) was added. Thus, a water-dispersed pressure-sensitive adhesive composition was prepared.

In this water-dispersed pressure-sensitive adhesive composition, the carboxyl group- containing vinyl monomer concentration is 0.65 mmol / g. In this calculation, the molecular weight of acrylic acid was calculated as 72.
In this water-dispersed pressure-sensitive adhesive composition, the concentration of the phosphoric acid group- containing vinyl monomer is 0.04 mmol / g. In this calculation, the molecular weight (average molecular weight) of mono [poly (propylene oxide) methacrylate] phosphate ester (average degree of polymerization of propylene oxide of about 5.0) was set to 456.
(Formation of adhesive layer)
A 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, and then It dried for 2 minutes at 100 degreeC with the hot-air circulation type oven, and formed the adhesive layer on the release film.
(Preparation of optical film)
A polyvinyl alcohol film (thickness 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 polarizer. Obtained. A triacetyl cellulose film as a transparent protective film was adhered to both sides of the polarizer using a polyvinyl alcohol adhesive to obtain an optical film.

Example 1
(Formation of antistatic layer)
Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corp.) is diluted with a mixed solution of water / isopropanol (1: 1 by weight) to a solid content of 0.5% by weight to prevent antistatic A layer coating solution was prepared. This coating solution was coated on one side of an optical film using a Mayer bar # 5 and dried at 40 ° C. for 2 minutes to form an antistatic layer.
(Preparation of adhesive optical film)
A release film on which an adhesive layer was formed was bonded to one side of an optical film on which an antistatic layer was formed to produce an adhesive optical film.

Example 2
In the preparation of the coating solution for the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation), Denatron P502RG (manufactured by Nagase ChemteX Corporation, polythiophene-based conductive polymer), Changed to Epocros WS-700 (oxazoline group-containing acrylic polymer, manufactured by Nippon Shokubai Co., Ltd.), so that the solid content is 1.0 wt% for Denatron P502RG and 0.25 wt% for Epocros WS-700. Except having changed, it processed like Example 1 and formed the antistatic layer, and then produced the adhesion type optical film.

Example 3
In the preparation of the coating solution for the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation) was replaced with ORGATIZ ZB-125 (zirconium chloride compound, ZrO ₂ content ratio 15%, Matsumoto). Change to a water / isopropanol (1: 1 by weight ratio) mixed solution to a water / ethanol (1: 1 weight ratio) mixed solution, and the ZrO ₂ content ratio is changed to An antistatic layer was formed in the same manner as in Example 1 except that the content was changed to 2% by weight, and then an adhesive optical film was produced.

Example 4
In the formation of the antistatic layer of Example 3, except that the ZrO ₂ content ratio of the coating solution was changed from 2% to 5%, the same treatment as in Example 3 was performed to form the antistatic layer, An adhesive optical film was produced.
Example 5
In the formation of the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corp.) was replaced with ORGATICS 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.), except that the Ti content ratio of the coating solution was changed to 2% Were treated in the same manner as in Example 1 to form an antistatic layer, and then an adhesive optical film was produced.

Example 6
In the formation of the antistatic layer of Example 5, an antistatic layer was formed by the same treatment as in Example 5 except that the Ti content ratio of the coating solution was changed from 2% to 5%. A mold optical film was prepared.
Example 7
In the formation of the antistatic layer of Example 3, ORGATIZ ZB-125 (zirconium chloride compound, ZrO ₂ content 15%, manufactured by Matsumoto Pharmaceutical Co., Ltd.) was replaced with ORGATIZ ZB-125 (zirconium chloride compound, ZrO _2). The content ratio was changed to 15%, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and Poliment SK-1000 (ethyleneimine modified acrylic polymer, manufactured by Nippon Shokubai Co., Ltd.), and water / ethanol (1: 1 by weight). ) Treated in the same manner as in Example 3 except that the mixed solution was changed to water and the ZrO ₂ content ratio of Orgatics ZB-125 was changed to 2% and the solid content of Poliment SK-1000 was changed to 2%. Then, an antistatic layer was formed, and then an adhesive optical film was produced.

Example 8
In the formation of the antistatic layer of Example 7, the antistatic layer was treated in the same manner as in Example 7 except that the ZrO ₂ content ratio of ORGATICS ZB-125 was changed from 2 wt% to 5 wt%. Then, an adhesive optical film was produced.
Example 9
In the formation of the antistatic layer of Example 5, Olgatrix TC-400 (diisopropoxytitanium bis (triethanolamate), (C ₃ H ₇ O) ₂ Ti (C ₆ H ₁₄ O ₃ N) ₂ , Ti-containing 8% ratio, manufactured by Matsumoto Pharmaceutical Co., Ltd.), ORGATIX 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.) and Polyment SK-1000 (ethyleneimine modified acrylic polymer, manufactured by Nippon Shokubai Co., Ltd.), the Ti content ratio of the coating solution is 2%. Except that the solid content of Poliment SK-1000 was changed to 2%, the same treatment as in Example 1 was performed to form an antistatic layer, and then an adhesive optical film was produced. It was.

Example 10
In the formation of the antistatic layer in Example 9, the antistatic layer was formed by the same treatment as in Example 9 except that the Ti content ratio of the coating solution was changed from 2% to 5%. A mold optical film was prepared.
Example 11
In the preparation of the coating solution for the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation) was replaced with ORGATIZ ZB-125 (zirconium chloride compound, ZrO ₂ content ratio 15%, Matsumoto). And Epocross WS-700 (oxazoline group-containing acrylic resin, solid content 25%, manufactured by Nippon Shokubai Co., Ltd.)) and water / ethanol (weight ratio is 1: 1). ) Same as Example 1 except that the mixed solution was changed to water so that the ZrO ₂ content of Orgatics ZB-125 was 2% by weight and the solid content of Epocros WS-700 was 2%. The antistatic layer was formed by processing, and then an adhesive optical film was produced.

Example 12
In the preparation of the coating solution for the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation) was replaced with ORGATIZ ZB-125 (zirconium chloride compound, ZrO ₂ content ratio 15%, Matsumoto). Manufactured by Pharmaceutical Industry Co., Ltd.), Epocross WS-700 (oxazoline group-containing acrylic resin, solid content 25%, manufactured by Nippon Shokubai Co., Ltd.)) and Poise 532A (acrylic acid / maleic acid copolymer ammonium salt, number The average molecular weight is about 10,000, manufactured by Kao Corporation), and the ZrO ₂ content ratio of Orgatics ZB-125 is 2% by weight, the solid content of Epocross WS-700 is 2% by weight, and the solid content of Poise 532A is 0%. Except for the change to 1% by weight, the same treatment as in Example 1 was carried out to form an antistatic layer, followed by adhesion To produce an optical film.

Example 13
In the preparation of the coating solution for the antistatic layer of Example 1, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation), polyaniline sulfonic acid (PAS, weight average molecular weight in terms of polystyrene of 150,000, Mitsubishi Rayon Co., Ltd.) Except for the change to (made)), the same treatment as in Example 1 was performed to form an antistatic layer, and then an adhesive optical film was produced.

Example 14
In the preparation of the coating solution for the antistatic layer of Example 2, Denatron P502RG (polythiophene-based conductive polymer, manufactured by Nagase ChemteX Corporation), polyaniline sulfonic acid (PAS, polystyrene-converted weight average molecular weight 150,000, Mitsubishi Rayon Co., Ltd.) Except for the change to (made)), the same treatment as in Example 2 was carried out to form an antistatic layer, and then an adhesive optical film was produced.

Comparative Example 1
In Example 1, an adhesive optical film was produced in the same manner as in Example 1 except that the antistatic layer was not formed.
(Evaluation)
1) Surface resistance of optical film In each example and comparative example, an optical film provided with only an antistatic layer (that is, an adhesive optical film before forming an adhesive layer) was placed in an atmosphere of 23 ° C. and 60% RH. Left under. 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 antistatic layer was formed was measured. The results are shown in Table 1.
2) Adhesive strength between the pressure-sensitive adhesive layer and the optical film The pressure-sensitive adhesive optical films of each Example and Comparative Example were cut into a size of 25 × 120 mm and used as a sample. This sample was aged for 1 day at 23 ° C. in an atmosphere of 60% RH and in an atmosphere of 50 ° C., respectively. After aging, the release film is peeled off, a polypropylene porous membrane is attached to the adhesive surface of the sample, and an adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) is attached onto the polypropylene porous membrane. After reinforced, they were left for 24 hours or more in an atmosphere of 60% RH at 23 ° C. and an atmosphere of 50 ° C., respectively. Thereafter, a SUS304 steel plate was attached to the back of the sample after standing (the surface on the optical film side of the adhesive optical film) using a double-sided tape, and polypropylene was perforated at a speed of 300 mm / min in the 180 ° direction by a tensile tester. After peeling at the interface between the membrane and the sample and confirming that the pressure-sensitive adhesive layer was attached to the polypropylene porous membrane, the peeling stress was measured. The results are shown in Table 1.
3) Adhesive fixing property of adhesive optical film After the adhesive optical film of each Example and Comparative Example was cut into a size of 230 × 310 mm, the release film was peeled off, and this was removed with a thickness of 0.7 mm. Affixed to a glass plate (Corning # 1737, manufactured by Corning Corp.), left in an autoclave at 50 ° C. and 0.5 MPa for 15 minutes, and then in an atmosphere of 90 ° C. and an atmosphere of 60 ° C./90% RH Below, it heated for 500 hours, respectively, and the presence or absence of peeling of the adhesion type optical film was confirmed by visual observation. The results are shown in Table 1.

In addition, about the presence or absence of peeling of an adhesive optical film, it confirmed on the following reference | standard.
○: No change such as peeling was observed Δ: Peeling of 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 4) Haze In each example and comparative example, an optical film provided with only an antistatic layer (that is, an adhesive optical film before forming an adhesive layer) was cut into 50 × 50 mm, and a haze computer HZ-1 (Suga test) Haze was measured with a machine). The results are shown in Table 1. In addition, it is preferable that a haze is 2.0% or less normally, and when it exceeds 2%, it looks white visually and is not preferable.

It is an expanded sectional view of one embodiment of the adhesive film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Antistatic layer 3 Adhesive layer

Claims (12)

A base material, an adhesive layer laminated on at least one side of the base material, and an antistatic layer interposed between the base material and the adhesive layer,
The pressure-sensitive adhesive layer is
(Meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group, carboxyl group-containing vinyl monomer, phosphate group-containing vinyl monomer represented by the following general formula (1) and optionally copolymerizable with the monomer A pressure-sensitive adhesive composition obtained by polymerizing a raw material monomer containing a copolymerizable vinyl monomer ,
The blending ratio of the raw material monomers is 60 to 99 parts by weight of the (meth) acrylic acid alkyl ester with respect to 100 parts by weight of the total amount of raw material monomers, and the carboxyl group-containing vinyl monomer, the phosphate group-containing vinyl monomer, and The total amount of the copolymerizable vinyl monomer is 1 to 40 parts by weight,
In the raw material monomer, the carboxyl group-containing vinyl monomer concentration represented by the following formula (4) is 0.05 to 1.50 mmol / g, and the phosphate group-containing vinyl monomer concentration represented by the following formula (5) is is 0.01 to 0.45 mmol / g,
The adhesive film, wherein the antistatic layer contains a water-soluble or water-dispersible conductive material.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a polyoxyalkylene group represented by the following general formula (2), and X represents the following general formula (3). A phosphoric acid group or a salt thereof.

(In general formula (2), n represents an integer of 1 to 4, and m represents an integer of 2 or more.)

(In General Formula (3), M ¹ and M ² each independently represent a hydrogen atom or a cation.)
The carboxyl group-containing vinyl monomer concentration [mmol / g] = 1000 × {(the blending weight of the carboxyl group-containing vinyl monomer [g]) / (the molecular weight of the carboxyl group-containing vinyl monomer [g / mol])} / (the above Total weight of raw material monomer [g]) (4)
Concentration of the phosphate group-containing vinyl monomer [mmol / g] = 1000 × {(Blend weight of the phosphate group-containing vinyl monomer [g]) / (Molecular weight of the phosphate group-containing vinyl monomer [g / mol])} / (Total weight of raw material monomers [g]) (5) The pressure-sensitive adhesive composition further contains an alkoxysilyl group-containing vinyl monomer as the copolymerizable vinyl monomer,
The pressure-sensitive adhesive film according to claim 1, wherein the blending ratio is 0.001 to 1 part by weight with respect to 100 parts by weight of the total amount of raw material monomers.   The pressure-sensitive adhesive film according to claim 1 or 2, wherein the pressure-sensitive adhesive composition is a water-dispersed pressure-sensitive adhesive composition.   The pressure-sensitive adhesive film according to claim 1, wherein the water-soluble or water-dispersible conductive material is a conductive polymer.   The pressure-sensitive adhesive film according to claim 4, wherein the conductive polymer is polyaniline and / or polythiophene.   The pressure-sensitive adhesive film according to claim 1, wherein the water-soluble or water-dispersible conductive material is an organometallic compound.   The pressure-sensitive adhesive film according to claim 6, wherein the organometallic compound is at least one selected from the group consisting of an organozirconium compound, an organotitanium compound, and an organoaluminum compound.   The pressure-sensitive adhesive film according to claim 1, wherein the antistatic layer further contains an oxazoline group-containing polymer.   The pressure-sensitive adhesive film according to any one of claims 1 to 7, wherein the antistatic layer further contains a mixture of an oxazoline group-containing polymer and a compound containing a plurality of carboxyl groups.   The pressure-sensitive adhesive film according to claim 1, wherein the antistatic layer further contains a polyamine polymer.   The pressure-sensitive adhesive film according to claim 1, wherein the substrate is an optical film.   An image display device using at least one adhesive film according to claim 11.

Images