TW201434925A - Antistatic layer, antistatic adhesive sheet, and optical film - Google Patents

Abstract

Provided are: an antistatic layer which has excellent antistatic properties, heat resistance, transparency and low contamination properties and is capable of especially suppressing breakage of an electronic component due to static electricity or adhesion of dirt, dust or the like an antistatic adhesive sheet which comprises the antistatic layer and an optical film. An antistatic layer which is characterized by being formed from an antistatic agent composition that contains a crosslinking agent and a (meth)acrylic polymer which contains a reactive ionic liquid as a monomer unit.

Description

Antistatic layer, antistatic charged adhesive sheet, and optical film

The present invention relates to an antistatic layer, an antistatic charging sheet, and an optical film. More specifically, the present invention relates to an anti-charged property which is excellent in antistatic property, heat resistance, transparency, and low pollution, and in particular, can suppress damage of electronic components caused by adhesion of dirt, dust, or the like and static electricity. a layer, an antistatic charging sheet having the above antistatic layer, and an optical film.

Products having high insulation resistance such as plastics have the property of being able to store (charge) static electricity generated by rubbing or sticking of plastics or other objects. Therefore, adsorption of dirt or dust in the air or the like occurs, or papers adhere to each other or the film, or in addition to the discomfort caused by electric shock, there are also in electronic, electrical equipment or OA (Office Automation). In equipment and the like, various electrostatic failures such as malfunction due to static electricity or memory damage are caused. In order to avoid such a failure, it is necessary to control the surface specific resistance of the charged body, and therefore, an antistatic agent is usually used.

In general, as a method of antistatic charging of a plastic product, a method of internally adding (mixing in) an antistatic agent and a method of coating on a surface are known. Further, regarding an adhesive sheet (adhesive tape) or a surface protective film which is required to have antistatic property, it is known that an adhesive layer is provided on one side of a plastic substrate film to which an antistatic agent is added, or in a plastic substrate film. An adhesive layer is provided on one side and an antistatic layer is provided on the opposite side, or an antistatic agent is added to the adhesive layer.

However, the plastic substrate film to which the antistatic agent is added has the original characteristic damage, and when the antistatic layer is provided on the opposite side to the adhesive layer, In the case where, for example, an easy-to-print layer or a hard coat layer is formed on the antistatic layer, there is a problem that the adhesion is lowered. In addition, there is a possibility that the antistatic layer may fall off due to friction, abrasion, or water immersion, and the antistatic property may not be maintained. Further, when an antistatic agent is added to the adhesive layer, the antistatic agent oozes to the side of the adherend (protected body) which is in contact with the adhesive layer, which contaminates the adherend or lowers the adhesive property. (Patent Document 1).

Moreover, as a method of providing antistatic property to an adhesive sheet or the like, a method of providing an intermediate layer (antistatic layer) having an antistatic property between a base film and an adhesive layer is known (Patent Documents 2 and 3). Since the above-mentioned antistatic layer is an intermediate layer, it is possible to eliminate the problem that the antistatic layer is detached as the antistatic layer provided on the outer surface of the substrate film or the antistatic agent bleeds to the side of the adherend. However, in the case of the above-mentioned antistatic layer, the counter anion of the ionic functional group constituting the ionic binder resin as the antistatic agent is chloride ion, so that it has a function of causing poor heat resistance and causing corrosion. After that.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-128539

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-31534

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-55894

Accordingly, it is an object of the present invention to provide an antistatic property, heat resistance, transparency, and low pollution, and particularly to suppress contamination, in order to eliminate the problems in the prior antistatic layer or the antistatic charging sheet. An antistatic layer that is damaged by adhesion of an object or dust or the like and an electronic component caused by static electricity, an antistatic charging sheet having the above antistatic layer, and an optical film.

That is, the antistatic layer of the present invention is characterized in that it contains a reactive The sub-liquid is formed as an antistatic agent composition of a (meth)acrylic polymer of a monomer unit and a crosslinking agent.

In the antistatic layer of the present invention, the reactive ionic liquid is preferably a reactive ionic liquid represented by any one of the following formulas (1) to (4).

CH ₂ =C(R ¹ )COOZX ⁺ Y ^- (1)

CH ₂ =C(R ¹ )CONHZX ⁺ Y ^- (2)

CH ₂ =C(R ¹ )COOX ⁺ Y ^- (3)

CH ₂ =C(R ¹ )CONHX ⁺ Y ^- (4)

[In the formulae (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cationic moiety, Y ^- is an anion; and Z represents an alkylene group having a carbon number of 1 to 3]

In the antistatic layer of the present invention, it is preferred that the cation portion is a quaternary ammonium group.

In the antistatic layer of the present invention, it is preferred that the anion is a fluorine-containing anion.

The antistatic layer of the present invention preferably comprises the above (meth)acrylic polymer comprising an oxyalkylene group having an average addition molar number of from 3 to 100, which is represented by the following formula (5). The monomer of the base acts as a monomer unit.

CH ₂ =C(R ₁ )-COO-(C _m H _2m O) _n -(C _p H _2p O) _q -R ₂ (5)

[In the formula (5), R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, and n and q are 0 or an integer of 2 to 100, and n and q is 0 at the same time]

In the antistatic layer of the present invention, it is preferred that the (meth)acrylic polymer contains a hydroxyl group-containing (meth)acrylic monomer as a monomer unit.

In the antistatic layer of the present invention, it is preferred that the crosslinking agent is an isocyanate crosslinking agent.

In the antistatic layer of the present invention, it is preferred that the antistatic composition contains a conductive agent.

The antistatic charging sheet of the present invention preferably has the antistatic layer formed on at least one side of the base film and has an adhesive layer on the antistatic layer.

In the antistatic charging sheet of the present invention, it is preferred that the substrate film is a plastic film.

The antistatic charging sheet of the present invention is preferably used for surface protection purposes.

The antistatic charging sheet of the present invention is preferably used in the steps of manufacturing and shipping electronic parts.

In the optical film with an antistatic charging sheet of the present invention, it is preferred that the above-mentioned antistatic charging sheet is attached to an optical film.

In the optical film with an antistatic film according to the present invention, it is preferable that the antistatic layer is formed on at least one side of the base film, an adhesive layer is formed on the antistatic layer, and the adhesive layer is subsequently applied. In the optical film.

1‧‧‧potentiometer

2‧‧‧Adhesive sheets

3‧‧‧Polar plate

4‧‧‧Acrylic board

5‧‧‧ fixed table

10‧‧‧Anti-static adhesive sheet (adhesive sheet)

11‧‧‧ spacer

12‧‧‧Adhesive layer

13‧‧‧Anti-static layer

14‧‧‧Base film

Fig. 1 is a schematic view for explaining the constitution of an antistatic charging sheet.

Fig. 2 is a schematic view for explaining a peeling tape voltage test.

Hereinafter, embodiments of the present invention will be described in detail.

<Anti-chargeable adhesive sheet>

The antistatic charging sheet of the present invention preferably has an antistatic layer formed on at least one side of the substrate film and an adhesive layer on the antistatic layer. Specifically, a typical configuration example of the above-described antistatic charging sheet is schematically shown in Fig. 1 . Here, the antistatic charging sheet 10 includes a base film (for example, a polyester film) 14 , an antistatic layer 13 provided on one surface thereof, and an adhesive layer 12 on the antistatic layer 13 . The adhesive sheet 10 is used by attaching the above-mentioned adhesive layer 12 to an adherend (a surface to be protected, for example, an optical component such as a polarizing plate). The adhesive sheet 10 before use (that is, before being attached to the adherend) can protect the adhesive layer 12 by the spacer 11 which becomes the peeling surface on the side of the adhesive layer 12 as shown in FIG. The surface (attached to the surface of the adherend) exists. Hereinafter, the configuration of the above-described antistatic charging sheet (hereinafter sometimes simply referred to as "adhesive sheet") will be described in detail.

<Anti-charged composition and anti-static layer>

The antistatic layer of the present invention is characterized by containing a reactive ionic liquid It is formed as a (meth)acrylic polymer of a monomer unit and an antistatic agent composition of a crosslinking agent. Further, the (meth)acrylic polymer in the present invention means an acrylic polymer and/or a methacrylic polymer, and the term "(meth)acrylate" means acrylate and/or Methacrylate.

The antistatic composition used in the formation of the antistatic layer of the present invention contains, as an essential component, a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit. In addition, the "reactive ionic liquid" in the present invention means that the cation portion and/or the anion portion (either or both) constituting the ionic liquid contain a polymerizable (reactive double bond) functional group. The base ionic liquid is liquid (liquid) at any temperature in the range of 0 to 150 ° C and is transparent in the form of a non-volatile molten salt. In addition, examples of the polymerizable functional group include a vinyl group, an allyl group, and a (meth)acryl fluorenyl group. Among them, from the viewpoint of copolymerizability, a (meth) acrylonitrile group or a vinyl group is preferred, and a (meth) acryl fluorenyl group is preferred.

The cationic portion of the reactive ionic liquid can be used without particular limitation, and examples thereof include a quaternary ammonium cation, an imidazolium cation, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a quaternary phosphonium cation, and a trioxane. a ruthenium cation, a pyrrole cation, a pyrazolium cation, a phosphonium cation, etc., wherein a quaternary ammonium cation, an imidazolium cation, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a quaternary phosphonium cation is more preferably used. , a trialkyl phosphonium cation.

Further, in the anion portion constituting the reactive ionic liquid, examples of the anion include SCN ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , and CH ₃ SO _{3 .} ^- , CF ₃ SO ₃ ^- , (FSO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , HF ₂ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ ) (CF ₃ CO N ^- , B(CN) ₄ ^- , C(CN) ₃ ^- , N(CN) ₂ ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₄ H ₉ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , p-sulfonyl anion, ethyl 2-(2-methoxyethyl) anion, (C ₂ F ₅ ) ₃ PF ₃ ^-, etc., in particular, An anionic component (fluorine-containing anion) containing a fluorine atom can obtain an ionic liquid having a low melting point and is excellent in antistatic property, and is preferable in this respect. Further, as the anion, it is preferable to use no chlorine ion, bromide ion or the like in terms of corrosiveness.

The reactive ionic liquid system is appropriately selected from the combination of the cation portion and the anion portion, and specific examples thereof include various ionic liquids described below.

Examples of the imidazolium cation-based ionic liquid include 1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, and 1-alkyl-3- Vinyl imidazolium heptafluorobutyrate, 1-alkyl-3-vinylimidazolium trifluoromethanesulfonate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl -3-vinylimidazolium bis(trifluoromethanesulfonate)imide, 1-alkyl-3-vinylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl-3-vinylimidazole Tris(trifluoromethanesulfonate)imide, 1-alkyl-3-vinylimidazolium hexafluorophosphate, 1-alkyl-3-vinylimidazolium (trifluoromethanesulfonyl)trifluoroethyl 1-Alkyl-3-vinylimidazolium cations, such as decylamine, 1-alkyl-3-vinylimidazolium dicyanoguanamine, 1-alkyl-3-vinylimidazolium thiocyanate Ionic liquid, 1,2-dialkyl-3-vinylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium bis(trifluoromethanesulfonate)imide 1,2-dialkyl-3-vinylimidazolium dicyanamide, 1,2-dialkyl-3-vinylimidazolium thiocyanate, etc. containing 1,2-dialkyl-3 -vinylimidazolium cation Ionic liquid, 2-alkyl-1,3-divinylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-divinylimidazolium bis(trifluoromethanesulfonate) Amine, 2-alkyl-1,3-divinylimidazolium dicyanoguanamine, 2-alkyl-1,3-divinylimidazolium thiocyanate, etc. containing 2-alkyl-1,3 - Ionic liquid of divinylimidazolium cation, 1-vinylimidazolium bis(fluorosulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonate)imide, 1-vinylimidazolium Ionic liquid containing 1-vinylimidazolium cation, such as cyanoguanamine or 1-vinylimidazolium thiocyanate, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium tetrafluoroboric acid Salt, 1-alkyl-3- (Meth)acryloxyalkylimidazolium trifluoroacetate, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium heptafluorobutyrate, 1-alkyl-3-( Methyl)propenyloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3 -(Meth)propenyloxyalkylimidazolium bis(trifluoromethanesulfonate)imide, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium bis(pentafluoroethanesulfonate) Imine, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium tris(trifluoromethanesulfonate)imide, 1-alkyl-3-(methyl)propene decyloxyalkylene Imidazolium hexafluorophosphate, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-alkyl-3-(A 1-propenyloxyalkylimidazolium dicyanoguanamine, 1-alkyl-3-(methyl)propenyloxyalkylimidazolium thiocyanate, etc. containing 1-alkyl-3-(A) Ionic ionic liquid of 1-propenyloxyalkylimidazolium cation, 1-alkyl-3-(methyl)propenylaminoalkylimidazolium tetrafluoroborate, 1-alkyl-3-(methyl Acetyl mercaptoalkyl imidazolium trifluoroacetate 1-alkyl-3-(methyl)propenylaminoalkylalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(methyl)propenylaminoalkylimidazolium trifluoromethanesulfonate Acid salt, 1-alkyl-3-(methyl) propylene decylaminoalkyl imidazolium perfluorobutane sulfonate, 1-alkyl-3-(methyl) propylene decylaminoalkyl imidazolium Bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-(methyl)propenylaminoalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl-3-( Methyl) propylene decylaminoalkyl imidazolium tris(trifluoromethanesulfonate)imide, 1-alkyl-3-(methyl)propenylaminoalkylimidazolium hexafluorophosphate, 1- Alkyl-3-(methyl)propenylaminoalkylimidazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-alkyl-3-(methyl)propenylaminoalkyl 1-alkyl-3-(methyl)propenylamino group containing imidazolium dicyanamide, 1-alkyl-3-(methyl)propenylaminoalkylimidazolium thiocyanate Ionic liquid of alkylimidazolium cation, 1,2-dialkyl-3-(methyl)propenyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3- (methyl) propylene oxiranyl alkyl imidazolium bis(trifluoromethanesulfonate) imine, 1 ,2-dialkyl-3-(methyl)propenyloxyalkylimidazolium dicyanoguanamine, 1,2-dialkyl-3-(methyl)propenyloxyalkylimidazolium sulfur 1,2-dialkyl-3-(methyl)propene oxime Ionic liquid of alkylalkyl imidazolium cation, 1,2-dialkyl-3-(methyl)acrylamidoaminoalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl- 3-(Methyl)acrylamidoaminoalkylimidazolium bis(trifluoromethanesulfonate)imide, 1,2-dialkyl-3-(methyl)propenylguanidinoalkylimidazolium 1,2-Dialkyl-3-(methyl)propene oxime, such as cyanoguanamine, 1,2-dialkyl-3-(methyl)propenylaminoalkylimidazolium thiocyanate An ionic liquid of a hydroxyalkylimidazolium cation, 2-alkyl-1,3-di(methyl)propenyloxyalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1, 3-bis(methyl)propenyloxyalkylimidazolium bis(trifluoromethanesulfonate)imide, 2-alkyl-1,3-di(methyl)propenyloxyalkylimidazolium dicyandiamide a 2-alkyl-1,3-bis(methyl)propenyloxyalkyl group such as a guanamine or a 2-alkyl-1,3-di(meth) propylene oxime oxyimidazolium thiocyanate Ionic liquid of imidazolium cation, 2-alkyl-1,3-di(methyl)propenylaminoaminoalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-di ( Methyl) propylene decylaminoalkyl imidazolium bis(trifluoromethanesulfonate)imide, 2-alkyl-1 , 3-di(meth)acrylamidoaminoalkylimidazolium dicyanoguanamine, 2-alkyl-1,3-di(methyl)propenylguanidinolimidazolium thiocyanate, etc. Ionic liquid of 2-alkyl-1,3-bis(methyl)propenyloxyalkylimidazolium cation, 1-(methyl)propenyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1-(Methyl)propenyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(methyl)propenyloxyalkylimidazolium dicyanoguanamine, 1-(methyl An ionic liquid containing 1-(methyl)propenyloxyalkylimidazolium cation, such as propylene methoxyalkylimidazolium thiocyanate, 1-(methyl)propenylaminoalkylimidazolium (Fluorosulfonyl)imine, 1-(methyl)acrylamidoaminoalkylimidazolium bis(trifluoromethanesulfonate)imide, 1-(methyl)propenylaminoalkylimidazolium An ionic liquid containing a 1-(methyl)propenylaminoalkyl imidazolium cation such as cyanoguanamine or 1-(methyl)acrylamidoaminoalkyl imidazolium thiocyanate.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.

Examples of the pyridinium cation-based ionic liquid include 1-vinylpyridinium bis(fluorosulfonyl)imide, 1-vinylpyridinium bis(trifluoromethanesulfonate)imide, and 1-vinylpyridinium II. Ionic liquid containing 1-vinylpyridinium cation, such as cyanoguanamine or 1-vinylpyridinium thiocyanate, 1-(methyl)propenyloxyalkylpyridinium bis(fluorosulfonyl)imide , 1-(methyl)propenyloxyalkylpyridinium bis(trifluoromethanesulfonate)imide, 1-(methyl)propenyloxyalkylpyridinium dicyanoguanamine, 1-(A) Ionic liquid containing 1-(methyl)propenyloxyalkylpyridinium cation, such as acryloxyalkylpyridinium thiocyanate, 1-(methyl)propenylaminoalkylpyridinium Bis(fluorosulfonyl)imide, 1-(methyl)propenylaminoalkylpyridinium bis(trifluoromethanesulfonate)imide, 1-(methyl)propenylaminoalkylpyridinium Ionic liquid containing 1-(methyl)propenylaminoalkylpyridinium cation, such as dicyanamide, 1-(methyl)propenylaminoalkylpyridinium thiocyanate, 2-alkane -1-vinylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-vinylpyridinium bis ( 2-Alkyl-1-ethylene containing fluoromethanesulfonate, imine, 2-alkyl-1-vinylpyridinium dicyanoguanamine, 2-alkyl-1-vinylpyridinium thiocyanate Ionic liquid of pyridinium cation, 2-alkyl-1-(methyl)propenyloxyalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-(methyl)propene oxime Alkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(methyl)propenyloxyalkylpyridinium dicyanoguanamine, 2-alkyl-1-(A) Ionic liquid containing 2-alkyl-1-(methyl)propenyloxyalkylpyridinium cation, such as acryloxyalkylpyridinium thiocyanate, 2-alkyl-1-(methyl Ethyl decylaminoalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-(methyl)propenylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(methyl)propenylaminoalkylpyridinium dicyanoguanamine, 2-alkyl-1-(methyl)propenylaminoalkylpyridinium thiocyanate An ionic liquid containing a 2-alkyl-1-(methyl)propenylaminoalkylpyridinium cation, 3-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonate)imide, 3-alkyl-1-ethylene Ionic liquid containing 3-alkyl-1-vinylpyridinium cation such as pyridinium dicyanoguanamine or 3-alkyl-1-vinylpyridinium thiocyanate, 3-alkyl-1-( Methyl)propenyloxyalkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(methyl)propenyloxyalkylpyridinium bis(trifluoromethanesulfonate)imide, 3-alkyl-1-(methyl)propenyloxyalkylpyridinium dicyanoguanamine, 3-alkyl-1-(methyl)propenyloxyalkylpyridinium thiocyanate, etc. Ionic liquid of 3-alkyl-1-(methyl)propenyloxyalkylpyridinium cation, 3-alkyl-1-(methyl)propenylaminoalkylpyridinium bis(fluorosulfonate) Imine, 3-alkyl-1-(methyl)propenylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 3-alkyl-1-(methyl)propenylamino 3-alkyl-1-(methyl)propenyl fluorenyl group, such as alkyl pyridinium dicyanoguanamine, 3-alkyl-1-(methyl)propenylaminoalkylpyridinium thiocyanate Aminoalkylpyridinium cation ionic liquid, 4-alkane 1-vinylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonate)imide, 4-alkyl-1-vinylpyridinium Ionic liquid containing 4-alkyl-1-vinylpyridinium cation such as dicyanamide or 4-alkyl-1-vinylpyridinium thiocyanate, 4-alkyl-1-(methyl) Propylene methoxyalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(methyl)propenyloxyalkylpyridinium bis(trifluoromethanesulfonate)imide, 4-alkane 4-Alkenyl-1-(methyl)propenyloxyalkylpyridinium dicyanoguanamine, 4-alkyl-1-(methyl)propenyloxyalkylpyridinium thiocyanate, etc. Ionic liquid of -1-(methyl)propenyloxyalkylpyridinium cation, 4-alkyl-1-(methyl)propenylaminoalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(methyl)propenylaminoalkylpyridinium bis(trifluoromethanesulfonate)imide, 4-alkyl-1-(methyl)propenylaminoalkylpyridine Di-cyanoguanamine, 4-alkyl-1-(methyl) propylene oxime An ionic liquid containing a 4-alkyl-1-(methyl)propenylaminoalkylpyridinium cation such as an aminoalkylpyridinium thiocyanate.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Examples of the piperidinium cation-based ionic liquid include 1-alkyl-1-vinylalkylpiperidinium bis(fluorosulfonyl)imide and 1-alkyl-1-vinylalkylpiperidinium. (Trifluoromethanesulfonyl)imine, 1-alkyl-1-vinylalkylpiperidinium dicyanamide, 1-alkyl-1-vinylalkylpiperidinium thiocyanate, etc. Ionic liquid of 1-alkyl-1-vinylalkylpiperidinium cation, 1-alkyl-1-(methyl)propenyloxyalkylpiperidinium bis(fluorosulfonyl)imide, 1- Alkyl-1-(methyl)propenyloxyalkylpiperidinium bis(trifluoromethanesulfonate)imide, 1-alkyl-1-(methyl)propenyloxyalkylpiperidinium 1-alkyl-1-(methyl)propenyloxyalkyl piperidine, such as cyanoguanamine, 1-alkyl-1-(methyl)propenyloxyalkylpiperidinium thiocyanate Ionic liquid of phosphonium cation, 1-alkyl-1-(methyl)propenylaminoalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(methyl)propenyl fluorenyl Aminoalkylpiperidinium bis(trifluoromethanesulfonate)imide, 1-alkyl-1-(methyl)propenylaminoalkylalkylpiperidinium dicyanoguanamine, 1-alkyl- 1-(methyl)propenylaminoalkylpiperidinium thiocyanate or the like Ionic liquid of 1-alkyl-1-(methyl)propenylaminoalkylpiperidinium cation.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Examples of the pyrrolidinium cation-based ionic liquid include 1-alkyl-1-vinylalkylpyrrolidinium bis(fluorosulfonyl)imide and 1-alkyl-1-vinylalkylpyrrolidinium double (Trifluoromethanesulfonate) imine, 1-alkyl-1-vinylalkylpyrrolidinium dicyanoguanamine, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanate, etc. An ionic liquid of a 1-alkyl-1-vinylalkylpyrrolidinium cation, 1-alkyl-1-(methyl)propenyloxyalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(methyl)propenyloxyalkylpyrrolidinium double (Trifluoromethanesulfonate) imine, 1-alkyl-1-(methyl)propenyloxyalkylpyrrolidinium dicyanoguanamine, 1-alkyl-1-(methyl)propene oxime Ionic liquid containing 1-alkyl-1-(methyl)propenyloxyalkylpyrrolidinium cation, such as alkylalkylpyrrolidinium thiocyanate, 1-alkyl-1-(methyl)propene oxime Aminoalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(methyl)propenylaminoalkylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1 -alkyl-1-(methyl)acrylamidoaminoalkylpyrrolidinium dicyanoguanamine, 1-alkyl-1-(methyl)propenylaminoalkylpyrrolidinium thiocyanate An ionic liquid containing a 1-alkyl-1-(methyl)propenylaminoalkylpyrrolidinium cation as a salt or the like.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Examples of the trialkylsulfonium cation-based ionic liquid include dialkyl(vinyl)fluorene bis(fluorosulfonyl)imide, dialkyl(vinyl)fluorene bis(trifluoromethanesulfonate)imide, and An ionic liquid containing a dialkyl (vinyl) phosphonium cation such as an alkyl (vinyl) decyl cyanoguanamine or a dialkyl (vinyl) sulfonium thiocyanate, or a dialkyl ((meth) acrylonitrile) Oxyalkyl) bis(fluorosulfonyl)imide, dialkyl ((meth)acryloxyalkyl) bis(trifluoromethanesulfonyl)imide, dialkyl ((methyl)) Dialkyl ((meth) propylene decyloxyalkyl), such as propylene methoxyalkyl) quinodicyanoguanamine, dialkyl ((meth) propylene oxyalkyl) thiocyanate An ionic liquid of a ruthenium cation, a dialkyl ((meth) acryloylaminoalkyl) bis(fluorosulfonyl)imide, a dialkyl ((meth) propylene decylamino) hydrazine Bis(trifluoromethanesulfonyl)imide, dialkyl ((meth)acryloylaminoalkyl) decanocyanoguanamine, dialkyl ((meth) propylene decylamino) An ionic liquid containing a dialkyl ((meth) acrylamidoalkyl) sulfonium cation such as thiocyanate.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Examples of the quaternary phosphonium cation-based ionic liquid include trialkyl (vinyl) bis(fluorosulfonyl)imide, trialkyl (vinyl) bis(trifluoromethanesulfonate) imine, and trioxane. An ionic liquid containing a trialkyl (vinyl) phosphonium cation such as a bis(cyano) decyl decylamine or a trialkyl (vinyl) sulfonium thiocyanate, a trialkyl ((meth) propylene oxime) Alkyl) bis(fluorosulfonyl)imide, trialkyl ((meth) propylene oxyalkyl) bis(trifluoromethanesulfonyl)imide, trialkyl (meth) propylene a trialkyl ((meth) propylene decyloxyalkyl group) such as a decyloxyalkyl) quinodicyanoguanamine or a trialkyl ((meth) propylene oxyalkyl) thiocyanate Ionic liquid of cerium cation, trialkyl ((meth) acrylamidoalkyl) bis(fluorosulfonyl)imide, trialkyl ((meth) acrylamidoalkyl) fluorene (Trifluoromethanesulfonate) imine, trialkyl ((meth)acryloylaminoalkyl) decanocyanoguanamine, trialkyl ((meth) propylene decylamino) hydrazine An ionic liquid containing a trialkyl ((meth) acrylamidoalkyl) sulfonium cation such as thiocyanate.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Further, examples of the quaternary ammonium cation-based ionic liquid include N,N,N-trialkyl-N-vinylammonium tetrafluoroborate, and N,N,N-trialkyl-N-vinylammonium Fluoroacetate, N,N,N-trialkyl-N-vinylammonium heptafluorobutyrate, N,N,N-trialkyl-N-vinylammonium triflate, N,N , N-trialkyl-N-vinylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-vinylammonium bis(trifluoromethanesulfonate)imide, N,N,N -Trialkyl-N-vinylammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium tris(trifluoromethanesulfonate)imide, N,N , N-trialkyl-N-vinylammonium hexafluorophosphate, N,N,N-trialkyl-N-vinylammonium (trifluoromethanesulfonyl)trifluoroacetamide, N,N, N,N,N-trialkyl-N-, such as N-trialkyl-N-vinylammonium dicyanoguanamine, N,N,N-trialkyl-N-vinylammonium thiocyanate Ionic liquid of vinyl ammonium cation, N, N, N-trialkyl-N-(methyl) propylene oxyalkyl ammonium tetrafluoroborate, N, N, N-trialkyl-N- (A Acryloxyalkylammonium trifluoroacetate, N,N,N-trialkyl-N-(A) Acryloxyalkylammonium heptafluorobutyrate, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium triflate, N,N,N -Trialkyl-N-(methyl)propenyloxyalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium double ( Trifluoromethanesulfonate)imine, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-three Alkyl-N-(methyl)propenyloxyalkylammonium tris(trifluoromethanesulfonate)imide, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium Hexafluorophosphate, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium (trifluoromethanesulfonyl)trifluoroacetamide, N,N,N-trioxane Base-N-(methyl)propenyloxyalkylammonium dicyanoguanamine, N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium thiocyanate, etc. N,N,N-trialkyl-N-(methyl)propenyloxyalkylammonium cation ionic liquid, N,N,N-trialkyl-N-(methyl)propenylamino alkane Ammonium tetrafluoroborate, N,N,N-trialkyl-N-(methyl)propenylaminoalkylammonium trifluoroacetate, N,N,N-trialkyl-N-(A Propylene decylaminoalkyl ammonium heptafluorobutane Salt, N,N,N-trialkyl-N-(methyl)propenylaminoalkylammonium triflate, N,N,N-trialkyl-N-(methyl)propene Mercaptoalkylaminoammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(methyl)propenylaminoalkylammonium bis(trifluoromethanesulfonate)imide, N ,N,N-trialkyl-N-(methyl)propenylaminoalkylalkyl ammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-trialkyl-N-(methyl) Propylene decylaminoalkyl ammonium tris(trifluoromethanesulfonate)imide, N,N,N-trialkyl-N-(methyl)propenylaminoalkylammonium hexafluorophosphate, N, N,N-trialkyl-N-(methyl)propenylaminoalkylammonium (trifluoromethanesulfonyl)trifluoroacetamide, N,N,N-trialkyl-N-(A Acetyl mercaptoalkylamino ammonium dicyanoguanamine, N,N,N-trialkyl-N-(methyl)propenylaminoalkyl ammonium thiocyanate, etc. containing N,N, An ionic liquid of N-trialkyl-N-(methyl) propylene decylaminoalkyl ammonium cation.

Further, the alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably a carbon number of 1 to 12, and still more preferably 1 to 6 carbon atoms.

Further, the reactive ionic liquid can be used without particular limitation, and more preferably a reactive ionic liquid represented by any one of the following formulas (1) to (4). Anti-charge agent group The compound contains a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit, whereby the antistatic layer formed of the above antistatic composition can incorporate the above reactive ionic liquid exhibiting an antistatic effect It is in the polymer skeleton, so that the bleed out of the antistatic component can be suppressed. Further, the reactive ionic liquid is liquid (liquid) at any temperature in the range of 0 to 150 ° C, and has transparency in the form of a non-volatile molten salt, so that the obtained antistatic layer can satisfy the prevention It is useful for chargeability (high conductivity), heat resistance (thermal stability), transparency, and low pollution. In addition, since the antistatic agent component is a liquid reactive ionic liquid, when it is applied to the base film, when it is applied to the base film, it is easy to form a uniform coating film, and the workability is excellent. It is better in this respect.

CH ₂ =C(R ¹ )COOZX ⁺ Y ^- (1)

CH ₂ =C(R ¹ )CONHZX ⁺ Y ^- (2)

CH ₂ =C(R ¹ )COOX ⁺ Y ^- (3)

CH ₂ =C(R ¹ )CONHX ⁺ Y ^- (4)

Further, in the above formulae (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, and Y ^- is an anion. Z represents an alkylene group having 1 to 3 carbon atoms.

Examples of the cationic moiety (X ⁺ ) constituting the reactive ionic liquid represented by any one of the above formulas (1) to (4) include a quaternary ammonium group, an imidazolium group, a pyridinium group, and a piperidinyl group. , pyrrolidinyl, pyrrolyl, quaternary fluorenyl, trialkyl fluorenyl, pyrazolyl, fluorenyl and the like. Among these, particularly in the case of a quaternary ammonium group, transparency is excellent, and it is preferable in terms of electronic and optical use. Further, the quaternary ammonium group is an unsaturated bond other than the polymerizable functional group in the molecule, and it is presumed that it is difficult to inhibit the usual radical polymerization reaction during ultraviolet (UV) curing, and the curability is high, so that it is preferably formed. Anti-static layer.

Specific examples of the quaternary ammonium group include a trimethylammonium group, a triethylammonium group, a tripropylammonium group, a methyldiethylammonium group, an ethyldimethylammonium group, and a methyl group. Dipropylammonium, dimethylbenzylammonium, diethylbenzylammonium, methyldibenzylammonium, ethyldibenzylammonium, etc., among which, it is easy to obtain inexpensive industrial materials. In terms of aspects, A trimethylammonium group or a methylbenzylammonium group is preferred.

Further, in the anion (site) (Y ^- ) of the reactive ionic liquid represented by any one of the above formulas (1) to (4), examples of the anion include SCN ^- , BF ₄ ^- , and PF _{6 .} ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (FSO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , HF ₂ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , B(CN) ₄ ^- , C(CN) ₃ ^- , N(CN) ₂ ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₄ H ₉ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , p-sulfonyl anion, ethyl 2-(2-methoxyl sulfate An ethyl acrylate anion, (C ₂ F ₅ ) ₃ PF ₃ ^- or the like, particularly an anion component (fluorine-containing anion) containing a fluorine atom, can obtain an ionic liquid having a low melting point, and is excellent in antistatic property, and in this respect, good. Further, as the anion, it is preferable to use no chlorine ion, bromide ion or the like in terms of corrosiveness.

The combination of the above cation (site) and anion (site) constituting the reactive ionic liquid represented by any one of the above formulas (1) to (4) is preferably propylene decylaminopropyltrimethylammonium. Bis(trifluoromethanesulfonate)imide, methacryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonate)imide, acryloylaminopropyldimethylbenzylammonium bis ( Trifluoromethanesulfonate)imine, propylene methoxyethyl trimethylammonium bis(trifluoromethanesulfonate)imide, propylene methoxyethyl dimethyl benzyl ammonium bis(trifluoromethanesulfonate) Imine, methacryloxyethyl 3-methylammonium bis(trifluoromethanesulfonate)imide, acryloylaminopropyltrimethylammonium bis(fluorosulfonyl)imide, methacryl Aminopropyltrimethylammonium bis(fluorosulfonyl)imide, acryloylaminopropyldimethylbenzylammonium bis(fluorosulfonyl)imide, propylene methoxyethyltrimethylammonium Bis(fluorosulfonyl)imide, propylene methoxyethyl benzyl ammonium bis(fluorosulfonyl)imide, methacryloxyethyltrimethylammonium bis(fluorosulfonyl)imide , propylene decyl propyl trimethyl ammonium triflate, methacryl fluorenyl Trimethylammonium triflate, propylene decylaminopropyl benzyl ammonium trifluoromethanesulfonate, propylene methoxyethyl trimethyl ammonium trifluoromethanesulfonate, propylene醯 oxyethyl dimethyl benzyl ammonium triflate, methacryloxy group Ethyltrimethylammonium triflate or the like.

In all the structural units (all monomer units (components): 100% by mass) of the (meth)acrylic polymer, the reactive ionic liquid preferably contains 15 to 99% by mass, more preferably 20 to 98%. The mass% is particularly preferably 30 to 97% by mass. When the blending ratio of the reactive ionic liquid is within the above range, it is preferable from the viewpoint of exhibiting excellent antistatic property, transparency, heat resistance (thermal stability), and low contamination.

The usual synthesis method of the reactive ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and the literature "Ion Liquid - Development of the Forefront and Future" - [CMC Co., Ltd.], literature "Polymer, Vol. 52, P.1469-1482 (2011)", the "Terminal Material System One Point 2 Ionic Liquid" [Kyoritsu Co., Ltd. Publishing] is described in the four-stage/ion exchange method, direct The quaternization method, the carbonate quaternization method, the hydroxide method, the acid ester method, the wrong method, and the neutralization method.

In addition, as a monomer unit constituting the (meth)acrylic polymer contained in the antistatic composition used in the present invention, a polymerizable monomer unit (component) other than the reactive ionic liquid may be used. As the alkyl (meth)acrylate, a more preferred aspect is to use an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms. One type or two or more types may be used as the alkyl (meth)acrylate.

In the present invention, specific examples of the alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate. N-butyl methacrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-(meth)acrylate An ester, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and the like.

All structural units of the above (meth)acrylic polymer (all monomer units In the case of 100% by mass, preferably, the alkyl (meth)acrylate is contained in an amount of from 0 to 65% by mass as a monomer unit (component), more preferably from 0 to 60% by mass. When the monomer unit (component) is in the above range, it is preferable from the viewpoint of obtaining an appropriate ion conductivity and cohesive force in the antistatic composition.

Further, as a monomer unit constituting the (meth)acrylic polymer contained in the antistatic composition used in the present invention, a monomer unit (component) having polymerization other than the reactive ionic liquid is more preferable. It is preferred to use an oxyalkylene group represented by the following formula (5), which has an average addition molar amount of from 3 to 100, and an alkylene group having an alkyl group. When a reactive ionic liquid as used in the present invention contains a cationic portion (positive charge) and an anion (negative charge), the electrostatic force (Coulomb force) generated between the two charges and the medium of the two charges are compared. The electrical constant is inversely proportional (Coulomb's law). Further, in the present invention, it is presumed that the above-mentioned oxygen-containing alkylene group monomer (high relative dielectric constant) functions as a medium for the reactive ionic liquid, and the electrostatic force between the two charges is lowered to promote the reactivity. Ion dissociation of the ionic liquid, and further, as the oxy group of the oxygen-containing alkyl group-forming monomer moves toward the molecular chain of the alkyl chain, the ion is easily transported, and the ion dissociation and ion transport of the reactive ionic liquid are promoted. This ion conductivity is improved, and the antistatic property is more excellent.

CH ₂ =C(R ₁ )-COO-(C _m H _2m O) _n -(C _p H _2p O) _q -R ₂ (5)

In the above formula (5), R ₁ is hydrogen or methyl, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, and n and q are 0 or an integer of 2 to 100, and n and q is the case of 0 at the same time. Further, in the case where R ₂ is an organic group, it is preferably a methyl group, a lauryl group, a phenyl group, a stearyl group or an octyl group, and m and p are preferably 2, and n and q are preferably 2 to 20 Integer. When it is in the above range, the oxyalkylene chain of the monomer having an oxyalkylene group easily interacts with the reactive ionic liquid, and the ions constituting the reactive ionic liquid are easily dissociated, which is preferable.

Specific examples of the above-mentioned oxygen-containing alkylene group-containing monomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (meth) acrylate. Ester, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-poly Butylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate Ester, octyloxy polyethylene glycol (meth) acrylate, lauryloxy polyethylene glycol (meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy poly ethane Glycol (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate Ester, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy glycol-polypropylene glycol (meth) acrylate, octyloxy polyethylene glycol-polypropylene glycol (methyl) Acrylate, polybutylene glycol (meth) acrylate, polybutylene glycol-polyethylene glycol (meth) acrylate, polybutylene glycol-polypropylene glycol (meth) acrylate, polybutylene Glycol-polybutylene glycol (meth) acrylate, propylene glycol-polybutylene glycol (meth) acrylate, and the like. One type or two or more types of the alkyl group having an alkylene group may be used.

In all the structural units (all monomer units (components): 100% by mass) of the (meth)acrylic polymer, the monomer having an alkyloxy group-containing alkyl group is preferably 0 to 60% by mass, more preferably 5 ~50% by mass, most preferably 10 to 40% by mass. When it is in the above range, the alkyl group having an oxyalkylene group is easily molecularly moved, and the transporting action of ions constituting the reactive ionic liquid is improved, which is preferable.

Further, the polymerizable monomer other than the alkyl (meth)acrylate may have a purpose of improving cohesiveness, heat resistance, crosslinkability, etc., and may optionally be copolymerized with the above alkyl (meth)acrylate. Other polymerizable monomer units (components) (copolymerizable monomers). Further, other polymerizable monomer units (components) can be used in a range in which the balance between the cohesive force and the ion conductivity is not compromised. In particular, unlike the adhesive layer, adhesiveness does not occur, and therefore it is preferred to use a glass transition temperature higher than that of the monomer unit used in the adhesive layer. By using such a monomer unit, the operability of the antistatic layer (film) can be improved, which is effective. These monomer compounds may be used singly or in combination of two or more.

In the present invention, when the (meth)acrylic polymer is a copolymer (example) For example, in the antistatic composition or the adhesive composition, the glass transition temperature (Tg) is a value calculated based on the following formula (6) (Fox formula).

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+Wn/Tg _n (6)

[In the formula (6), Tg represents the glass transition temperature of the copolymer (unit: K), and Tg _i (i = 1, 2, ..., n) represents the glass transition temperature when the monomer i forms a homopolymer (unit: K) ), W _i (i = 1, 2, ... n) represents the mass fraction of all monomer components of monomer i]

Further, the glass transition temperature Tgi of the monomer i is a nominal value described in the literature (for example, Polymer Handbook, Adhesive Handlog, etc.).

In the present specification, the term "glass transition temperature at the time of forming a homopolymer" means "the glass transition temperature of the homopolymer of the monomer", and means that only a certain monomer is formed (sometimes referred to as " Monomer X") The glass transition temperature (Tg) of the polymer as a monomer component. Specifically, the numerical value in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989) is mentioned.

Further, the glass transition temperature (Tg) of the homopolymer not described in the above literature means, for example, a value obtained by the following measurement method.

In the reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction pipe, and a reflux cooling pipe, 100 parts by mass of the monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and ethyl acetate as a polymerization solvent are charged. 200 parts by mass, and the mixture was stirred for 1 hour while introducing nitrogen gas. After the oxygen in the polymerization system was thus removed, the temperature was raised to 63 ° C and reacted for 10 hours. Then, it was cooled to room temperature, and a homopolymer solution having a solid content concentration of 33% by mass was obtained. Then, the homopolymer solution was cast-coated on a release liner, and dried to prepare a test sample (a sheet-like homopolymer) having a thickness of about 2 mm. Further, about 1-2 mg of the test sample was weighed and placed in an aluminum open cell, and a temperature-modulated DSC (Differential Scanning Calorimeter) (trade name "Q-2000", manufactured by TA Instruments) was used. The Reversing Heat Flow behavior of the homopolymer was obtained at a heating rate of 5 ° C/min under a nitrogen atmosphere of 50 ml/min.

With reference to JIS-K-7121, a straight line equidistant from the line connecting the reference line on the low temperature side of the obtained Reversing Heat Flow and the reference line on the high temperature side in the direction of the longitudinal axis is stepped with the glass transition. The temperature at the point where the curve of the varying portion intersects is set to the glass transition temperature (Tg) at the time of making the homopolymer.

Specific examples of the other polymerizable monomer unit (copolymerizable monomer) include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, and anti- a carboxyl group-containing monomer such as butenedioic acid, crotonic acid or methacrylic acid; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, methacrylic acid (4) a hydroxyl group-containing monomer such as a hydroxyalkyl (meth) acrylate such as hydroxymethylcyclohexyl) methyl ester; an acid anhydride group-containing monomer such as maleic anhydride or itaconic acid anhydride; styrenesulfonic acid or allylic acid; Sulfonic acid, 2-(meth)acrylamidoxime-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxyloxy a sulfonic acid group-containing monomer such as naphthalenesulfonic acid; a phosphate group-containing monomer such as 2-hydroxyethyl propylene decyl phosphate; (meth) acrylamide, N,N-dimethyl(meth) propylene oxime Amine, N, N-II (meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl) N,N-dialkyl(meth)acrylamide, (methyl) acrylamide, N,N-di(t-butyl)(meth)acrylamide, N-ethyl (methyl) Acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-methylol (methyl ) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-A Oxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-propylene fluorenyl (N-substituted) decylamine monomer; N-(methyl) propylene oxime oxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene amber Amber quinone imine monomer such as quinone imine or N-(methyl) propylene decyl-8-oxyhexamethylene succinimide; N-cyclohexyl maleimide, N-iso a maleimide monomer such as propyl maleimide, N-lauryl maleimide or N-phenyl maleimide; N-methylide Companion, N-ethyl Ikonium imine, N-butyl Ikonide, N-octyl Icinoimine, N-2-ethylhexylkkonium imine, N- Cyclohexyl ikonium imine, N-Lauryl Ikonide imine and other Ikonium imine monomers; vinyl acetate, vinyl propionate and other vinyl esters; N-vinyl-2-pyrrolidone , N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl Oxazole, N-(methyl)propenyl-2-pyrrolidone, N-(methyl)propenylpyridinium, N-(methyl)propenylpyrrolidine, N-vinyl Porphyrin, N-vinyl-2-piperidone, N-vinyl-3- Linoleone, N-vinyl-2-caprolactam, N-vinyl-1,3- 2-ketone, N-vinyl-3,5- Dioxadione, N-vinylpyrazole, N-vinyl iso Oxazole, N-vinylthiazole, N-vinylisothiazole, N-vinyl anthracene a nitrogen-containing heterocyclic monomer; N-vinyl carboxamide; an internal guanamine monomer such as N-vinyl caprolactam; a cyanoacrylate monomer such as acrylonitrile or methacrylonitrile; Aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylic acid Aminoalkyl (meth) acrylate monomer such as tributylaminoethyl ester; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, or propyl (meth)acrylate Alkoxyalkyl (meth)acrylate monomer such as oxyethyl ester, butoxyethyl (meth)acrylate or ethoxypropyl (meth)acrylate; alkoxy group, α-methyl group An alkoxy monomer such as an alkoxy group; an epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate; a diol-based acrylate monomer such as methoxyethylene glycol (meth) acrylate or methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate or a fluorine atom (methyl group) Acrylate, polyoxymethylene (meth)acrylic acid An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; and a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; Vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as vinyl toluene and alkoxy; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; a vinyl ether such as ether; a vinyl chloride; a sodium sulfonate-containing sulfonic acid group-containing monomer; a cyclohexyl maleimide, an isopropyl maleimide or the like; Monomer; isocyanate group-containing monomer such as 2-isocyanate ethyl (meth)acrylate; Porphyrin; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid An (meth) acrylate having an alicyclic hydrocarbon group such as an ester or a dicyclopentanyl (meth) acrylate; an aromatic hydrocarbon group such as phenyl (meth) acrylate or phenoxyethyl (meth) acrylate; Methyl) acrylate; (meth) acrylate obtained from a terpene compound derivative alcohol;

In particular, the monomer unit preferably uses the above hydroxyl group-containing monomer (hydroxyl group-containing (meth)acrylic monomer) together with the above reactive ionic liquid. By using the above-mentioned hydroxyl group-containing (meth)acrylic monomer, crosslinking of the antistatic agent composition or the like can be easily controlled, or a moderate cohesive force can be obtained. Further, unlike a carboxyl group or a sulfonate group which can function as a crosslinking site, the hydroxyl group has an ionic compound (alkali metal salt, ionic liquid, etc.) which can be added (adapted) as a conductive agent (antistatic agent). Moderate interaction, therefore, can also be preferably used for anti-chargeability aspects.

In all the structural units (all monomer units (components): 100% by mass) of the (meth)acrylic polymer, the hydroxyl group-containing (meth)acrylic monomer is preferably from 1 to 15% by mass, more preferably Preferably, it is 2 to 12% by mass, and most preferably 3 to 10% by mass. When it is in the above range, it is easy to control the reaction with the crosslinking agent and the cohesive force, which is preferable.

In the present invention, the polymerizable monomer other than the hydroxyl group-containing (meth)acrylic monomer is preferably all structural units (all monomer units (components)) of the above (meth)acrylic polymer. The medium is 0 to 65 mass%, more preferably 0 to 60 mass%, and particularly preferably 0 to 55 mass%. By using the above other polymerizable monomer in the above range, the cohesive force and the adhesion to the base film can be appropriately adjusted.

The polymerization method of the (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit used in the present invention is not particularly limited, and may be carried out by solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or radiation hardening polymerization. When the antistatic charging sheet of the present embodiment is used for the surface protection application described below, it is preferable to use solution polymerization from the viewpoint of productivity of the adhesive sheet. Emulsion polymerization. Further, the obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.

Further, the antistatic agent composition further preferably contains a conductive agent. Especially as The conductive agent (antistatic agent) preferably contains an ionic compound or an ion conductive polymer, and more preferably an alkali metal salt or an ionic liquid plasma compound. The ionic compound is not preferably reacted with the reactive ionic liquid, but is contained as an additive, and is more excellent in antistatic property, so that it is preferable. Further, the ionic compound has a large interaction property with the reactive ionic liquid incorporated in the skeleton of the (meth)acrylic polymer, and it is preferable because it does not have to be bleed out and is excellent in low contamination.

The content of the conductive agent used in the present invention is preferably 0 to 40 parts by mass, more preferably 0.5 to 35 parts by mass based on 100 parts by mass of the (meth)acrylic polymer contained in the antistatic agent composition. The mass part, more preferably, is 1 to 30 parts by mass. When the content exceeds 40 parts by mass, there is a tendency to cause bleed out, which is not preferable.

The antistatic layer in the present invention is characterized in that the above antistatic composition is crosslinked. By appropriately adjusting the structural unit of the (meth)acrylic polymer, the composition ratio, the selection of the crosslinking agent, the addition ratio, and the like, and crosslinking, it is possible to further obtain an antistatic layer (antistatic charging sheet) excellent in heat resistance. material).

As the crosslinking agent used in forming the above antistatic layer, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, or the like can be used. An oxazoline crosslinking agent, a polyfluorene crosslinking agent, a decane crosslinking agent, and a metal chelate compound. Among them, an isocyanate compound or an epoxy compound is more preferably used from the viewpoint of obtaining a moderate aggregating power, and an isocyanate compound (isocyanate-based crosslinking agent) is particularly preferable. These compounds may be used singly or in combination of two or more.

Examples of the isocyanate compound (isocyanate-based crosslinking agent) include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate, and cyclopentyl diisocyanate and cyclohexyl diisocyanate. An alicyclic isocyanate such as phorone diisocyanate, an aromatic isocyanate such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or benzodimethyl diisocyanate; trimethylolpropane/ Toluene diisocyanate trimer adduct (trade name Coronate L, Nippon Polyurethane Produced by Industry, Trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry), isocyanurate body of hexamethylene diisocyanate ( The trade name is Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like isocyanate adduct. Alternatively, a compound having at least one or more isocyanate groups and one or more unsaturated bonds in one molecule, specifically, 2-isocyanate ethyl (meth)acrylate or the like may be used as the isocyanate crosslinking agent. These compounds may be used singly or in combination of two or more.

Examples of the epoxy compound include bisphenol A, an epichlorohydrin type epoxy resin, an extended ethylene glycidyl ether, a polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerol triglycidyl. Ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl -m-xylylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, Mitsubishi Gas Chemical Company) and so on. These compounds may be used singly or in combination of two or more.

Examples of the melamine-based resin include hexamethylol melamine and the like. In addition, as the aziridine derivative, for example, the product name of the commercial product is HDU (manufactured by Mutual Pharmaceutical Co., Ltd.), the product name is TAZM (manufactured by Mutual Pharmaceutical Co., Ltd.), and the product name is TAZO (manufactured by Mutual Pharmaceutical Co., Ltd.). )Wait. These compounds may be used singly or in combination of two or more.

Examples of the metal chelate compound include aluminum, iron, tin, titanium, nickel, and the like as a metal component, and acetylene, ethyl acetacetate, ethyl lactate, and the like as a chelate component. These compounds may be used singly or in combination of two or more.

The content of the above-mentioned crosslinking agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the (meth)acrylic polymer contained in the antistatic agent composition. Further preferably, it contains 0.5 to 15 parts by mass, and particularly preferably contains 0.5%. 10 parts by mass. When the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent becomes insufficient, and the cohesive force of the antistatic agent composition becomes small, and sufficient heat resistance cannot be obtained. On the other hand, when the content exceeds 30 parts by mass, there is a tendency that gelation impurities are generated in the antistatic composition due to the crosslinking reaction in a short period of time, which causes a poor appearance.

The antistatic composition may further contain a compound which undergoes keto-enol tautomerization. By containing the above compound, it is possible to suppress the excessive viscosity increase or gelation of the antistatic agent composition after the crosslinking agent is blended, thereby realizing the effect of prolonging the pot life of the antistatic composition. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly useful for a compound containing a keto-enol tautomerism. This technique can be preferably applied, for example, to the case where the above antistatic composition is in the form of an organic solvent solution or a solventless form.

As the above-mentioned compound which undergoes keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples thereof include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane- Β-diketones such as 2,4-dione and 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl acetate, isopropyl acetate, and Acetyl acetate such as tributyl phthalate; ethyl acetonide, ethyl acetonide, isopropyl acetate, butyl phthalate, etc.; acetoacetate; Ethyl butyrate ethyl acetate, isobutyl hydrazine acetate, isobutyl phthalate acetate, etc.; isoamyl acetate such as methyl malonate or ethyl malonate; Classes, etc. Among them, preferred examples of the compound include acetamidineacetone and acetamidine acetate. The keto-enol tautomerization compound may be used singly or in combination of two or more.

The content of the keto-enol tautomerization compound is, for example, 0.1 to 20 parts by mass, and usually preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (for example, it is preferably 0.5 to 15 parts by mass). 1 to 10 parts by mass). When the content of the above compound is less than 0.1 part by mass, it may become difficult to exhibit a sufficient use effect. On the other hand, if the above When the amount exceeds 20 parts by mass, the antistatic layer may remain and the antistatic property may be lowered.

Further, in the present invention, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds may be added as a crosslinking agent. In this case, the antistatic composition is crosslinked by irradiation of radiation or the like. Examples of the polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule include radiation having two or more kinds of vinyl groups, acryl groups, methacryl groups, vinyl groups, and the like. One or two or more kinds of radiation-reactive group polyfunctional monomer components which are subjected to crosslinking treatment (hardening). Further, as the polyfunctional monomer, it is usually preferred to use 10 or less radiation-reactive unsaturated bonds. These compounds may be used singly or in combination of two or more.

Specific examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and new Pentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, divinylbenzene, N,N'-methylenebisacrylamide, and the like.

The blending amount of the above polyfunctional monomer is appropriately selected by the balance with the above (meth)acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance, it is usually preferably 0.1 to 30 parts by mass based on 100 parts by mass of the above (meth)acryl-based polymer. In addition, it is more preferably 10 parts by mass or less based on 100 parts by mass of the (meth)acryl-based polymer in terms of flexibility.

Examples of the radiation include ultraviolet rays, thunder rays, α rays, β rays, γ rays, X rays, and electron beams. In terms of controllability and workability, and cost, it is preferred to use ultraviolet rays. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. Further, when ultraviolet rays are used as the radiation, the photopolymerization initiator shown below can be added to the antistatic composition.

The photopolymerization initiator is used as long as it is based on a radiation-reactive component. The type irradiation may be a substance which generates ultraviolet rays at an appropriate wavelength of the initiator of the polymerization reaction to generate radicals or cations.

Examples of the photoradical polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, methyl phthalic acid benzoate, benzoin ethyl ether, benzoin isopropyl ether, and α-methyl benzoin. Acetophenones such as benzophenone dimethyl ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylbenzene Acetone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc., benzophenone, benzophenone, methyl benzophenone, p-chlorobenzophenone, p-dimethylamino group Benzophenone and other benzophenones, 2-chloro 9-oxosulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 9-oxosulfur Class, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, (2,4,6- A fluorenylphosphine oxide such as trimethylbenzhydryl)-(ethoxy)-phenylphosphine oxide, benzophenone, dibenzocycloheptanone or α-mercaptodecyl ester. These compounds may be used singly or in combination of two or more.

In addition, examples of the photocationic polymerization initiator include an onium salt such as an aromatic diazonium salt, an aromatic onium salt or an aromatic onium salt, or an iron-arene complex and a titanocene complex. Organic metal complexes such as aryl stanol-aluminum complexes, nitrobenzyl, sulfonic acid derivatives, phosphates, phenolsulfonates, diazonaphthoquinones, N-hydroxy sulfilimine sulfonates, etc. . These compounds may be used singly or in combination of two or more.

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass, based on 100 parts by mass of the (meth)acryl-based polymer. When it is in the above range, it is preferable to control the polymerization reaction from the viewpoint of obtaining an appropriate molecular weight.

Further, a photoinitial polymerization aid such as an amine may be used in combination. Examples of the photo-initiating aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylamino group. Isoamyl benzoate and the like. These compounds may be used singly or in combination of two or more. Polymerization initiation aid relative to (A 100 parts by mass of the acrylic polymer, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass. When it is in the above range, it is preferable to control the polymerization reaction from the viewpoint of obtaining an appropriate molecular weight.

In the case where a photopolymerization initiator of an optional component is added as described above, the antistatic layer can be obtained by applying the antistatic composition to one side or both sides of the substrate film and then irradiating with light. The antistatic layer is usually obtained by photopolymerization of ultraviolet light having an illuminance of from 1 to 200 mW/cm ² at a wavelength of from 300 to 400 nm at an irradiation light amount of about 200 to 4,000 mJ/cm ² .

Further, the antistatic composition may contain other known additives. For example, a powder such as a colorant or a pigment, a surfactant, a plasticizer, an adhesion promoter, a low molecular weight polymer, or a surface may be appropriately added depending on the intended use. Lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, decane coupling agents, inorganic or organic fillers, metal powders, particulates, foils, and the like.

A preferred aspect of the above antistatic layer is a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit, a crosslinking agent, and the like as needed, by dispersing or dissolving a suitable solvent. A liquid composition (an antistatic agent composition, an antistatic agent solution) of a component (a conductive agent or the like) is formed on at least one side of a base film. For example, a method in which the above-mentioned antistatic agent composition (antistatic agent solution) is applied to one surface of a base film and dried, and if necessary, a curing treatment (heat treatment, ultraviolet treatment, or the like) is carried out.

The solvent constituting the liquid composition (antistatic composition and antistatic agent solution) is preferably one which can stably dissolve or disperse the component (raw material) used when forming the antistatic layer. The solvent may be an organic solvent, water, or a mixed solvent of these. As the organic solvent, for example, one or two or more selected from the group consisting of ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; methyl ethyl ketone, acetone, cyclohexanone, and the like can be used. Ketones such as methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone, and acetamidine; tetrahydrofuran (THF), a cyclic ether such as an alkane; an aliphatic or alicyclic hydrocarbon such as n-hexane or cyclohexane; an aromatic hydrocarbon such as toluene or xylene; or a fat such as methanol, ethanol, n-propanol, isopropanol or cyclohexanol. Group or alicyclic alcohols; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether A glycol ether acetate such as acetate.

A coating method for forming the above-described antistatic layer can be appropriately used by a known coating method, and specific examples thereof include roll coating, gravure coating, reverse coating, roll coating, spray coating, and air knife coating. Impregnation and curtain coating methods.

The thickness of the antistatic layer of the present invention is usually preferably 0.005 to 10 μm, more preferably about 0.01 to 5 μm, still more preferably about 0.02 to 3 μm, still more preferably about 0.03 to 1 μm, and most preferably 0.05 to 0.5 μm. about. If it is in the above range, the base film which forms the antistatic layer is less likely to have heat resistance, solvent resistance, and flexibility, and thus it is preferable.

<Substrate film>

The base film constituting the adhesive sheet of the present invention can be used by a known one, and is not particularly limited, and is preferably a plastic film having heat resistance and solvent resistance and having flexibility. The base film is flexible, whereby the antistatic composition can be applied by a roll coater or the like, and can be wound into a roll shape.

The plastic film is not particularly limited as long as it is formed into a sheet shape or a film shape, and examples thereof include polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene. , ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/vinyl alcohol copolymer, polyolefin film, polyethylene terephthalate Polyester film such as ester, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, nylon 6,6, partially aromatic polyamine An amine film, a polyvinyl chloride film, a polyvinylidene chloride film, a polycarbonate film, or the like.

Further, the base film may be treated as follows: a release agent and an antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty amide-based release agent, cerium oxide powder or the like. , or acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, purple The external treatment or the like is easily followed by treatment, and the antistatic treatment such as a coating type, a mixing type, or a vapor deposition type.

Further, in the case where the adhesive sheet of the present invention is used as a film for surface protection use, it is preferable that the base film is an antistatic treatment plastic film. By using the above-mentioned base film, the charging of the surface protective film itself at the time of peeling can be more effectively suppressed, and thus it is an antistatic surface protective film in the technical field related to optical and electronic parts where charging or contamination is a particularly serious problem. very useful. Further, the base film is a plastic film, and the anti-charge treatment of the plastic film reduces the electrification of the surface protective film itself, and further improves the anti-static energy to the adherend (protected body).

In the present invention, the antistatic treatment of the plastic film is not particularly limited, and unlike the above-described antistatic layer formed of the antistatic composition, at least one side of the film for normal use can be additionally provided. A method of preventing an electrified layer, or a method of kneading a mixed type antistatic agent in a plastic film. A method of providing an antistatic layer on at least one side of the film, a method of applying an antistatic resin formed of an antistatic agent and a resin component, or a conductive resin containing a conductive polymer or a conductive material, or The method of depositing or plating a conductive material assumes that the adhesive sheet of the present invention is composed of a base film (a plastic film and an antistatic layer), an antistatic layer, and an adhesive layer.

Examples of the antistatic agent (conductive agent) include a quaternary ammonium salt, a pyridinium salt, a cationic antistatic agent having a cationic functional group such as a first, second, or third amine group, and a sulfonate or Anionic antistatic agent having an anionic functional group such as a sulfate salt, a phosphonate or a phosphate salt, an alkylbetaine and a derivative thereof, an imidazoline and a derivative thereof, an alanine and a derivative thereof, and the like A nonionic antistatic agent such as a charged agent, an amino alcohol and a derivative thereof, glycerin and a derivative thereof, a polyethylene glycol or a derivative thereof, and the like, and an ion having the above cationic, anionic or zwitterionic type An ion conductive polymer obtained by polymerizing or copolymerizing a monomer of a conductive group. These compounds may be used singly or in combination of two or more.

Examples of the cationic antistatic agent include alkyltrimethylammonium. Salt, mercaptoguanidinopropyltrimethylammonium methyl sulfate, alkylbenzylmethylammonium salt, mercaptocholine chloride, polydimethylaminoethyl methacrylate, etc. a (meth) acrylate copolymer, polyvinyl benzyl trimethyl ammonium chloride or the like having a quaternary ammonium group alkoxy copolymer, polydiallyl dimethyl ammonium chloride or the like having four stages Ammonium-based diallylamine copolymer and the like. These compounds may be used singly or in combination of two or more.

Examples of the anionic antistatic agent include an alkylsulfonate, an alkylbenzenesulfonate, an alkylsulfate, an alkylethoxysulfate, an alkyl phosphate, and a sulfonic acid. Alkoxy copolymer. These compounds may be used singly or in combination of two or more.

Examples of the above-mentioned zwitterionic antistatic agent include graft copolymerization of an alkylbetaine, an alkylimidazolium betaine, and a carboxybetaine. These compounds may be used singly or in combination of two or more.

Examples of the nonionic antistatic agent include fatty acid alkanolamine, bis(2-hydroxyethyl)alkylamine, polyoxyethylene alkylamine, fatty acid glyceride, and polyoxyethylene glycol fatty acid. Ester, sorbitan fatty acid ester, polyoxysorbate fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, polyether and polyester And a copolymer of polyamine, methoxy polyethylene glycol (meth) acrylate, and the like. These compounds may be used singly or in combination of two or more.

Examples of the conductive polymer include polyaniline, polypyrrole, and polythiophene.

Examples of the conductive material include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, and cobalt. , copper iodide, and alloys or mixtures thereof.

As the resin component used in the antistatic resin and the conductive resin, a general-purpose resin such as polyester, acrylic resin, polyethylene, urethane, melamine, or epoxy resin can be used. Further, in the case of a polymer type antistatic agent, a resin component may be contained. Further, a compound such as a melamine-based or urea-based melamine-based, urea-based, glyoxal-based or acrylamide-based compound, an epoxy compound or an isocyanate compound may be contained as a crosslinking agent in the antistatic resin component. .

The method for forming the antistatic layer is formed by, for example, diluting the antistatic resin, the conductive polymer, and the conductive resin with a solvent such as an organic solvent or water, applying the coating liquid to a plastic film, and drying the coating liquid. .

Examples of the organic solvent for forming the above antistatic layer include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, and Alkane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, isopropanol, and the like. These solvents may be used singly or in combination of two or more.

A coating method for forming the above-described antistatic layer can be appropriately used by a known coating method, and specific examples thereof include roll coating, gravure coating, reverse coating, roll coating, spray coating, and air knife coating. Impregnation and curtain coating methods.

The thickness of the layer (antistatic layer) formed of the antistatic resin, the conductive polymer, or the conductive resin is usually 0.01 μm to 5 μm, preferably about 0.03 μm to 1 μm.

Examples of the method of vapor deposition or plating of the conductive material include vacuum deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, electroless plating, and plating.

The thickness of the layer (antistatic layer) formed of the conductive material is usually 2 nm to 1000 nm, preferably 5 nm to 500 nm.

In addition, the amount of the antistatic agent to be added is 20% by mass or less, preferably 0.05 to 10% by mass based on the total weight of the base film (plastic film). If it is in the above range, it is preferable that the base film (plastic film) is less likely to have heat resistance, solvent resistance, and flexibility. The mixing method is a method in which the antistatic agent is uniformly mixed in the resin used for the base film (plastic film), and There is no particular limitation, and for example, a heating roll, a Banbury mixer, a pressure kneader, a twin-shaft kneader, or the like can be used.

The thickness of the base film constituting the adhesive sheet of the present invention (the thickness including the above-mentioned antistatic layer when the plastic film has an antistatic layer) is usually 5 to 200 μm, preferably 10 to 100 μm. about. When the thickness of the base film is within the above range, it is preferable because it has excellent adhesion to the adherend and peeling workability from the adherend.

<Adhesive Composition and Adhesive Layer>

The adhesive layer constituting the antistatic charging sheet of the present invention can be used, and is not particularly limited, and a (meth)acrylic polymer, a rubber-based polymer, a polyoxymethylene-based polymer, or a poly A urethane-based polymer, a polyester-based polymer or the like is generally used as various polymers of an adhesive. More preferably, it is formed of an adhesive composition containing a (meth)acrylic polymer containing an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as Main component (monomer unit). Further, the (meth)acrylic polymer in the present invention means an acrylic polymer and/or a methacrylic polymer, and (meth)acrylate means an acrylate and/or a methyl group. Acrylate. In addition, the "main component" is a monomer which has the highest composition ratio in the monomer unit (component) which comprises the said (meth)acrylic-type polymer.

As the monomer unit (component) constituting the (meth)acrylic polymer of the present invention, in terms of obtaining adhesive properties, it is preferred to use a linear or branched alkyl group having 1 to 20 carbon atoms ( The alkyl (meth)acrylate is more preferably an alkyl (meth)acrylate having an alkyl group having 6 to 14 carbon atoms. The alkyl (meth)acrylate may be used alone or in combination of two or more.

The (meth)acrylic polymer containing the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as a main component preferably contains 50 to 99.9% by mass of the above carbon number 1 to 20. The alkyl (meth) acrylate of the alkyl group is preferably a monomer unit (component), and more preferably contains 60 to 97% by mass. If the above monomer unit (component) is within the above range, it is sticky The coating composition is preferred from the viewpoint of obtaining moderate wettability and cohesiveness.

In the present invention, specific examples of the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate. N-butyl methacrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-(meth)acrylate An ester, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and the like.

In the case where the adhesive sheet of the present invention is used as a surface protective film, preferred examples thereof include hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (methyl). ) n-octyl acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate (n-decyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. having a carbon number of 6 to 14 (methyl) ) alkyl acrylate. By using an alkyl (meth)acrylate having an alkyl group having 6 to 14 carbon atoms, it is easy to control the adhesion to the adherend to be low, and it is excellent in re-peelability.

Further, as another monomer unit (component) having polymerizability, the glass transition temperature (Tg) can be made 0 ° C or less within the range in which the effect of the present invention is not impaired for the purpose of easily obtaining the balance of the adhesive properties (usually A polymerizable monomer or the like for adjusting the glass transition temperature (Tg) or the releasability of the (meth)acrylic polymer is used in a manner of -100 ° C or higher.

As the other polymerizable monomer used in the above (meth)acrylic polymer, in particular, in terms of control for easy crosslinking, it is preferred to use a (meth) acrylate having a hydroxyl group (including a hydroxyl (meth)acrylic monomer). Further, in addition to the above-mentioned hydroxyl group-containing (meth)acrylic monomer copolymerizable with the above (meth)acrylic acid alkyl ester, it may be further modified, in addition to the above-mentioned (meth)acrylic acid alkyl ester, in order to improve the cohesive force, heat resistance, crosslinkability, and the like. Contains other monomers Fraction (copolymerizable monomer). These monomer compounds may be used singly or in combination of two or more.

By using the above-mentioned hydroxyl group-containing (meth)acrylic monomer, it becomes easy to control the crosslinking of the adhesive composition, etc., and it is easy to control the improvement of the wettability by the flow and the adhesion in the peeling. Reduce the balance. Further, in general, unlike the above-mentioned carboxyl group or sulfonate group which functions as a crosslinking site, the hydroxyl group has a moderate degree of an ionic compound (alkali metal salt or ionic liquid) which can be added (adapted) as an antistatic agent. The interaction is therefore also preferably used for anti-chargeability. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)acrylate Ester, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.

In the case of containing the above-mentioned hydroxyl group-containing (meth)acrylic monomer, all structural units (all monomer units (components): 100% by mass) of the above (meth)acrylic polymer, hydroxyl group-containing The (meth)acrylic monomer is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 12% by mass, most preferably from 1 to 10% by mass. If it is in the above range, it becomes easy to control the balance between the wettability and the cohesive force of the adhesive composition, which is preferable.

Specific examples of the other copolymerizable monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isobutylene. a carboxyl group-containing monomer such as an acid; an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, and 2-(methyl)acrylamidamine-2-methyl a sulfonic acid group-containing monomer such as propanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethyl phosphate a phosphate group-containing monomer such as acryl oxime ester; (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, N , N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di(n-butyl) (meth) acrylamide, N, N,N-dialkyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl (N-di(t-butyl)(methyl) acrylamide, etc. Methyl) acrylamide, N-butyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl ( Methyl) acrylamide, N-butoxymethyl (meth) acrylamide, N-propylene fluorenyl (N-substituted) decylamine monomer; N-(methyl) propylene oxime oxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene amber Amber quinone imine monomer such as quinone imine or N-(methyl) propylene decyl-8-oxyhexamethylene succinimide; N-cyclohexyl maleimide, N-iso a maleimide monomer such as propyl maleimide, N-lauryl maleimide or N-phenyl maleimide; N-methylide Companion, N-ethyl Ikonium imine, N-butyl Ikonide, N-octyl Icinoimine, N-2-ethylhexylkkonium imine, N- Cyclohexyl ikonium imine, N-Lauryl Ikonide imine and other Ikonium imine monomers; vinyl acetate, vinyl propionate and other vinyl esters; N-vinyl-2-pyrrolidone , N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl Oxazole, N-(methyl)propenyl-2-pyrrolidone, N-(methyl)propenylpyridinium, N-(methyl)propenylpyrrolidine, N-vinyl Porphyrin, N-vinyl-2-piperidone, N-vinyl-3- Linoleone, N-vinyl-2-caprolactam, N-vinyl-1,3- 2-ketone, N-vinyl-3,5- Dioxadione, N-vinylpyrazole, N-vinyl iso Oxazole, N-vinylthiazole, N-vinylisothiazole, N-vinyl anthracene a nitrogen-containing heterocyclic monomer; N-vinyl carboxamide; an internal guanamine monomer such as N-vinyl caprolactam; a cyanoacrylate monomer such as acrylonitrile or methacrylonitrile; Aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylic acid Aminoalkyl (meth) acrylate monomer such as tributylaminoethyl ester; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propyl (meth) acrylate Alkoxyalkyl (meth)acrylate monomer such as oxyethyl ester, butoxyethyl (meth)acrylate or ethoxypropyl (meth)acrylate; alkoxy group, α-methyl group An alkoxy monomer such as an alkoxy group; an epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate; a diol-based acrylate monomer such as methoxyethylene glycol (meth) acrylate or methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate or a fluorine atom (methyl group) Acrylate, polyoxymethylene (meth)acrylic acid An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; and a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; Vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as vinyl toluene and alkoxy; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; a vinyl ether such as ether; a vinyl chloride; a sulfonate group-containing monomer such as sodium vinyl sulfonate; a quinone imine group such as cyclohexylmethyleneimine or isopropyl maleimide Monomer; isocyanate group-containing monomer such as 2-isocyanate ethyl (meth)acrylate; Porphyrin; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid An (meth) acrylate having an alicyclic hydrocarbon group such as an ester or a dicyclopentanyl (meth) acrylate; an aromatic hydrocarbon group such as phenyl (meth) acrylate or phenoxyethyl (meth) acrylate; Methyl) acrylate; (meth) acrylate obtained from a terpene compound derivative alcohol; Further, these copolymerizable monomers may be used singly or in combination of two or more.

In the present invention, the polymerizable monomer other than the hydroxyl group-containing (meth)acrylic monomer may be used singly or in combination of two or more kinds, preferably in the above (meth)acrylic acid. The total structural unit (all monomer units (components)) of the polymer is 0 to 40% by mass, more preferably 0 to 35% by mass, and particularly preferably 0 to 30% by mass. The re-peelability can be appropriately adjusted by using the above other polymerizable monomer in the above range.

The weight average molecular weight (Mw) of the (meth)acrylic polymer contained in the adhesive composition used in the present invention is preferably from 100,000 to 5,000,000, more preferably from 200,000 to 4,000,000, and further Good for 300,000 to 3 million, especially for 300,000 to 1 million. When the weight average molecular weight is less than 100,000, there is a tendency that the sticking force of the adhesive composition becomes small and the paste remains. On the other hand, when the weight average molecular weight exceeds 5 million, there is a case where the fluidity of the polymer is lowered, for example, the wetting of the adherend is insufficient, and the adhesive force is insufficient. Further, the weight average molecular weight is obtained by measurement by GPC (gel permeation chromatography).

Further, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0 ° C or lower, more preferably -10 ° C or lower, further preferably -41 ° C or lower, and particularly preferably -51 ° C or lower. The optimum is -61 ° C or less (usually -100 ° C or more). When the glass transition temperature is higher than 0 ° C, there is a case where the polymer does not easily flow, for example, the wetting of the adherend becomes insufficient, and the adhesion is insufficient. In particular, by setting the glass transition temperature to -61 ° C or lower, it is easy to obtain an adhesive composition which is excellent in wettability and light peelability to an adherend (such as a polarizing plate). Further, the glass transition temperature of the (meth)acrylic polymer can be adjusted to the above range by appropriately changing the monomer component or composition ratio used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and it can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or radiation hardening polymerization. When the antistatic charging sheet of the present embodiment is used for the surface protection application described below, solution polymerization or emulsion polymerization can be preferably used from the viewpoint of productivity of the adhesive sheet. Further, the obtained polymer may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer or the like.

The adhesive layer in the present invention is preferably obtained by crosslinking an adhesive composition containing the above (meth)acrylic polymer or the like. Further, by appropriately adjusting the structural unit of the (meth)acrylic polymer, the composition ratio, the selection of the crosslinking agent, the addition ratio, and the like, and further crosslinking, an adhesive layer excellent in heat resistance (antistatic charging sheet) can be further obtained. material).

As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, or the like can be used. An oxazoline crosslinking agent, a polyfluorene crosslinking agent, a decane crosslinking agent, and a metal chelate compound. Among them, an isocyanate compound or an epoxy compound is more preferably used from the viewpoint of obtaining a moderate aggregating power, and an isocyanate compound (isocyanate-based crosslinking agent) is particularly preferable. These compounds may be used singly or in combination of two or more.

Examples of the isocyanate compound (isocyanate-based crosslinking agent) include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate, and cyclopentyl diisocyanate and cyclohexyl diisocyanate. Alicyclic isocyanates such as phorone diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate An aromatic isocyanate such as an ester or benzyl diisocyanate, a trimethylolpropane/toluene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry), trimethylolpropane/sixa Isocyanate such as methyl diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene diisocyanate isocyanurate body (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) Additives, etc. Alternatively, a compound having at least one or more isocyanate groups and one or more unsaturated bonds in one molecule, specifically 2-isocyanate ethyl (meth)acrylate or the like may be used as the isocyanate crosslinking agent. These compounds may be used singly or in combination of two or more.

Examples of the epoxy compound include bisphenol A, an epichlorohydrin type epoxy resin, an extended ethylene glycidyl ether, a polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerol triglycidyl. Ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl -m-xylylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, Mitsubishi Gas Chemical Company) and so on. These compounds may be used singly or in combination of two or more.

Examples of the melamine-based resin include hexamethylol melamine and the like. In addition, as the aziridine derivative, for example, the product name of the commercial product is HDU (manufactured by Mutual Pharmaceutical Co., Ltd.), the product name is TAZM (manufactured by Mutual Pharmaceutical Co., Ltd.), and the product name is TAZO (manufactured by Mutual Pharmaceutical Co., Ltd.). )Wait. These compounds may be used singly or in combination of two or more.

Examples of the metal chelate compound include aluminum, iron, tin, titanium, nickel, and the like as a metal component, and acetylene, ethyl acetacetate, ethyl lactate, and the like as a chelate component. These compounds may be used singly or in combination of two or more.

The content of the crosslinking agent used in the adhesive composition of the present invention is relative to the above (meth) The acrylic polymer is preferably contained in an amount of from 0.01 to 20 parts by mass, more preferably from 0.5 to 15 parts by mass, even more preferably from 0.5 to 10 parts by mass, per 100 parts by mass of the acrylic polymer. When the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent may be insufficient, the cohesive force of the adhesive composition may become small, and sufficient heat resistance may not be obtained, and the paste may be obtained. The tendency of the cause of residue. On the other hand, when the content exceeds 20 parts by mass, there is a case where the cohesive force of the polymer is large and the fluidity is lowered, for example, the wetting of the adherend is insufficient, and the adhesive force is insufficient.

The adhesive compositions disclosed herein may in turn contain compounds which undergo keto-enol tautomerization. For example, an adhesive composition containing a crosslinking agent or an adhesive composition which can be used for blending a crosslinking agent can preferably adopt a form containing the above-described compound which undergoes keto-enol tautomerization. Thereby, it is possible to achieve an effect of suppressing an excessive viscosity increase or gelation of the adhesive composition after the crosslinking agent is formulated, and prolonging the pot life of the composition. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly meaningful to contain a compound which undergoes keto-enol tautomerization. This technique can be preferably used, for example, in the case where the above-mentioned adhesive composition is in the form of an organic solvent solution or a solvent-free form.

As the above-mentioned compound which undergoes keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples thereof include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane- Β-diketones such as 2,4-dione and 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl acetate, isopropyl acetate, and Acetyl acetate such as tributyl phthalate; ethyl acetonide, ethyl acetonide, isopropyl acetate, butyl phthalate, etc.; acetoacetate; Ethyl butyrate ethyl acetate, isobutyl hydrazine acetate, isobutyl phthalate acetate, etc.; isoamyl acetate such as methyl malonate or ethyl malonate; Classes, etc. Among them, preferred examples of the compound include acetamidineacetone and acetamidine acetate. The keto-enol tautomerization compound may be used singly or in combination of two or more.

The above-mentioned keto-enol tautomerization compound is used in an amount relative to the above (meth) 100 parts by mass of the acrylic polymer can be, for example, 0.1 to 20 parts by mass, and usually preferably 0.5 to 15 parts by mass (for example, 1 to 10 parts by mass). When the amount of the above compound is too small, it may become difficult to exhibit a sufficient use effect. On the other hand, if the above-mentioned compound is used in a large amount as necessary, the adhesive layer may remain in the adhesive layer and the cohesive force may be lowered.

Further, in the present invention, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds may be added as a crosslinking agent. In this case, the adhesive composition is crosslinked by irradiation of radiation or the like. Examples of the polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule include radiation having two or more vinyl groups, acrylonitrile groups, methacryl fluorenyl groups, and vinyl benzyl groups. One or two or more kinds of radioactive group-containing polyfunctional monomer components which are cross-linked (hardened). Further, as the polyfunctional monomer, it is usually preferred to use 10 or less radiation-reactive unsaturated bonds. These compounds may be used singly or in combination of two or more.

Specific examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and new Pentandiol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (Meth) acrylate, divinyl benzene, N, N'-methylene bis acrylamide, and the like.

The blending amount of the above polyfunctional monomer is appropriately selected depending on the balance with the (meth)acrylic polymer to be crosslinked, and further depending on the intended use of the adhesive sheet. In order to obtain sufficient heat resistance by the cohesive force of the acrylic adhesive, it is usually preferably 0.1 to 30 parts by mass based on 100 parts by mass of the (meth)acrylic polymer. In addition, it is more preferably 10 parts by mass or less based on 100 parts by mass of the (meth)acryl-based polymer in terms of flexibility and adhesion.

Examples of the radiation include ultraviolet rays, thunder rays, α rays, β rays, γ rays, X rays, and electron beams. In terms of controllability and workability, and cost, it is preferred to use ultraviolet rays. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. Further, when ultraviolet rays are used as the radiation, the photopolymerization initiator shown below can be added to the acrylic adhesive.

The photopolymerization initiator may be one which generates radicals or cations by irradiation with ultraviolet rays of an appropriate wavelength which is an initiator of the polymerization reaction depending on the type of the radiation-reactive component.

Examples of the photoradical polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, methyl phthalic acid benzoate, benzoin ethyl ether, benzoin isopropyl ether, and α-methyl benzoin. Acetophenones such as benzophenone dimethyl ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylbenzene Acetone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc., benzophenone, benzophenone, methyl benzophenone, p-chlorobenzophenone, p-dimethylamino group Benzophenone and other benzophenones, 2-chloro 9-oxosulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 9-oxosulfur Class, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, (2,4,6- A fluorenylphosphine oxide such as trimethylbenzhydryl)-(ethoxy)-phenylphosphine oxide, benzophenone, dibenzocycloheptanone or α-mercaptodecyl ester. These compounds may be used singly or in combination of two or more.

In addition, examples of the photocationic polymerization initiator include an onium salt such as an aromatic diazonium salt, an aromatic onium salt or an aromatic onium salt, or an iron-arene complex and a titanocene complex. Organic metal complexes such as aryl stanol-aluminum complexes, nitrobenzyl, sulfonic acid derivatives, phosphates, phenolsulfonates, diazonaphthoquinones, N-hydroxy sulfilimine sulfonates, etc. . These compounds may be used singly or in combination of two or more.

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass, based on 100 parts by mass of the (meth)acryl-based polymer. When it is in the above range, it is preferable to control the polymerization reaction from the viewpoint of obtaining an appropriate molecular weight.

Further, a photoinitial polymerization aid such as an amine may be used in combination. Examples of the photo-initiating aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylamino group. Isoamyl benzoate and the like. These compounds may be used singly or in combination of two or more. The polymerization initiator is preferably formulated in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer. When it is in the above range, it is preferable to control the polymerization reaction from the viewpoint of obtaining an appropriate molecular weight.

When the photopolymerization initiator of any component is added as described above, the above-mentioned adhesive composition can be directly applied to the adherend (protected body) or applied to a specific spacer or the like. After coating the body or applying a single side on the antistatic layer, light irradiation is performed to obtain an adhesive layer. Usually, an adhesive layer is obtained by irradiating ultraviolet rays having an illuminance of from 1 to 200 mW/cm ² at a wavelength of from 300 to 400 nm at a wavelength of about 200 to 4000 mJ/cm ² and photopolymerizing them.

Further, the above-mentioned adhesive composition may contain other known additives. For example, a conductive agent (antistatic agent), a colorant, a pigment, or the like may be appropriately added depending on the intended use, a surfactant, a plasticizer, and an adhesion-imparting agent. , low molecular weight polymer, surface lubricant, leveling agent, antioxidant, anticorrosive, light stabilizer, UV absorber, polymerization inhibitor, decane coupling agent, inorganic or organic filler, metal powder, particulate, foil And so on. In particular, as the above-mentioned conductive agent (antistatic agent), for example, an alkali metal salt or an ionic liquid (including the above reactive ionic liquid) plasma compound is preferably used.

The adhesive sheet of the present invention is formed by forming the above-mentioned adhesive layer on the antistatic layer. In this case, the crosslinking of the adhesive composition is usually carried out after the application of the adhesive composition, or the crosslinking may be carried out. The adhesive layer of the adhesive composition is transferred onto the antistatic layer.

Further, the method of forming the pressure-sensitive adhesive layer on the antistatic layer is not particularly limited. For example, by applying the above-mentioned pressure-sensitive adhesive composition (solution) to the antistatic layer, the polymerization solvent or the like is dried and removed, and the adhesive layer is formed on the adhesive layer. Made on the anti-charge layer. After that, you can also adjust the adhesion. The component of the agent layer is cured by moving the component or adjusting the crosslinking reaction. Further, when the pressure-sensitive adhesive layer (solution) is applied to the antistatic layer to form an antistatic layer, one or more solvents other than the polymerization solvent may be newly added to the adhesive composition to be uniformly coated. On the charged layer.

Further, as a method of forming the adhesive layer in the production of the adhesive sheet of the present invention, a known method for producing an adhesive tape can be used. Specific examples thereof include roll coating, gravure coating, reverse coating, roll coating, spray coating, air knife coating, and extrusion coating using a die coater.

The adhesive sheet of the present invention is usually produced such that the thickness of the adhesive layer is from 3 to 100 μm, preferably from about 5 to 50 μm, more preferably from about 10 to 30 μm. When the thickness of the adhesive layer is within the above range, it is easy to obtain a balance between moderate removability and adhesion, which is preferable.

The adhesive sheet (surface protective film) of the present invention may be bonded to the surface of the adhesive layer in order to protect the adhesive surface as needed.

As the material constituting the separator, there is a paper or a plastic film, and in terms of excellent surface smoothness, a plastic film is preferably used. The film is not particularly limited as long as it is a film that can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethylpentene film. , a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm, and more preferably about 15 to 50 μm. When it is in the above range, it is preferable because the adhesiveness of the adhesive layer and the peeling workability of the self-adhesive layer are excellent. The separator may be treated as follows: a release agent and an antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl or fatty amide-based release agent, cerium oxide powder, or the like, or Anti-static treatment such as coating type, mixing type, and vapor deposition type.

The antistatic charging sheet having the antistatic layer of the present invention contains an antistatic layer having excellent antistatic properties, and thus can be used for surface protection applications or electronic component manufacturing and shipping steps. Among the above-mentioned applications, there is a problem that the adhesion of dirt, dust, or the like due to static electricity and the destruction of electronic components caused by static electricity are generated. Therefore, it is useful to suppress such conditions.

The antistatic charging sheet having the antistatic layer of the present invention can be attached to an optical film and used as an optical film with an antistatic charging sheet. It is useful to protect the surface of the optical film by attaching the above-mentioned antistatic charging sheet to the above optical film. In particular, the above-mentioned antistatic charging sheet can be used in a plastic product or the like which is likely to generate static electricity, and is therefore useful as an antistatic treatment in the technical field related to optical and electronic parts in which charging is a particularly problematic.

Further, the antistatic layer of the present invention is formed on at least one side of the base film, and the antistatic property of the adhesive layer formed on the antistatic layer is then (immobilized) on the optical film, whereby An optical film with an antistatic film followed by a sheet. By continuing the above-described antistatic charging sheet, it is possible to prevent the antistatic layer from falling off and to prevent deterioration of optical characteristics caused by damage of the optical film. Further, the above-mentioned adhesive layer is not required to be re-peelable (light-peelability) as in the above-mentioned adhesive layer, but is subsequently (immobilized) to the above-mentioned optical film for permanent or semi-permanent follow-up For the purpose of the situation. Further, as the above-mentioned adhesive layer (adhesive composition), a known one can be used.

[Examples]

In the following, several embodiments of the present invention are described, but the present invention is not intended to be limited to the specific examples. In addition, the "parts" and "%" in the following description are the quality standards unless otherwise specified.

<Preparation of Reactive Ionic Liquid (DMAEA-TFSI)>

In a 1 L three-necked flask, 100 parts of a chlorinated 2-(acryloxy)ethyltrimethylammonium chloride solution (DMAEA-Q manufactured by Kohjin Co., Ltd.) was stirred while being heated at 60 ° C. The addition of 114 parts of potassium bis(trifluoromethanesulfonate)imide in 80 parts of ion-exchanged water was added. After 2 hours, the oil layer portion of the lower layer separated by two layers was extracted, washed three times with ion-exchanged water, and then the residual trace amount of water was removed under reduced pressure to obtain 2-(acryloxy)ethyltrimethyl. Alkyl ammonium-bis(trifluoromethanesulfonate)imide (DMAEA-TFSI).

<Preparation of Reactive Ionic Liquid (DMAPAA-TFSI)>

In a 1 L three-necked flask, 100 parts of a 75% aqueous solution of chlorinated (3-acrylamidopropyl)trimethylammonium (DMAPAA-Q manufactured by Kohjin Co., Ltd.) was stirred, and added to the ion exchange under heating at 60 ° C. A mixture of 116 parts of potassium bis(trifluoromethanesulfonate)imide was added to 80 parts of water. After 2 hours, the oil layer portion of the lower layer separated by two layers was extracted, washed with ion-exchanged water for 3 times, and the residual trace amount of water was removed under reduced pressure to obtain (3-acrylamidopropyl)trimethyl group. Ammonium-bis(trifluoromethanesulfonate)imide (DMAPAA-TFSI).

<Preparation of (meth)acrylic polymer (A) for antistatic layer>

400 parts of methyl ethyl ketone, 40 parts of 2-(acryloxy)ethyltrimethylammonium-bis(trifluoromethanesulfonate)imide (DMAEA-TFSI), 55 parts of methyl methacrylate, Five parts of 2-hydroxyethyl methacrylate was placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Further, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 4 hours, followed by reaction at 80 ° C. 4 hours. Thereafter, 0.1 part of 2,2'-azobisisobutyronitrile was charged, and the reaction was carried out at 80 ° C for 1 hour. Thereafter, 0.17 parts of 2,2'-azobisisobutyronitrile was introduced at 70 ° C, and the reaction was carried out for 4 hours, followed by reaction at 80 ° C for 4 hours to obtain a (meth)acrylic polymer for an antistatic layer ( A).

<Preparation of (meth)acrylic polymer (B) for antistatic layer>

400 parts of methyl ethyl ketone, 2-(acryloxy)ethyltrimethylammonium-bis(trifluoromethanesulfonate)imide (DMAEA-TFSI) 95 parts, 2-hydroxyethyl methacrylate Five parts were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. And, after stirring at 70 ° C for 1 hour under a nitrogen atmosphere, it was put into a polymerization initiator. 0.2 part of 2,2'-azobisisobutyronitrile was reacted at 70 ° C for 4 hours, followed by reaction at 80 ° C for 1 hour. Thereafter, 0.1 part of 2,2'-azobisisobutyronitrile was charged, and the reaction was carried out at 80 ° C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was introduced at 70 ° C, and the reaction was carried out for 4 hours, followed by reaction at 80 ° C for 4 hours to obtain a (meth)acrylic polymer for an antistatic layer ( B).

<Preparation of (meth)acrylic polymer (C) for antistatic layer>

400 parts of methyl ethyl ketone, (3-propenylaminopropyl) trimethylammonium-bis(trifluoromethanesulfonate)imide (DMAPAA-TFSI) 95 parts, 2-hydroxyethyl methacrylate 5 The fraction was placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Further, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 4 hours, followed by reaction at 80 ° C. 1 hour. Thereafter, 0.1 part of 2,2'-azobisisobutyronitrile was charged, and the reaction was carried out at 80 ° C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was introduced at 70 ° C, and the reaction was carried out for 4 hours, followed by reaction at 80 ° C for 4 hours to obtain a (meth)acrylic polymer for an antistatic layer ( C).

<Preparation of (meth)acrylic polymer (D) for antistatic layer>

400 parts of methyl ethyl ketone, 85 parts of 2-(acryloxy)ethyltrimethylammonium-bis(trifluoromethanesulfonate)imide (DMAEA-TFSI), methoxy-terminated polyethylene 10 parts of diol methacrylate (average addition mole number 23, Blemmer PME-1000 by Nippon Oil Co., Ltd.) and 5 parts of 2-hydroxyethyl methacrylate were put into a stirring blade, a thermometer, a nitrogen introduction tube, A four-necked flask of a condenser and a dropping funnel. Further, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 4 hours, followed by reaction at 80 ° C. 1 hour. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was charged, and the mixture was reacted at 80 ° C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was introduced at 70 ° C, and the reaction was carried out for 4 hours, followed by reaction at 80 ° C for 4 hours to obtain a (meth)acrylic polymer for an antistatic layer ( D).

<Preparation of (meth)acrylic polymer (E) for antistatic layer>

400 parts of methyl ethyl ketone, 2-(acryloxy)ethyltrimethylammonium-bis(trifluoromethanesulfonate) 醯)imine (DMAEA-TFSI) 65 parts, methoxy-terminated polyethylene glycol methacrylate (average addition mole number 23, Blemmer PME-1000 manufactured by Nippon Oil Co., Ltd.) 30 parts, methyl Five parts of 2-hydroxyethyl acrylate was placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. Further, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 4 hours, followed by reaction at 80 ° C. 1 hour. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was charged, and the reaction was carried out at 80 ° C for 5 hours to obtain a (meth)acrylic polymer (E) for an antistatic layer. Further, the weight average molecular weight was 150,000.

<Preparation of (meth)acrylic polymer (F) for adhesive layer>

Adding 200 parts of 2-ethylhexyl acrylate and 8 parts of 2-hydroxyethyl acrylate to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel, as a polymerization initiator 2 0.4 parts of 2'-azobisisobutyronitrile and 312 parts of ethyl acetate, and nitrogen gas was introduced while stirring slowly, and the liquid temperature in the flask was maintained at around 65 ° C, and polymerization was carried out for 6 hours to prepare an adhesive. A (meth)acrylic polymer (F) solution (40% by mass) was used for the layer. The glass transition temperature (Tg) calculated from the Fox formula of the obtained (meth)acrylic polymer (F) was -68 ° C, and the weight average molecular weight was 550,000.

<Preparation of Adhesive Composition>

500 parts (100 parts of polymer) of the solution in which the above-mentioned adhesive layer was diluted with 20% by mass of the (meth)acrylic polymer (F) solution (40% by mass) with ethyl acetate, and added as a cross. Coronate L (solid solution of trimethylolpropane/toluene diisocyanate trimer adduct, 75 mass% ethyl acetate solution, manufactured by Nippon Polyurethane Industry Co., Ltd.), 5.3 parts, two laurels as cross-linking catalyst 3.0 parts of dioctyltin acid (1% by mass ethyl acetate solution) was mixed and stirred at 25 ° C for about 5 minutes to prepare an acrylic adhesive solution (1).

[Example 1] (Preparation of antistatic agent solution)

Into 2381 parts (100 parts of a polymer) obtained by diluting the above (meth)acrylic-based polymer (A) solution (20% by mass) to 4.2% by mass with methyl ethyl ketone, a crosslinking agent was added as a crosslinking agent. Coronate L (solid solution of trimethylolpropane/toluene diisocyanate trimer adduct, 75 mass% ethyl acetate solution, manufactured by Nippon Polyurethane Industry Co., Ltd.), 4.0 parts of DMAEA-TFSI as a conductive agent, 3.0 parts of dioctyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst was mixed and stirred at 25 ° C for about 5 minutes to prepare an antistatic agent solution (1).

(Preparation of anti-static treatment film)

The above antistatic agent solution (1) was applied to a polyethylene terephthalate (PET) film (thickness: 38 μm, manufactured by Toray Co., Ltd., Lumirror S10) using a Meyer bar, and dried at 130 ° C. After 1 minute, the solvent was removed to form an antistatic layer (thickness: 0.5 μm), and an antistatic treatment film (1) was produced.

(Production of adhesive sheet)

The acrylic pressure-sensitive adhesive solution (1) was applied onto the antistatic treatment surface of the above antistatic treatment film (1), and heated at 130 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm.

Then, a polyfluorene-treated surface of a polyethylene terephthalate film (separator) having a thickness of 25 μm which was subjected to polyfluorination treatment on one surface was bonded to the surface of the above-mentioned pressure-sensitive adhesive layer to prepare an adhesive sheet.

[Embodiment 2] (Preparation of antistatic agent solution)

An antistatic agent solution (2) was prepared in the same manner as in Example 1 except that 10.0 parts of DMAEA-TFSI was used instead of 5.0 parts of the above DMAEA-TFSI.

(Preparation of anti-static treatment film)

An antistatic treatment film (2) was produced in the same manner as in Example 1 except that the above antistatic agent solution (2) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (2) was used instead of the above antistatic treatment film (1).

[Example 3] (Preparation of antistatic agent solution)

An antistatic agent solution (3) was prepared in the same manner as in Example 1 except that 20.0 parts of DMAEA-TFSI was used instead of the above DMAEA-TFSI 5.0 parts.

(Preparation of anti-static treatment film)

An antistatic treatment film (3) was produced in the same manner as in Example 1 except that the above antistatic agent solution (3) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (3) was used instead of the above antistatic treatment film (1).

[Example 4] (Preparation of antistatic agent solution)

3.0 parts of Coronate HX (isocyanurate body of hexamethylene diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used instead of the above-mentioned Coronate L (solid content of trimethylolpropane/toluene diisocyanate trimer adduct) An antistatic agent solution (4) was prepared in the same manner as in Example 1 except that 4.0 parts of a 75 mass% ethyl acetate solution (manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5.0 parts of DMAEA-TFSI as a conductive agent were not used. .

(Preparation of anti-static treatment film)

An antistatic treatment film (4) was produced in the same manner as in Example 1 except that the above antistatic agent solution (4) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (4) was used instead of the above antistatic treatment film (1).

[Example 5] (Preparation of antistatic agent solution)

The above (meth)acrylic polymer (B) was used in the same manner as in Example 1 except that the (meth)acrylic polymer (A) was used instead of 5.0 parts of DMAEA-TFSI as a conductive agent. The antistatic agent solution (5) was prepared in the same manner.

(Preparation of anti-static treatment film)

An antistatic treatment film (5) was produced in the same manner as in Example 1 except that the above antistatic agent solution (5) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (5) was used instead of the above antistatic treatment film (1).

[Embodiment 6] (Preparation of antistatic agent solution)

The above (meth)acrylic polymer (C) was used in place of the above (meth)acrylic polymer (A), and the same as in Example 1, except that 5.0 parts of DMAEA-TFSI as a conductive agent was not used. The antistatic agent solution (6) was prepared in the same manner.

(Preparation of anti-static treatment film)

An antistatic treatment film (6) was produced in the same manner as in Example 1 except that the above antistatic agent solution (6) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (6) was used instead of the above antistatic treatment film (1).

[Embodiment 7] (Preparation of antistatic agent solution)

Using the above (meth)acrylic polymer (C) in place of the above (meth)acrylic polymer (A), N-butyl-3-methylpyridinium-bis(trifluoromethanesulfonate)imide was used. (BMP in Table 1 - An antistatic agent solution (7) was prepared in the same manner as in Example 1 except that 20.0 parts of TFSI) was used as a conductive agent instead of DMAEA-TFSI 5.0 parts.

(Preparation of anti-static treatment film)

An antistatic treatment film (7) was produced in the same manner as in Example 1 except that the above antistatic agent solution (7) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (7) was used instead of the above antistatic treatment film (1).

[Embodiment 8] (Preparation of antistatic agent solution)

The above (meth)acrylic polymer (C) was used instead of the above (meth)acrylic polymer (A), and 20.0 parts of DMAPAA-TFSI was used instead of 5.0 parts of DMAEA-TFSI as a conductive agent, and the same was carried out. An antistatic agent solution (8) was prepared in the same manner as in Example 1.

(Preparation of anti-static treatment film)

An antistatic treatment film (8) was produced in the same manner as in Example 1 except that the above antistatic agent solution (8) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (8) was used instead of the above antistatic treatment film (1).

[Embodiment 9] (Preparation of antistatic agent solution)

The above (meth)acrylic polymer (D) was used in the same manner as in Example 1 except that the (meth)acrylic polymer (A) was used instead of 5.0 parts of DMAEA-TFSI as a conductive agent. The antistatic solution (9) was prepared in the same manner.

(Preparation of anti-static treatment film)

The above antistatic agent solution (1) of the above antistatic agent solution (1) will be replaced by a Meyer rod (9) It was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10, manufactured by Toray Co., Ltd.), and dried at 130 ° C for 1 minute to remove the solvent to form an antistatic layer (thickness: 0.1 μm). , and an antistatic treatment film (9) is produced.

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (9) was used instead of the above antistatic treatment film (1).

[Embodiment 10] (Preparation of antistatic agent solution)

The above (meth)acrylic polymer (E) was used in the same manner as in Example 1 except that the above (meth)acrylic polymer (A) was used, and 5.0 parts of DMAEA-TFSI as a conductive agent was not used. The antistatic agent solution (10) was prepared in the same manner.

(Preparation of anti-static treatment film)

The above antistatic agent solution (10) in place of the above antistatic agent solution (1) was applied to a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10 manufactured by Toray Co., Ltd.) using a Meyer rod. The film was dried at 130 ° C for 1 minute to remove the solvent to form an antistatic layer (thickness 0.25 μm), thereby producing an antistatic treatment film (10).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (10) was used instead of the above antistatic treatment film (1).

[Example 11] (Preparation of anti-static treatment film)

The above antistatic agent solution (10) in place of the above antistatic agent solution (1) was applied to a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10 manufactured by Toray Co., Ltd.) using a Meyer rod. The film was dried at 130 ° C for 1 minute to remove the solvent to form an antistatic layer (thickness: 0.1 μm), thereby producing an antistatic treatment film (11).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (11) was used instead of the above antistatic treatment film (1).

[Comparative Example 1] (Preparation of antistatic agent solution)

An acrylic resin (Bondeip PA-200 (32% by mass), ion conductive polymer) manufactured by copolymerization of quaternary ammonium chloride using a mixed solvent of isopropyl alcohol: soft water = 2:1 It is 2.1% by mass. To 100 parts of the solution, 25 parts of an epoxy resin (Bondeip PA-100 (8.2% by mass) manufactured by Konishi Co., Ltd.) as a curing agent was added, and the mixture was stirred at 25 ° C for about 5 minutes to prepare 2.5 mass %. Antistatic solution (11).

(Preparation of anti-static treatment film)

The above antistatic agent solution (11) was used instead of the above antistatic agent solution (1), and a polyethylene terephthalate (PET) film (thickness: 38 μm, manufactured by Mitsubishi Plastics Co., Ltd., Diafoil T100C) was used instead of the poly pair. An antistatic treatment film (12) was produced in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film (thickness: 38 μm, manufactured by Toray Co., Ltd., Lumirror S10) was used.

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above antistatic treatment film (12) was used instead of the above antistatic treatment film (1).

[Comparative Example 2] (Preparation of anti-static treatment film)

An antistatic treatment film (13) was produced in the same manner as in Example 1 except that the above antistatic agent solution (11) was used instead of the above antistatic agent solution (1).

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned antistatic treatment film (13) was used instead of the above antistatic treatment film (1).

<Measurement of Weight Average Molecular Weight (Mw)>

The weight average molecular weight (Mw) of the (meth)acrylic polymer (E) for the antistatic layer was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Co., Ltd. The measurement conditions are as follows. Further, the weight average molecular weight was determined by using a polymethyl methacrylate conversion value.

Sample concentration: 0.1% by weight (1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solution)

Sample injection amount: 20μl

Dissolution: HFIP + 10 mM sodium trifluoroacetate

Flow rate: 0.3ml/min

Measuring temperature: 40 ° C

Column:

Sample column: TSKgel SuperAWM-H (6.0mmI.D.×15cm) (2)

Detector: Differential Refractometer (RI)

Further, the weight average molecular weight (Mw) of the (meth)acrylic polymer (F) for the pressure-sensitive adhesive layer was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Co., Ltd. The measurement conditions are as follows. Further, the weight average molecular weight was determined by using a polystyrene equivalent value.

Sample concentration: 0.2% by weight (tetrahydrofuran (THF) solution)

Sample injection amount: 10μl

Dissolution: THF

Flow rate: 0.6ml/min

Measuring temperature: 40 ° C

Column:

Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)

Reference column: TSKgel SuperH-RC (1 root)

Detector: Differential Refractometer (RI)

<Low speed peel test: 180° peel adhesion>

The adhesive sheet of each of the examples and the comparative examples was cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, and then pressure-bonded to a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, by a hand roller). The surface of the width: 70 mm, length: 100 mm) was laminated under the pressure bonding conditions of 0.25 MPa and 0.3 m/min, and an evaluation sample (an optical film with an antistatic charging sheet) was prepared.

After laminating, it was allowed to stand in an environment of 23 ° C × 50% RH for 30 minutes, and then the surface opposite to the triacetyl cellulose polarizing plate was fixed to an acrylic plate with a double-sided adhesive tape, and the universal tensile tester was used. The end portion of the above-mentioned adhesive sheet was peeled off at a tensile speed of 0.3 m/min (low-speed peeling) and a peeling angle of 180°, and the adhesive force at this time was measured. The measurement was carried out in an environment of 23 ° C × 50% RH. As the adhesive force at the time of low-speed peeling, from the viewpoint of suppressing the bulging or peeling of the adhesive tape, it is preferable to set 0.07 N/25 mm or more, and it is set to be less than 0.07 N/25 mm. Further, the measurement results are shown in Table 2.

<High speed peel test: 180° peel adhesion>

The adhesive sheet of each of the examples and the comparative examples was cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, and then pressure-bonded to a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, by a hand roller). The surface of the width: 70 mm, length: 100 mm) was laminated under the pressure bonding conditions of 0.25 MPa and 0.3 m/min, and an evaluation sample (an optical film with an antistatic charging sheet) was prepared.

After laminating, it was allowed to stand in an environment of 23 ° C × 50% RH for 30 minutes, and then the surface opposite to the triacetyl cellulose polarizing plate was fixed to an acrylic plate with a double-sided adhesive tape, and the universal tensile tester was used. The end of the adhesive sheet was peeled off at a tensile speed of 30 m/min (high-speed peeling) and a peeling angle of 180°, and the adhesive force at this time was measured. The measurement was carried out in an environment of 23 ° C × 50% RH. It is good to set the adhesion force at the time of high-speed peeling to less than 6.0 N/25 mm, and to be worse than 6.0N/25 mm or more. The measurement results are shown in Table 2.

<Measurement of peeling tape voltage>

As shown in Fig. 2, the adhesive sheet 2 of each of the examples and the comparative examples was cut into a size of 70 mm in width and 130 mm in length, and after peeling off the separator, the end portion was extended by 30 mm so as to be crimped to the surface by a hand roller. A polarizing plate 3 (manufactured by Nitto Denko Corporation, SEG1425DU, width: 70 mm, length: 100 mm) of an acrylic plate 4 (manufactured by Mitsubishi Rayon Co., Ltd., thickness: 1 mm, width: 70 mm, length: 100 mm) .

After standing for one day in an environment of 23 ° C × 50% RH, as shown in Fig. 2, the sample was placed at a specific position of the sample fixing table 5. One end of the extension of 30 mm was fixed to the automatic reel, and peeling was performed so that the peeling angle was 150 degrees, and the drawing speed was 30 m/min (high-speed peeling). The potential measuring machine 1 (manufactured by Kasuga Electric Co., Ltd., KSD-0103) which is used to fix the potential of the surface of the polarizing plate which is generated at this time to a specific position is measured and set as the value of the peeling band voltage. The measurement was carried out in an environment of 23 ° C × 50% RH. Further, as the peeling tape voltage, the absolute value is preferably 1.0 kV or less, more preferably 0.5 kV or less. If it is in the above range, it is useful to prevent electrostatic discharge caused by static electricity or electrostatic breakdown of electronic parts.

<Evaluation of pollution>

After the peeling tape voltage was measured, the pressure was again applied by hand to cause air bubbles to be mixed between the peeled adhesive sheet and the polarizing plate after the measurement to prepare an evaluation sample.

After the evaluation sample was allowed to stand at room temperature (23 ° C) for one week, the adhesive sheet was peeled off from the adherend by hand to visually observe the state of contamination of the surface of the adherend at this time. The evaluation criteria are as follows.

. No contamination confirmed: ○

. Confirmation of pollution: ×

<Measurement of Surface Resistivity (Normal)>

The adhesive sheet of each of the examples and the comparative examples was allowed to stand in an environment of 23° C.×50% RH for 2 hours, and then the separator was peeled off and measured by a surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450 type). The surface resistivity of the surface of the adhesive. The application was carried out at a voltage of 100 V and an application time of 30 seconds. Further, the surface resistivity is preferably 10 ¹³ or less, more preferably 10 ¹² or less. If it is in the above range, it is useful to prevent electrostatic discharge caused by static electricity or electrostatic breakdown of electronic parts.

<Measurement of surface resistivity (heat resistance)>

The separator of the adhesive sheet of each of the examples and the comparative examples was peeled off, left at 170 ° C for 30 minutes, and then left in an environment of 23 ° C × 50% RH for 2 hours, and was fabricated by a surface resistivity measuring device (Mitsubishi Chemical Co., Ltd.). , Hiresta UP MCP-HT450) Determine the surface resistivity of the adhesive surface. The application was carried out at a voltage of 100 V and an application time of 30 seconds. Further, the surface resistivity is preferably 10 ¹³ or less, more preferably 10 ¹² or less.

<grassability>

The adhesive sheet of each of the examples and the comparative examples was cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, and then pressure-bonded to a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, by a hand roller). After the surface of the width: 70 mm, length: 100 mm), lamination was carried out under a pressure bonding condition of 0.25 MPa and 0.3 m/min, and an evaluation sample (an optical film with an antistatic charging sheet) was prepared. After laminating, it was allowed to stand in an environment of 23 ° C × 50% RH for 30 minutes, and then the surface opposite to the triacetyl cellulose polarizing plate was fixed to an acrylic plate with a double-sided adhesive tape, and the universal tensile tester was used. When the stretching speed was 30 m/min (high-speed peeling) and the peeling angle was 180°, when one end portion of the adhesive sheet was peeled off, it was visually judged whether or not an adhesive (residue remaining) remained on the surface of the triacetone cellulose polarizing plate.

No paste residue: ○

The situation of the residue of the paste: ×

<Transparency: Haze>

After the adhesive sheet of each of the examples and the comparative examples was cut into a size of 50 mm in width and 50 mm in length, the release liner was peeled off, and the haze was measured by a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.). If the haze is less than 10%, it is good, and 10% or more is bad. The measurement results are shown in Table 2.

Note) The parts in Table 1 indicate the solid content. Further, Comparative Examples 1 and 2 are not described in Table 1. In addition, the "coating thickness" in Table 1 means "the thickness when the antistatic layer is dried".

According to the results of Table 2, it was confirmed that in all of Examples 1 to 11 using the antistatic charging sheet produced according to the present invention, the surface resistivity after normal and heating was 10 ¹³ or less, and the peeling band voltage was also ±1.0 kV. Within the range, it is anti-charged. Further, the haze value is also 10% or less, which satisfies transparency, and further satisfies low contamination or grip. In addition, it was confirmed that the adhesion (low-speed peeling, high-speed peeling) of the adhesive sheet (surface protection use, etc.) which can be used for re-peeling is maintained.

On the other hand, in Comparative Example 1, an antistatic charging sheet in which an antistatic layer containing an antistatic agent containing an acrylic resin obtained by copolymerizing a quaternary ammonium chloride was formed on a substrate film subjected to corona treatment was formed. However, the result is that the stripping voltage exceeds ±1.0 kV, and the surface resistivity after heating exceeds 10 ¹³ (beyond the detection limit). Further, in Comparative Example 2, the substrate film was not subjected to corona treatment as compared with Comparative Example 1, and as a result, it was confirmed that the gripping property was insufficient, and the adhesive sheet itself which could be evaluated was not obtained. Therefore, in Comparative Examples 1 and 2, it was confirmed that all of the antistatic properties (peeling tape voltage, surface resistivity), adhesion characteristics, low contamination, grip properties, and transparency were not obtained.

From the above results, it was confirmed that an antistatic layer formed of an antistatic agent composition containing a (meth)acrylic polymer containing a reactive (polymerizable) ionic liquid as a monomer unit was provided as an intermediate layer for antistatic charging. The sheet was a good result in any of the evaluations, and an excellent effect which was not previously obtained was obtained.

Claims (14)

An antistatic layer characterized in that it is formed of an antistatic composition containing a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit and a crosslinking agent. The antistatic layer of claim 1, wherein the reactive ionic liquid is a reactive ionic liquid represented by any one of the following formulas (1) to (4), CH ₂ = C(R ¹ )COOZX ⁺ Y ^- (1) CH ₂ =C(R ¹ )CONHZX ⁺ Y ^- (2) CH ₂ =C(R ¹ )COOX ⁺ Y ^- (3) CH ₂ =C(R ¹ )CONHX ⁺ Y ^- (4) In (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, Y ^- is an anion; and Z is an alkylene group having 1 to 3 carbon atoms. The antistatic layer of claim 2, wherein the cation moiety is a quaternary ammonium group. The antistatic layer of claim 2, wherein the anion is a fluorine-containing anion. The antistatic layer of claim 1, wherein the (meth)acrylic polymer comprises an oxyalkylene group represented by the following formula (5) having an average addition molar number of from 3 to 100. A monomer of an alkyl group as a monomer unit, CH ₂ =C(R ₁ )-COO-(C _m H _2m O) _n -(C _p H _2p O) _q -R ₂ (5) [in the formula (5) R ₁ is hydrogen or methyl, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, n and q are 0 or an integer of 2 to 100, and no n and q are 0 at the same time. ]. The antistatic layer of claim 1, wherein the (meth)acrylic polymer comprises a hydroxyl group-containing (meth)acrylic monomer as a monomer unit. The antistatic layer of claim 1, wherein the crosslinking agent is an isocyanate crosslinking agent. The antistatic layer of claim 1, wherein the antistatic composition comprises a conductive agent. An antistatic charged adhesive sheet characterized in that it will be as claimed in any one of claims 1 to 8. The antistatic layer is formed on at least one side of the substrate film, and has an adhesive layer on the antistatic layer. The antistatic charging sheet according to claim 9, wherein the substrate film is a plastic film. An antistatic charging sheet according to claim 9 or 10, which is used for surface protection purposes. The anti-static adhesive sheet of claim 9 or 10 is used in the manufacturing and shipping steps of electronic parts. An optical film with an antistatic charged adhesive sheet, characterized in that an antistatic charging sheet according to claim 11 is attached to an optical film. An optical film with an anti-chargeable adhesive sheet, characterized in that an antistatic layer according to any one of claims 1 to 8 is formed on at least one side of a substrate film, and is formed on the antistatic layer. The agent layer is followed by the above adhesive layer on the optical film.