TWI624504B - Anti-static layer, anti-static adhesive sheet, and optical film - Google Patents

Abstract

The present invention provides an antistatic layer having excellent antistatic properties, heat resistance, transparency, and low pollution, and particularly capable of suppressing the destruction of electronic parts caused by the adhesion of dirt, dust, etc. and static electricity, and has the above antistatic layer Anti-static adhesive sheet and optical film.

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

Description

Anti-static layer, anti-static adhesive sheet, and optical film

The invention relates to an antistatic layer, an antistatic adhesive sheet, and an optical film. More specifically, the present invention relates to an antistatic device which is excellent in antistatic properties, heat resistance, transparency, and low pollution, and particularly suppresses damage to electronic parts caused by adhesion of dirt, dust, and the like and static electricity. Layer, an antistatic adhesive sheet having the antistatic layer, and an optical film.

Products with high insulation resistance, such as plastics, have the property that they cannot be stored (charged) by electrostatic leakage generated when the plastics are rubbed against each other or with other objects or peeled off after being attached. Therefore, the adsorption of dirt or dust in the air or the adhesion of paper or film to each other, or in addition to the discomfort caused by electric shock, there are also electronic, electrical equipment or OA (Office Automation) Various types of static electricity failures, such as malfunctions caused by static electricity or memory destruction, may occur in equipment. In order to avoid such a failure, it is necessary to control the inherent resistance of the surface of the charged body. 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 the surface are known. Also, it is known that an adhesive layer (adhesive tape) or a surface protective film, etc., which requires antistatic properties, is provided with an adhesive layer on one side of a plastic substrate film with an antistatic agent added inside, or a plastic substrate film. A method of setting an adhesive layer on one side and an anti-static layer on the opposite side, or adding an anti-static agent to the adhesive layer.

However, the plastic base film with an antistatic agent inside may be damaged in its original characteristics. In the case where an antistatic layer is provided on the side opposite to the adhesive layer, the above When, for example, an easy-printing layer or a hard coat layer is formed on the anti-static layer, there is a possibility that a problem of a decrease in adhesion occurs. 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. In addition, when an antistatic agent is added to the adhesive layer, the antistatic agent may leak to the adherend (protected body) side that is in contact with the adhesive layer, which may contaminate the adherend or reduce the adhesive properties. (Patent Document 1).

In addition, as a method for imparting antistatic properties to an adhesive sheet or the like, a method is known in which an intermediate layer (antistatic layer) having antistatic properties is provided between a base film and an adhesive layer (Patent Documents 2 and 3). The above-mentioned antistatic layer is an intermediate layer, so that problems such as the antistatic layer provided on the outer surface of the base film falling off or the antistatic agent from oozing out to the adherend can be eliminated. However, in the case of the above-mentioned antistatic layer, the counter anion constituting the ionic functional group of the ionic adhesive resin serving as the antistatic agent is a chloride ion, and therefore, there is a problem that it exerts its function to make the heat resistance poor and causes corrosion. Fear.

[Prior technical literature] [Patent Literature]

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

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

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

Therefore, an object of the present invention is to provide an antistatic property, heat resistance, transparency, and low pollution property in order to eliminate the problems in the previous antistatic layer or antistatic adhesive sheet, and particularly to suppress the pollution An antistatic layer, an antistatic layer, and an optical film having an antistatic layer and the destruction of electronic components caused by static electricity, dust, and the like.

That is, the antistatic layer of the present invention is characterized in that An antistatic agent composition of a (meth) acrylic polymer and a crosslinking agent as a subunit liquid as a monomer unit is formed.

The antistatic layer of the present invention is preferably such that the reactive ionic liquid is a reactive ionic liquid represented by any one of the following general formulae (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, and Y ⁻ is an anion; Z represents an alkylene group having 1 to 3 carbon atoms]

In the antistatic layer of the present invention, it is preferable that the above-mentioned cation portion is a quaternary ammonium group.

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

The antistatic layer of the present invention is preferably an oxygen-containing alkylene having an average addition mole number of 3 to 100 of the (meth) acrylic polymer containing an oxyalkylene unit represented by the following general formula (5) Basic monomers are used as monomer units.

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

[In 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 integers of 0 or 2 to 100, and n and When q is 0 at the same time]

The antistatic layer of the present invention is preferably such 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, the above-mentioned crosslinking agent is preferably an isocyanate-based crosslinking agent.

The antistatic layer of the present invention is preferably such that the antistatic agent composition contains a conductive agent.

In the anti-static adhesive sheet of the present invention, it is preferable that the anti-static layer is formed on at least one side of a base film, and an adhesive layer is provided on the anti-static layer.

In the anti-static adhesive sheet of the present invention, the substrate film is preferably a plastic film.

The anti-static adhesive sheet of the present invention is preferably used for surface protection.

The anti-static adhesive sheet of the present invention is preferably used in the steps of manufacturing and shipping electronic parts.

In the optical film with an antistatic adhesive sheet of the present invention, the antistatic adhesive sheet is preferably attached to the optical film.

In the optical film with an antistatic adhesive sheet of the present invention, the antistatic layer is preferably formed on at least one side of the base film, an adhesive layer is formed on the antistatic layer, and the adhesive layer is bonded. On optical film.

1‧‧‧ Potentiometer

2‧‧‧ Adhesive sheet

3‧‧‧ polarizing plate

4‧‧‧ acrylic board

5‧‧‧ fixed table

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

11‧‧‧ septa

12‧‧‧ Adhesive layer

13‧‧‧Anti-charge layer

14‧‧‧ substrate film

FIG. 1 is a schematic diagram illustrating the configuration of an antistatic adhesive sheet.

FIG. 2 is a schematic diagram illustrating a peeling voltage test.

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

<Antistatic adhesive sheet>

The anti-static adhesive sheet of the present invention preferably has an anti-static layer formed on at least one side of the substrate film, and has an adhesive layer on the anti-static layer. Specifically, as a said antistatic adhesive sheet, a typical structural example is shown typically in FIG. Here, the antistatic adhesive sheet 10 includes a base film (for example, a polyester film) 14, an antistatic layer 13 provided on one side thereof, and an adhesive layer 12 on the antistatic layer 13. The adhesive sheet 10 is used by attaching the adhesive layer 12 to an adherend (a surface to be protected, such as an optical component such as a polarizing plate). The above-mentioned adhesive sheet 10 before use (that is, before being attached to the adherend) is as shown in FIG. 1, which can protect the adhesive layer 12 by the spacer 11 which becomes the release surface at least on the adhesive layer 12 side. The surface (attached to the surface of the adherend) exists. Hereinafter, the structure of the said antistatic adhesive sheet (it may be hereafter called only "adhesive sheet") is demonstrated in detail.

<Antistatic composition and antistatic layer>

The anti-charge layer of the present invention is characterized in that: A (meth) acrylic polymer which is a monomer unit, and an antistatic agent composition of a crosslinking agent are formed. The (meth) acrylic polymer in the present invention refers to an acrylic polymer and / or a methacrylic polymer, and the (meth) acrylate refers to an acrylate and / or Methacrylate.

The antistatic agent composition used in forming the antistatic layer of the present invention contains a (meth) acrylic polymer as an essential component, and the (meth) acrylic polymer contains a reactive ionic liquid as a monomer unit. In addition, the "reactive ionic liquid" in the present invention means that the cationic part and / or anionic part (either or both) constituting the ionic liquid contains a polymerizable (reactive double bond) function Based ionic liquids are liquid (liquid) at any temperature in the range of 0 to 150 ° C, and have transparency in the form of non-volatile molten salts. Examples of the polymerizable functional group include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, and the like. Among these, from the viewpoint of copolymerizability, a (meth) acrylfluorenyl group and a vinyl group are preferred, and a (meth) acrylfluorenyl group is particularly preferred.

The cationic portion of the reactive ionic liquid may 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. Sulfonium cation, pyrrole cation, pyrazolium cation, guanidinium cation, etc., among them, it is more preferable to use quaternary ammonium cation, imidazolium cation, pyridinium cation, piperidinium cation, pyrrolidinium cation, and quaternary phosphonium cation , Trialkylphosphonium cation.

Further, the configuration of the anionic portion of the ionic liquid reactions, as the anion, _{^{include: SCN -, BF 4 -,}} 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 -, anions of sulfonic acyl, ethyl sulfate, 2- (2-methoxyethyl) carbonate _{anions, (C 2 F 5) 3} PF 3 - , etc., in particular, 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 properties, which is preferable in this respect. Moreover, as an anion, it is preferable not to use a chloride ion, a bromide ion, etc. from the point which has a corrosiveness.

The reactive ionic liquid system is appropriately selected from the combination of the cation part and the anion part and is used by the user, and specifically, various ionic liquids shown below are listed.

Examples of the imidazolium cationic ionic liquid include 1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, and 1-alkyl-3- Vinylimidazolium heptafluorobutyrate, 1-alkyl-3-vinylimidazolium triflate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl -3-vinylimidazolium bis (trifluoromethanesulfonyl) imine, 1-alkyl-3-vinylimidazolium bis (pentafluoroethanesulfonyl) imine, 1-alkyl-3-vinylimidazole Onium tris (trifluoromethanesulfonyl) imine, 1-alkyl-3-vinylimidazolium hexafluorophosphate, 1-alkyl-3-vinylimidazolium (trifluoromethanesulfonyl) trifluoroethyl Imidamine, 1-alkyl-3-vinylimidazolium dicyanofluorene, 1-alkyl-3-vinylimidazolium thiocyanate, and the like containing 1-alkyl-3-vinylimidazolium cations Ionic liquid, 1,2-dialkyl-3-vinylimidazolium bis (fluorosulfonaminium) imine, 1,2-dialkyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imine 1,1,2-dialkyl-3-vinylimidazolium dicyanoamidamine, 1,2-dialkyl-3-vinylimidazolium thiocyanate, etc. containing 1,2-dialkyl-3 -Vinyl imidazolium cation Ionic liquid, 2-alkyl-1,3-divinylimidazolium bis (fluorosulfonaminium) imine, 2-alkyl-1,3-divinylimidazolium bis (trifluoromethanesulfonyl) imine Amine, 2-alkyl-1,3-divinylimidazolium dicyanofluorenamine, 2-alkyl-1,3-divinylimidazolium thiocyanate, etc. containing 2-alkyl-1,3 -Divinylimidazolium ionic ionic liquids, 1-vinylimidazolium bis (fluorosulfonium) imine, 1-vinylimidazolium bis (trifluoromethanesulfonyl) imine, 1-vinylimidazolium Ionic liquids containing 1-vinylimidazolium cations, such as cyanamide, 1-vinylimidazolium thiocyanate, 1-alkyl-3- (meth) acryloxyalkylimidazolium tetrafluoroborate Salt, 1-alkyl-3- (Meth) acryloxyalkylimidazolium trifluoroacetate, 1-alkyl-3- (meth) acryloxyalkylimidazolium heptafluorobutyrate, 1-alkyl-3- ( (Meth) acryloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3- (meth) acryloxyalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3 -(Meth) acryloxyalkylimidazolium bis (trifluoromethanesulfonyl) imine, 1-alkyl-3- (meth) acryloxyalkylimidazolium bis (pentafluoroethanesulfonyl) ) Imine, 1-alkyl-3- (meth) propenyloxyalkylimidazolium tris (trifluoromethanesulfonyl) imine, 1-alkyl-3- (meth) propenyloxyalkylene Imidazolium hexafluorophosphate, 1-alkyl-3- (meth) propenyloxyalkylimidazolium (trifluoromethanesulfonyl) trifluoroacetamidamine, 1-alkyl-3- (methyl Propyl) propenyloxyalkylimidazolium dicyanoamidamine, 1-alkyl-3- (meth) propenyloxyalkylimidazolium thiocyanate, etc. ) Acrylic alkoxyalkyl imidazolium cation ionic liquid, 1-alkyl-3- (meth) acryl fluorenylamino alkyl imidazolium tetrafluoroborate, 1-alkyl-3- (methyl ) Acrylamidoaminoalkylimidazolium trifluoroacetate 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium heptafluorobutyrate, 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium trifluoromethanesulfonate Acid salt, 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium Bis (trifluoromethanesulfonyl) imine, 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium bis (pentafluoroethanesulfonyl) imine, 1-alkyl-3- ( (Meth) acrylfluorenylaminoalkylimidazolium tris (trifluoromethanesulfonium) imine, 1-alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium hexafluorophosphate, 1- Alkyl-3- (meth) acrylfluorenylaminoalkylimidazolium (trifluoromethanesulfonyl) trifluoroacetamidine, 1-alkyl-3- (meth) acrylfluorenylaminoalkyl Imidazolium dicyanofluorenamine, 1-alkyl-3- (meth) acrylfluorenylamino imidazolium thiocyanate, etc. containing 1-alkyl-3- (meth) acrylfluorenylamine Ionic liquids of alkylimidazolium cations, 1,2-dialkyl-3- (meth) acryloxyalkylimidazolium bis (fluorosulfonyl) imine, 1,2-dialkyl-3- (Meth) acryloxyalkylimidazolium bis (trifluoromethanesulfonyl) imine, 1 , 2-dialkyl-3- (meth) propenyloxyalkylimidazolium dicyanofluorenamine, 1,2-dialkyl-3- (meth) propenyloxyalkylimidazolium sulfide 1,2-dialkyl-3- (meth) acrylic acid containing cyanate Ionic liquids based on alkyl alkylimidazolium cations, 1,2-dialkyl-3- (meth) acrylfluorenylaminoalkylimidazolium bis (fluorosulfonyl) imine, 1,2-dialkyl- 3- (meth) acrylfluorenylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imine, 1,2-dialkyl-3- (meth) acrylfluorenylaminoalkylimidazolium di 1,2-dialkyl-3- (meth) acrylamide containing cyanofluorenamine, 1,2-dialkyl-3- (meth) acrylfluorenylaminoalkyl imidazolium thiocyanate, etc. Ionic liquids based on aminoaminoalkylimidazolium cations, 2-alkyl-1,3-di (meth) acryloxyalkylimidazolium bis (fluorosulfonyl) imine, 2-alkyl-1, 3-Di (meth) acryloxyalkylimidazolium bis (trifluoromethanesulfonyl) imine, 2-alkyl-1,3-bis (meth) acryloxyalkylimidazolium dicyanide 2-alkyl-1,3-di (meth) propenyloxyalkyl groups containing 2-alkyl-1,3-bis (meth) propenyloxyimidazolium thiocyanate, etc. Imidazolium ionic ionic liquids, 2-alkyl-1,3-di (meth) acrylfluorenylaminoalkyl imidazolium bis (fluorosulfonyl) imine, 2-alkyl-1,3-bis ( (Meth) acrylfluorenylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imine, 2-alkyl-1 , 3-Di (meth) acrylfluorenylaminoalkyl imidazolium dicyanofluorenamine, 2-alkyl-1,3-bis (meth) acrylfluorenylamino imidazolium thiocyanate, etc. 2-alkyl-1,3-di (meth) acryloxyalkylimidazolium cation ionic liquid, 1- (meth) acryloxyalkylimidazolium bis (fluorosulfonyl) imine, 1- (meth) acryloxyalkylimidazolium bis (trifluoromethanesulfonyl) imine, 1- (meth) acryloxyalkylimidazolium dicyanoamidine, 1- (methyl ) Ionic liquids containing 1- (meth) acryloxyalkylimidazolium cations, such as propenyloxyalkylimidazolium thiocyanate, 1- (meth) acrylfluorenylaminoalkylimidazolium bis (Fluorosulfonium) imine, 1- (meth) acrylfluorenylaminoalkylimidazolium bis (trifluoromethanesulfonium) imine, 1- (meth) acrylfluorenylaminoalkylimidazolium di Ionic liquids containing 1- (meth) acrylfluorenylaminoalkylimidazolium cations, such as cyanofluorenamine and 1- (meth) acrylfluorenylaminoalkylimidazolium thiocyanate.

The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12, and further preferably 1 to 6 carbon atoms.

Examples of the pyridinium cationic ionic liquid include 1-vinylpyridinium bis (fluorosulfonium) imine, 1-vinylpyridinium bis (trifluoromethanesulfonyl) imine, and 1-vinylpyridinium diimide. Ionic liquids containing 1-vinylpyridinium cations, such as cyanoamidinium amine, 1-vinylpyridinium thiocyanate, 1- (meth) acryloyloxyalkylpyridinium bis (fluorosulfonyl) imine 1- (meth) acryloxyalkylpyridinium bis (trifluoromethanesulfonyl) imine, 1- (meth) acryloxyalkylpyridinium dicyanofluorinamide, 1- (methyl Group) Ionic liquids containing 1- (meth) acryloxyalkylpyridinium cations, such as propenyloxyalkylpyridinium thiocyanate, 1- (meth) propenylaminoalkylpyridinium Bis (fluorosulfonaminium) imine, 1- (meth) acrylfluorenylaminoalkylpyridinium bis (trifluoromethanesulfonium) imine, 1- (meth) acrylfluorenylaminoalkylpyridinium Ionic liquids containing 1- (meth) propenylaminoalkylpyridinium cations, such as dicyanofluorenamine, 1- (meth) propenylaminoaminopyridinium thiocyanate, 2-alkane 1-vinylpyridinium bis (fluorosulfonium) imine, 2-alkyl-1-vinylpyridinium bis ( 2-methanesulfonium sulfonium) imine, 2-alkyl-1-vinylpyridinium dicyanofluorenamine, 2-alkyl-1-vinylpyridinium thiocyanate and other 2-alkyl-1-ethylene containing Pyridinium cation ionic liquid, 2-alkyl-1- (meth) propenyloxyalkylpyridinium bis (fluorosulfonyl) imine, 2-alkyl-1- (meth) acrylic acid Alkylalkylpyridinium bis (trifluoromethanesulfonium sulfonium) imine, 2-alkyl-1- (meth) propenyloxyalkylpyridinium dicyanomidine, 2-alkyl-1- (methyl Ionic liquids containing 2-alkyl-1- (meth) propenyloxyalkylpyridinium cations such as propenyloxyalkylpyridinium thiocyanate, 2-alkyl-1- (methyl ) Propenylaminoaminoalkylpyridinium bis (fluorosulfonaminium) imine, 2-alkyl-1- (meth) propenylaminoaminopyridinium bis (trifluoromethanesulfonyl) imine, 2-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium dicyanofluorenamine, 2-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium thiocyanate Ionic liquids containing 2-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium cations, 3-alkyl-1-vinylpyridinium bis (fluorosulfonaminium) imine, 3-alkyl-1-vinylpyridinium bis (trifluoromethanesulfonyl) imine, 3-alkyl-1-ethylene Ionic liquids containing 3-alkyl-1-vinylpyridinium cations such as pyridinium dicyanoamidoamine, 3-alkyl-1-vinylpyridinium thiocyanate, 3-alkyl-1- ( (Meth) acryloxyalkylpyridinium bis (fluorosulfonaminium) imine, 3-alkyl-1- (meth) acryloxyalkylpyridinium bis (trifluoromethanesulfonyl) imine, 3-alkyl-1- (meth) propenyloxyalkylpyridinium dicyanofluorenamine, 3-alkyl-1- (meth) propenyloxyalkylpyridinium thiocyanate, etc. 3-alkyl-1- (meth) propenyloxyalkylpyridinium cation ionic liquid, 3-alkyl-1- (meth) propenylaminoaminoalkylpyridinium bis (fluorosulfonyl) Imine, 3-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium bis (trifluoromethanesulfonyl) imine, 3-alkyl-1- (meth) acrylfluorenylamino Alkylpyridinium dicyanofluorenamine, 3-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium thiocyanate, etc. containing 3-alkyl-1- (meth) acrylfluorenyl Aminoalkylpyridinium cation ionic liquid, 4-alkane 1-vinylpyridinium bis (fluorosulfonaminium) imine, 4-alkyl-1-vinylpyridinium bis (trifluoromethanesulfonyl) imine, 4-alkyl-1-vinylpyridinium Ionic liquids containing 4-alkyl-1-vinylpyridinium cations, such as dicyanamide, 4-alkyl-1-vinylpyridinium thiocyanate, 4-alkyl-1- (methyl) Acrylic alkoxyalkylpyridinium bis (fluorosulfonaminium) imine, 4-alkyl-1- (meth) acrylic alkoxyalkylpyridinium bis (trifluoromethanesulfonyl) imine, 4-alkane 4-Alkane-containing compounds such as methyl-1- (meth) propenyloxyalkylpyridinium dicyanofluoride, 4-alkyl-1- (meth) propenyloxyalkylpyridinium thiocyanate, and the like Ionic liquids of 1- (1- (meth) acryloyloxyalkylpyridinium cations), 4-alkyl-1- (meth) propenylaminoalkylpyridinium bis (fluorosulfonyl) imines, 4-alkyl-1- (meth) propenylaminoaminopyridinium bis (trifluoromethanesulfonyl) imine, 4-alkyl-1- (meth) propenylaminoaminopyridine Onium dicyanohydrazone, 4-alkyl-1- (meth) acrylic acid Ionic liquids containing 4-alkyl-1- (meth) acrylfluorenylaminoalkylpyridinium cations such as aminoaminoalkylpyridinium thiocyanate.

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

Examples of the piperidinium cationic ionic liquid include 1-alkyl-1-vinylalkylpiperidinium bis (fluorosulfonium) imine, 1-alkyl-1-vinylalkylpiperidinium bis (Trifluoromethanesulfonium sulfonium) imine, 1-alkyl-1-vinylalkylpiperidinium dicyanohydrazone, 1-alkyl-1-vinylalkylpiperidinium thiocyanate, etc. Ionic liquid of 1-alkyl-1-vinylalkylpiperidinium cation, 1-alkyl-1- (meth) acryloxyalkylpiperidinium bis (fluorosulfonyl) imine, 1- Alkyl-1- (meth) acryloxyalkylpiperidinium bis (trifluoromethanesulfonyl) imine, 1-alkyl-1- (meth) acryloxyalkylpiperidinium di 1-alkyl-1- (meth) propenyloxyalkylpiperidine containing 1-alkyl-1- (meth) propenyloxyalkylpiperidinium thiocyanate, etc. Onium cation ionic liquids, 1-alkyl-1- (meth) acrylfluorenylaminoalkylpiperidinium bis (fluorosulfonyl) imine, 1-alkyl-1- (meth) acrylfluorenyl Aminoalkylpiperidinium bis (trifluoromethanesulfonium) imine, 1-alkyl-1- (meth) acrylfluorenylaminopiperidinium dicyanofluorenamine, 1-alkyl- 1- (Meth) acrylfluorenylaminoalkyl piperidinium thiocyanate and the like Ionic liquid of 1-alkyl-1- (meth) acrylfluorenylaminoalkylpiperidinium cation.

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

Examples of the pyrrolidinium cationic ionic liquid include 1-alkyl-1-vinylalkylpyrrolidinium bis (fluorosulfonium) imine, and 1-alkyl-1-vinylalkylpyrrolidiniumbis (Trifluoromethanesulfonium sulfonium) imine, 1-alkyl-1-vinylalkylpyrrolidinium dicyanamide, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanate, etc. 1-alkyl-1-vinylalkylpyrrolidinium cation ionic liquid, 1-alkyl-1- (meth) propenyloxyalkylpyrrolidinium bis (fluorosulfonium) imine, 1-alkyl-1- (meth) propenyloxyalkylpyrrolidinium bis (Trifluoromethanesulfonium sulfonium) imine, 1-alkyl-1- (meth) propenyloxyalkylpyrrolidinium dicyanofluorenamine, 1-alkyl-1- (meth) acrylic acid Ionic liquids containing 1-alkyl-1- (meth) acryloxyalkylpyrrolidinium cations, such as alkylalkylpyrrolidinium thiocyanate, 1-alkyl-1- (meth) acrylic acid Aminoaminoalkylpyrrolidinium bis (fluorosulfonaminium) imine, 1-alkyl-1- (meth) propenylaminoalkylpyrrolidinium bis (trifluoromethanesulfonyl) imine, 1 -Alkyl-1- (meth) acrylfluorenylaminoalkylpyrrolidinium dicyanofluorenamine, 1-alkyl-1- (meth) acrylfluorenylaminoalkylpyrrolidinium thiocyanate Ionic liquids containing salts such as 1-alkyl-1- (meth) acrylfluorenylaminoalkylpyrrolidinium cations.

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

Examples of the trialkylsulfonium cation-based ionic liquid include dialkyl (vinyl) fluorene bis (fluorosulfonylhydrazone) imine, dialkyl (vinyl) fluorene bis (trifluoromethanesulfonylfluorene) imine, and Ionic liquids containing dialkyl (vinyl) 鋶 cations, such as alkyl (vinyl) 鋶 dicyanofluorenamine, dialkyl (vinyl) 鋶 thiocyanate, dialkyl ((meth) acrylic acid) Oxyalkyl) 鋶 bis (fluorosulfonyl) imine, dialkyl ((meth) acryl 醯 oxyalkyl) 鋶 bis (trifluoromethanesulfonyl) imine, dialkyl ((methyl) Dialkyl ((meth) acryloxyalkyl) containing dialkyl ((meth) acryloxyalkyl), dialkyl ((meth) acryloxyalkyl), thiocyanate, etc. ) 鋶 ionic ionic liquids, dialkyl ((meth) acrylfluorenylaminoalkyl), bis (fluorosulfonyl) imine, dialkyl ((meth) acrylfluorenylaminoalkyl) 鋶Bis (trifluoromethanesulfonyl) imine, dialkyl ((meth) acrylfluorenylaminoalkyl), dicyanofluorenamine, dialkyl ((meth) acrylfluorenylaminoalkyl) Ionic liquids containing dialkyl ((meth) acrylfluorenylaminoalkyl) hydrazone cations such as thiocyanate.

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

Examples of the quaternary phosphonium cationic ionic liquid include trialkyl (vinyl) bis (fluorosulfonyl) imine, trialkyl (vinyl) bis (trifluoromethanesulfonyl) imine, and trioxane Ionic liquids containing trialkyl (vinyl) fluorene cations, such as tri (vinyl) fluorenedicyanamide, trialkyl (vinyl) fluorthiocyanate, and trialkyl ((meth) acrylic acid) Alkyl) fluorene bis (fluorosulfonyl) imine, trialkyl ((meth) propylene fluorenyloxyalkyl) bis (trifluoromethanesulfonyl) imine, trialkyl ((meth) propylene Trialkyl ((meth) propenyloxyalkyl) containing trialkyl ((meth) propenyloxyalkyl), thiocyanate, etc.鏻 cationic ionic liquid, trialkyl ((meth) propenylfluorenylaminoalkyl) 鏻 bis (fluorosulfonyl) imine, trialkyl ((meth) propenylfluorenylaminoalkyl) 鏻 bis (Trifluoromethanesulfonyl) imine, trialkyl ((meth) acrylfluorenylaminoalkyl), dicyanofluorenamine, trialkyl ((meth) acrylfluorenylaminoalkyl) 鏻Ionic liquids containing thiocyanate and trialkyl ((meth) acrylfluorenylaminoalkyl) phosphonium cations.

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

Examples of the quaternary ammonium cation-based ionic liquid include N, N, N-trialkyl-N-vinyl ammonium tetrafluoroborate and N, N, N-trialkyl-N-vinyl ammonium trifluoromethane. Fluoroacetate, N, N, N-trialkyl-N-vinyl ammonium heptafluorobutyrate, N, N, N-trialkyl-N-vinyl ammonium trifluoromethanesulfonate, N, N , N-trialkyl-N-vinylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N-vinylammonium bis (trifluoromethanesulfonyl) imine, N, N, N -Trialkyl-N-vinylammonium bis (pentafluoroethanesulfonaminium) imine, N, N, N-trialkyl-N-vinylammonium tri (trifluoromethanesulfonyl) imine, N, N , N-trialkyl-N-vinylammonium hexafluorophosphate, N, N, N-trialkyl-N-vinylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N, N-trialkyl-N-vinyl ammonium dicyanofluoride, N, N, N-trialkyl-N-vinyl ammonium thiocyanate, etc. containing N, N, N-trialkyl-N- Vinyl ammonium cation ionic liquid, N, N, N-trialkyl-N- (meth) acryloxyalkylammonium tetrafluoroborate, N, N, N-trialkyl-N- (formaldehyde) Propyl) propenyloxyalkylammonium trifluoroacetate, N, N, N-trialkyl-N- (methyl Propyl) propenyloxyalkylammonium heptafluorobutyrate, N, N, N-trialkyl-N- (meth) propenyloxyalkylammonium trifluoromethanesulfonate, N, N, N -Trialkyl-N- (meth) acryloxyalkylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N- (meth) acryloxyalkylammonium bis ( Trifluoromethanesulfonyl) imine, N, N, N-trialkyl-N- (meth) propenyloxyalkylammonium bis (pentafluoroethanesulfonyl) imine, N, N, N-tris Alkyl-N- (meth) acryloxyalkylammonium tris (trifluoromethanesulfonyl) imine, N, N, N-trialkyl-N- (meth) acryloxyalkylammonium Hexafluorophosphate, N, N, N-trialkyl-N- (meth) propenyloxyalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N, N-trioxane -N- (meth) propenyloxyalkylammonium dicyanamide, N, N, N-trialkyl-N- (meth) propenyloxyalkylammonium thiocyanate, etc. N, N, N-trialkyl-N- (meth) propenyloxyalkylammonium cation ionic liquid, N, N, N-trialkyl-N- (meth) propenylaminoaminoalkane Ammonium tetrafluoroborate, N, N, N-trialkyl-N- (meth) acrylfluorenylaminoalkylammonium trifluoroacetate, N, N, N-trialkyl-N- (methyl Propyl) propenylaminoaminoalkylammonium heptafluorobutane Salt, N, N, N-trialkyl-N- (meth) propenylaminoaminoalkylammonium triflate, N, N, N-trialkyl-N- (meth) propene Fluorenylaminoalkylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N- (meth) propenylaminoaminoalkylammonium bis (trifluoromethanesulfonyl) imine, N , N, N-Trialkyl-N- (meth) acrylfluorenylaminoalkylammonium bis (pentafluoroethanesulfonaminium) imine, N, N, N-trialkyl-N- (methyl) Propylamidoaminoalkylammonium tri (trifluoromethanesulfonyl) imine, N, N, N-trialkyl-N- (meth) propenamidoaminoalkylammonium hexafluorophosphate, N, N, N-trialkyl-N- (meth) acrylfluorenylaminoalkylammonium (trifluoromethanesulfonyl) trifluoroacetamidine, N, N, N-trialkyl-N- (formyl Group) N, N, N, N, N, N-trialkyl-N- (meth) acrylfluorenylaminoalkylammonium thiocyanate, etc. Ionic liquid of N-trialkyl-N- (meth) acrylfluorenylaminoalkylammonium cation.

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

Furthermore, as said reactive ionic liquid, it can use without a restriction | limiting especially, It is more preferable that it is a reactive ionic liquid represented by any one of following General formulas (1)-(4). Anti-charge agent group The composition contains a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit, whereby the anti-static layer formed from the anti-static agent composition described above can incorporate the above-mentioned reactive ionic liquid exhibiting anti-static effects. Into the polymer backbone, it is possible to suppress the exudation of antistatic components. In addition, the above-mentioned 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 the anti-charge layer obtained can meet the requirements It is useful because it has 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 the antistatic agent composition (solution) is prepared, if it is coated on a substrate film, it is easy to form a uniform coating film, and the workability is also excellent. , Better in this regard.

^{_{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, and Y ⁻ is an anion. Z represents an alkylene group having 1 to 3 carbon atoms.

Examples of the cationic portion (X ⁺ ) constituting the reactive ionic liquid represented by any of the general formulae (1) to (4) include a quaternary ammonium group, an imidazolium group, a pyridinium group, and a piperidinyl group. , Pyrrolidinium, pyrrolyl, quaternary fluorenyl, trialkylfluorenyl, pyrazolium, guanidinium and the like. Among these, especially when it is a quaternary ammonium group, it is excellent in transparency, and becomes a preferable aspect for electronic and optical use. In addition, the quaternary ammonium group does not have unsaturated bonds other than polymerizable functional groups in the molecule. It is presumed that it is difficult to hinder ordinary radical polymerization reaction during ultraviolet (UV) hardening, and the hardening property is high. Anti-charge layer.

Specific examples of the quaternary ammonium group include trimethylammonium group, triethylammonium group, tripropylammonium group, methyldiethylammonium group, ethyldimethylammonium group, and methyl group. Dipropylammonium group, dimethylbenzylammonium group, diethylbenzylammonium group, methyldibenzylammonium group, ethyldibenzylammonium group, etc. Among them, it is easy to obtain cheap industrial materials In terms of Trimethylammonium and methylbenzylammonium groups are preferred.

And constituting the above general formula (1) to (4) represented by the formula in any one of an anionic reactive ionic liquids (parts) (Y ^-) within, as the anion, _{^{include: SCN -, BF 4 -,}} 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 -, anions of sulfonic acyl, ethyl sulfate, 2- (2-methoxy Ethyl) ester anion, (C ₂ F ₅ ) ₃ PF ₃ ^- etc., especially the anion component (fluorine-containing anion) containing a fluorine atom can obtain an ionic liquid with a low melting point, and is excellent in antistatic properties. good. Moreover, as an anion, it is preferable not to use a chloride ion, a bromide ion, etc. from the point which has a corrosiveness.

As the combination of the cation (site) and anion (site) constituting the reactive ionic liquid represented by any one of the above general formulae (1) to (4), acrylaminoaminopropyltrimethylammonium is particularly preferred. Bis (trifluoromethanesulfonyl) imine, methacrylfluorenylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imine, acrylfluorenylaminopropyldimethylbenzylammonium bis ( Trifluoromethanesulfonium sulfonium imine, propylene fluorenyl ethyl trimethylammonium bis (trifluoromethanesulfonium sulfonium) imine, propylene fluorenyl ethyl dimethylbenzyl ammonium bis (trifluoromethanesulfonium) Imine, methacryl ethoxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imine, propylene fluorenylaminopropyltrimethylammonium bis (fluorosulfonyl) imine, methacrylium Propylaminopropyltrimethylammonium bis (fluorosulfonaminium) imine, propenylaminopropylpropyldimethylbenzylammonium bis (fluorosulfonaminium) imine, allyloxyethyltrimethylammonium Bis (fluorosulfonium) imine, propylene fluorenylethyldimethylbenzyl ammonium bis (fluorosulfonium) imine, methacryl methoxyethyltrimethylammonium bis (fluorosulfonyl) imine Methacrylamidoaminopropyltrimethylammonium triflate, methacrylamidoamino Trimethylammonium trifluoromethanesulfonate, propenylaminoaminopropyldimethylbenzylammonium triflate, propenyloxyethyltrimethylammonium triflate, propene Ethoxyethyl dimethyl benzyl ammonium triflate, methacrylic acid Ethyltrimethylammonium triflate and the like.

Among all 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, and more preferably contains 20 to 98. Mass%, particularly preferably 30 to 97 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 properties, transparency, heat resistance (thermal stability), and low pollution.

As a general synthetic method of a reactive ionic liquid, there is no particular limitation as long as the target ionic liquid can be obtained. For example, a document "Ionic liquid-development front and future-" [CMC Co., Ltd. publication], literature, etc. "Polymer, Vol. 52, P. 1469-1482 (2011)", document "Front-end material system One Point 2 ionic liquid" [quasi-levelization / ion exchange method described in Kyoritsu Co., Ltd. publication], direct Quaternization method, carbonate quaternization method, hydroxide method, ester method, error method, and neutralization method.

In addition, as a monomer unit constituting the (meth) acrylic polymer contained in the antistatic agent composition used in the present invention, a polymerizable monomer unit (component) other than the above-mentioned reactive ionic liquid may be An alkyl (meth) acrylate is used, and more preferably, an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms is used. As said alkyl (meth) acrylate, 1 type, or 2 or more types can be used.

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

All structural units (all monomer units (formula) of the (meth) acrylic polymer (Point): 100% by mass), preferably contains 0 to 65% by mass of the above (meth) acrylic acid alkyl ester as a monomer unit (component), and more preferably contains 0 to 60% by mass. When the said monomer unit (component) is in the said range, it is preferable from a viewpoint that the antistatic agent composition acquires moderate ion conductivity and cohesion.

In addition, as the monomer units constituting the (meth) acrylic polymer contained in the antistatic agent composition used in the present invention, polymerizable monomer units (components) other than the above-mentioned reactive ionic liquid are more It is preferable to use an oxyalkylene-containing monomer having an average addition mole number of 3 to 100 of an oxyalkylene unit represented by the following general formula (5). When a cationic part (positive charge) and an anion (negative charge) are included like the reactive ionic liquid used in the present invention, the relative force between the electrostatic force (Coulomb force) generated between the two charges and the above-mentioned two-charged medium The electrical constant is inversely proportional (Coulomb's law). In addition, it is presumed in the present invention that the above-mentioned oxyalkylene-containing monomer (with a high relative dielectric constant) functions as a medium of the reactive ionic liquid, reduces the electrostatic force between the two charges, and promotes the reactivity. The ion dissociation of the ionic liquid, and furthermore, with the molecular movement of the oxyalkylene chain of the above-mentioned oxyalkylene-containing monomer, it becomes easier to transport the ions, and the ionic dissociation and ion transport of the reactive ionic liquid are promoted. This ion conductivity is improved, and more excellent antistatic properties can be exhibited.

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, n and q are integers of 0 or 2 to 100, and n and When q is 0 at the same time. When R ₂ is an organic group, methyl, lauryl, phenyl, stearyl, and octyl are preferred, m and p are preferably 2, and n and q are preferably 2 to 20. Integer. Within the above range, the oxyalkylene chain of the oxyalkylene-containing monomer and the reactive ionic liquid are likely to interact with each other, and the ions constituting the reactive ionic liquid are easily dissociated, which is preferable.

Specific examples of the above-mentioned oxyalkylene-containing monomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (meth) acrylic acid. 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, stearyloxy polyethylene glycol (meth) acrylate, phenoxy polyethylene Glycol (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate Ester, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy ethylene 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 Diol-polybutylene glycol (meth) acrylate, propylene glycol-polybutylene glycol (meth) acrylate, and the like. The oxyalkylene-containing monomer may be used singly or in combination of two or more kinds.

Of all the structural units (all monomer units (components): 100% by mass) of the (meth) acrylic polymer, the above-mentioned oxyalkylene-containing monomer is preferably 0 to 60% by mass, more preferably 5 ~ 50% by mass, preferably 10 ~ 40% by mass. If it is within the above range, the oxyalkylene chain of the oxyalkylene-containing monomer is easy to carry out molecular motion, and the transporting action of ions constituting the reactive ionic liquid is improved, which is preferable.

In addition, other polymerizable monomers other than the aforementioned (meth) acrylic acid alkyl esters can also improve cohesion, heat resistance, and crosslinkability for the purpose, and if necessary, contain a copolymerizable with the aforementioned (meth) acrylic acid alkyl esters. Other polymerizable monomer units (components) (copolymerizable monomers). In addition, other polymerizable monomer units (components) can be used within the range of non-destructive cohesive force and ion conductivity. In particular, unlike the adhesive layer, it does not exhibit adhesiveness. Therefore, it is preferable to use the one having a higher glass transition temperature than 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 more effective. These monomer compounds may be used singly or in combination of two or more kinds.

In the present invention, when the (meth) acrylic polymer is a copolymer (example For example, those included in the antistatic agent 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 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]

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

In addition, in this specification, the "glass transition temperature when forming a homopolymer" means "the glass transition temperature of the homopolymer of the monomer", and means that only a certain monomer is formed (sometimes called " Monomer X ") The glass transition temperature (Tg) of the polymer as a monomer component. Specifically, the values are listed in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989).

The glass transition temperature (Tg) of a homopolymer that is not described in the aforementioned document refers to a value obtained by the following measurement method, for example.

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

Taking JIS-K-7121 as a reference, a straight line of equal distance from the straight line extended from the low temperature side reference line and the high temperature side reference line of the obtained Reversing Heat Flow in the vertical axis direction and the step shape of glass transfer The temperature at the point where the curves of the changing portions intersect is set as the glass transition temperature (Tg) when the homopolymer is made.

Specific examples of the other polymerizable monomer units (copolymerizable monomers) include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and transpolymer. Carboxylic monomers such as butenedioic acid, butenoic acid, 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 -Hydroxy-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxymethylcyclohexyl) methyl ester; acid-anhydride-containing monomers such as maleic anhydride and itaconic anhydride; styrene sulfonic acid, allyl Sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylamidooxy Monosulfonic acid-containing monomers such as naphthalenesulfonic acid; Phosphate-containing monomers such as 2-hydroxyethylpropenyl phosphate; (meth) acrylamide, N, N-dimethyl (meth) acrylic acid Amine, N, N-Di (Meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) N, N-dialkyl (meth) acrylamide, such as (meth) acrylamide, N, N-di (third butyl) (meth) acrylamide, N-ethyl (methyl) Acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-hydroxymethyl (methyl) Acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-formyl Oxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-acrylamide (N-substituted) fluorene amine monomers such as phospholine; N- (meth) acryl fluorenyloxymethylene succinimide, N- (meth) acryl fluorenyl-6-oxyhexamethylene amber Ammonium imine, N- (meth) acrylfluorenyl-8-oxyhexamethylene succinimide, and other succinimide-based imine monomers; N-cyclohexylcis-butene diimide, N-iso Maleic monomers such as propyl maleimide, N-lauryl maleimide, and N-phenyl maleimide, and N-methylimide Conamide, N-ethyl Ikonimide, N-Butyl Ikonimide, N-octyl Ikonimide, N-2-Ethylhexyl Ikonimide, N- Cyclohexyl Ikonimide, N-Lauryl Ikonimide and other Ikonimide monomers; Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone , N-methyl vinyl pyrrolidone, N-vinyl pyridine, N-vinyl piperidone, N-vinyl pyrimidine, N-vinyl piperidine N-vinylpyridine , N-vinylpyrrole, N-vinylimidazole, N-vinyl Azole, N- (meth) acrylfluorenyl-2-pyrrolidone, N- (meth) acrylfluorenylpiperidine, N- (meth) acrylfluorenylpyrrolidine, N-vinyl Porphyrin, N-vinyl-2-piperidone, N-vinyl-3- Porphyrinone, N-vinyl-2-caprolactam, N-vinyl-1,3- -2-one, N-vinyl-3,5- Porphyrindione, N-vinylpyrazole, N-vinyliso Azole, N-vinylthiazole, N-vinylisothiazole, N-vinyl And other nitrogen-containing heterocyclic monomers; N-vinylcarboxamides; N-vinylcaprolactam and other lactamamine monomers; acrylonitrile, methacrylonitrile and other cyanoacrylate monomers; Ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, Aminoalkyl (meth) acrylate monomers such as tributylaminoethyl; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and propyl (meth) acrylate (Meth) acrylic alkoxyalkyl ester-based monomers such as ethoxyethyl, butoxyethyl (meth) acrylate, and ethoxypropyl (meth) acrylate; alkoxy, α-methyl Alkoxy-based monomers such as alkoxy; epoxy-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, Glycol acrylate monomers such as methoxyethylene glycol (meth) acrylate and methoxy polypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, (methyl) containing fluorine atoms ) Acrylate, poly (meth) acrylic acid And other acrylate monomers such as heterocyclic, halogen, and silicon atoms; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; Vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as vinyl toluene and alkoxy; olefins or diene such as ethylene, butadiene, isoprene, isobutene; vinyl alkyl Vinyl ethers such as ethers; vinyl chloride; monomers containing sulfonic acid groups, such as sodium vinyl sulfonate; Monomers; 2-isocyanate ethyl (meth) acrylate-containing monomers; isopropenyl groups Phthaloline; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, iso (meth) acrylate (Meth) acrylic acid esters having alicyclic hydrocarbon groups such as esters, dicyclopentyl (meth) acrylic acid; phenyl (meth) acrylates, phenoxyethyl (meth) acrylate, and the like ( (Meth) acrylates; (meth) acrylates obtained from terpene compound derivative alcohols; etc.

In particular, as the monomer unit, it is preferable to use the above-mentioned hydroxyl-containing monomer (a hydroxyl-containing (meth) acrylic monomer) together with the reactive ionic liquid. By using the aforementioned (meth) acrylic monomer containing a hydroxyl group, it is possible to easily control the cross-linking and the like of the antistatic agent composition, or to obtain a moderate cohesive force. Furthermore, unlike carboxyl or sulfonate groups, which generally function as cross-linking sites, hydroxyl groups have ionic compounds (alkali metal salts, ionic liquids, etc.) that can be added (dispensed) as conductive agents (anti-static agents). ) Moderate interaction, so it can also be used for anti-static properties.

Among 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 1 to 15% by mass, more It is preferably 2 to 12% by mass, and most preferably 3 to 10% by mass. If it is in the said range, it will become easy to control the reaction and cohesion force with a crosslinking agent, and it is preferable.

In the present invention, the polymerizable monomer other than the hydroxyl-containing (meth) acrylic monomer is preferably all the structural units (all monomer units (components)) of the (meth) acrylic polymer. Medium is 0 to 65% by mass, more preferably 0 to 60% by mass, and even more preferably 0 to 55% by mass. By using the other polymerizable monomer in the above range, it is possible to appropriately adjust the cohesive force and the adhesiveness to the base film.

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 can be polymerized by solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, and radiation hardening polymerization. When polymerization is performed by a known method, and when the antistatic adhesive sheet of this embodiment is used for the following surface protection applications, from the viewpoint of productivity of the adhesive sheet, solution polymerization, Emulsion polymerization. The obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

The antistatic agent composition further preferably contains a conductive agent. Especially, as The conductive agent (anti-static agent) more preferably contains an ionic compound or an ion conductive polymer, and more preferably an ionic compound such as an alkali metal salt or an ionic liquid. The ionic compound may not react with the reactive ionic liquid, but may be contained as an additive to exhibit more excellent antistatic properties, so it is preferred. In addition, since the ionic compound and the reactive ionic liquid incorporated in the skeleton of the (meth) acrylic polymer have a large interaction, there is no need to worry about bleeding, and low pollution is also excellent, so it is preferable.

The content of the conductive agent used in the present invention is preferably from 0 to 40 parts by mass, more preferably from 0.5 to 35, with respect to 100 parts by mass of the (meth) acrylic polymer contained in the antistatic agent composition. It is more preferably 1 to 30 parts by mass. When the content exceeds 40 parts by mass, there is a possibility that bleeding may occur, which is not preferable.

The antistatic layer in the present invention is characterized by cross-linking the antistatic agent composition. By appropriately adjusting the structural unit, the composition ratio, the selection of the cross-linking agent, and the addition ratio of the (meth) acrylic polymer and performing cross-linking, an anti-static layer (anti-static adhesive sheet with excellent heat resistance) can be obtained. material).

As the crosslinking agent used when forming the antistatic layer, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, An oxazoline crosslinking agent, a polysiloxane crosslinking agent, a silane crosslinking agent, and a metal chelate compound. Among these, from the viewpoint of mainly obtaining a moderate cohesive force, it is more preferable to use an isocyanate compound or an epoxy compound, and it is more preferable to use an isocyanate compound (isocyanate-based crosslinking agent). These compounds may be used singly or in combination of two or more kinds.

Examples of the isocyanate compound (isocyanate-based cross-linking agent) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isocyanate. Aliphatic isocyanates such as furone diisocyanate, aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / Toluene diisocyanate trimer adduct (trade name Coronate L, Nippon Polyurethane Industry company), trimethylolpropane / hexamethylene diisocyanate terpolymer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry), isocyanurate body of hexamethylene diisocyanate ( Coronate HX, manufactured by Nippon Polyurethane Industry) and other isocyanate adducts. 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, etc. can also be used as the isocyanate-based crosslinking agent. These compounds may be used singly or in combination of two or more kinds.

Examples of the epoxy compound include bisphenol A, an epoxy resin of epichlorohydrin type, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerol 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 Company) or 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, Mitsubishi Gas Chemical Co., Ltd.). These compounds may be used singly or in combination of two or more kinds.

Examples of the melamine-based resin include hexamethylolmelamine. Examples of the aziridine derivative include, for example, commercially available products under the trade name HDU (manufactured by Kakuya Kogyo Co., Ltd.), under the trade name TAZM (manufactured by Kakuya Kogyo Co., Ltd.), and under the trade name TAZO (manufactured by Kakuya Kogyo Co., Ltd.). )Wait. These compounds may be used singly or in combination of two or more kinds.

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

The content of the crosslinking agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer contained in the antistatic agent composition. It is more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 15 parts. 10 parts by mass. When the content is less than 0.01 parts by mass, the cross-linking formation by the cross-linking agent may become insufficient, the cohesive force of the antistatic agent composition may be reduced, and sufficient heat resistance may not be obtained. On the other hand, when the content exceeds 30 parts by mass, there is a tendency that a gel-like impurity is generated in the antistatic agent composition due to a cross-linking reaction in a short period of time, which may cause a poor appearance.

The antistatic agent composition may further contain a compound that undergoes keto-enol tautomerization. By containing the above-mentioned compound, the excessive increase in viscosity or gelation of the antistatic agent composition after the cross-linking agent is suppressed can achieve the effect of extending the pot life of the antistatic agent composition. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly significant for a compound containing a keto-enol tautomer. This technique can be preferably applied, for example, when the antistatic agent composition is in the form of an organic solvent solution or a solvent-free form.

As the keto-enol tautomerization compound described above, various β-dicarbonyl compounds can be used. Specific examples include acetoacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane- Β-diketones such as 2,4-dione, 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl ethyl acetate, isopropyl ethyl acetate, ethyl acetate Acetyl acetate such as tert-butyl acetate; Propionate ethyl acetate, ethyl propyl acetate, isopropyl propyl acetate, tertiary butyl acetate, etc .; isobutyl acetic acid Isobutylammonium acetates such as ethyl acetate, ethyl isobutylammonium acetate, isopropyl isobutylammonium acetate, and tert-butyl isobutylammonium acetate; malonates such as methyl malonate and ethyl malonate Class, etc. Among them, preferred compounds include acetoacetone and acetoacetate. The keto-enol tautomerization compound may be used alone or in combination of two or more kinds.

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

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 agent 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-capable radiation such as vinyl, acryl, methacryl, and vinyl benzyl. A polyfunctional monomer component of one or two or more types of radiation-reactive groups subjected to a crosslinking treatment (curing). In addition, as the polyfunctional monomer, it is generally preferable to use one having 10 or less radiation-reactive unsaturated bonds. These compounds may be used singly or in combination of two or more kinds.

Specific examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and Pentylene 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 polyfunctional monomer is appropriately selected by the balance with the above-mentioned (meth) acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance, it is generally preferred to be formulated in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (meth) acrylic polymer. Moreover, it is more preferable that it is 10 mass parts or less with respect to 100 mass parts of (meth) acrylic-type polymers in terms of flexibility.

Examples of the radiation include ultraviolet rays, lightning rays, α rays, β rays, γ rays, X rays, and electron beams. In terms of good controllability and operability, and cost, it is preferable to use ultraviolet rays. More preferably, ultraviolet rays with a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated with a suitable light source such as a high-pressure mercury lamp, a microwave-excited lamp, or a chemical lamp. When ultraviolet rays are used as the radiation, a photopolymerization initiator shown below may be added to the antistatic agent composition.

As the above-mentioned photopolymerization initiator, any kind of photopolymerization initiator It is sufficient to irradiate ultraviolet rays of an appropriate wavelength which can be the initiator of the polymerization reaction to generate radicals or cations.

Examples of the photoradical polymerization initiator include benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, methyl benzoate benzoate-p-benzoin ethyl ether, benzoin isopropyl ether, and α-methyl benzoin, Acetophenones such as acetophenone ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylbenzene Phenylacetone such as acetone, 2-hydroxy-4'-isopropyl-2-methylphenylacetone, benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminodiphenyl Benzophenones such as benzophenone, 2-chloro9-oxosulfur 2-ethyl 9-oxysulfur , 2-isopropyl 9-oxysulfur 9-oxysulfur Class, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, (2,4,6- Trimethyl benzamidine)-(ethoxy) -phenylphosphine oxide and other fluorenyl phosphine oxides, benzophenazine, dibenzocycloheptanone, α-fluorenyl oxime ester and the like. These compounds may be used singly or in combination of two or more kinds.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic sulfonium salts, and aromatic sulfonium salts, or iron-arene complexes, titanocene complexes, and the like. Organometallic complexes such as arylsilanol-aluminum complexes, nitrobenzyl, sulfonic acid derivatives, phosphate esters, phenolsulfonates, diazonaphthoquinones, N-hydroxyphosphonium imine sulfonates, etc. . These compounds may be used singly or in combination of two or more kinds.

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, and preferably in a range of 0.2 to 7 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer. If it is in the said range, it is preferable from a viewpoint of being easy to control a polymerization reaction and obtaining a moderate molecular weight.

Furthermore, you may use together photoinitiation polymerization adjuvants, such as amines. Examples of the photo-starting aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, and p-dimethylamino Isoamyl benzoate and the like. These compounds may be used singly or in combination of two or more kinds. Polymerization starter Based) 100 parts by mass of the acrylic polymer, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass. If it is in the said range, it is preferable from a viewpoint of being easy to control a polymerization reaction and obtaining a moderate molecular weight.

In the case where a photopolymerization initiator of an arbitrary component is added as described above, the antistatic agent layer can be obtained by applying the antistatic agent composition to one or both sides of a base film and then irradiating with light. An antistatic layer is usually obtained by photopolymerization by irradiating ultraviolet rays with an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm at a light amount of 200 to 4000 mJ / cm ² .

Furthermore, the antistatic agent composition may contain other well-known additives. For example, powders such as colorants and pigments, surfactants, plasticizers, adhesion-imparting agents, low-molecular-weight polymers, and surfaces may be appropriately added according to the application. Lubricants, leveling agents, antioxidants, anticorrosives, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils, etc.

The preferred aspect of the antistatic layer is by dispersing or dissolving in a suitable solvent a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit, a cross-linking agent, and others as needed The liquid composition (anti-static agent composition, anti-static agent solution) of a component (conductive agent etc.) is obtained by forming at least one surface of a base film. For example, a method of applying the above-mentioned antistatic agent composition (antistatic agent solution) to one side of a base film, drying it, and performing a hardening treatment (heat treatment, ultraviolet treatment, etc.) as necessary may be preferably used.

As a solvent constituting the liquid composition (anti-static agent composition, anti-static agent solution), a component (raw material) used when forming the anti-static layer is preferably dissolved or dispersed stably. The solvent may be an organic solvent, water, or a mixed solvent thereof. As the organic solvent, for example, one or two or more components selected from the group consisting of esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; methyl ethyl ketone, acetone, cyclohexanone, Ketones such as methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone, acetoacetone; tetrahydrofuran (THF), two Cyclic ethers such as alkanes; Aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; Aromatic hydrocarbons such as toluene and xylene; Fats such as methanol, ethanol, n-propanol, isopropanol, and cyclohexanol Family or alicyclic alcohols; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Glycol ether acetates, such as acetate.

The coating method for forming the antistatic layer may be a known coating method. Specific examples include roll coating, gravure coating, reverse coating, roller brush coating, spray coating, air knife coating, and the like. Impregnation and curtain coating method.

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, particularly preferably about 0.03 to 1 μm, and most preferably 0.05 to 0.5 μm. about. If it is in the said range, there is little possibility that the heat resistance, solvent resistance, and flexibility of the base film which forms the said antistatic layer will be impaired, and it becomes a preferable aspect.

<Substrate film>

A known film can be used as a base film constituting the adhesive sheet of the present invention, and it is not particularly limited. A plastic film having heat resistance and solvent resistance and having flexibility is preferred. The base film has flexibility, whereby the antistatic agent 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 in a sheet shape or a film shape, and examples thereof include polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene. , Polyethylene film such as ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, polyethylene terephthalate Polyester film such as polyester, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, nylon 6,6, partially aromatic polyamines and other polyfluorene Amine film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film, etc.

In addition, if necessary, the above-mentioned base film may be subjected to the following treatments: release and antifouling treatments using polysiloxane-based, fluorine-based, long-chain alkyl-based or fatty ammonium-based release agents, silicon dioxide, and the like. , Or acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, purple Easy-to-adhere treatment such as outside line treatment, anti-static treatment such as coating type, mixed type, vapor deposition type.

Furthermore, when the adhesive sheet of the present invention is used as a film for surface protection, it is preferable that the substrate film is a plastic film subjected to antistatic treatment. By using the above-mentioned base film, it is possible to more effectively suppress the electrification of the surface protective film itself at the time of peeling. Therefore, it is used as an anti-static surface protective film in the technical field related to optical and electronic parts where electrification or pollution becomes a particularly deep problem. very useful. In addition, the substrate film is a plastic film, and the anti-static treatment is performed on the plastic film to reduce the charging of the surface protective film itself and make the anti-static energy of the adherend (protected body) more excellent.

In the present invention, the antistatic treatment for the plastic film is not particularly limited. Unlike the antistatic layer formed of the antistatic agent composition described above, at least one side of the film used for ordinary use can be additionally provided. The method of antistatic layer, or the method of kneading mixed antistatic agent in plastic film. Examples of a method for providing an antistatic layer on at least one side of the film include 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 substance, or The method of vapor-depositing or plating a conductive substance 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 quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as first, second, and third amine groups, sulfonates, or Anionic anti-charge agents with anionic functional groups such as sulfate salts, phosphonates, and phosphate ester salts; amphoteric anti-static agents such as alkyl betaine and its derivatives, imidazoline and its derivatives, and alanine and its derivatives Non-ionic anti-charge agents such as charging agents, amino alcohols and their derivatives, glycerol and its derivatives, polyethylene glycol and its derivatives, and examples of the cations, anions, and zwitterions Ionic conductive polymer obtained by polymerizing or copolymerizing a conductive group monomer. These compounds may be used singly or in combination of two or more kinds.

Examples of the cationic antistatic agent include alkyltrimethylammonium Quaternary ammonium, such as salt, fluorenylaminoaminopropyltrimethylammonium methylsulfate, alkylbenzylmethylammonium salt, fluorenylcholine chloride, dimethylaminoethylmethacrylate, etc. (Meth) acrylic acid ester copolymers, alkoxy copolymers having quaternary ammonium groups such as polyvinyl benzyltrimethylammonium chloride, etc. Ammonium-based diallylamine copolymers and the like. These compounds may be used singly or in combination of two or more kinds.

Examples of the anionic antistatic agent include alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate, alkyl ethoxy sulfate, alkyl phosphate, and sulfonic acid. Alkoxy copolymer. These compounds may be used singly or in combination of two or more kinds.

Examples of the zwitterionic antistatic agent include alkyl betaine, alkyl imidazolium betaine, and carboxy betaine graft copolymerization. These compounds may be used singly or in combination of two or more kinds.

Examples of the non-ionic antistatic agent include fatty acid alkanolamines, bis (2-hydroxyethyl) alkylamines, polyoxyethylene alkylamines, fatty acid glycerides, and polyoxyethylene glycol fatty acids. Esters, sorbitan fatty acid esters, polyoxy sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycols, polyoxyethylene diamines, including polyethers and polyesters Copolymers of polyamines, methoxypolyethylene glycol (meth) acrylate, etc. These compounds may be used singly or in combination of two or more kinds.

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 of these.

As the resin component used in the antistatic resin and the conductive resin, general resins such as polyester, acrylic resin, polyethylene, urethane, melamine, and epoxy resin can be used. In the case of a polymer-type antistatic agent, a resin component may be contained. In addition, the anti-charge resin component may contain methylolated or hydroxyalkylated melamine-based, urea-based, glyoxal-based, acrylamide-based compounds, epoxy compounds, and isocyanate-based compounds as a crosslinking agent. .

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

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

The coating method for forming the antistatic layer may be a known coating method. Specific examples include roll coating, gravure coating, reverse coating, roller brush coating, spray coating, air knife coating, and the like. Impregnation and curtain coating method.

The thickness of the layer (anti-charge layer) made of the anti-static resin, the conductive polymer, or the conductive resin is usually 0.01 μm to 5 μm, and preferably about 0.03 μm to 1 μm.

Examples of the method for depositing or plating a conductive substance include vacuum deposition, sputtering, ion plating, chemical vapor deposition, spray thermal decomposition, chemical plating, and electroplating.

The thickness of the above-mentioned layer (anti-static layer) made of a conductive material is usually 2 nm to 1000 nm, and preferably 5 nm to 500 nm.

In addition, the blending amount of the antistatic agent is used in a range of 20% by mass or less, and preferably 0.05 to 10% by mass based on the total weight of the base film (plastic film). If it is in the said range, there is little possibility of impairing the heat resistance, solvent resistance, and flexibility of the said base film (plastic film), and it is preferable. As the mixing method, as long as the antistatic agent is uniformly mixed with the resin used for the substrate film (plastic film), the combination It does not specifically limit, For example, a heating roller, a Banbury mixer, a pressure kneader, a biaxial kneader, etc. can be used.

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

<Adhesive composition and adhesive layer>

As the adhesive layer constituting the antistatic adhesive sheet of the present invention, a known one can be used without any particular limitation, and a (meth) acrylic polymer, a rubber polymer, a silicone polymer, a polymer Various polymers such as urethane-based polymers and polyester-based polymers are commonly used as adhesives. It is particularly preferably formed from an adhesive composition containing a (meth) acrylic polymer including an (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as the The main component (monomer unit). The (meth) acrylic polymer in the present invention refers to an acrylic polymer and / or a methacrylic polymer, and the (meth) acrylate refers to an acrylate and / or a methyl group. Acrylate. The "main component" means a monomer having the highest composition ratio among the monomer units (components) constituting the (meth) acrylic polymer.

As a monomer unit (component) constituting the (meth) acrylic polymer of the present invention, in order to obtain adhesive properties, it is preferable 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. These (meth) acrylic acid alkyl esters can be used alone or in combination of two or more.

As the (meth) acrylic polymer containing the above-mentioned alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as a main component, it is preferable to contain 50 to 99.9% by mass of the aforementioned having a carbon number of 1 to 20 The alkyl (meth) acrylate is preferably a monomer unit (component) containing 60 to 97% by mass. If the above-mentioned monomer unit (component) is within the above range, the viscosity The adhesive composition is preferred from the viewpoint of obtaining moderate wettability and cohesion.

In the present invention, as specific examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-butyl methacrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate Ester, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.

Among them, when the adhesive sheet of the present invention is used as a surface protection film, as a preferable one, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl ) N-octyl acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate (N-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. ) Alkyl acrylate. By using an alkyl (meth) acrylate having an alkyl group having 6 to 14 carbon atoms, it becomes easy to control the adhesion to the adherend to be low, and it becomes an excellent re-peelability.

In addition, as other polymerizable monomer units (components), the glass transition temperature (Tg) can be made 0 ° C. or lower (usually within a range that does not impair the effect of the present invention, for the reason that it is easy to obtain a balance of adhesion properties. The temperature is -100 ° C or higher), and a polymerizable monomer for adjusting the glass transition temperature (Tg) of the (meth) acrylic polymer or the peelability is used.

As another polymerizable monomer used in the (meth) acrylic polymer, it is preferable to use a (meth) acrylate (containing (Hydroxy (meth) acrylic monomer). In addition, in order to improve the cohesive force, heat resistance, crosslinkability, etc., in addition to the above-mentioned hydroxyl group-containing (meth) acrylic monomer that can be copolymerized with the above-mentioned (meth) acrylic acid alkyl ester, if necessary, further Contains other monomers (Co-monomer). These monomer compounds may be used singly or in combination of two or more kinds.

By using the above-mentioned hydroxyl-containing (meth) acrylic monomer, it becomes easy to control the cross-linking of the adhesive composition and the like, and it becomes even easier to control the improvement of wettability caused by flow and the adhesion during peeling. Reduced balance. Furthermore, unlike the carboxyl group, sulfonate group, etc., which can function as a cross-linking site, the hydroxyl group generally has a modest degree with an ionic compound (alkali metal salt, ionic liquid, etc.) that can be added (prepared) as an antistatic agent. Because of their interaction, they can also be used for antistatic properties. Examples of the hydroxyl-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) methacrylate Esters, N-hydroxymethyl (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.

When the hydroxyl group-containing (meth) acrylic monomer is included, the hydroxyl group-containing (meth) acrylic polymer is contained in all the structural units (all monomer units (components): 100% by mass) of the above-mentioned (meth) acrylic polymer. The (meth) acrylic monomer is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, and most preferably 1 to 10% by mass. If it is in the said range, since it will become easy to control the balance of the wettability and cohesive force of an adhesive composition, it is preferable.

Specific examples of other copolymerizable monomers include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, butenoic acid, and isobutylene. Monomers containing carboxyl groups such as acids; monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methyl Sulfonic acid group-containing monomers such as propanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylic acid naphthalenesulfonic acid; 2-hydroxyethyl phosphate Phosphonium-containing monomers such as allyl phosphate; (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-di (third butyl) (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl ( (Meth) 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 ( (Meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-acrylamide (N-substituted) fluorene amine monomers such as phospholine; N- (meth) acryl fluorenyloxymethylene succinimide, N- (meth) acryl fluorenyl-6-oxyhexamethylene amber Ammonium imine, N- (meth) acrylfluorenyl-8-oxyhexamethylene succinimide, and other succinimide-based imine monomers; N-cyclohexylcis-butene diimide, N-iso Maleic monomers such as propyl maleimide, N-lauryl maleimide, and N-phenyl maleimide, and N-methylimide Conamide, N-ethyl Ikonimide, N-Butyl Ikonimide, N-octyl Ikonimide, N-2-Ethylhexyl Ikonimide, N- Cyclohexyl Ikonimide, N-Lauryl Ikonimide and other Ikonimide monomers; Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone , N-methyl vinyl pyrrolidone, N-vinyl pyridine, N-vinyl piperidone, N-vinyl pyrimidine, N-vinyl piperidine N-vinylpyridine , N-vinylpyrrole, N-vinylimidazole, N-vinyl Azole, N- (meth) acrylfluorenyl-2-pyrrolidone, N- (meth) acrylfluorenylpiperidine, N- (meth) acrylfluorenylpyrrolidine, N-vinyl Porphyrin, N-vinyl-2-piperidone, N-vinyl-3- Porphyrinone, N-vinyl-2-caprolactam, N-vinyl-1,3- -2-one, N-vinyl-3,5- Porphyrindione, N-vinylpyrazole, N-vinyliso Azole, N-vinylthiazole, N-vinylisothiazole, N-vinyl And other nitrogen-containing heterocyclic monomers; N-vinylcarboxamides; N-vinylcaprolactam and other lactamamine monomers; acrylonitrile, methacrylonitrile and other cyanoacrylate monomers; Ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (Aminoalkyl (meth) acrylate-based monomers such as tributylaminoethyl ester; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propyl (meth) acrylate) (Meth) acrylic alkoxyalkyl ester-based monomers such as ethoxyethyl, butoxyethyl (meth) acrylate, and ethoxypropyl (meth) acrylate; alkoxy, α-methyl Alkoxy-based monomers such as alkoxy; epoxy-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, Glycol acrylate monomers such as methoxyethylene glycol (meth) acrylate and methoxy polypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, (methyl) containing fluorine atoms ) Acrylate, poly (meth) acrylic acid And other acrylate monomers such as heterocyclic, halogen, and silicon atoms; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; Vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as vinyl toluene and alkoxy; olefins or diene such as ethylene, butadiene, isoprene, isobutene; vinyl alkyl Vinyl ethers such as ethers; vinyl chloride; monomers containing sulfonate groups, such as sodium vinyl sulfonate; fluorenimine groups, such as cyclohexylcis butene difluorene imide, isopropyl cis butene difluorene imine Monomers; 2-isocyanate ethyl (meth) acrylate and other monomers containing isocyanate groups; acrylic fluorenyl groups Phthaloline; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, iso (meth) acrylate (Meth) acrylic acid esters having alicyclic hydrocarbon groups such as esters, dicyclopentyl (meth) acrylic acid; phenyl (meth) acrylates, phenoxyethyl (meth) acrylate, and the like ( (Meth) acrylates; (meth) acrylates obtained from terpene compound derivative alcohols; etc. In addition, these copolymerizable monomers can be used individually or in combination of 2 or more types.

In the present invention, the polymerizable monomers other than the above-mentioned hydroxyl-containing (meth) acrylic monomers may be used alone, or two or more kinds may be used in combination, preferably the above (meth) acrylic 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 even more preferably 0 to 30% by mass. By using the other polymerizable monomer in the above range, the re-peelability can be appropriately adjusted.

The weight average molecular weight (Mw) of the (meth) acrylic polymer contained in the adhesive composition used in the present invention is preferably 100,000 to 5 million, more preferably 200,000 to 4 million, and more preferably It is preferably 300,000 to 3 million, and particularly preferably 300,000 to 1 million. When the weight average molecular weight is less than 100,000, there is a tendency that a paste residue tends to occur because the cohesive force of the adhesive composition becomes small. On the other hand, when the weight average molecular weight exceeds 5 million, there are cases where the fluidity of the polymer decreases, for example, the wetting of the adherend becomes insufficient, and the adhesive force is insufficient. In addition, a weight average molecular weight means the thing obtained by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C or lower, more preferably -10 ° C or lower, even more preferably -41 ° C or lower, even more preferably -51 ° C or lower, The most preferable temperature is -61 ° C or lower (usually -100 ° C or higher). When the glass transition temperature is higher than 0 ° C, there are cases where the polymer is not easy to flow, for example, the wetting of the adherend becomes insufficient, and the adhesive force is insufficient. In particular, when the glass transition temperature is −61 ° C. or lower, it becomes easy to obtain an adhesive composition having excellent wettability and light peelability to an adherend (such as a polarizing plate). The glass transition temperature of the (meth) acrylic polymer can be adjusted within 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 known methods such as solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, and radiation hardening polymerization. When the anti-static adhesive sheet of this embodiment is used for the following surface protection applications, from the viewpoint of productivity of the adhesive sheet, solution polymerization and emulsion polymerization can be preferably used. 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 formed by crosslinking an adhesive composition containing the (meth) acrylic polymer or the like. By appropriately adjusting the structural unit, the composition ratio, the selection of the cross-linking agent, and the addition ratio of the (meth) acrylic polymer described above, and performing cross-linking, an adhesive layer (anti-static adhesive sheet) having excellent heat resistance 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, An oxazoline crosslinking agent, a polysiloxane crosslinking agent, a silane crosslinking agent, and a metal chelate compound. Among these, from the viewpoint of mainly obtaining a moderate cohesive force, it is more preferable to use an isocyanate compound or an epoxy compound, and it is more preferable to use an isocyanate compound (isocyanate-based crosslinking agent). These compounds may be used singly or in combination of two or more kinds.

Examples of the isocyanate compound (isocyanate-based cross-linking agent) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isocyanate. Cycloaliphatic isocyanates such as furone diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate Aromatic isocyanates such as esters, xylylene diisocyanate, trimethylolpropane / toluene diisocyanate terpolymer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry), trimethylolpropane / hexadecane Isocyanates such as methyl diisocyanate terpolymer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry), hexamethylene diisocyanate isocyanurate (trade name Coronate HX, manufactured by Nippon Polyurethane Industry) Adducts, 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 can also be used as an isocyanate-based crosslinking agent. These compounds may be used singly or in combination of two or more kinds.

Examples of the epoxy compound include bisphenol A, an epoxy resin of epichlorohydrin type, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerol 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 Company) or 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, Mitsubishi Gas Chemical Co., Ltd.). These compounds may be used singly or in combination of two or more kinds.

Examples of the melamine-based resin include hexamethylolmelamine. Examples of the aziridine derivative include, for example, commercially available products under the trade name HDU (manufactured by Kakuya Kogyo Co., Ltd.), under the trade name TAZM (manufactured by Kakuya Kogyo Co., Ltd.), and under the trade name TAZO (manufactured by Kakuya Kogyo Co., Ltd.). )Wait. These compounds may be used singly or in combination of two or more kinds.

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

The content of the cross-linking agent used in the adhesive composition of the present invention is higher than that of the (methyl) 100 parts by mass of the acrylic polymer, preferably 0.01 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass. When the content is less than 0.01 parts by mass, the cross-linking formation by the cross-linking agent may become insufficient, the cohesive force of the adhesive composition may become small, and sufficient heat resistance may not be obtained. In addition, it may become a paste. Residual tendencies. On the other hand, when the content exceeds 20 parts by mass, there are cases where the polymer has a large cohesive force and the fluidity decreases, for example, the wetting of the adherend becomes insufficient and the adhesive force is insufficient.

The adhesive composition disclosed herein may further contain a compound that undergoes keto-enol tautomerism. For example, the adhesive composition containing the cross-linking agent or the adhesive composition in which the cross-linking agent is formulated and used may preferably adopt a state including the above-mentioned keto-enol tautomerization compound. Thereby, the effect of suppressing excessive viscosity increase or gelation of the adhesive composition after the cross-linking agent is formulated, and extending the pot life of the composition can be achieved. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly meaningful to include a compound that undergoes keto-enol tautomerism. This technique can be preferably used, for example, when the above-mentioned adhesive composition is in the form of an organic solvent solution or a solvent-free form.

As the keto-enol tautomerization compound described above, various β-dicarbonyl compounds can be used. Specific examples include acetoacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane- Β-diketones such as 2,4-dione, 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl ethyl acetate, isopropyl ethyl acetate, ethyl acetate Acetyl acetate such as tert-butyl acetate; Propionate ethyl acetate, ethyl propyl acetate, isopropyl propyl acetate, tertiary butyl acetate, etc .; isobutyl acetic acid Isobutylammonium acetates such as ethyl acetate, ethyl isobutylammonium acetate, isopropyl isobutylammonium acetate, and tert-butyl isobutylammonium acetate; malonates such as methyl malonate and ethyl malonate Class, etc. Among them, preferred compounds include acetoacetone and acetoacetate. The keto-enol tautomerization compound may be used alone or in combination of two or more kinds.

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

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, acrylfluorenyl, methacrylfluorenyl, and vinylbenzyl groups. A polyfunctional monomer component of one or two or more types of radiation-reactive groups in a crosslinking treatment (hardening). In addition, as the polyfunctional monomer, it is generally preferable to use one having 10 or less radiation-reactive unsaturated bonds. These compounds may be used singly or in combination of two or more kinds.

Specific examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and Pentylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol six (Meth) acrylate, divinylbenzene, N, N'-methylenebispropenamide and the like.

The blending amount of the above-mentioned polyfunctional monomer is appropriately selected according to the use application of the adhesive sheet by balancing with the (meth) acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance by the cohesive force of an acrylic pressure-sensitive adhesive, it is usually preferred to be formulated in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (meth) acrylic polymer. Moreover, in terms of flexibility and adhesiveness, it is more preferable to mix 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer.

Examples of the radiation include ultraviolet rays, lightning rays, α rays, β rays, γ rays, X rays, and electron beams. In terms of good controllability and operability, and cost, it is preferable to use ultraviolet rays. More preferably, ultraviolet rays with a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated with a suitable light source such as a high-pressure mercury lamp, a microwave-excited lamp, or a chemical lamp. When an ultraviolet ray is used, a photopolymerization initiator shown below may be added to the acrylic adhesive.

The photopolymerization initiator may be any substance that generates radicals or cations by irradiating ultraviolet rays of an appropriate wavelength that can be an initiator of the polymerization reaction in accordance with the type of the radiation-reactive component.

Examples of the photoradical polymerization initiator include benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, methyl benzoate benzoate-p-benzoin ethyl ether, benzoin isopropyl ether, and α-methyl benzoin, Acetophenones such as acetophenone ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylbenzene Phenylacetone such as acetone, 2-hydroxy-4'-isopropyl-2-methylphenylacetone, benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminodiphenyl Benzophenones such as benzophenone, 2-chloro9-oxosulfur 2-ethyl 9-oxysulfur , 2-isopropyl 9-oxysulfur 9-oxysulfur Class, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, (2,4,6- Trimethyl benzamidine)-(ethoxy) -phenylphosphine oxide and other fluorenyl phosphine oxides, benzophenazine, dibenzocycloheptanone, α-fluorenyl oxime ester and the like. These compounds may be used singly or in combination of two or more kinds.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic sulfonium salts, and aromatic sulfonium salts, or iron-arene complexes, titanocene complexes, and the like. Organometallic complexes such as arylsilanol-aluminum complexes, nitrobenzyl, sulfonic acid derivatives, phosphate esters, phenolsulfonates, diazonaphthoquinones, N-hydroxyphosphonium imine sulfonates, etc. . These compounds may be used singly or in combination of two or more kinds.

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, and preferably in a range of 0.2 to 7 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer. If it is in the said range, it is preferable from a viewpoint of being easy to control a polymerization reaction and obtaining a moderate molecular weight.

Furthermore, you may use together photoinitiation polymerization adjuvants, such as amines. Examples of the photo-starting aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, and p-dimethylamino Isoamyl benzoate and the like. These compounds may be used singly or in combination of two or more kinds. The polymerization initiation aid is preferably blended in an amount of 0.05 to 10 parts by mass, and more preferably in a range of 0.1 to 7 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer. If it is in the said range, it is preferable from a viewpoint of being easy to control a polymerization reaction and obtaining a moderate molecular weight.

In the case of adding a photopolymerization initiator with an arbitrary component as described above, the above-mentioned adhesive composition can be directly applied to an adherend (protected body) or a specific substrate such as a separator. After coating the body or after coating on one side of the antistatic layer, light irradiation is performed to obtain an adhesive layer. Generally, an adhesive layer is obtained by irradiating ultraviolet rays having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm at a light amount of about 200 to 4000 mJ / cm ² to obtain an adhesive layer.

Furthermore, the above-mentioned adhesive composition may contain other well-known additives, for example, powders such as a conductive agent (antistatic agent), a colorant, and a pigment, a surfactant, a plasticizer, and an adhesion-imparting agent may be appropriately added according to the use application. , Low molecular weight polymers, surface lubricants, leveling agents, antioxidants, anticorrosives, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils Things. In particular, as the conductive agent (anti-charge agent), for example, it is preferable to use an ionic compound such as an alkali metal salt or an ionic liquid (including the above-mentioned reactive ionic liquid).

The adhesive sheet of the present invention is formed by forming the above-mentioned adhesive layer on the anti-charge layer. At this time, the crosslinking of the adhesive composition is usually performed after the adhesive composition is applied, and after the cross-linking is also included, The adhesive layer of the adhesive composition is transferred onto the antistatic layer.

The method for forming the adhesive layer on the antistatic layer is not particularly limited. For example, the adhesive composition (solution) is coated on the antistatic layer, and the polymerization solvent is dried to remove the adhesive layer. It is made on the anti-static layer. Later, you can also adjust the adhesion The components of the agent layer are cured for the purpose of migration or adjustment of the crosslinking reaction. In addition, when an adhesive composition (solution) is coated on the antistatic layer to prepare an antistatic layer, one or more solvents other than the polymerization solvent may be added to the adhesive composition to uniformly apply the antistatic layer. On the charged layer.

As a method for forming the adhesive layer when producing the adhesive sheet of the present invention, a known method used when producing adhesive tapes can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brush coating, spray coating, air knife coating, and extrusion coating using a die coater.

The adhesive sheet of the present invention is generally produced in such a manner that the thickness of the above-mentioned adhesive layer is 3 to 100 μm, preferably approximately 5 to 50 μm, and more preferably approximately 10 to 30 μm. If the thickness of the adhesive layer is within the above-mentioned range, it is easy to obtain a moderate balance between re-peelability and adhesion, which is preferable.

The adhesive sheet (surface protection film) of the present invention may, as necessary, adhere a separator on the surface of the adhesive layer in order to protect the adhesive surface.

As a material constituting the separator, there is a paper or a plastic film. In terms of excellent surface smoothness, a plastic film is preferably used. The film is not particularly limited as long as it can protect the adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethylpentene film. , Polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, and 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. If it is in the said range, since it is excellent in the adhesiveness property with respect to an adhesive layer, and peeling workability from a self-adhesive layer, it is preferable. If necessary, the above-mentioned separators may be processed as follows: release and antifouling treatments using polysiloxane-based, fluorine-based, long-chain alkyl-based or fatty ammonium-based mold release agents, silicon dioxide, or the like, or Anti-static treatment such as coating type, mixing type, vapor deposition type.

The anti-static adhesive sheet having the anti-static layer of the present invention includes an anti-static layer having excellent anti-static properties, and thus can be used for surface protection purposes or applications for manufacturing and shipping steps of electronic parts. Among the above-mentioned applications, there is a possibility that adhesion of dirt, dust, etc. caused by static electricity, and destruction of electronic parts caused by static electricity may occur, so it is useful to be able to suppress these situations.

The anti-static adhesive sheet having the anti-static layer of the present invention can be attached to an optical film and used as an optical film with an anti-static adhesive sheet. Since the above-mentioned optical film is attached to the anti-static adhesive sheet, it is useful to protect the surface of the optical film. In particular, the above-mentioned anti-static adhesive sheet can be used in plastic products and the like that are prone to generate static electricity. Therefore, the anti-static adhesive sheet is very useful in anti-static applications in the technical fields related to optical and electronic parts where electrification becomes a particularly deep problem.

In addition, the antistatic layer of the present invention is formed on at least one side of a base film, and an antistatic adhesive sheet having an adhesive layer formed on the antistatic layer is adhered (fixed) to the optical film, thereby being usable. An optical film with an anti-static adhesive sheet. By adhering the above-mentioned anti-static adhesive sheet, it is useful to prevent the anti-static layer from falling off and to prevent degradation of the optical characteristics caused by damage to the optical film. In addition, the above-mentioned adhesive layer does not require re-peelability (light-peelability) or the like as the above-mentioned adhesive layer, but is adhered (fixed) to the optical film for permanent or semi-permanent adhesion. For the purpose of the situation. As the adhesive layer (adhesive composition), a known one can be used.

[Example]

Hereinafter, several embodiments related to the present invention will be described, but the present invention is not intended to limit the present invention to those shown in the specific examples. In addition, "part" and "%" in the following description are quality standards unless otherwise specified.

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

In a 1 L three-necked flask, 100 parts of a 79% aqueous solution of 2- (propenyloxy) ethyltrimethylammonium chloride (DMAEA-Q manufactured by Kohjin) was stirred while heating at 60 ° C. Next, it was made by diluting 114 parts of potassium bis (trifluoromethanesulfonium) imide in 80 parts of ion-exchanged water. After 2 hours, the lower oil layer portion separated by two layers was extracted and washed three times with ion exchange water, and the remaining trace moisture was removed under reduced pressure to obtain 2- (propenyloxy) ethyltrimethyl Ammonium-bis (trifluoromethanesulfonium) imine (DMAEA-TFSI).

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

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

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

400 parts of methyl ethyl ketone, 40 parts of 2- (propenyloxy) ethyltrimethylammonium-bis (trifluoromethanesulfonyl) imine (DMAEA-TFSI), 55 parts of methyl methacrylate, Five parts of 2-hydroxyethyl methacrylate was put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was added, and the reaction was performed at 70 ° C for 4 hours, and then at 80 ° C. 4 hours. Then, 0.1 part of 2,2'-azobisisobutyronitrile was put in, and it was made to react at 80 degreeC for 1 hour. Thereafter, 0.17 parts of 2,2'-azobisisobutyronitrile was added at 70 ° C, and the reaction was carried out for 4 hours, followed by a reaction at 80 ° C for 4 hours. Thus, a (meth) acrylic polymer for an antistatic layer was obtained ( A).

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

400 parts of methyl ethyl ketone, 95 parts of 2- (propenyloxy) ethyltrimethylammonium-bis (trifluoromethanesulfonyl) imine (DMAEA-TFSI), and 2-hydroxyethyl methacrylate Five parts were put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour under a nitrogen atmosphere, it was charged as a polymerization initiator. 0.2 parts of 2,2'-azobisisobutyronitrile were reacted at 70 ° C for 4 hours, and then at 80 ° C for 1 hour. Then, 0.1 part of 2,2'-azobisisobutyronitrile was put in, and it was made to react at 80 degreeC for 3 hours. Thereafter, 0.2 parts of 2,2'-azobisisobutyronitrile was added at 70 ° C, and the reaction was carried out for 4 hours, followed by a 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, 95 parts of (3-acrylamidopropyl) trimethylammonium-bis (trifluoromethanesulfonyl) imine (DMAPAA-TFSI), 2-hydroxyethyl methacrylate 5 A portion was put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was added, and the reaction was performed at 70 ° C for 4 hours, and then at 80 ° C. 1 hour. Then, 0.1 part of 2,2'-azobisisobutyronitrile was put in, and it was made to react at 80 degreeC for 3 hours. Thereafter, 0.2 parts of 2,2'-azobisisobutyronitrile was added at 70 ° C, and the reaction was carried out for 4 hours, followed by a 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- (propenyloxy) ethyltrimethylammonium-bis (trifluoromethanesulfonyl) imine (DMAEA-TFSI), methoxy-terminated polyethylene 10 parts of diol methacrylate (average addition mole number 23, Blemmer PME-1000 manufactured 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 with a condenser and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was added, and the reaction was performed at 70 ° C for 4 hours, and then at 80 ° C. 1 hour. Then, 0.2 part of 2,2'-azobisisobutyronitrile was put in, and it was made to react at 80 degreeC for 3 hours. Thereafter, 0.2 parts of 2,2'-azobisisobutyronitrile was added at 70 ° C, and the reaction was carried out for 4 hours, followed by a 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- (propenyloxy) ethyltrimethylammonium-bis (trifluoromethanesulfonate) 醯) 65 parts of imine (DMAEA-TFSI), 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 put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was added, and the reaction was performed at 70 ° C for 4 hours, and then at 80 ° C. 1 hour. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was charged and reacted at 80 ° C for 5 hours to obtain a (meth) acrylic polymer (E) for an antistatic layer. The weight average molecular weight was 150,000.

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

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

<Preparation of Adhesive Composition>

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

[Example 1] (Preparation of antistatic agent solution)

To 2381 parts (100 parts of polymer) of a solution obtained by diluting the (meth) acrylic polymer (A) solution (20% by mass) to 4.2% by mass with methyl ethyl ketone, added as a crosslinking agent Coronate L (a solid content of 75% by mass of ethyl acetate solution of trimethylolpropane / toluene diisocyanate terpolymer adduct, manufactured by Nippon Polyurethane Industry) 4.0 parts, DMAEA-TFSI 5.0 parts as a conductive agent, 3.0 parts of dioctyltin dilaurate (1% by mass ethyl acetate solution) as a cross-linking catalyst was mixed and stirred at 25 ° C. for about 5 minutes to prepare an antistatic agent solution (1).

(Production of anti-static treatment film)

The above-mentioned antistatic agent solution (1) was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm, manufactured by Toray, 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 adhesive solution (1) was coated on the antistatic treatment surface of the antistatic treatment film (1), and heated at 130 ° C for 2 minutes to form an adhesive layer with a thickness of 20 µm.

Then, the surface of the above-mentioned adhesive layer was bonded to the silicon-treated surface of a polyethylene terephthalate film (separator) having a thickness of 25 μm that had been subjected to a silicon-treated treatment on one side to produce an adhesive sheet.

[Example 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.

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the antistatic treatment film (2) was used instead of the 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 5.0 parts of the above-mentioned DMAEA-TFSI.

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 4] (Preparation of antistatic agent solution)

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

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 5] (Preparation of antistatic agent solution)

The same (meth) acrylic polymer (B) was used instead of the (meth) acrylic polymer (A), and 5.0 parts of DMAEA-TFSI was not used as a conductive agent. A solution of antistatic agent (5) was prepared.

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 6] (Preparation of antistatic agent solution)

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

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 7] (Preparation of antistatic agent solution)

Use the (meth) acrylic polymer (C) instead of the (meth) acrylic polymer (A), and use N-butyl-3-methylpyridinium-bis (trifluoromethanesulfonyl) imine (BMP- in Table 1 TFSI) 20.0 parts were used instead of 5.0 parts of DMAEA-TFSI as a conductive agent, and an antistatic agent solution (7) was prepared in the same manner as in Example 1.

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 8] (Preparation of antistatic agent solution)

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

(Production of anti-static treatment film)

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

(Production of adhesive sheet)

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

[Example 9] (Preparation of antistatic agent solution)

The same (meth) acrylic polymer (D) as used in place of the (meth) acrylic polymer (A) was used, and 5.0 parts of DMAEA-TFSI was not used as a conductive agent. A solution of antistatic agent (9) was prepared.

(Production of anti-static treatment film)

The use of a Meyer stick will replace the antistatic solution (9) of the antistatic solution (1) It was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10 manufactured by Toray), and dried at 130 ° C. for 1 minute to remove the solvent and 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 antistatic treatment film (9) was used instead of the antistatic treatment film (1).

[Example 10] (Preparation of antistatic agent solution)

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

(Production of anti-static treatment film)

Using the Mayer rod, the antistatic agent solution (10) instead of the antistatic agent solution (1) was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10 manufactured by Toray). Then, it was dried at 130 ° C. for 1 minute, thereby removing the solvent, forming an antistatic layer (thickness: 0.25 μm), and preparing an antistatic film (10).

(Production of adhesive sheet)

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

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

Using the Mayer rod, the antistatic agent solution (10) instead of the antistatic agent solution (1) was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm, Lumirror S10 manufactured by Toray). Then, it was dried at 130 ° C. for 1 minute, thereby removing the solvent, forming an antistatic layer (thickness: 0.1 μm), and preparing an antistatic film (11).

(Production of adhesive sheet)

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

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

Acrylic resin (Bondeip PA-200 (32% by mass), ion-conductive polymer) made by copolymerizing quaternary ammonium chloride with a mixed solvent of isopropyl alcohol: soft water = 2: 1, adjusted It was 2.1% by mass. To 100 parts of this solution, 25 parts of an epoxy resin (Bondeip PA-100 (8.2 mass%) manufactured by Konishi Co., Ltd.) as a hardener was added, and mixed and stirred at 25 ° C for about 5 minutes to prepare 2.5 mass% of Anti-charge agent solution (11).

(Production of anti-static treatment film)

The antistatic agent solution (11) was used in place of the antistatic agent solution (1), and a corona-treated polyethylene terephthalate (PET) film (thickness: 38 μm, manufactured by Mitsubishi Resin Corporation, Diafoil T100C) was used instead of the polymer pair. Except for an ethylene phthalate (PET) film (thickness: 38 μm, manufactured by Toray, Lumirror S10), an antistatic treatment film (12) was produced in the same manner as in Example 1.

(Production of adhesive sheet)

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

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

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

(Production of adhesive sheet)

An adhesive sheet was produced in the same manner as in Example 1 except that the antistatic treatment film (13) was used instead of the 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 is measured using a GPC device (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows. In addition, a weight average molecular weight is calculated | required by the polymethyl methacrylate conversion value.

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

Sample injection volume: 20 μl

Eluent: HFIP + 10mM sodium trifluoroacetate

Flow rate: 0.3ml / min

Measurement temperature: 40 ° C

Tubing:

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

Detector: Differential refractometer (RI)

The weight average molecular weight (Mw) of the (meth) acrylic polymer (F) for the adhesive layer was measured using a GPC device (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows. In addition, a weight average molecular weight is calculated | required by the polystyrene conversion value.

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

Sample injection volume: 10 μl

Eluent: THF

Flow rate: 0.6ml / min

Measurement temperature: 40 ° C

Tubing:

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

Reference column: TSKgel SuperH-RC (1)

Detector: Differential refractometer (RI)

<Low-speed peeling test: 180 ° peeling adhesion>

The adhesive sheets of each example and comparative example were cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, followed by pressure bonding to a triethyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, Width: 70 mm, length: 100 mm), and then laminated under a pressure bonding condition of 0.25 MPa and 0.3 m / min to prepare an evaluation sample (an optical film with an anti-static adhesive sheet).

After the above lamination, it was left to stand in an environment of 23 ° C. × 50% RH for 30 minutes, and the opposite side of the triethyl cellulose cellulose polarizing plate was fixed on an acrylic plate with a double-sided adhesive tape. One end of the adhesive sheet was peeled 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 performed under the 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, a value of 0.07N / 25mm or more is considered good, and a value of less than 0.07N / 25mm is considered poor. The measurement results are shown in Table 2.

<High-speed peeling test: 180 ° peeling adhesion>

The adhesive sheets of each example and comparative example were cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, followed by pressure bonding to a triethyl cellulose polarizing plate (manufactured by Nitto Denko, SEG1425DU, Width: 70 mm, length: 100 mm), and then laminated under a pressure bonding condition of 0.25 MPa and 0.3 m / min to prepare an evaluation sample (an optical film with an anti-static adhesive sheet).

After the above lamination, it was left to stand in an environment of 23 ° C. × 50% RH for 30 minutes, and the opposite side of the triethyl cellulose cellulose polarizing plate was fixed on an acrylic plate with a double-sided adhesive tape. One end of the adhesive sheet was peeled 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 performed under the environment of 23 ° C. × 50% RH. The adhesive force at the time of high-speed peeling is less than 6.0N / 25mm, and it is set to be good, and the adhesive force at 6.0N / 25mm or more is set to be defective. The measurement results are shown in Table 2.

<Measurement of peeling voltage>

As shown in FIG. 2, the adhesive sheet 2 of each example and comparative example was cut into a width of 70 mm and a length of 130 mm. After the separator was peeled off, the one end was extended by 30 mm to be pressed onto the sticker with a hand pressure roller. Polarized plate 3 (manufactured by Nitto Denko, SEG1425DU, width: 70mm, length: 100mm) on the surface of a previously destaticized acrylic plate 4 (manufactured by Mitsubishi Rayon, Acrylite, thickness: 1mm, width: 70mm, length: 100mm) .

After being left for one day in an environment of 23 ° C. × 50% RH, as shown in FIG. 2, a sample is placed at a specific position on the sample fixing table 5. One end portion extended by 30 mm was fixed to an automatic winder, and peeled at a peeling angle of 150 ° and a stretching speed of 30 m / min (high-speed peeling). The measurement was performed with a potentiometer 1 (manufactured by Kasuga Electric Corporation, KSD-0103) to fix the potential of the surface of the polarizing plate generated at a specific position at this time, and the value was set to the value of the peeling voltage. The measurement was performed under the environment of 23 ° C. × 50% RH. The absolute peeling voltage is preferably 1.0 kV or less, and more preferably 0.5 kV or less. Within the above range, it is useful to prevent dust collection caused by static electricity or electrostatic failure of electronic parts.

<Evaluation of Pollution>

After the peeling voltage was measured, bonding was performed again by hand so that air bubbles were mixed between the peeled adhesive sheet and the polarizing plate after the measurement to prepare an evaluation sample.

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

． No pollution confirmed: ○

． Contamination confirmed: ×

<Measurement of surface resistivity (normal state)>

After the adhesive sheets of each example and comparative example were allowed to stand in an environment of 23 ° C. × 50% RH for 2 hours, the separator was peeled off and measured with a surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450). Surface resistivity of the adhesive surface. The application was performed at an applied voltage of 100 V and an applied time of 30 seconds. The surface resistivity is preferably 10 ¹³ or less, and more preferably 10 ¹² or less. Within the above range, it is useful to prevent dust collection caused by static electricity or electrostatic failure of electronic parts.

<Measurement of surface resistivity (heat resistance)>

The separators of the adhesive sheets of each of the Examples and Comparative Examples were peeled, and left at 170 ° C for 30 minutes, and then left to stand in an environment of 23 ° C x 50% RH for 2 hours. The surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation) , Hiresta UP MCP-HT450)) to measure the surface resistivity of the adhesive surface. The application was performed at an applied voltage of 100 V and an applied time of 30 seconds. The surface resistivity is preferably 10 ¹³ or less, and more preferably 10 ¹² or less.

<Grasping properties>

The adhesive sheets of each example and comparative example were cut into a size of 25 mm in width and 100 mm in length, and the release liner was peeled off, followed by pressure bonding to a triethyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, Width: 70 mm, length: 100 mm), and then laminated under a pressure bonding condition of 0.25 MPa and 0.3 m / min to produce an evaluation sample (an optical film with an anti-static adhesive sheet). After the above lamination, it was left to stand in an environment of 23 ° C. × 50% RH for 30 minutes, and the opposite side of the triethyl cellulose cellulose polarizing plate was fixed on an acrylic plate with a double-sided adhesive tape. When one end of the adhesive sheet was peeled at a stretching speed of 30 m / min (high-speed peeling) and a peeling angle of 180 °, it was visually judged whether an adhesive (paste residue) remained on the surface of the triethyl cellulose cellulose polarizing plate.

No paste residue: ○

Case of paste residue: ×

<Transparency: Haze>

The adhesive sheet of each Example and Comparative Example was cut into a width of 50 mm and a length of 50 mm, and then the release liner was peeled off, and the haze was measured with a haze meter (Murakami Color Technology Research Institute Co., Ltd.). Those with a haze of less than 10% were regarded as good, and those with a haze of 10% or more were regarded as poor. The measurement results are shown in Table 2.

Note) The parts in Table 1 indicate the solid content. In addition, in Comparative Examples 1 and 2, the number of copies is not shown in Table 1. The "coating thickness" in Table 1 means "thickness when it becomes an antistatic layer after drying".

According to the results in Table 2, it can be confirmed that in all Examples 1 to 11 using the anti-static adhesive sheet produced according to the present invention, the surface resistivity in normal state and after heating is 10 ¹³ or less, and the peeling band voltage is also ± 1.0 kV. Within, meet anti-static properties. In addition, the haze value is also 10% or less, which satisfies the transparency, and further satisfies the low pollution property and the grip property. Moreover, it was also confirmed that the adhesive force (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, Comparative Example 1 is an antistatic electrified adhesive sheet on which a corona-treated base film is formed with an antistatic layer using an antistatic agent containing an acrylic resin copolymerized with quaternary ammonium chloride. , But the result is that the peeling band voltage exceeds ± 1.0kV, and the surface resistivity after heating exceeds 10 ¹³ (exceeds the detection limit). In addition, in Comparative Example 2, as compared with Comparative Example 1, the base film was not subjected to corona treatment. As a result, it was confirmed that the gripping property was insufficient, and an adhesive sheet itself capable of being evaluated could not be obtained. Therefore, in Comparative Examples 1 and 2, it was confirmed that it was not possible to obtain those which satisfied all of the antistatic properties (peel-off voltage, surface resistivity), adhesion properties, low staining properties, grip properties, and transparency.

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

Claims (14)

An antistatic layer, characterized in that it is formed of an antistatic agent composition containing a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit and a crosslinking agent. The reactive ionic liquid system An ionic liquid containing a polymerizable (reactive double bond) functional group in the cation part and / or the anion part (either or both) constituting the ionic liquid, at any temperature in the range of 0 to 150 ° C It is liquid (liquid) and transparent in the form of a non-volatile molten salt. The antistatic layer of the requested item 1, wherein the reactive ionic liquid represented by the following general formula (1) to (4) represented by a formula according to any of the reactive ionic ^{_{liquid, 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) [ formula (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cationic moiety, and Y ⁻ is an anion; Z represents an alkylene group having 1 to 3 carbon atoms]. The anti-charge layer according to claim 2, wherein the cation part is a quaternary ammonium group. The antistatic layer according to claim 2, wherein the anion is a fluorine-containing anion. The antistatic layer according to claim 1, wherein the (meth) acrylic polymer contains an oxyalkylene group having an average addition mole number of 3 to 100 of an oxyalkylene unit represented by the following general formula (5): An alkyl monomer is used as a monomer unit, and CH ₂ = C (R ₁ ) -COO- (C _m H _2m O) _n- (C _p H _2p O) _q -R ₂ (5) [in 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 integers of 0 or 2 to 100, and there is no case where n and q are 0 at the same time ]. The antistatic layer according to claim 1, wherein the (meth) acrylic polymer contains a hydroxyl group-containing (meth) acrylic monomer as a monomer unit. The antistatic layer according to claim 1, wherein the crosslinking agent is an isocyanate crosslinking agent. The antistatic layer according to claim 1, wherein the antistatic agent composition contains a conductive agent. An anti-static adhesive sheet, characterized in that the anti-static layer according to any one of claims 1 to 8 is formed on at least one side of a base film, and has an adhesive layer on the anti-static layer. The antistatic adhesive sheet according to claim 9, wherein the base film is a plastic film. The anti-static adhesive sheet according to claim 9 or 10, which is used for surface protection. If the anti-static adhesive sheet of item 9 or 10 is used, it is used in the manufacturing and shipping steps of electronic parts. An optical film with an anti-static adhesive sheet is characterized in that the anti-static adhesive sheet as claimed in claim 11 is attached to the optical film. An optical film with an anti-static adhesive sheet is characterized in that an anti-static layer according to any one of claims 1 to 8 is formed on at least one side of a base film, and an adhesive is formed on the anti-static layer An adhesive layer, and the adhesive layer is adhered to the optical film.