WO2014103964A1 - Antistatic layer, antistatic adhesive sheet, and optical film - Google Patents

Abstract

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

Description

Antistatic layer, antistatic adhesive sheet, and optical film

The present invention relates to an antistatic layer, an antistatic pressure-sensitive adhesive sheet, and an optical film. More specifically, the present invention is excellent in antistatic property, heat resistance, transparency, and low contamination, and in particular, an antistatic layer capable of suppressing adhesion of dust, dust and the like, and destruction of electronic components due to static electricity. The present invention relates to an antistatic pressure-sensitive adhesive sheet having the antistatic layer and an optical film.

Products with high insulation resistance, such as plastic, have the property of not being able to leak static electricity generated when they are rubbed with each other or with other objects, or when they are peeled off after application, and accumulate (charge). Have. For this reason, adsorption of dust and dust in the air, sticking between papers and films, or discomfort due to electric shock, malfunctions due to static electricity in electronic / electrical equipment and OA equipment, etc. And may cause various static electricity failures such as memory destruction. In order to avoid such an obstacle, it is necessary to control the surface specific resistance of the member to be charged, and therefore an antistatic agent is usually used.

Generally, as an antistatic method for plastic products, a method of internally adding (kneading) an antistatic agent and a method of applying it to the surface are known. In addition, pressure-sensitive adhesive sheets (adhesive tape) and surface protective films that require antistatic properties are provided with a pressure-sensitive adhesive layer on one side of a plastic base film with an antistatic agent added internally, or A method is known in which an adhesive layer is provided on one side and an antistatic layer is provided on the opposite side, or an antistatic agent is added to the adhesive layer.

However, the plastic base film internally added with the antistatic agent may impair the original characteristics, and when an antistatic layer is provided on the opposite side of the adhesive layer, on the antistatic layer, For example, when an easily printable layer or a hard coat layer is formed, there is a possibility that a problem that adhesiveness is lowered may occur. In addition, there is a possibility that the antistatic layer may fall off due to friction, rubbing or water so that the antistatic property cannot be maintained. In addition, when an antistatic agent is added to the pressure-sensitive adhesive layer, the antistatic agent bleeds out to the adherend (protected body) side in contact with the pressure-sensitive adhesive layer, and contaminates the adherend. There exists a possibility of reducing an adhesive characteristic (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 antistatic intermediate layer (antistatic layer) is provided between a base film and an adhesive layer (Patent Document 2). And 3). Since the antistatic layer is an intermediate layer, it is possible to solve the problem of falling off or bleeding out of the antistatic agent to the adherend side, like the antistatic layer provided on the outer surface of the base film. . However, in the case of the antistatic layer, since the counter anion of the ionic functional group constituting the ionic binder resin that is an antistatic agent is a chlorine ion, this acts to deteriorate the heat resistance and cause corrosion. May occur.

JP-A-6-128539 JP 2007-31534 A JP-A-10-55894

Therefore, the object of the present invention is to provide excellent antistatic properties, heat resistance, transparency, and low contamination to solve the problems of conventional antistatic layers and antistatic pressure-sensitive adhesive sheets. An object of the present invention is to provide an antistatic layer capable of suppressing adhesion of dust and the like and destruction of electronic components due to static electricity, an antistatic pressure-sensitive adhesive sheet having the antistatic layer, and an optical film.

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

In the antistatic layer of the present invention, the reactive ionic liquid is preferably a reactive ionic liquid represented by any one of the following general formulas (1) to (4).
CH ₂ = C (R ¹ ) COOZX ⁺ Y ⁻ (1)
CH ₂ = C (R ¹ ) CONHZX ⁺ Y ⁻ (2)
CH ₂ = C (R ¹ ) COOX ⁺ Y ⁻ (3)
CH ₂ = C (R ¹ ) CONHX ⁺ Y ⁻ (4)
[In the formulas (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, and Y ⁻ is an anion. Z represents an alkylene group having 1 to 3 carbon atoms. ]

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

In the antistatic layer of the present invention, the anion is preferably a fluorine-containing anion.

In the antistatic layer of the present invention, the (meth) acrylic polymer contains, as a monomer unit, an oxyalkylene group-containing monomer having an average addition mole number of oxyalkylene units represented by the following general formula (5) of 3 to 100 It is preferable.
CH ₂ ═C (R ₁ ) —COO— (C _m H _2m O) _n — (C _p H _2p O) _q —R ₂ (5)
[In the formula (5), R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, and n and q are 0 or 2 to 100 It is an integer, and n and q are not 0 simultaneously. ]

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

In the antistatic layer of the present invention, the crosslinking agent is preferably an isocyanate crosslinking agent.

In the antistatic layer of the present invention, the antistatic agent composition preferably contains a conductive agent.

In the antistatic pressure-sensitive adhesive sheet of the present invention, it is preferable that the antistatic layer is formed on at least one surface of a base film, and the pressure-sensitive adhesive layer is provided on the antistatic layer.

In the antistatic pressure-sensitive adhesive sheet of the present invention, the base film is preferably a plastic film.

The antistatic pressure-sensitive adhesive sheet of the present invention is preferably used for surface protection.

The antistatic pressure-sensitive adhesive sheet of the present invention is preferably used in an electronic component manufacturing / shipping process.

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 formed on at least one surface of a base film, an adhesive layer is formed on the antistatic layer, and the adhesive layer is formed on the optical film. It is preferable to adhere to.

It is the schematic explaining the structure of an antistatic adhesive sheet. It is the schematic explaining a peeling voltage test.

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

<Antistatic adhesive sheet>
In the antistatic pressure-sensitive adhesive sheet of the present invention, it is preferable that an antistatic layer is formed on at least one surface of a base film, and the pressure-sensitive adhesive layer is provided on the antistatic layer. Specifically, FIG. 1 schematically shows a typical configuration example of the antistatic pressure-sensitive adhesive sheet. Here, the antistatic pressure-sensitive adhesive sheet 10 includes a base film (for example, a polyester film) 14, an antistatic layer 13 provided on one side thereof, and a pressure-sensitive adhesive layer 12 on the antistatic layer 13. Is mentioned. The pressure-sensitive adhesive sheet 10 is used by attaching the pressure-sensitive adhesive layer 12 to an adherend (a surface to be protected, for example, the surface of an optical component such as a polarizing plate). As shown in FIG. 1, the pressure-sensitive adhesive sheet 10 before use (that is, before sticking to an adherend) is such that the surface of the pressure-sensitive adhesive layer 12 (sticking surface to the adherend) is at least the pressure-sensitive adhesive layer 12 side. You may exist in the form protected by the separator 11 used as the peeling surface. The structure of the antistatic pressure-sensitive adhesive sheet (hereinafter sometimes simply referred to as “pressure-sensitive adhesive sheet”) will be described in detail below.

<Antistatic composition and antistatic layer>
The antistatic layer of the present invention 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. In the present invention, the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer, and the (meth) acrylate refers to acrylate and / or methacrylate.

The antistatic agent composition used when forming the antistatic layer of the present invention contains a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit as an essential component. The “reactive ionic liquid” in the present invention is a cation part and / or anion part (either or both) constituting a functional group having a polymerizable property (reactive double bond) in the ionic liquid. Means an ionic liquid which is liquid (liquid) in a range of 0 to 150 ° C. and is a non-volatile molten salt having transparency. Examples of the polymerizable functional group include a vinyl group, an allyl group, and a (meth) acryloyl group. Among these, from the viewpoint of copolymerization, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

The cation part of the reactive ionic liquid can be used without any particular limitation, but includes a quaternary ammonium cation, an imidazolium cation, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a quaternary phosphonium cation, and a trialkyl. Examples include sulfonium cation, pyrrole cation, pyrazolium cation, guanidinium cation, etc. Among them, quaternary ammonium cation, imidazolium cation, pyridinium cation, piperidinidinium cation, pyrrolidinium cation, quaternary phosphonium More preferably, a cation or a trialkylsulfonium cation is used.

Among the anion moieties constituting the reactive ionic liquid, the anions include SCN ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , and CH ₃ SO ₃ ^−. , CF ₃ SO ₃ ⁻ , (FSO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , HF ₂ ⁻ , (CN) ₂ N ⁻ , C ₄ F ₉ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , C ₃ F ₇ COO ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ , B (CN) ₄ ⁻ , C (CN) ₃ ⁻ , N (CN) ₂ ⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , C ₄ H ₉ OSO ₃ ⁻ , C ₆ H _{13 ^{OSO 3 -, C 8 H 17}} OSO 3 -, p Toluenesulfonate anion, 2- (2-methoxyethyl) ethyl sulfate _{anion, (C 2 F 5) 3} PF 3 - is like, in particular, an anionic component (fluorine-containing anion) containing a fluorine atom, a low melting point An ionic liquid can be obtained and it is preferable at the point which is excellent in antistatic property. In addition, it is preferable not to use a chlorine ion, a bromine ion, etc. as an anion at the point which has corrosivity.

The reactive ionic liquid is appropriately selected from the combination of the cation part and the anion part, and specifically includes various ionic liquids shown below.

As an imidazolium cationic ionic liquid,
1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, 1-alkyl-3-vinylimidazolium heptafluorobutyrate, 1-alkyl-3-vinylimidazolium trifluoro Lomethanesulfonate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imide, 1-alkyl-3-vinylimidazolium bis (pentafluoroethanesulfonyl) imide 1-alkyl-3-vinylimidazolium tris (trifluoromethanesulfonyl) imide, 1-alkyl-3-vinylimidazolium hexafluorophosphate, 1-alkyl-3-vinyl Ionic liquids containing 1-alkyl-3-vinylimidazolium cations such as imidazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-alkyl-3-vinylimidazolium dicyanamide, 1-alkyl-3-vinylimidazolium thiocyanate, etc. ,
1,2-dialkyl-3-vinylimidazolium bis (fluorosulfonyl) imide, 1,2-dialkyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imide, 1,2-dialkyl-3-vinylimidazolium dicyan 1,2-dialkyl-3-vinylimidazolium cation-containing ionic liquid such as amide, 1,2-dialkyl-3-vinylimidazolium thiocyanate,
2-alkyl-1,3-divinylimidazolium bis (fluorosulfonyl) imide, 2-alkyl-1,3-divinylimidazolium bis (trifluoromethanesulfonyl) imide, 2-alkyl-1,3-divinylimidazolium dicyan 2-alkyl-1,3-divinylimidazolium cation-containing ionic liquid such as amide, 2-alkyl-1,3-divinylimidazolium thiocyanate,
Contains 1-vinyl imidazolium cation such as 1-vinyl imidazolium bis (fluorosulfonyl) imide, 1-vinyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-vinyl imidazolium dicyanamide, 1-vinyl imidazolium thiocyanate Ionic liquid,
1-alkyl-3- (meth) acryloyloxyalkylimidazolium tetrafluoroborate, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium trifluoroacetate, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium Heptafluorobutyrate, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3- (meth) Acryloyloxyalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium bis (pentafluoroe Sulfonyl) imide, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium tris (trifluoromethanesulfonyl) imide, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium hexafluorophosphate, 1-alkyl-3 -(Meth) acryloyloxyalkylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium dicyanamide, 1-alkyl-3- (meth) acryloyloxyalkylimidazolium 1-alkyl-3- (meth) acryloyloxyalkylimidazolium cation-containing ionic liquids such as thiocyanate,
1-alkyl-3- (meth) acryloylaminoalkylimidazolium tetrafluoroborate, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium trifluoroacetate, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium Heptafluorobutyrate, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3- (meth) Acryloylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium bis (pentafluoroe Sulfonyl) imide, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium tris (trifluoromethanesulfonyl) imide, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium hexafluorophosphate, 1-alkyl-3 -(Meth) acryloylaminoalkylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium dicyanamide, 1-alkyl-3- (meth) acryloylaminoalkylimidazolium 1-alkyl-3- (meth) acryloylaminoalkylimidazolium cation-containing ionic liquids such as thiocyanate,
1,2-dialkyl-3- (meth) acryloyloxyalkylimidazolium bis (fluorosulfonyl) imide, 1,2-dialkyl-3- (meth) acryloyloxyalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1,2 1,2-dialkyl-3- (meth) acryloyloxy such as dialkyl-3- (meth) acryloyloxyalkylimidazolium dicyanamide, 1,2-dialkyl-3- (meth) acryloyloxyalkylimidazolium thiocyanate, etc. Ionic liquid containing alkylimidazolium cation,
1,2-dialkyl-3- (meth) acryloylaminoalkylimidazolium bis (fluorosulfonyl) imide, 1,2-dialkyl-3- (meth) acryloylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1,2 1,2-dialkyl-3- (meth) acryloylamino such as dialkyl-3- (meth) acryloylaminoalkylimidazolium dicyanamide, 1,2-dialkyl-3- (meth) acryloylaminoalkylimidazolium thiocyanate, etc. Ionic liquid containing alkylimidazolium cation,
2-alkyl-1,3-di (meth) acryloyloxyalkylimidazolium bis (fluorosulfonyl) imide, 2-alkyl-1,3-di (meth) acryloyloxyalkylimidazolium bis (trifluoromethanesulfonyl) imide, 2 -Alkyl-1,3-di (meth) acryloyloxyalkylimidazolium dicyanamide, 2-alkyl-1,3-di (meth) acryloyloxyimidazolium thiocyanate, etc. 2-alkyl-1,3-di ( (Meth) acryloyloxyalkylimidazolium cation-containing ionic liquid,
2-alkyl-1,3-di (meth) acryloylaminoalkylimidazolium bis (fluorosulfonyl) imide, 2-alkyl-1,3-di (meth) acryloylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imide, 2 -Alkyl-1,3-di (meth) acryloylaminoalkylimidazolium dicyanamide, 2-alkyl-1,3-di (meth) acryloylaminoimidazolium thiocyanate, etc. 2-alkyl-1,3-di ( (Meth) acryloyloxyalkylimidazolium cation-containing ionic liquid,
1- (meth) acryloyloxyalkylimidazolium bis (fluorosulfonyl) imide, 1- (meth) acryloyloxyalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1- (meth) acryloyloxyalkylimidazolium dicyanamide, 1 -(Meth) acryloyloxyalkylimidazolium thiocyanate, 1- (meth) acryloyloxyalkylimidazolium cation-containing ionic liquid,
1- (meth) acryloylaminoalkylimidazolium bis (fluorosulfonyl) imide, 1- (meth) acryloylaminoalkylimidazolium bis (trifluoromethanesulfonyl) imide, 1- (meth) acryloylaminoalkylimidazolium dicyanamide, 1 1- (meth) acryloylaminoalkylimidazolium cation-containing ionic liquids such as-(meth) acryloylaminoalkylimidazolium 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.

As pyridinium cationic ionic liquid,
1-vinylpyridinium cation-containing ionic liquids such as 1-vinylpyridinium bis (fluorosulfonyl) imide, 1-vinylpyridinium bis (trifluoromethanesulfonyl) imide, 1-vinylpyridinium dicyanamide, 1-vinylpyridinium thiocyanate,
1- (meth) acryloyloxyalkylpyridinium bis (fluorosulfonyl) imide, 1- (meth) acryloyloxyalkylpyridinium bis (trifluoromethanesulfonyl) imide, 1- (meth) acryloyloxyalkylpyridinium dicyanamide, 1- (meth ) 1- (meth) acryloyloxyalkylpyridinium cation-containing ionic liquid such as acryloyloxyalkylpyridinium thiocyanate,
1- (meth) acryloylaminoalkylpyridinium bis (fluorosulfonyl) imide, 1- (meth) acryloylaminoalkylpyridinium bis (trifluoromethanesulfonyl) imide, 1- (meth) acryloylaminoalkylpyridinium dicyanamide, 1- (meth ) 1- (meth) acryloylaminoalkylpyridinium cation-containing ionic liquid such as acryloylaminoalkylpyridinium thiocyanate,
2-alkyl-1-vinylpyridinium bis (fluorosulfonyl) imide, 2-alkyl-1-vinylpyridinium bis (trifluoromethanesulfonyl) imide, 2-alkyl-1-vinylpyridinium dicyanamide, 2-alkyl-1-vinyl Ionic liquids containing 2-alkyl-1-vinylpyridinium cations such as pyridinium thiocyanate,
2-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (fluorosulfonyl) imide, 2-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (trifluoromethanesulfonyl) imide, 2-alkyl-1- (meth) 2-alkyl-1- (meth) acryloyloxyalkylpyridinium cation-containing ionic liquid such as acryloyloxyalkylpyridinium dicyanamide, 2-alkyl-1- (meth) acryloyloxyalkylpyridinium thiocyanate,
2-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (fluorosulfonyl) imide, 2-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (trifluoromethanesulfonyl) imide, 2-alkyl-1- (meth) 2-alkyl-1- (meth) acryloylaminoalkylpyridinium cation-containing ionic liquids such as acryloylaminoalkylpyridinium dicyanamide, 2-alkyl-1- (meth) acryloylaminoalkylpyridinium thiocyanate,
3-alkyl-1-vinylpyridinium bis (fluorosulfonyl) imide, 3-alkyl-1-vinylpyridinium bis (trifluoromethanesulfonyl) imide, 3-alkyl-1-vinylpyridinium dicyanamide, 3-alkyl-1-vinyl Ionic liquids containing 3-alkyl-1-vinylpyridinium cations such as pyridinium thiocyanate,
3-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (fluorosulfonyl) imide, 3-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (trifluoromethanesulfonyl) imide, 3-alkyl-1- (meth) Ionic liquids containing 3-alkyl-1- (meth) acryloyloxyalkylpyridinium cations such as acryloyloxyalkylpyridinium dicyanamide, 3-alkyl-1- (meth) acryloyloxyalkylpyridinium thiocyanate,
3-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (fluorosulfonyl) imide, 3-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (trifluoromethanesulfonyl) imide, 3-alkyl-1- (meth) 3-alkyl-1- (meth) acryloylaminoalkylpyridinium cation-containing ionic liquids such as acryloylaminoalkylpyridinium dicyanamide, 3-alkyl-1- (meth) acryloylaminoalkylpyridinium thiocyanate,
4-alkyl-1-vinylpyridinium bis (fluorosulfonyl) imide, 4-alkyl-1-vinylpyridinium bis (trifluoromethanesulfonyl) imide, 4-alkyl-1-vinylpyridinium dicyanamide, 4-alkyl-1-vinyl 4-alkyl-1-vinylpyridinium cation-containing ionic liquids such as pyridinium thiocyanate,
4-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (fluorosulfonyl) imide, 4-alkyl-1- (meth) acryloyloxyalkylpyridinium bis (trifluoromethanesulfonyl) imide, 4-alkyl-1- (meth) 4-alkyl-1- (meth) acryloyloxyalkylpyridinium cation-containing ionic liquids such as acryloyloxyalkylpyridinium dicyanamide, 4-alkyl-1- (meth) acryloyloxyalkylpyridinium thiocyanate,
4-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (fluorosulfonyl) imide, 4-alkyl-1- (meth) acryloylaminoalkylpyridinium bis (trifluoromethanesulfonyl) imide, 4-alkyl-1- (meth) 4-alkyl-1- (meth) acryloylaminoalkylpyridinium cation-containing ionic liquids such as acryloylaminoalkylpyridinium dicyanamide and 4-alkyl-1- (meth) acryloylaminoalkylpyridinium 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.

As piperidinium cation ionic liquid,
1-alkyl-1-vinylalkylpiperidinium bis (fluorosulfonyl) imide, 1-alkyl-1-vinylalkylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1-vinylalkylpiperidinium dicyan 1-alkyl-1-vinylalkylpiperidinium cation-containing ionic liquids such as amide, 1-alkyl-1-vinylalkylpiperidinium thiocyanate,
1-alkyl-1- (meth) acryloyloxyalkylpiperidinium bis (fluorosulfonyl) imide, 1-alkyl-1- (meth) acryloyloxyalkylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1 1-alkyl-1- (meth) acryloyloxyalkylpiperidinium cations such as-(meth) acryloyloxyalkylpiperidinium dicyanamide, 1-alkyl-1- (meth) acryloyloxyalkylpiperidinium thiocyanate, etc. Ionic liquid,
1-alkyl-1- (meth) acryloylaminoalkylpiperidinium bis (fluorosulfonyl) imide, 1-alkyl-1- (meth) acryloylaminoalkylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1 1-alkyl-1- (meth) acryloylaminoalkylpiperidinium cations such as-(meth) acryloylaminoalkylpiperidinium dicyanamide, 1-alkyl-1- (meth) acryloylaminoalkylpiperidinium thiocyanate, etc. Ionic liquid.
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.

As pyrrolidinium cationic ionic liquid,
1-alkyl-1-vinylalkylpyrrolidinium bis (fluorosulfonyl) imide, 1-alkyl-1-vinylalkylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1-vinylalkylpyrrolidinium dicyan Ionic liquids containing 1-alkyl-1-vinylalkylpyrrolidinium cations such as amide, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanate,
1-alkyl-1- (meth) acryloyloxyalkylpyrrolidinium bis (fluorosulfonyl) imide, 1-alkyl-1- (meth) acryloyloxyalkylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1 -1-alkyl-1- (meth) acryloyloxyalkylpyrrolidinium cations such as (meth) acryloyloxyalkylpyrrolidinium dicyanamide, 1-alkyl-1- (meth) acryloyloxyalkylpyrrolidinium thiocyanate, etc. Ionic liquid,
1-alkyl-1- (meth) acryloylaminoalkylpyrrolidinium bis (fluorosulfonyl) imide, 1-alkyl-1- (meth) acryloylaminoalkylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-alkyl-1 -1-alkyl-1- (meth) acryloylaminoalkylpyrrolidinium cations such as (meth) acryloylaminoalkylpyrrolidinium dicyanamide, 1-alkyl-1- (meth) acryloylaminoalkylpyrrolidinium thiocyanate, etc. Ionic liquid.
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.

As trialkylsulfonium cation ionic liquid,
Dialkyl (vinyl) sulfonium cation containing dialkyl (vinyl) sulfonium bis (fluorosulfonyl) imide, dialkyl (vinyl) sulfonium bis (trifluoromethanesulfonyl) imide, dialkyl (vinyl) sulfonium dicyanamide, dialkyl (vinyl) sulfonium thiocyanate, etc. Ionic liquid,
Dialkyl ((meth) acryloyloxyalkyl) sulfonium bis (fluorosulfonyl) imide, dialkyl ((meth) acryloyloxyalkyl) sulfonium bis (trifluoromethanesulfonyl) imide, dialkyl ((meth) acryloyloxyalkyl) sulfonium dicyanamide, dialkyl Dialkyl ((meth) acryloyloxyalkyl) sulfonium cation-containing ionic liquids such as ((meth) acryloyloxyalkyl) sulfonium thiocyanate,
Dialkyl ((meth) acryloylaminoalkyl) sulfonium bis (fluorosulfonyl) imide, dialkyl ((meth) acryloylaminoalkyl) sulfonium bis (trifluoromethanesulfonyl) imide, dialkyl ((meth) acryloylaminoalkyl) sulfonium dicyanamide, dialkyl And dialkyl ((meth) acryloylaminoalkyl) sulfonium cation-containing ionic liquids such as ((meth) acryloylaminoalkyl) sulfonium 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.

As a quaternary phosphonium cation ionic liquid,
Trialkyl (vinyl) phosphonium bis (fluorosulfonyl) imide, trialkyl (vinyl) phosphonium bis (trifluoromethanesulfonyl) imide, trialkyl (vinyl) phosphonium dicyanamide, trialkyl (vinyl) phosphonium thiocyanate, etc. Vinyl) phosphonium cation-containing ionic liquid,
Trialkyl ((meth) acryloyloxyalkyl) phosphonium bis (fluorosulfonyl) imide, trialkyl ((meth) acryloyloxyalkyl) phosphonium bis (trifluoromethanesulfonyl) imide, trialkyl ((meth) acryloyloxyalkyl) phosphonium dicyan Trialkyl ((meth) acryloyloxyalkyl) phosphonium cation-containing ionic liquids such as amide, trialkyl ((meth) acryloyloxyalkyl) phosphonium thiocyanate,
Trialkyl ((meth) acryloylaminoalkyl) phosphonium bis (fluorosulfonyl) imide, trialkyl ((meth) acryloylaminoalkyl) phosphonium bis (trifluoromethanesulfonyl) imide, trialkyl ((meth) acryloylaminoalkyl) phosphonium dicyan Trialkyl ((meth) acryloylaminoalkyl) phosphonium cation-containing ionic liquids such as amides, trialkyl ((meth) acryloylaminoalkyl) phosphonium thiocyanate, and the like.
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.

In addition, as the quaternary ammonium cation ionic liquid,
N, N, N-trialkyl-N-vinylammonium tetrafluoroborate, N, N, N-trialkyl-N-vinylammonium trifluoroacetate, N, N, N-trialkyl-N-vinylammonium heptafluorobuty Rate, N, N, N-trialkyl-N-vinylammonium trifluoromethanesulfonate, N, N, N-trialkyl-N-vinylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N-vinylammonium bis (Trifluoromethanesulfonyl) imide, N, N, N-trialkyl-N-vinylammonium bis (pentafluoroethanesulfonyl) imide, N, N, N-trialkyl-N-vinylammonium tris (trifluoromethanesulfonyl) imide, N, N, -Trialkyl-N-vinylammonium hexafluorophosphate, N, N, N-trialkyl-N-vinylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N, N-trialkyl-N-vinylammonium dicyanamide N, N, N-trialkyl-N-vinylammonium cation-containing ionic liquid such as N, N, N-trialkyl-N-vinylammonium thiocyanate,
N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium tetrafluoroborate, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium trifluoroacetate, N, N, N- Trialkyl-N- (meth) acryloyloxyalkylammonium heptafluorobutyrate, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium trifluoromethanesulfonate, N, N, N-trialkyl-N- (Meth) acryloyloxyalkylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium bis (trifluoromethanesulfonyl) imide, N, N, N-trialkyl-N (Meth) acryloyloxyalkylammonium bis (pentafluoroethanesulfonyl) imide, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium tris (trifluoromethanesulfonyl) imide, N, N, N-trialkyl -N- (meth) acryloyloxyalkylammonium hexafluorophosphate, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N, N-trialkyl- N, N, N-trialkyl such as N- (meth) acryloyloxyalkylammonium dicyanamide, N, N, N-trialkyl-N- (meth) acryloyloxyalkylammonium thiocyanate N- (meth) acryloyloxy alkyl ammonium cation-containing ion liquid,
N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium tetrafluoroborate, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium trifluoroacetate, N, N, N- Trialkyl-N- (meth) acryloylaminoalkylammonium heptafluorobutyrate, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium trifluoromethanesulfonate, N, N, N-trialkyl-N- (Meth) acryloylaminoalkylammonium perfluorobutanesulfonate, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium bis (trifluoromethanesulfonyl) imide, N, N, N-trialkyl-N (Meth) acryloylaminoalkylammonium bis (pentafluoroethanesulfonyl) imide, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium tris (trifluoromethanesulfonyl) imide, N, N, N-trialkyl -N- (meth) acryloylaminoalkylammonium hexafluorophosphate, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N, N-trialkyl- N, N, N-trialkyl such as N- (meth) acryloylaminoalkylammonium dicyanamide, N, N, N-trialkyl-N- (meth) acryloylaminoalkylammonium thiocyanate, etc. N- (meth) acryloyl amino alkyl ammonium cation-containing ionic liquid, and the like.
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, the reactive ionic liquid can be used without any particular limitation, but a reactive ionic liquid represented by any one of the following general formulas (1) to (4) is more preferable. By containing the (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit in the antistatic agent composition, the antistatic layer formed from the antistatic agent composition exhibits the antistatic effect. Since the cationic ionic liquid can be incorporated into the polymer skeleton, bleeding out of the antistatic component can be suppressed. Further, since the reactive ionic liquid is liquid (liquid) at any temperature within the range of 0 to 150 ° C. and is a non-volatile molten salt and has transparency, the resulting antistatic layer is charged It is useful because it can satisfy prevention (high conductivity), heat resistance (thermal stability), transparency, and low contamination. In addition, since the antistatic agent component is a liquid reactive ionic liquid, it is easy to form a uniform coating film when applied to a base film when preparing an antistatic agent composition (solution). It is also preferable from the viewpoint of excellent properties.
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 above formulas (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, and Y ⁻ is an anion. Z represents an alkylene group having 1 to 3 carbon atoms.

As the cation moiety (X ⁺ ) constituting the reactive ionic liquid represented by any one of the general formulas (1) to (4), a quaternary ammonium group, an imidazolium group, a pyridinium group, a piperidinium group, Examples include a pyrrolidinium group, a pyrrole group, a quaternary phosphonium group, a trialkylsulfonium group, a pyrazolium group, and a guanidinium group. Among these, in particular, a quaternary ammonium group is excellent in transparency and is a preferable embodiment for electronic / optical applications. In addition, the quaternary ammonium group has no unsaturated bond other than the polymerizable functional group in the molecule, and is difficult to inhibit a general radical polymerization reaction during ultraviolet (UV) curing, and is curable. Is presumed to be high, and it is suitable for forming an antistatic layer.

Specific examples of the quaternary ammonium group include trimethylammonium group, triethylammonium group, tripropylammonium group, methyldiethylammonium group, ethyldimethylammonium group, methyldipropylammonium group, dimethylbenzylammonium group, diethylbenzylammonium group. Group, methyldibenzylammonium group, ethyldibenzylammonium group, and the like. Among them, a trimethylammonium group and a methylbenzylammonium group are particularly preferable because inexpensive industrial materials can be easily obtained.

In the anion (site) (Y ⁻ ) constituting the reactive ionic liquid represented by any one of the general formulas (1) to (4), the anions 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 _{^{13 OSO 3 -, C 8 H}} 17 OSO 3 -, p- toluenesulfonate anion, 2- (2-methoxyethyl) ethyl sulfate _{anion, (C 2 F 5) 3} PF 3 - is like, in particular, a fluorine atom An anion component containing fluorine (fluorinated anion) is preferable in that an ionic liquid having a low melting point can be obtained and the antistatic property is excellent. In addition, it is preferable not to use a chlorine ion, a bromine ion, etc. as an anion at the point which has corrosivity.

As the combination of the cation (site) and the anion (site) constituting the reactive ionic liquid represented by any one of the general formulas (1) to (4), acryloylaminopropyltrimethylammonium is particularly preferable. Bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxy Ethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxyethyltrimethylammo Umbis (trifluoromethanesulfonyl) imide, acryloylaminopropyltrimethylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (fluorosulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (fluorosulfonyl) imide, acryloyloxyethyltrimethylammonium Bis (fluorosulfonyl) imide, acryloyloxyethyldimethylbenzylammonium bis (fluorosulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (fluorosulfonyl) imide, acryloylaminopropyltrimethylammonium trifluoromethanesulfonic acid, methacryloylaminopropyltrimethyl Ammonium trifluoromethanesulfonic acid, acryloylaminopropyldimethylbenzylammonium trifluoromethanesulfonic acid, acryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, acryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonic acid, methacryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, etc. .

In all the structural units (total monomer units (components): 100% by mass) of the (meth) acrylic polymer, the reactive ionic liquid is preferably contained in an amount of 15 to 99% by mass, more preferably 20 to 98% by mass. More preferred are those containing 30 to 97% by mass. When the mixing 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 contamination.

A general method for synthesizing a reactive ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but the document “ionic liquids—the forefront and future of development” [published by CMC Publishing Co., Ltd.] Quaternization, as described in the literature “Polymer, Vol. 52, P. 1469-1482 (2011)” 文献 and the literature “State-of-the-art Material System One Point 2 Ionic Liquid” [published by Kyoritsu Publishing Co., Ltd.] An ion exchange method, a direct quaternization method, a carbonate ester quaternization method, a hydroxide method, an acid ester method, a complex formation method, a neutralization method, and the like are used.

In addition, as a monomer unit constituting the (meth) acrylic polymer contained in the antistatic agent composition used in the present invention, a monomer unit (component) having other polymerizability other than the reactive ionic liquid, A (meth) acrylic acid alkyl ester can be used, and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms is more preferable. As said (meth) acrylic-acid alkylester, 1 type (s) or 2 or more types can be used.

In the present invention, specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) 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) Acu Rate and the like.

Among all the structural units (total monomer units (components): 100% by mass) of the (meth) acrylic polymer, those containing 0 to 65% by mass of the (meth) acrylic acid alkyl ester as a monomer unit (component). The content is preferably 0 to 60% by mass. When the monomer unit (component) is within the above range, it is preferable from the viewpoint of obtaining appropriate ion conductivity and cohesive strength in the antistatic agent composition.

In addition, as a monomer unit constituting the (meth) acrylic polymer contained in the antistatic agent composition used in the present invention, the monomer unit (component) having other polymerizability other than the reactive ionic liquid, It is preferable to use an oxyalkylene group-containing monomer having an average addition mole number of oxyalkylene units represented by the following general formula (5) of 3 to 100. When the cation portion (positive charge) and the anion (negative charge) are included as in the reactive ionic liquid used in the present invention, the electrostatic force (Coulomb force) generated between the two charges is the medium of the both charges. Is inversely proportional to the relative dielectric constant of (Coulomb's law). In the present invention, the oxyalkylene group-containing monomer (having a high relative dielectric constant) acts as a medium for the reactive ionic liquid, reduces the electrostatic force between the two charges, Promoting ion dissociation, and further, with the molecular motion of the oxyalkylene chain of the oxyalkylene group-containing monomer, the ions are easily transported, and the ion dissociation and ion transport of the reactive ionic liquid are promoted, It is presumed that the ionic 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 a methyl group, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, and n and q are 0 or 2 to 100 It is an integer, and n and q are not 0 simultaneously. When R ₂ is an organic group, it is preferably a methyl group, a lauryl group, a phenyl group, a stearyl group, or an octyl group, m and p are preferably 2, and n and q are 2 to 20 It is preferably an integer. Within the above range, the oxyalkylene chain of the oxyalkylene group-containing monomer and the reactive ionic liquid are likely to interact with each other, and the ions constituting the reactive ionic liquid are preferably dissociated.

Specific examples of the oxyalkylene group-containing monomer include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, and polypropylene. Glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauroxypolyethylene glycol (meth) Acrylate, stearoxy polyethylene glycol (meta Acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolyethyleneglycol-polypropyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, nonylphenoxypolypropyleneglycol (meth) acrylate, nonylphenoxypolyethyleneglycol (meth) acrylate, nonylphenoxyethylene Glycol-polypropylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, polytetramethylene glycol-polyethylene glycol (meth) acrylate, polytetramethylene glycol-polypropylene glycol Meth) acrylate, polytetramethylene glycol - polybutylene glycol (meth) acrylate, propylene glycol - such as polybutylene glycol (meth) acrylate. This oxyalkylene group-containing monomer can be used alone or in combination of two or more.

Of all the structural units (total monomer units (components): 100% by mass) of the (meth) acrylic polymer, the oxyalkylene group-containing monomer is preferably 0 to 60% by mass, and 5 to 50% by mass. More preferably, it is 10 to 40% by mass. Within the above range, the oxyalkylene chain of the oxyalkylene group-containing monomer is likely to undergo molecular motion, and the transporting action of ions constituting the reactive ionic liquid is improved.

Further, as other polymerizable monomers other than the (meth) acrylic acid alkyl ester, for the purpose of modifying cohesive force, heat resistance, crosslinkability and the like, the (meth) acrylic acid alkyl ester and Other copolymerizable monomer units (components) (copolymerizable monomers) may be included. Moreover, it can use as a monomer unit (component) which has other polymerizability in the range which does not impair the balance of cohesion force and ion conductivity. In particular, unlike the pressure-sensitive adhesive layer, it is preferable to use a glass transition temperature that is higher than that of the monomer unit used in the pressure-sensitive adhesive layer in order not to exhibit adhesiveness. Use of such a monomer unit is effective as an antistatic layer (film) because the handling property can be improved. These monomer compounds may be used alone or in admixture of two or more.

In the present invention, when the (meth) acrylic polymer is a copolymer (for example, one contained in an antistatic agent composition or an adhesive composition), its glass transition temperature (Tg) is expressed by the following formula (6 ) (Fox equation).

_{1 / Tg = W 1 / Tg} 1 + W 2 / Tg 2 + ··· + Wn / Tg n (6)
[In formula (6), Tg is the glass transition temperature (unit: K) of the copolymer, Tg _i (i = 1, 2,... N) is the glass transition when monomer i forms a homopolymer. Temperature (unit: K), W _i (i = 1, 2,... N) represents a mass fraction of all monomer components of monomer i. ]

Further, the glass transition temperature Tgi of the monomer i is a nominal value described in the literature (for example, polymer handbook, adhesive hand log, etc.)

In the present specification, “glass transition temperature when homopolymer is formed” means “glass transition temperature of homopolymer of the monomer”, and may be referred to as a certain monomer (“monomer X”). ) Is the glass transition temperature (Tg) of a polymer formed using only the monomer component. Specifically, numerical values are listed in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc, 1989).
In addition, the glass transition temperature (Tg) of the homopolymer which is not described in the said literature says the value obtained by the following measuring methods, for example.
That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 100 parts by weight of monomer X, 0.2 parts by weight of 2,2′-azobisisobutyronitrile, and ethyl acetate 200 as a polymerization solvent. Stirring is performed for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 63 ° C. and the reaction is carried out for 10 hours. Subsequently, it cools to room temperature and the homopolymer solution with a solid content concentration of 33 mass% is obtained. Next, this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of this test sample was weighed in an aluminum open cell, and a temperature-modulated DSC (trade name “Q-2000”, manufactured by TA Instruments Inc.) was used to measure 50 ml / min of nitrogen. The reversing heat flow (specific heat component) behavior of the homopolymer is obtained at a heating rate of 5 ° C./min in an atmosphere.
Referring to JIS-K-7121, the low temperature side baseline of the obtained Reversing Heat Flow and the straight line that is equidistant from the straight line that extends the high temperature side base line, and the stepwise change in the glass transition The temperature at the point where the partial curve intersects is the glass transition temperature (Tg) when the homopolymer is used.

As a specific example of the monomer unit having other polymerizability (copolymerizable monomer),
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
(Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, Hydroxyl group-containing monomers such as (meth) acrylic acid hydroxyalkyl such as (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, (4-hydroxymethylcyclohexyl) methyl methacrylate;
Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride;
Sulphonic acid groups such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Containing monomers;
Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl 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, N-dialkyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) such as (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide Acrylamide, N-butyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl ( (Meth) acrylamide, N-methoxyethyl (meta) Acrylamide, N- butoxymethyl (meth) acrylamide, N- acryloyl morpholine, etc. (N- substituted) amide monomers;
Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide;
Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide;
Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers;
Vinyl esters such as vinyl acetate and vinyl propionate;
N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, Contains nitrogen such as N-vinylisothiazole and N-vinylpyridazine Ring-based monomer;
N-vinylcarboxylic acid amides;
Lactam monomers such as N-vinylcaprolactam;
Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile;
(Meth) acrylic such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Acid aminoalkyl monomers;
(Meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid propoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid ethoxypropyl ;
Styrene monomers such as styrene and α-methylstyrene;
Epoxy group-containing acrylic monomers such as (meth) glycidyl acrylate;
Glycol-based acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol;
(Meth) acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth) acrylate, silicone (meth) acrylate and other heterocyclic rings, halogen atoms, silicon atoms and the like, acrylic ester monomers;
Olefin monomers such as isoprene, butadiene, 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 vinyltoluene and styrene;
Olefins or dienes such as ethylene, butadiene, isoprene, isobutylene;
Vinyl ethers such as vinyl alkyl ethers;
Vinyl chloride;
Sulfonic acid group-containing monomers such as sodium vinyl sulfonate;
Imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide;
Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth) acrylate;
Acryloylmorpholine;
(Meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate and phenoxyethyl (meth) acrylate;
(Meth) acrylic acid ester obtained from terpene compound derivative alcohol;
Etc.

In particular, it is preferable to use the hydroxyl group-containing monomer (hydroxyl group-containing (meth) acrylic monomer) together with the reactive ionic liquid as a monomer unit. By using the hydroxyl group-containing (meth) acrylic monomer, it is easy to control the crosslinking of the antistatic agent composition, and an appropriate cohesive force can be obtained. Furthermore, unlike carboxyl groups and sulfonate groups that can generally act as crosslinking sites, hydroxyl groups can be added (blended) as conductive agents (antistatic agents) (ionic compounds such as alkali metal salts and ionic liquids). Etc.) can be suitably used also in terms of antistatic properties.

Of all the structural units of the (meth) acrylic polymer (total monomer units (components): 100% by mass), the hydroxyl group-containing (meth) acrylic monomer is preferably 1 to 15% by mass. The content is more preferably 12% by mass, and most preferably 3 to 10% by mass. Within the above range, the reaction with the crosslinking agent and the cohesive force can be easily controlled, which is preferable.

In the present invention, the other polymerizable monomer other than the hydroxyl group-containing (meth) acrylic monomer is 0 to 65% by mass in the total constituent units (total monomer units (components)) of the (meth) acrylic polymer. It is preferably 0 to 60% by mass, more preferably 0 to 55% by mass. By using the other polymerizable monomer within the above range, the cohesive force and the adhesion to the substrate film can be appropriately adjusted.

The polymerization method of the (meth) acrylic polymer containing the reactive ionic liquid used in the present invention as a monomer unit is not particularly limited, and includes solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, radiation curable polymerization, and the like. However, when the antistatic pressure-sensitive adhesive sheet of the present embodiment is used for surface protection described later, solution polymerization and emulsion polymerization can be preferably used from the viewpoint of productivity of the pressure-sensitive adhesive sheet. . Further, the polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

Moreover, it is preferable that the antistatic agent composition further contains a conductive agent. In particular, the conductive agent (antistatic agent) 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. Since the ionic compound can be added as an additional additive without reacting with the reactive ionic liquid and can exhibit more excellent antistatic properties, it is a preferred embodiment. In addition, the ionic compound has a high interaction property with the reactive ionic liquid incorporated in the skeleton of the (meth) acrylic polymer, suppresses the fear of bleeding out, and is excellent in low contamination. ,preferable.

The content of the conductive agent used in the present invention is preferably 0 to 40 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer contained in the antistatic agent composition. The content is more preferably 5 to 35 parts by mass, and further preferably 1 to 30 parts by mass. If the content exceeds 40 parts by mass, bleeding out may occur, which is not preferable.

The antistatic layer in the present invention is characterized by being formed by crosslinking the antistatic agent composition. An antistatic layer (an antistatic pressure-sensitive adhesive sheet) having better heat resistance is obtained by appropriately adjusting the structural unit, the structural ratio, the selection and addition ratio of the crosslinking agent, etc. of the (meth) acrylic polymer. be able to.

Examples of the crosslinking agent used when forming the antistatic layer include isocyanate compounds, epoxy compounds, melamine resins, aziridine derivatives, oxazoline crosslinking agents, silicone crosslinking agents, silane crosslinking agents, and metal chelate compounds. . Of these, isocyanate compounds and epoxy compounds are more preferably used mainly from the viewpoint of obtaining an appropriate cohesive force, and isocyanate compounds (isocyanate-based crosslinking agents) are particularly preferred. These compounds may be used alone or in combination of two or more.

Examples of the isocyanate compound (isocyanate-based crosslinking agent) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, and cyclohexyl. Alicyclic isocyanates such as diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate Aromatic isocyanates such as trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate Trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene di Isocyanurate of isocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) isocyanate, such as - such as theft adduct, and the like. Alternatively, a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule, specifically, 2-isocyanatoethyl (meth) acrylate or the like may be used as an isocyanate-based crosslinking agent. Can do. These compounds may be used alone or in combination of two or more.

Examples of the epoxy compound include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane. Triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company) and 1,3-bis (N , N-diglycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.). These compounds may be used alone or in combination of two or more.

Examples of the melamine resin include hexamethylol melamine. In addition, examples of the aziridine derivative include a commercial product name HDU (manufactured by mutual medicine company), a trade name TAZM (manufactured by mutual medicine company), and a trade name TAZO (manufactured by mutual medicine company). . These compounds may be used alone or in combination of two or more.

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

The content of the crosslinking agent is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer contained in the antistatic agent composition, More preferably, it is contained in an amount of ˜20 parts by mass, more preferably 0.5-15 parts by mass, and particularly preferably 0.5-10 parts by mass. When the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the antistatic agent composition becomes small, and sufficient heat resistance may not be obtained. On the other hand, when the content exceeds 30 parts by mass, a gelling foreign matter is generated in the antistatic agent composition due to the progress of the crosslinking reaction in a short time, which tends to cause poor appearance.

The antistatic agent composition may further contain a compound that causes keto-enol tautomerism. By containing the compound, an effect of suppressing an excessive increase in viscosity and gelation of the antistatic agent composition after blending the crosslinking agent and extending the pot life of the antistatic agent composition can be realized. When at least an isocyanate compound is used as the crosslinking agent, it is particularly meaningful to contain a compound that causes keto-enol tautomerism. This technique can be preferably applied when, for example, the antistatic agent composition is in an organic solvent solution or a solvent-free form.

As the compound that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- Β-diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; malonic acid esters such as methyl malonate and ethyl malonate; etc. And the like. Among these, acetylacetone and acetoacetic acid esters are preferable compounds. Such compounds producing keto-enol tautomerism may be used alone or in combination of two or more.

The content of the compound causing keto-enol tautomerism can be, for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, and usually 0.5 to 15 parts by mass. Part (for example, 1 to 10 parts by mass) is appropriate. When the content of the compound is less than 0.1 parts by mass, it may be difficult to achieve a sufficient use effect. On the other hand, if the amount of the compound exceeds 20 parts by mass, it may remain in the antistatic layer and reduce the antistatic property.

In the present invention, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds can be added as a crosslinking agent. In such a case, the antistatic agent composition is crosslinked by irradiating with radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, for example, it can be crosslinked (cured) by irradiation with radiation such as vinyl group, acryloyl group, methacryloyl group, vinylbenzyl group. Examples thereof include a polyfunctional monomer component having two or more radiation reactive groups of one kind or two or more kinds. As the polyfunctional monomer, generally, those having 10 or less radiation-reactive unsaturated bonds are preferably used. These compounds may be used alone or in combination of two or more.

Specific examples of the polyfunctional monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexanediol. Examples thereof include di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N′-methylenebisacrylamide.

The blending amount of the polyfunctional monomer is appropriately selected depending on the balance with the (meth) acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance, it is generally preferable to add 0.1 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. Moreover, it is more preferable to mix | blend at 10 mass parts or less with respect to 100 mass parts of (meth) acrylic-type polymers from the point of a softness | flexibility.

Examples of the radiation include ultraviolet rays, laser beams, α rays, β rays, γ rays, X rays, and electron beams, and ultraviolet rays are preferably used from the viewpoints of controllability, good handleability, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. In addition, when using an ultraviolet-ray as a radiation, the photoinitiator shown below can be added to an antistatic agent composition.

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

Examples of the photo radical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, benzyl dimethyl ketal, Acetophenones such as trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc. Benzophenones such as propiophenones, benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, 2-chlorothioxanthate Thioxanthones such as 2-ethylthioxanthone and 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6- Acylphosphine oxides such as trimethylbenzoyl)-(ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime esters and the like. These compounds may be used alone or in combination of two or more.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like. These compounds may be used alone or in combination of two or more.

The photopolymerization initiator is usually blended in an amount of 0.1 to 10 parts by weight and preferably in a range of 0.2 to 7 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Within the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

It is also possible to use a photoinitiated polymerization aid such as amines in combination. Examples of the photoinitiator aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. These compounds may be used alone or in combination of two or more. The polymerization initiation assistant is preferably added in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. Within the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

When the photopolymerization initiator as an optional component is added as described above, the antistatic agent layer is obtained by applying the antistatic agent composition to one or both sides of the base film and then irradiating with light. Can do. Usually, an antistatic layer is obtained by photopolymerization by irradiating ultraviolet rays having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm and a light amount of about 200 to 4000 mJ / cm ² .

Furthermore, the antistatic agent composition may contain other known additives such as powders such as colorants and pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, and the like. , Surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils Or the like can be added as appropriate according to the use for which the material is used.

In the antistatic layer, a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit, a crosslinking agent, and other components (such as a conductive agent) used as necessary are dispersed or dissolved in an appropriate solvent. It is a preferable embodiment that the liquid composition (antistatic agent composition, antistatic agent solution) is obtained by forming it on at least one side of the substrate film. For example, a method of applying the antistatic agent composition (antistatic agent solution) to one side of the substrate film and drying it, and performing a curing treatment (heat treatment, ultraviolet treatment, etc.) as necessary can be preferably employed.

As a solvent constituting the liquid composition (antistatic agent composition, antistatic agent solution), a solvent that can stably dissolve or disperse components (raw materials) used in forming the antistatic layer. preferable. As the solvent, an organic solvent, water, or a mixed solvent thereof can be used. Examples of the organic solvent include esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; ketones such as methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone, and acetylacetone; Cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol, n-propanol, isopropanol, Aliphatic or alicyclic alcohols such as cyclohexanol; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether; May be used alone or two or more selected from the like; monomethyl ether acetate, diethylene glycol ether acetates, such as monoethyl ether acetate.

As a coating method in forming the antistatic layer, a known coating method is appropriately used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating, impregnation and curtain are used. The coating method can be given.

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. Most preferably, it is about 0.05 to 0.5 μm. Within the above range, there is little possibility of impairing the heat resistance, solvent resistance, and flexibility of the base film that forms the antistatic layer, which is a preferred embodiment.

<Base film>
As the base film constituting the pressure-sensitive adhesive sheet of the present invention, a known film can be used, and is not particularly limited, but is preferably a plastic film having heat resistance and solvent resistance and having flexibility. When the base film has flexibility, the antistatic agent composition can be applied by a roll coater or the like, and can be wound into a roll.

The plastic film is not particularly limited as long as it can be formed into a sheet shape or a film shape. For example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene・ Polypropylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, polyolefin film such as ethylene / vinyl alcohol copolymer, polyethylene terephthalate, polyethylene naphthalate, Polyester film such as polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6, nylon 6,6, polyamide film such as partially aromatic polyamide, polyvinyl chloride film, polyvinylidene chloride And polycarbonate film.

In addition, the base film may be subjected to release treatment and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, acid treatment, alkali treatment, if necessary Further, easy adhesion treatment such as primer treatment, corona treatment, plasma treatment, and ultraviolet treatment, and antistatic treatment such as coating type, kneading type, and vapor deposition type can also be performed.

Furthermore, when the pressure-sensitive adhesive sheet of the present invention is used as a film for surface protection, it is preferable that the base film is a plastic film that has been subjected to antistatic treatment. By using the base film, the surface protection film itself is more effectively prevented from being charged when it is peeled off. Therefore, charging and contamination are particularly serious problems. It becomes very useful as a surface protective film. In addition, the base film is a plastic film, and the antistatic treatment is performed on the plastic film, thereby reducing the charge of the surface protective film itself, and in the antistatic ability to the adherend (protected body). , A better one is obtained.

In the present invention, the antistatic treatment to be applied to the plastic film is not particularly limited, but apart from the antistatic layer formed from the antistatic agent composition described above, at least one of the commonly used films. A method of separately providing an antistatic layer on one surface, a method of kneading a kneading type antistatic agent into a plastic film, or the like is used. As a method of providing an antistatic layer on at least one surface of the film, an antistatic resin or conductive polymer comprising an antistatic agent and a resin component, a method of applying a conductive resin containing a conductive substance, or a conductive material may be used. Examples of the pressure-sensitive adhesive sheet of the present invention include configurations such as a base film (plastic film and antistatic layer), an antistatic layer, and a pressure-sensitive adhesive layer.

Examples of the antistatic agent (conductive agent) include a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a first, a second, and a third amino group, and a sulfonate. An anionic antistatic agent having an anionic functional group such as sulfate salt, phosphonate, phosphate ester salt, amphoteric antistatic agent such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, Nonionic antistatic agents such as aminoalcohol and derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof, and monomers or monomers having cationic conductive, anionic and zwitterionic ion conductive groups are polymerized or copolymerized. An ion conductive polymer obtained in this manner can be mentioned. These compounds may be used alone or in combination of two or more.

Examples of the cationic antistatic agent include a quaternary ammonium group such as alkyltrimethylammonium salt, acyloylamidopropyltrimethylammonium methosulfate, alkylbenzylmethylammonium salt, acylcholine chloride, polydimethylaminoethyl methacrylate (meta ) Acrylate copolymer, styrene copolymer having quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride, diallylamine copolymer having quaternary ammonium group such as polydiallyldimethylammonium chloride. These compounds may be used alone or in combination of two or more.

Examples of the anionic antistatic agent include alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, alkyl phosphate ester salt, and sulfonate group-containing styrene copolymer. These compounds may be used alone or in combination of two or more.

Examples of the zwitterionic antistatic agent include alkylbetaines, alkylimidazolium betaines, and carbobetaine graft copolymers. These compounds may be used alone or in combination of two or more.

Examples of the nonionic antistatic agent include fatty acid alkylolamide, di (2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, and polyoxysorbitan. Examples thereof include fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycols, polyoxyethylene diamines, copolymers composed of polyethers, polyesters and polyamides, and methoxypolyethylene glycol (meth) acrylates. These compounds may be used alone or in combination of two or more.

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

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

General-purpose resins such as polyester, acrylic, polyvinyl, urethane, melamine, and epoxy are used as the resin component used for the antistatic resin and the conductive resin. In the case of a polymer type antistatic agent, it is not necessary to contain a resin component. Further, the antistatic resin component can contain a methylol- or alkylol-containing melamine-based, urea-based, glyoxal-based, acrylamide-based compound, epoxy compound, or isocyanate-based compound as a crosslinking agent.

The antistatic layer can be formed by, for example, diluting the antistatic resin, conductive polymer or conductive resin with a solvent such as an organic solvent or water, and applying and drying the coating liquid on a plastic film. Is done.

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

As a coating method in forming the antistatic layer, a known coating method is appropriately used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating, impregnation and The curtain coat method is mentioned.

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

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

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

The blending amount of the antistatic agent is 20% by mass or less, preferably 0.05 to 10% by mass with respect to the total weight of the base film (plastic film). When it exists in the said range, since possibility that the heat resistance of the said base film (plastic film), solvent resistance, and flexibility will be impaired is small, it is preferable. The kneading method is not particularly limited as long as the antistatic agent can be uniformly mixed with the resin used for the base film (plastic film). For example, a heating roll, a Banbury mixer, a pressure kneader, A biaxial kneader or the like is used.

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

<Adhesive composition and adhesive layer>
As the pressure-sensitive adhesive layer constituting the antistatic pressure-sensitive adhesive sheet of the present invention, a known layer can be used, and is not particularly limited, and is a (meth) acrylic polymer, rubber-based polymer, silicone-based polymer, polyurethane-based polymer, polyester-based material. Various polymers generally used as pressure-sensitive adhesives such as polymers can be used. In particular, it is preferably formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer having a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a main component (monomer unit). The (meth) acrylic polymer in the present invention refers to an acrylic polymer and / or a methacrylic polymer, and (meth) acrylate refers to an acrylate and / or methacrylate. The “main component” means a monomer having the highest constituent ratio among the monomer units (components) constituting the (meth) acrylic polymer.

As the monomer unit (component) constituting the (meth) acrylic polymer of the present invention, a (meth) acrylic acid having a linear or branched alkyl group having 1 to 20 carbon atoms can be obtained because an adhesive property is obtained. Alkyl esters are preferably used, and more preferably (meth) acrylic acid alkyl esters having an alkyl group having 6 to 14 carbon atoms. As said (meth) acrylic-acid alkylester, 1 type (s) or 2 or more types can be used.

The (meth) acrylic polymer having as a main component the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms includes the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms. Is preferably a monomer unit (component) containing 50 to 99.9% by mass, more preferably 60 to 97% by mass. When the monomer unit (component) is within the above range, it is preferable from the viewpoint of obtaining appropriate wettability and cohesive strength in the pressure-sensitive adhesive composition.

In the present invention, specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) 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) Acu Rate and the like.

In particular, when the pressure-sensitive adhesive sheet of the present invention is used as a surface protective film, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) 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. Suitable examples include (meth) acrylic acid alkyl esters having an alkyl group having 6 to 14 carbon atoms. By using a (meth) acrylic acid alkyl ester having an alkyl group having 6 to 14 carbon atoms, it becomes easy to control the adhesive force to the adherend to be low, and the removability is excellent.

As another monomer unit (component) having polymerizability, the glass transition temperature (Tg) is set to 0 ° C. or lower (usually −100 ° C. or higher) for the purpose of easily balancing the adhesion performance. ) A polymerizable monomer for adjusting the glass transition temperature (Tg) and peelability of the acrylic polymer can be used as long as the effects of the present invention are not impaired.

As the other polymerizable monomer used in the (meth) acrylic polymer, a (meth) acrylate having a hydroxyl group (a hydroxyl group-containing (meth) acrylic monomer) is preferably used because crosslinking can be easily controlled. It is done. In addition to the hydroxyl group-containing (meth) acrylic monomer that can be copolymerized with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesion, heat resistance, crosslinkability, etc. Further, other monomer components (copolymerizable monomers) may be included. These monomer compounds may be used alone or in admixture of two or more.

By using the hydroxyl group-containing (meth) acrylic monomer, it becomes easy to control the crosslinking of the pressure-sensitive adhesive composition, and thus it becomes easy to control the balance between improvement of wettability by flow and reduction of adhesive strength in peeling. . Furthermore, unlike the above-mentioned carboxyl groups and sulfonate groups, which can generally act as crosslinking sites, hydroxyl groups can be added (blended) as antistatic agents (alkali metal salts, ionic liquids, etc.) Therefore, it can be suitably used also in terms of antistatic properties. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl. (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxy Examples thereof include ethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.

In the case where the hydroxyl group-containing (meth) acrylic monomer is included, the hydroxyl group-containing (meth) acrylic polymer with respect to all the structural units of the (meth) acrylic polymer (total monomer units (components): 100% by mass). The monomer content is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, and most preferably 1 to 10% by mass. Within the above range, it is easy to control the balance between wettability and cohesive force of the pressure-sensitive adhesive composition, which is preferable.

As specific examples of other copolymerizable monomers,
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride;
Sulphonic acid groups such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Containing monomers;
Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl 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, N-dialkyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) such as (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide Acrylamide, N-butyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl ( (Meth) acrylamide, N-methoxyethyl (meta) Acrylamide, N- butoxymethyl (meth) acrylamide, N- acryloyl morpholine, etc. (N- substituted) amide monomers;
Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide;
Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide;
Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers;
Vinyl esters such as vinyl acetate and vinyl propionate;
N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, Contains nitrogen such as N-vinylisothiazole and N-vinylpyridazine Ring-based monomer;
N-vinylcarboxylic acid amides;
Lactam monomers such as N-vinylcaprolactam;
Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile;
(Meth) acrylic such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Acid aminoalkyl monomers;
(Meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid propoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid ethoxypropyl ;
Styrene monomers such as styrene and α-methylstyrene;
Epoxy group-containing acrylic monomers such as (meth) glycidyl acrylate;
Glycol-based acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol;
(Meth) acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth) acrylate, silicone (meth) acrylate and other heterocyclic rings, halogen atoms, silicon atoms and the like, acrylic ester monomers;
Olefin monomers such as isoprene, butadiene, 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 vinyltoluene and styrene;
Olefins or dienes such as ethylene, butadiene, isoprene, isobutylene;
Vinyl ethers such as vinyl alkyl ethers;
Vinyl chloride;
Sulfonate group-containing monomers such as sodium vinyl sulfonate;
Imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide;
Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth) acrylate;
Acryloylmorpholine;
(Meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate and phenoxyethyl (meth) acrylate;
(Meth) acrylic acid ester obtained from terpene compound derivative alcohol;
Etc. These copolymerizable monomers can be used alone or in combination of two or more.

In the present invention, other polymerizable monomers other than the hydroxyl group-containing (meth) acrylic monomer may be used alone or in combination of two or more. It is preferably 0 to 40% by mass, more preferably 0 to 35% by mass, and particularly preferably 0 to 30% by mass in the total constitutional units (all monomer units (components)) of the acrylic polymer. . By using the other polymerizable monomer within the above range, the removability can be appropriately adjusted.

The weight average molecular weight (Mw) of the (meth) acrylic polymer contained in the pressure-sensitive adhesive composition used in the present invention is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, still more preferably 30. It is preferably from 30,000 to 3,000,000, particularly preferably from 300,000 to 1,000,000. When the weight average molecular weight is smaller than 100,000, there is a tendency that adhesive residue is generated due to the reduced cohesive force of the pressure-sensitive adhesive composition. On the other hand, when the weight average molecular weight exceeds 5,000,000, the fluidity of the polymer is lowered, and for example, the wettability may be insufficient with respect to the adherend, and the adhesive strength may be insufficient. In addition, a weight average molecular weight means what was 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, still more preferably −41 ° C. or lower, particularly preferably −51 ° C. or lower, most preferably. -61 ° C or lower (usually -100 ° C or higher). When the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow, and for example, the wetness to the adherend becomes insufficient and the adhesive strength may be insufficient. In particular, when the glass transition temperature is −61 ° C. or less, an adhesive composition excellent in wettability to an adherend (such as a polarizing plate) and light release properties can be easily obtained. In addition, the glass transition temperature of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.

The polymerization method of the (meth) acrylic polymer is not particularly limited, and can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or radiation curing polymerization. When using the antistatic pressure-sensitive adhesive sheet of the present embodiment for surface protection applications described later, solution polymerization and emulsion polymerization can be suitably used from the viewpoint of productivity of the pressure-sensitive adhesive sheet. Further, the polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

The pressure-sensitive adhesive layer in the present invention is preferably formed by crosslinking a pressure-sensitive adhesive composition containing the (meth) acrylic polymer or the like. Obtaining a pressure-sensitive adhesive layer (antistatic pressure-sensitive adhesive sheet) with better heat resistance by appropriately adjusting the structural unit, the structural ratio, the selection and addition ratio of the crosslinking agent, etc. of the (meth) acrylic polymer. Can do.

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 silicone crosslinking agent, a silane crosslinking agent, a metal chelate compound, and the like are used. Of these, isocyanate compounds and epoxy compounds are more preferably used mainly from the viewpoint of obtaining an appropriate cohesive force, and isocyanate compounds (isocyanate-based crosslinking agents) are particularly preferred. These compounds may be used alone or in combination of two or more.

Examples of the isocyanate compound (isocyanate-based crosslinking agent) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, and cyclohexyl. Alicyclic isocyanates such as diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate Aromatic isocyanates such as trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate Trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene di Isocyanurate of isocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) isocyanate, such as - such as theft adduct, and the like. Alternatively, a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule, specifically, 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent. Can do. These compounds may be used alone or in combination of two or more.

Examples of the epoxy compound include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane. Triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company) and 1,3-bis (N , N-diglycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.). These compounds may be used alone or in combination of two or more.

Examples of the melamine resin include hexamethylol melamine. In addition, examples of the aziridine derivative include a commercial product name HDU (manufactured by mutual medicine company), a trade name TAZM (manufactured by mutual medicine company), and a trade name TAZO (manufactured by mutual medicine company). . These compounds may be used alone or in combination of two or more.

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

The content of the crosslinking agent used in the pressure-sensitive adhesive composition of the present invention is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, and preferably 0.5 to 15 More preferably, it is contained in an amount of 0.5 to 10 parts by mass. When the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the pressure-sensitive adhesive composition becomes small, and sufficient heat resistance may not be obtained, and the adhesive residue There is a tendency to cause. On the other hand, when the content exceeds 20 parts by mass, the cohesive force of the polymer is large and the fluidity is lowered. For example, the wettability to the adherend becomes insufficient and the adhesive force may be insufficient.

The pressure-sensitive adhesive composition disclosed herein can further contain a compound that causes keto-enol tautomerism. For example, in a pressure-sensitive adhesive composition containing a cross-linking agent or a pressure-sensitive adhesive composition that can be used by blending a cross-linking agent, an embodiment including a compound that causes the keto-enol tautomerism can be preferably employed. Thereby, the excessive viscosity raise and gelation of the adhesive composition after a crosslinking agent mixing | blending can be suppressed, and the effect of extending the pot life of this composition may be implement | achieved. When at least an isocyanate compound is used as the crosslinking agent, it is particularly meaningful to contain a compound that causes keto-enol tautomerism. This technique can be preferably applied when, for example, the pressure-sensitive adhesive composition is in an organic solvent solution or a solvent-free form.

As the compound that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- Β-diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; malonic acid esters such as methyl malonate and ethyl malonate; etc. And the like. Among these, acetylacetone and acetoacetic acid esters are preferable compounds. Such compounds producing keto-enol tautomerism may be used alone or in combination of two or more.

The amount of the compound that generates keto-enol tautomerism can be, for example, 0.1 to 20 parts by mass, and usually 0.5 to 15 parts per 100 parts by mass of the (meth) acrylic polymer. It is appropriate to set it to parts by mass (for example, 1 to 10 parts by mass). If the amount of the compound is too small, it may be difficult to achieve a sufficient use effect. On the other hand, if the compound is used more than necessary, it may remain in the pressure-sensitive adhesive layer and reduce the cohesive force.

In the present invention, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds can be added as a crosslinking agent. In such a case, the pressure-sensitive adhesive composition is crosslinked by irradiating with radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, for example, it can be crosslinked (cured) by irradiation with radiation such as vinyl group, acryloyl group, methacryloyl group, vinylbenzyl group. Examples thereof include a polyfunctional monomer component having two or more radiation reactive groups of one kind or two or more kinds. As the polyfunctional monomer, generally, those having 10 or less radiation-reactive unsaturated bonds are preferably used. These compounds may be used alone or in combination of two or more.

Specific examples of the polyfunctional monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexanediol. Examples thereof include di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N′-methylenebisacrylamide.

The blending amount of the polyfunctional monomer is appropriately selected depending on the balance with the (meth) acrylic polymer to be crosslinked, and further depending on the use application of the pressure-sensitive adhesive sheet. In order to obtain sufficient heat resistance due to the cohesive strength of the acrylic pressure-sensitive adhesive, it is generally preferable to add 0.1 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. Moreover, it is more preferable to mix | blend at 10 mass parts or less with respect to 100 mass parts of (meth) acrylic-type polymers from the point of a softness | flexibility and adhesiveness.

Examples of the radiation include ultraviolet rays, laser beams, α rays, β rays, γ rays, X rays, and electron beams, and ultraviolet rays are preferably used from the viewpoints of controllability, good handleability, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. In addition, when using an ultraviolet-ray as a radiation, the photoinitiator shown below can be added to an acrylic adhesive.

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

Examples of the photo radical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, benzyl dimethyl ketal, Acetophenones such as trichloroacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc. Benzophenones such as propiophenones, benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, 2-chlorothioxanthate Thioxanthones such as 2-ethylthioxanthone and 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6- Acylphosphine oxides such as trimethylbenzoyl)-(ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime esters and the like. These compounds may be used alone or in combination of two or more.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like. These compounds may be used alone or in combination of two or more.

The photopolymerization initiator is usually blended in an amount of 0.1 to 10 parts by weight and preferably in a range of 0.2 to 7 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Within the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

It is also possible to use a photoinitiated polymerization aid such as amines in combination. Examples of the photoinitiator aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. These compounds may be used alone or in combination of two or more. The polymerization initiation assistant is preferably added in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. Within the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

When the photopolymerization initiator as an optional component is added as described above, the pressure-sensitive adhesive composition is directly coated on an adherend (protected body) or a predetermined coated body such as a separator. After the coating, or after coating on one side of the antistatic layer, the pressure-sensitive adhesive layer can be obtained by light irradiation. Usually, the pressure-sensitive adhesive layer is obtained by photopolymerization by irradiating an ultraviolet ray having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm with a light amount of about 200 to 4000 mJ / cm ² .

Furthermore, the pressure-sensitive adhesive composition may contain other known additives. For example, powders such as conductive agents (antistatic agents), colorants, pigments, surfactants, plasticizers, and pressure-sensitive adhesives. Imparting agent, low molecular weight polymer, surface lubricant, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, ultraviolet absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filler, metal powder, It can be added as appropriate depending on the application in which particles, foils, etc. are used. In particular, as the conductive agent (antistatic agent), for example, it is preferable to use an ionic compound such as an alkali metal salt or an ionic liquid (including the reactive ionic liquid).

The pressure-sensitive adhesive sheet of the present invention is formed by forming the pressure-sensitive adhesive layer on an antistatic layer, and in this case, the pressure-sensitive adhesive composition is generally crosslinked after application of the pressure-sensitive adhesive composition. However, it is also possible to transfer the pressure-sensitive adhesive layer comprising the crosslinked pressure-sensitive adhesive composition onto the antistatic layer.

The method for forming the pressure-sensitive adhesive layer on the antistatic layer is not particularly limited.For example, the pressure-sensitive adhesive composition (solution) is applied onto the antistatic layer, and the polymerization solvent is removed by drying. It is produced by forming an adhesive layer on the antistatic layer. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction. In addition, when preparing the antistatic layer by applying the pressure sensitive adhesive composition (solution) on the antistatic layer, it is a kind other than the polymerization solvent in the pressure sensitive adhesive composition so that it can be uniformly applied on the antistatic layer. The above solvent may be newly added.

In addition, as a method for forming the pressure-sensitive adhesive layer when producing the pressure-sensitive adhesive sheet of the present invention, a known method used for the production of pressure-sensitive adhesive tapes is used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

The pressure-sensitive adhesive sheet of the present invention is usually produced so that the thickness of the pressure-sensitive adhesive layer is 3 to 100 μm, preferably about 5 to 50 μm, more preferably about 10 to 30 μm. It is preferable for the thickness of the pressure-sensitive adhesive layer to be in the above-mentioned range since it is easy to obtain an appropriate balance between removability and pressure-sensitive adhesiveness.

In the pressure-sensitive adhesive sheet (surface protective film) of the present invention, a separator can be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface, if necessary.

The material constituting the separator includes paper and plastic film, but a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm, more preferably about 15 to 50 μm. It is preferable for it to be in the above-mentioned range since it is excellent in workability for bonding to the pressure-sensitive adhesive layer and workability for peeling from the pressure-sensitive adhesive layer. For the separator, if necessary, mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.

The antistatic pressure-sensitive adhesive sheet having an antistatic layer of the present invention has an antistatic layer having excellent antistatic properties, and therefore can be used in surface protection applications and electronic component manufacturing / shipping process applications. In the above-mentioned application, there is a possibility that adhesion of dust and dust due to static electricity and destruction of electronic parts due to static electricity may occur, which can be suppressed and useful.

The antistatic pressure-sensitive adhesive sheet having the antistatic layer of the present invention can be attached to an optical film and used as an optical film with an antistatic pressure-sensitive adhesive sheet. The surface of the optical film can be protected by sticking the antistatic pressure-sensitive adhesive sheet to the optical film, which is useful. In particular, the antistatic pressure-sensitive adhesive sheet can be used for plastic products and the like that are prone to generate static electricity. Therefore, in the technical fields related to optical and electronic parts where charging becomes a particularly serious problem, Useful.

Further, the antistatic layer of the present invention is formed on at least one surface of the base film, and an antistatic adhesive sheet having an adhesive layer formed on the antistatic layer is bonded (fixed) to the optical film. Therefore, it can be used as an optical film with an antistatic adhesive sheet. Adhesion of the antistatic adhesive sheet is useful because it can prevent the optical characteristics from being deteriorated due to damage to the optical film while preventing the antistatic layer from falling off. The adhesive layer is not required to have removability (light releasability) or the like as in the pressure-sensitive adhesive layer, and can be permanently bonded or bonded by bonding (fixing) to the optical film. Used for semi-permanent adhesion. In addition, a well-known thing can be used as said contact bonding layer (adhesive composition).

Hereinafter, some examples related to the present invention will be described. However, the present invention is not intended to be limited to the specific examples. In the following description, “part” and “%” are based on mass unless otherwise specified.

<Preparation of Reactive Ionic Liquid (DMAEA-TFSI)>
While stirring 100 parts of a 79% aqueous solution of 2- (acryloyloxy) ethyltrimethylammonium chloride (DMAEA-Q, manufactured by Kojin Co., Ltd.) in a 1 L three-necked flask, 114 parts of potassium bis (trifluoromethanesulfonyl) imide was ionized. What was diluted in 80 parts of exchange water was added under heating at 60 ° C. After 2 hours, the lower oil layer part separated into two layers was taken out, washed with ion-exchanged water three times, and then traced residual moisture was removed under reduced pressure to give 2- (acryloyloxy) ethyltrimethylammonium bis (trifluoromethane). Sulfonyl) imide (DMAEA-TFSI) was obtained.

<Preparation of Reactive Ionic Liquid (DMAPAA-TFSI)>
While exchanging 100 parts of a 75% aqueous solution of (3-acrylamidopropyl) trimethylammonium chloride (Kopasha DMAPAA-Q) in a 1 L three-necked flask, 116 parts of potassium bis (trifluoromethanesulfonyl) imide was ion-exchanged. Diluted in 80 parts of water was added under heating at 60 ° C. Two hours later, the lower oil layer part separated into two layers was taken out, washed with ion-exchanged water three times, and then a trace amount of residual water was removed under reduced pressure to obtain (3-acrylamidopropyl) trimethylammonium bis (trifluoromethanesulfonyl). ) Imide (DMAPAA-TFSI) was obtained.

<Preparation of (meth) acrylic polymer (A) for antistatic layer>
400 parts of methyl ethyl ketone, 40 parts of 2- (acryloyloxy) ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI), 55 parts of methyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, stirring blade, thermometer, nitrogen gas The solution was put into a four-necked flask equipped with an introduction tube, a cooler, and a dropping funnel. After stirring for 1 hour at 70 ° C. in a nitrogen atmosphere, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and reacted at 70 ° C. for 4 hours. The reaction was carried out at 4 ° C. for 4 hours. Thereafter, 0.1 part of 2,2′-azobisisobutyronitrile was added and reacted at 80 ° C. for 1 hour. Thereafter, 0.17 part of 2,2′-azobisisobutyronitrile was added at 70 ° C. and reacted for 4 hours, followed by reaction at 80 ° C. for 4 hours to obtain a (meth) acrylic polymer (antistatic layer) A) was obtained.

<Preparation of (meth) acrylic polymer (B) for antistatic layer>
400 parts of methyl ethyl ketone, 95 parts of 2- (acryloyloxy) ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI), 5 parts of 2-hydroxyethyl methacrylate, stirring blade, thermometer, nitrogen gas inlet tube, cooler Into a four-necked flask equipped with a dropping funnel. After stirring for 1 hour at 70 ° C. in a nitrogen atmosphere, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and reacted at 70 ° C. for 4 hours. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, 0.1 part of 2,2′-azobisisobutyronitrile was added and reacted at 80 ° C. for 3 hours. Thereafter, 0.2 part of 2,2′-azobisisobutyronitrile was added at 70 ° C. and reacted for 4 hours, followed by reaction at 80 ° C. for 4 hours to obtain a (meth) acrylic polymer (antistatic layer) B) was obtained.

<Preparation of (meth) acrylic polymer (C) for antistatic layer>
400 parts of methyl ethyl ketone, 95 parts of (3-acrylamidopropyl) trimethylammonium bis (trifluoromethanesulfonyl) imide (DMAPAA-TFSI), 5 parts of 2-hydroxyethyl methacrylate, stirring blade, thermometer, nitrogen gas inlet tube, condenser, It was put into a four-necked flask equipped with a dropping funnel. After stirring for 1 hour at 70 ° C. in a nitrogen atmosphere, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and reacted at 70 ° C. for 4 hours. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, 0.1 part of 2,2′-azobisisobutyronitrile was added and reacted at 80 ° C. for 3 hours. Thereafter, 0.2 part of 2,2′-azobisisobutyronitrile was added at 70 ° C. and reacted for 4 hours, followed by reaction at 80 ° C. for 4 hours to obtain a (meth) acrylic polymer ( C) was obtained.

<Preparation of (meth) acrylic polymer (D) for antistatic layer>
400 parts of methyl ethyl ketone, 85 parts of 2- (acryloyloxy) ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI), methoxy-terminated polyethylene glycol methacrylate (average number of moles of addition 23, Bremer PME-1000 manufactured by NOF Corporation) 10 parts and 5 parts of 2-hydroxyethyl methacrylate were charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, a cooler, and a dropping funnel. After stirring for 1 hour at 70 ° C. in a nitrogen atmosphere, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and reacted at 70 ° C. for 4 hours. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, 0.2 part of 2,2′-azobisisobutyronitrile was added and reacted at 80 ° C. for 3 hours. Thereafter, 0.2 part of 2,2′-azobisisobutyronitrile was added at 70 ° C. and reacted for 4 hours, followed by reaction at 80 ° C. for 4 hours to obtain a (meth) acrylic polymer for the antistatic layer ( D) was obtained.

<Preparation of (meth) acrylic polymer (E) for antistatic layer>
400 parts of methyl ethyl ketone, 65 parts of 2- (acryloyloxy) ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI), methoxy-terminated polyethylene glycol methacrylate (average number of moles of addition 23, Bremer PME-1000 manufactured by NOF Corporation) 30 parts and 5 parts of 2-hydroxyethyl methacrylate were charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, a cooler, and a dropping funnel. After stirring for 1 hour at 70 ° C. in a nitrogen atmosphere, 0.2 part of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and reacted at 70 ° C. for 4 hours. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, 0.2 part of 2,2′-azobisisobutyronitrile was added 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.

<Adjustment of (meth) acrylic polymer (F) for adhesive layer>
In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, condenser, and dropping funnel, 200 parts of 2-ethylhexyl acrylate, 8 parts of 2-hydroxyethyl acrylate, 2,2′-azo as a polymerization initiator Charge 0.4 parts of bisisobutyronitrile and 312 parts of ethyl acetate, introduce nitrogen gas with gentle stirring, and perform a polymerization reaction for 6 hours while maintaining the liquid temperature in the flask at around 65 ° C. A (meth) acrylic polymer (F) solution (40% by mass) for the layer was prepared. The glass transition temperature (Tg) calculated from the Fox formula of the obtained (meth) acrylic polymer (F) was −68 ° C., and the weight average molecular weight was 550,000.

<Preparation of pressure-sensitive adhesive composition>
To 500 parts (100 parts of polymer) of a solution obtained by diluting the (meth) acrylic polymer (F) solution (40% by weight) for the pressure-sensitive adhesive layer to 20% by weight with ethyl acetate, Coronate L (trimethylolpropane) was used as a crosslinking agent. / Solid part of tolylene diisocyanate trimer adduct 75 mass% ethyl acetate solution, manufactured by Nippon Polyurethane Industry Co., Ltd.) 5.3 parts, dioctyltin dilaurate (1 mass% ethyl acetate solution) 3.0 parts as a crosslinking catalyst In addition, an acrylic pressure-sensitive adhesive solution (1) was prepared by mixing and stirring at 25 ° C. for about 5 minutes.

[Example 1]
(Preparation of antistatic agent solution)
To 2381 parts (100 parts of polymer) of a solution obtained by diluting the above (meth) acrylic polymer (A) solution (20% by weight) to 4.2% by weight with methyl ethyl ketone, Coronate L (trimethylolpropane / tolylene diisocyanate) was used as a crosslinking agent. Trimer adduct solid content 75 mass% ethyl acetate solution, manufactured by Nippon Polyurethane Industry Co., Ltd. 4.0 parts, conductive agent DMAEA-TFSI 5.0 parts, dilauryl dilaurate (1 mass% ethyl acetate) as crosslinking catalyst (Solution) 3.0 parts were added and mixed and stirred at 25 ° C. for about 5 minutes to prepare an antistatic agent solution (1).

(Preparation of antistatic film)
The antistatic agent solution (1) was applied onto a polyethylene terephthalate (PET) film (thickness 38 μm, manufactured by Toray Industries Inc., Lumirror S10) using a Mayer bar, and the solvent was removed by drying at 130 ° C. for 1 minute. Then, an antistatic layer (thickness 0.5 μm) was formed, and an antistatic treatment film (1) was produced.

(Preparation of adhesive sheet)
The acrylic pressure-sensitive adhesive solution (1) was applied to the antistatic treatment surface of the antistatic treatment film (1) and heated at 130 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 μm.
Next, a silicone-treated surface of a polyethylene terephthalate film (separator) having a thickness of 25 μm, which was silicone-treated on one side, was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive 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 DMAEA-TFSI.

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

(Preparation of adhesive sheet)
A pressure-sensitive 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 DMAEA-TFSI.

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

(Preparation of adhesive sheet)
A pressure-sensitive 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 (isocyanurate of hexamethylene diisocyanate) instead of 4.0 parts of the above coronate L (trimethylolpropane / tolylene diisocyanate trimer adduct solid content 75 mass% ethyl acetate solution, manufactured by Nippon Polyurethane Industry Co., Ltd.) An antistatic agent solution (4) was prepared in the same manner as in Example 1, except that 3.0 parts of Nippon Polyurethane Industry Co., Ltd.) was used and 5.0 parts of DMAEA-TFSI was not used as the conductive agent.

(Preparation of antistatic 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 in place of the antistatic agent solution (1).

(Preparation of adhesive sheet)
A pressure-sensitive 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)
Example 1 was used except that the (meth) acrylic polymer (B) was used instead of the (meth) acrylic polymer (A), and 5.0 parts of DMAEA-TFSI was not used as the conductive agent. Thus, an antistatic agent solution (5) was prepared.

(Preparation of antistatic 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 in place of the antistatic agent solution (1).

(Preparation of adhesive sheet)
A pressure-sensitive 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)
Example 1 was used except that the (meth) acrylic polymer (C) was used in place of the (meth) acrylic polymer (A) and 5.0 parts of DMAEA-TFSI was not used as the conductive agent. Thus, an antistatic agent solution (6) was prepared.

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

(Preparation of adhesive sheet)
A pressure-sensitive 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)
Instead of the (meth) acrylic polymer (A), the (meth) acrylic polymer (C) is used, and as a conductive agent, instead of 5.0 parts of DMAEA-TFSI, N-butyl-3-methylpyridinium. An antistatic agent solution (7) was prepared in the same manner as in Example 1 except that 20.0 parts of bis (trifluoromethanesulfonyl) imide (BMP-TFSI in Table 1) was used.

(Preparation of antistatic 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 in place of the antistatic agent solution (1).

(Preparation of adhesive sheet)
A pressure-sensitive 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)
The (meth) acrylic polymer (C) was used in place of the (meth) acrylic polymer (A), and DMAPAA-TFSI 20.0 parts was used in place of 5.0 parts of DMAEA-TFSI as a conductive agent. Except for this, an antistatic agent solution (8) was prepared in the same manner as in Example 1.

(Preparation of antistatic 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 in place of the antistatic agent solution (1).

(Preparation of adhesive sheet)
A pressure-sensitive 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 as Example 1 except that the (meth) acrylic polymer (D) was used instead of the (meth) acrylic polymer (A) and that 5.0 parts of DMAEA-TFSI was not used as the conductive agent. Thus, an antistatic agent solution (9) was prepared.

(Preparation of antistatic film)
In place of the antistatic agent solution (1), the antistatic agent solution (9) is used and applied onto a polyethylene terephthalate (PET) film (thickness 38 μm, Lumirror S10 manufactured by Toray Industries, Inc.) using a Meyer bar. The solvent was removed by drying at 130 ° C. for 1 minute to form an antistatic layer (thickness 0.1 μm), and an antistatic treatment film (9) was produced.

(Preparation of adhesive sheet)
A pressure-sensitive 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)
Example 1 was used except that the (meth) acrylic polymer (E) was used instead of the (meth) acrylic polymer (A), and 5.0 parts of DMAEA-TFSI was not used as the conductive agent. Thus, an antistatic agent solution (10) was prepared.

(Preparation of antistatic film)
In place of the antistatic agent solution (1), the antistatic agent solution (10) is used and applied onto a polyethylene terephthalate (PET) film (thickness 38 μm, Lumirror S10 manufactured by Toray Industries, Inc.) using a Meyer bar. The solvent was removed by drying at 130 ° C. for 1 minute to form an antistatic layer (thickness of 0.25 μm), and an antistatic treatment film (10) was produced.

(Preparation of adhesive sheet)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the antistatic treatment film (10) was used in place of the antistatic treatment film (1).

Example 11
(Preparation of antistatic film)
In place of the antistatic agent solution (1), the antistatic agent solution (10) is used and applied onto a polyethylene terephthalate (PET) film (thickness 38 μm, Lumirror S10 manufactured by Toray Industries, Inc.) using a Mayer bar, The solvent was removed by drying at 130 ° C. for 1 minute to form an antistatic layer (thickness 0.1 μm), and an antistatic treatment film (11) was produced.

(Preparation of adhesive sheet)
A pressure-sensitive 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)
An acrylic resin copolymerized with quaternary ammonium chloride (manufactured by Konishi Co., Ltd., Bondip PA-200 (32 mass%), ion conductive polymer) is 2.1 mass in a mixed solvent of isopropyl alcohol: soft water = 2: 1. % Adjusted. To 100 parts of this solution, 25 parts of epoxy resin (Bondip PA-100 (8.2% by mass), manufactured by Konishi Co., Ltd.) was added as a curing agent, and the mixture was stirred at 25 ° C. for about 5 minutes. A 5 mass% antistatic agent solution (11) was prepared.

(Preparation of antistatic film)
Instead of the antistatic agent solution (1), the antistatic agent solution (11) is used, and instead of a polyethylene terephthalate (PET) film (thickness 38 μm, Lumirror S10 manufactured by Toray Industries, Inc.), corona-treated polyethylene terephthalate An antistatic film (12) was produced in the same manner as in Example 1 except that a (PET) film (thickness 38 μm, manufactured by Mitsubishi Plastics, Diafoil T100C) was used.

(Preparation of adhesive sheet)
A pressure-sensitive 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]
(Preparation of antistatic 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).

(Preparation of adhesive sheet)
A pressure-sensitive 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 was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows. In addition, the weight average molecular weight was calculated | required in the polymethylmethacrylate 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 + 10 mM sodium trifluoroacetate Flow rate: 0.3 ml / min
Measurement temperature: 40 ° C
column:
Sample column; TSKgel SuperAWM-H (6.0 mm ID × 15 cm) (2 pieces)
Detector: Differential refractometer (RI)

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

Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
Sample injection volume: 10 μl
Eluent: THF
Flow rate: 0.6 ml / min
Measurement temperature: 40 ° C
column:
Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1 piece)
Detector: Differential refractometer (RI)

<Low speed peel test: 180 ° peel adhesion>
The pressure-sensitive adhesive sheet according to each Example and Comparative Example was cut to a size of 25 mm in width and 100 mm in length, and after peeling the release liner, a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, width: 70 mm, length: 100 mm) was pressure-bonded with a hand roller and then laminated under pressure-bonding conditions of 0.25 MPa and 0.3 m / min to prepare an evaluation sample (an optical film with an antistatic pressure-sensitive adhesive sheet).

After the lamination, after leaving for 30 minutes in an environment of 23 ° C. × 50% RH, the opposite surface of the triacetyl cellulose polarizing plate was fixed to an acrylic plate with a double-sided adhesive tape, and the adhesive sheet was The adhesive strength when one end was peeled at a tensile speed of 0.3 m / min (low speed peeling) and a peeling angle of 180 ° was measured. The measurement was performed in an environment of 23 ° C. × 50% RH. As the adhesive strength at the time of low-speed peeling, from the viewpoint of suppressing the lifting and peeling of the adhesive tape, those having a thickness of 0.07 N / 25 mm or more were considered good, and those having a thickness of less than 0.07 N / 25 mm were judged as bad. The measurement results are shown in Table 2.

<High speed peel test: 180 degree peeling adhesive strength>
The pressure-sensitive adhesive sheet according to each Example and Comparative Example was cut to a size of 25 mm in width and 100 mm in length, and after peeling the release liner, a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, width: 70 mm, length: 100 mm) was pressure-bonded with a hand roller and then laminated under pressure-bonding conditions of 0.25 MPa and 0.3 m / min to prepare an evaluation sample (an optical film with an antistatic pressure-sensitive adhesive sheet).

After the above lamination, after standing for 30 minutes in an environment of 23 ° C. × 50% RH, the opposite surface of the triacetyl cellulose polarizing plate is fixed to an acrylic plate with a double-sided adhesive tape as shown in FIG. The adhesive strength was measured when one end of the sheet was peeled at a tensile speed of 30 m / min (high speed peeling) and a peeling angle of 180 °. The measurement was performed in an environment of 23 ° C. × 50% RH. Those having an adhesive strength of less than 6.0 N / 25 mm during high-speed peeling were considered good, and those having an adhesive strength of 6.0 N / 25 mm or more were considered defective. The measurement results are shown in Table 2.

<Measurement of peeling voltage>
As shown in FIG. 2, the pressure-sensitive adhesive sheet 2 according to each example and comparative example was cut into a size of 70 mm in width and 130 mm in length, the separator was peeled off, and then the acrylic plate 4 (Mitsubishi Rayon Co., Ltd.) was previously neutralized. Manufactured, acrylite, thickness: 1 mm, width: 70 mm, length: 100 mm) polarizing plate 3 (manufactured by Nitto Denko Corporation, SEG1425DU, width: 70 mm, length: 100 mm), one end on the surface is 30 mm It crimped | bonded with the hand roller so that it might protrude.
After being left for one day in an environment of 23 ° C. × 50% RH, the sample is set at a predetermined position on the sample fixing base 5 as shown in FIG. One end protruding 30 mm was fixed to an automatic winder, and peeled so that a peeling angle was 150 ° and a tensile speed was 30 m / min (high speed peeling). The potential of the polarizing plate surface generated at this time was measured with a potential measuring device 1 (KSD-0103, manufactured by Kasuga Denki Co., Ltd.), which was fixed at a predetermined position, and used as the value of the stripping voltage. The measurement was performed in an environment of 23 ° C. × 50% RH. In addition, as a peeling band voltage, it is preferable that an absolute value is 1.0 kV or less, and it is more preferable that it is 0.5 kV or less. Within this range, dust collection due to static electricity and static electricity failure of electronic components can be prevented, which is useful.

<Evaluation of contamination>
After the measurement of the stripping voltage, the peeled adhesive sheet was again attached by hand so that bubbles were mixed between the measured polarizing plate and an evaluation sample was prepared.

After the evaluation sample was allowed to stand at room temperature (23 ° C.) for 1 week, the pressure-sensitive adhesive sheet was peeled off from the adherend by hand, and the state of contamination of the adherend surface at that time was visually observed. The evaluation criteria are as follows.
・ If no contamination was found: ○
・ If contamination is found: ×

<Measurement of surface resistivity (normal state)>
The pressure-sensitive adhesive sheets according to the examples and comparative examples were allowed to stand in an environment of 23 ° C. × 50% RH for 2 hours, and then the separator was peeled off. , Hiresta UP MCP-HT450 type). The applied voltage was 100 V, and the application time was 30 seconds. The surface resistivity is preferably 10 ¹³ or less, and more preferably 10 ¹² or less. Within this range, dust collection due to static electricity and static electricity failure of electronic components can be prevented, which is useful.

<Measurement of surface resistivity (heat resistance)>
The separator of the pressure-sensitive adhesive sheet according to each example and comparative example was peeled off and allowed to stand at 170 ° C. for 30 minutes and then left in an environment of 23 ° C. × 50% RH for 2 hours to determine the surface resistivity of the pressure-sensitive adhesive surface. It was measured with a rate measuring device (manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450 type). The applied voltage was 100 V, and the application time was 30 seconds. The surface resistivity is preferably 10 ¹³ or less, and more preferably 10 ¹² or less.

<Throwing property>
The pressure-sensitive adhesive sheet according to each Example and Comparative Example was cut to a size of 25 mm in width and 100 mm in length, and after peeling the release liner, a triacetyl cellulose polarizing plate (manufactured by Nitto Denko Corporation, SEG1425DU, width: 70 mm, length: 100 mm) was pressure-bonded with a hand roller and then laminated under pressure-bonding conditions of 0.25 MPa and 0.3 m / min to prepare an evaluation sample (an optical film with an antistatic pressure-sensitive adhesive sheet). After the above lamination, after leaving for 30 minutes in an environment of 23 ° C. × 50% RH, the opposite surface of the triacetyl cellulose polarizing plate was fixed to an acrylic plate with a double-sided adhesive tape, and the adhesive sheet was When one end is peeled off at a tensile speed of 30 m / min (high-speed peeling) and a peeling angle of 180 °, whether or not the adhesive remains on the surface of the triacetyl cellulose polarizing plate (adhesive residue) is visually observed. It was judged.
When there is no adhesive residue: ○
When adhesive residue occurs: ×

<Transparency: Haze>
After the adhesive sheet according to each example and comparative example was cut to a size of 50 mm in width and 50 mm in length, the release liner was peeled off, and haze was measured with a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.). A sample having a haze of less than 10% was considered good, and a sample having a haze of 10% or more was judged defective. The measurement results are shown in Table 2.

Note) The number of parts in Table 1 indicates the solid content. In Comparative Examples 1 and 2, the number of copies is not shown in Table 1. Further, “application thickness” in Table 1 means “thickness when it becomes an antistatic layer after drying”.

 

From the results of Table 2, in all of Examples 1 to 11 using the antistatic pressure-sensitive adhesive sheet prepared according to the present invention, the surface resistivity after heating and heating was 10 ¹³ or less, and the stripping voltage was It was within ± 1.0 kV, and it was confirmed that the antistatic property was satisfied. Further, the haze value was 10% or less, which satisfied transparency, and further satisfied low contamination and anchoring properties. It was also confirmed that the adhesive strength (low-speed peeling / high-speed peeling) that can be used as a pressure-sensitive adhesive sheet for re-peeling (surface protection use, etc.) was maintained.

On the other hand, in Comparative Example 1, an antistatic pressure-sensitive adhesive sheet formed on a corona-treated base film with an antistatic layer using an antistatic agent made of an acrylic resin copolymerized with quaternary ammonium chloride. was produced, peeling electrification voltage exceeds ± 1.0 kV, the surface resistivity after heating (above the detection limit) of greater than 10 ¹³ resulted. Moreover, in Comparative Example 2, when the corona treatment was not performed on the base film as compared with Comparative Example 1, it was confirmed that the anchoring property was insufficient, and an adhesive sheet that can be evaluated was obtained. could not. Therefore, neither of Comparative Examples 1 and 2 can be obtained that satisfies all of antistatic properties (peeling voltage, surface resistivity), adhesive properties, low contamination, anchoring properties, and transparency. It was confirmed.

From the above results, the antistatic property in which an antistatic layer formed from an antistatic agent composition containing a (meth) acrylic polymer containing a reactive (polymerizable) ionic liquid as a monomer unit is provided as an intermediate layer. In any evaluation, the adhesive sheet was a good result, and it was confirmed that the outstanding effect which is not in the past can be acquired.

DESCRIPTION OF SYMBOLS 1 Electric potential measuring device 2 Adhesive sheet 3 Polarizing plate 4 Acrylic board 5 Fixing stand 10 Antistatic adhesive sheet (adhesive sheet)
11 Separator 12 Adhesive Layer 13 Antistatic Layer 14 Base Film

Claims (14)

1. An antistatic layer formed of an antistatic agent composition containing a (meth) acrylic polymer containing a reactive ionic liquid as a monomer unit and a crosslinking agent.
2. 2. The antistatic layer according to claim 1, wherein the reactive ionic liquid is a reactive ionic liquid represented by any one of the following general formulas (1) to (4).
   CH ₂ = C (R ¹ ) COOZX ⁺ Y ⁻ (1)
   CH ₂ = C (R ¹ ) CONHZX ⁺ Y ⁻ (2)
   CH ₂ = C (R ¹ ) COOX ⁺ Y ⁻ (3)
   CH ₂ = C (R ¹ ) CONHX ⁺ Y ⁻ (4)
   [In the formulas (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, and Y ⁻ is an anion. Z represents an alkylene group having 1 to 3 carbon atoms. ]
3. The antistatic layer according to claim 2, wherein the cation portion is a quaternary ammonium group.
4. The antistatic layer according to claim 2 or 3, wherein the anion is a fluorine-containing anion.
5. 2. The (meth) acrylic polymer contains, as a monomer unit, an oxyalkylene group-containing monomer having an average added mole number of oxyalkylene units represented by the following general formula (5) of 3 to 100. 5. The antistatic layer according to any one of 1 to 4.
   CH ₂ ═C (R ₁ ) —COO— (C _m H _2m O) _n — (C _p H _2p O) _q —R ₂ (5)
   [In the formula (5), R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a monovalent organic group, m and p are integers of 2 to 4, and n and q are 0 or 2 to 100 It is an integer, and n and q are not 0 simultaneously. ]
6. 6. The antistatic layer according to claim 1, wherein the (meth) acrylic polymer contains a hydroxyl group-containing (meth) acrylic monomer as a monomer unit.
7. The antistatic layer according to any one of claims 1 to 6, wherein the crosslinking agent is an isocyanate-based crosslinking agent.
8. The antistatic layer according to any one of claims 1 to 7, wherein the antistatic agent composition contains a conductive agent.
9. 9. An antistatic pressure-sensitive adhesive sheet, wherein the antistatic layer according to any one of claims 1 to 8 is formed on at least one surface of a base film, and an adhesive layer is provided on the antistatic layer. .
10. The antistatic pressure-sensitive adhesive sheet according to claim 9, wherein the base film is a plastic film.
11. The antistatic pressure-sensitive adhesive sheet according to claim 9 or 10, which is used for surface protection.
12. The antistatic pressure-sensitive adhesive sheet according to claim 9 or 10, which is used in an electronic component manufacturing / shipping process.
13. An optical film with an antistatic pressure-sensitive adhesive sheet, wherein the antistatic pressure-sensitive adhesive sheet according to claim 11 is attached to an optical film.
14. The antistatic layer according to any one of claims 1 to 8 is formed on at least one surface of a base film, an adhesive layer is formed on the antistatic layer, and the adhesive layer is formed on an optical film. An optical film with an antistatic adhesive sheet, which is bonded.

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