KR102132619B1 - Antistatic layer, antistatic adhesive sheet, and optical film - Google Patents

Abstract

Excellent antistatic property, heat resistance, transparency, and low contamination, and in particular, an antistatic layer capable of suppressing adhesion of dust or dust, destruction of electronic components due to static electricity, and an antistatic adhesive sheet and optics having the antistatic layer Provide a film. An antistatic layer comprising a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit and an antistatic agent composition containing a crosslinking agent.

Description

Antistatic layer, antistatic adhesive sheet and optical film {ANTISTATIC LAYER, ANTISTATIC ADHESIVE SHEET, AND OPTICAL FILM}

The present invention relates to an antistatic layer, an antistatic 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, antistatic layer capable of suppressing adhesion of particles or dust, destruction of electronic components due to static electricity, and the antistatic layer. The present invention relates to an antistatic adhesive sheet and an optical film.

Products with high insulation resistance, such as plastic, have the property of not accumulating (charged) static electricity generated during friction between plastics or other objects, or when peeling off after adhesion. For this reason, adsorption of dust or dust in the air occurs, adhesion between papers or films occurs, or in addition to the discomfort caused by electric shock, malfunction of electronics, electrical equipment, OA equipment, etc. causes static electricity malfunction or memory destruction. There is a risk of causing various static electricity disturbances such as. In order to avoid such obstacles, it is necessary to control the surface resistivity of the object to be covered, and for this purpose, an antistatic agent is usually used.

In general, as an antistatic method of a plastic product, a method of adding an antistatic agent internally (overlaying) and a method of applying it to a surface are known. In addition, the pressure-sensitive adhesive sheet (adhesive tape), surface protection film, or the like, which requires antistatic properties, forms an adhesive layer on one side of the plastic base film to which an antistatic agent is added internally, or an adhesive layer on one side of the plastic base film. There are known methods of forming, forming an antistatic layer on the opposite side, or adding an antistatic agent to the pressure-sensitive adhesive layer.

However, the plastic base film in which the antistatic agent is added internally may be damaged in its original properties, and when an antistatic layer is provided on the opposite side of the pressure-sensitive adhesive layer, on the antistatic layer, for example, an easily printable layer However, in the case of forming a hard coating layer, there is a concern that adhesion may be deteriorated. In addition, there is a possibility that the antistatic layer is removed due to friction, grazing, and immersion, 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 may bleed out to the adherend (protective body) side in contact with the pressure-sensitive adhesive layer, contaminating the adherend or deteriorating the adhesion properties. Yes (Patent Document 1).

In addition, as a method of imparting antistatic properties to an adhesive sheet or the like, a method of providing an intermediate layer (antistatic layer) having antistatic properties between a base film and an adhesive layer is known (Patent Documents 2 and 3). Since the antistatic layer is an intermediate layer, it is possible to solve the problem that the antistatic agent is eliminated or bleeds out 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 serving as the antistatic agent is a chlorine ion, there is a concern that this may affect the heat resistance and cause corrosion.

Japanese Patent Publication No. Hei 6-128539 Japanese Patent Publication No. 2007-31534 Japanese Patent Publication No. Hei 10-55894

Therefore, the object of the present invention is to solve the problems in the conventional antistatic layer or antistatic adhesive sheet, excellent antistatic property, heat resistance, transparency and low fouling property, in particular adhesion of dust or dust, Disclosed is an antistatic layer capable of suppressing destruction of electronic components due to static electricity, an antistatic adhesive sheet having the antistatic layer, and an optical film.

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

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

^{_{CH 2 = C (R 1)}} COOZX + Y - (1)

^{_{CH 2 = C (R 1)}} CONHZX + Y - (2)

^{_{CH 2 = C (R 1)}} COOX + Y - (3)

^{_{CH 2 = C (R 1)}} CONHX + Y - (4)

In 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, it is preferable that the cation portion is a quaternary ammonium group.

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

In the antistatic layer of the present invention, it is preferable that the (meth)acrylic polymer contains an oxyalkylene group-containing monomer having an average added mole number of 3 to 100 of the oxyalkylene unit represented by the following formula (5) as a monomer unit.

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

[In formula (5), R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a (1) valent organic group, m and p are integers from 2 to 4, n and q are 0 or integers from 2 to 100, , n and q are never zero at the same time]

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

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

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

It is preferable that the antistatic adhesive sheet of this invention forms the said antistatic layer on at least one side of a base film, and has an adhesive layer on the said antistatic layer.

In the antistatic adhesive sheet of the present invention, it is preferable that the base film is a plastic film.

It is preferable to use the antistatic adhesive sheet of this invention for surface protection use.

It is preferable to use the antistatic adhesive sheet of this invention in an electronic component manufacturing and shipment process.

It is preferable that the optical film with an antistatic pressure-sensitive adhesive sheet of the present invention adheres the antistatic pressure-sensitive adhesive sheet to an optical film.

The optical film with the antistatic adhesive sheet of the present invention preferably forms the antistatic layer on at least one side of the base film, forms an adhesive layer on the antistatic layer, and adheres the adhesive layer to the optical film. Do.

1 is a schematic view illustrating the configuration of an antistatic adhesive sheet.
2 is a schematic view for explaining a peeling high voltage test.

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

<Antistatic adhesive sheet>

It is preferable that the antistatic adhesive sheet of this invention forms an antistatic layer on at least one side of a base film, and has an adhesive layer on the said antistatic layer. Specifically, as the antistatic adhesive sheet, a typical configuration example is schematically illustrated in FIG. 1. Here, the antistatic adhesive sheet 10 includes a base film (eg, a polyester film) 14, an antistatic layer 13 provided on one side thereof, and an adhesive layer on the antistatic layer 13 ( And 12). The pressure-sensitive adhesive sheet 10 is used by attaching the pressure-sensitive adhesive layer 12 to an adherend (protection object, for example, the surface of an optical component such as a polarizing plate). The adhesive sheet 10 before use (i.e., before adhesion to the adherend) has at least one surface of the pressure-sensitive adhesive layer 12 (adhering surface to the adherend), as shown in FIG. 12) The side may exist in the form protected by the separator 11 which is a peeling surface. Hereinafter, the structure of the antistatic adhesive sheet (hereinafter sometimes simply referred to as "adhesive sheet") will be described in detail.

<Antistatic composition and antistatic layer>

The antistatic layer of the present invention is characterized by being formed of a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit, and an antistatic composition containing a crosslinking agent. In addition, (meth)acrylic-type polymer in this invention means an acryl-type polymer and/or methacryl-type polymer, and (meth)acrylate means 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. In addition, the "reactive ionic liquid" in the present invention is an ionic liquid having a functional group having a polymerizable (reactive double bond) in a cation portion constituting the ionic liquid, and/or an anion portion (either or both). It is a liquid (liquid phase) anywhere in the range of 0 to 150°C, and it is a non-volatile molten salt and means having transparency. Moreover, a vinyl group, an allyl group, a (meth)acryloyl group etc. are mentioned as a functional group which has the said polymerizability. Especially, from a viewpoint of copolymerization, a (meth)acryloyl group and a vinyl group are preferable, and a (meth)acryloyl group is especially preferable.

The cation portion of the reactive ionic liquid can be used without particular limitation, but quaternary ammonium cations, imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidinium cations, quaternary phosphonium cations, trialkyls Sulfonium cations, pyrrole cations, pyrazolium cations, guanidium cations, and the like, among others, quaternary ammonium cations, imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidinium cations, agents It is more preferable to use a quaternary phosphonium cation or a trialkylsulfonium cation.

In addition, as in the anion portion constituting the reactive ionic liquid, the _{^{anion, SCN -, BF 4 -,}} PF 6 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 _{^{SO 3 -, (FSO 2)}} 2 N -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, HF 2 _{^{-, (CN) 2 N -}} , C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N -, ^{_{B (CN) 4 -, C}} (CN) 3 -, N (CN) 2 -, CH 3 OSO 3 -, C 2 H 5 OSO 3 -, C 4 H 9 OSO 3 -, C 6 H 13 OSO 3 - ^{_{, C 8 H 17 OSO 3 -}} , p- toluenesulfonate anion, a 2- (2-methoxyethyl) ethyl sulfate _{anion, (C 2 F 5) 3} PF 3 - , and the like, in particular, a fluorine atom The anion component (fluorine-containing anion) contained 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 chlorine ions, bromine ions, and the like as anions because they have corrosive properties.

As the above-mentioned reactive ionic liquid, a suitable one is selected from a combination of the above-mentioned cation portion and anion portion, and specifically, various ionic liquids shown below are exemplified.

As an imidazolium cationic ion liquid,

1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, 1-alkyl-3-vinylimidazolium heptafluorobutyrate, 1-alkyl-3 -Vinylimidazolium trifluoromethanesulfonate, 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-vinylimidazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-alkyl-3-vinylimidazolium dicyanamide, 1- 1-alkyl-3-vinylimidazolium cation-containing ionic liquids such as alkyl-3-vinylimidazolium thiocyanate,

1,2-dialkyl-3-vinylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1, 1,2-dialkyl-3-vinylimidazolium cation-containing ionic liquids such as 2-dialkyl-3-vinylimidazolium dicyanamide and 1,2-dialkyl-3-vinylimidazolium thiocyanate ,

2-alkyl-1,3-divinylimidazolium bis(fluorosulfonyl)imide, 2-alkyl-1,3-divinylimidazolium bis(trifluoromethanesulfonyl)imide, 2- 2-alkyl-1,3-divinylimidazolium cation-containing ionic liquids such as alkyl-1,3-divinylimidazolium dicyanamide and 2-alkyl-1,3-divinylimidazolium thiocyanate ,

1-vinylimidazolium bis(fluorosulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium dicyanamide, 1-vinylimidazolium Ionic liquids containing 1-vinylimidazolium cations such as thiocyanate,

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)acrylic Loyloxyalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-( (Meth)acryloyloxyalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium tris(trifluoromethanesulfonyl)imide , 1-alkyl-3-(meth)acryloyloxyalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium(trifluoromethanesulfonyl)trifluoro 1-alkyl such as acetamide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium thiocyanate, etc. Ionic liquid containing -3-(meth)acryloyloxyalkylimidazolium cation,

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)acrylic Roylaminoalkylimidazolium perfluorobutanesulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-( (Meth)acryloylaminoalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium tris(trifluoromethanesulfonyl)imide , 1-alkyl-3-(meth)acryloylaminoalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium(trifluoromethanesulfonyl)trifluoro 1-alkyl such as roacetamide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium thiocyanate, etc. Ionic liquid containing -3-(meth)acryloylaminoalkylimidazolium cation,

1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium Bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acrylo 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium cation-containing ionic liquids such as monooxyimidazolium thiocyanate,

1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium Bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acrylo 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium cation-containing ionic liquid such as monoaminoalkylimidazolium thiocyanate,

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)acrylo 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium cation-containing ionic liquids such as monooxyimidazolium thiocyanate,

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)acrylo 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium cation-containing ionic liquid such as monoaminoimidazolium thiocyanate,

1-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1- Ion liquid containing 1-(meth)acryloyloxyalkylimidazolium cation, such as (meth)acryloyloxyalkylimidazolium dicyanamide, 1-(meth)acryloyloxyalkylimidazolium thiocyanate ,

1-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 1-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1- Ion liquid containing 1-(meth)acryloylaminoalkylimidazolium cation, such as (meth)acryloylaminoalkylimidazolium dicyanamide, 1-(meth)acryloylaminoalkylimidazolium thiocyanate Can be mentioned.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

As a pyridinium cation-based ionic liquid,

1-vinylpyridinium bis(fluorosulfonyl)imide, 1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 1-vinylpyridinium disyanamide, 1-vinylpyridinium thiocyanate, etc. Ionic liquid containing 1-vinylpyridinium cation,

1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 1-(meth )Ionic liquid containing 1-(meth)acryloyloxyalkylpyridinium cations, such as acryloyloxyalkylpyridinium dicyanamide, 1-(meth)acryloyloxyalkylpyridinium thiocyanate,

1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 1-(meth )Ionic liquid containing 1-(meth)acryloylaminoalkylpyridinium cation, such as acryloylaminoalkylpyridinium dicyanamide, 1-(meth)acryloylaminoalkylpyridinium thiocyanate,

2-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-vinylpyridinium dish 2-alkyl-1-vinylpyridinium cation-containing ionic liquids such as anamide and 2-alkyl-1-vinylpyridinium thiocyanate,

2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl) ) 2-alkyl-1 such as imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate, etc. -(Meth)acryloyloxyalkylpyridinium cation-containing ionic liquid,

2-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl) ) 2-alkyl-1 such as imide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. -(Meth)acryloylaminoalkylpyridinium cation-containing ionic liquid,

3-alkyl-1-vinylpyridiniumbis(fluorosulfonyl)imide, 3-alkyl-1-vinylpyridiniumbis(trifluoromethanesulfonyl)imide, 3-alkyl-1-vinylpyridiniumdisc 3-alkyl-1-vinylpyridinium cation-containing ionic liquids such as anamide and 3-alkyl-1-vinylpyridinium thiocyanate,

3-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl) ) 3-alkyl-1 such as imide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate, and the like. -(Meth)acryloyloxyalkylpyridinium cation-containing ionic liquid,

3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl) )Alkyl, such as imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. -(Meth)acryloylaminoalkylpyridinium cation-containing ionic liquid,

4-alkyl-1-vinylpyridiniumbis(fluorosulfonyl)imide, 4-alkyl-1-vinylpyridiniumbis(trifluoromethanesulfonyl)imide, 4-alkyl-1-vinylpyridiniumdisc Ion liquid containing 4-alkyl-1-vinylpyridinium cation, such as anamide and 4-alkyl-1-vinylpyridinium thiocyanate,

4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl) ) 4-alkyl-1 such as imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate, etc. -(Meth)acryloyloxyalkylpyridinium cation-containing ionic liquid,

4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl) ) 4-alkyl-1 such as imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. And ionic liquids containing -(meth)acryloylaminoalkylpyridinium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

As a piperidinium cation-based ionic liquid,

1-alkyl-1-vinylalkylpiperidiniumbis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-alkyl-1- 1-alkyl-1-vinylalkylpiperidinium cation-containing ionic liquids such as vinylalkylpiperidiniumdicyanamide and 1-alkyl-1-vinylalkylpiperidiniumthiocyanate,

1-alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(trifluoromethane) Sulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium disyanamide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidiniumthiocyanate, etc. 1 Ionic liquid containing an alkyl-1-(meth)acryloyloxyalkylpiperidinium cation,

1-alkyl-1-(meth)acryloylaminoalkylpiperidiniumbis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidiniumbis(trifluoromethane) Sulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium disyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidiniumthiocyanate, etc. 1 And ionic liquids containing -alkyl-1-(meth)acryloylaminoalkylpiperidinium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

As a pyrrolidinium cation-based ionic liquid,

1-alkyl-1-vinylalkylpyrrolidiniumbis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-alkyl-1- 1-alkyl-1-vinylalkylpyrrolidinium cation-containing ionic liquids such as vinylalkylpyrrolidiniumdicyanamide and 1-alkyl-1-vinylalkylpyrrolidiniumthiocyanate,

1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(trifluoromethane) Sulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium disyanamide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidiniumthiocyanate, and the like 1 -Alkyl-1-(meth)acryloyloxyalkylpyrrolidinium cation-containing ionic liquid,

1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(trifluoromethane) Sulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium disyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidiniumthiocyanate, and the like 1 And ionic liquids containing -alkyl-1-(meth)acryloylaminoalkylpyrrolidinium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

As a trialkylsulfonium cationic ion liquid,

Dialkyl (vinyl) sulfonium bis (fluorosulfonyl) imide, dialkyl (vinyl) sulfonium bis (trifluoromethanesulfonyl) imide, dialkyl (vinyl) sulfonium dicyanamide, dialkyl ( Ionic liquids containing dialkyl (vinyl) sulfonium cations such as vinyl) sulfonium thiocyanate,

Dialkyl((meth)acryloyloxyalkyl)sulfonium bis(fluorosulfonyl)imide, dialkyl((meth)acryloyloxyalkyl)sulfonium bis(trifluoromethanesulfonyl)imide, Dialkyl ((meth)acryloyloxyalkyl) sulfides such as dialkyl ((meth)acryloyloxyalkyl) sulfonium dicyanamide, dialkyl ((meth)acryloyloxyalkyl) sulfonium thiocyanate, etc. Ionic liquid containing phonium cations,

Dialkyl((meth)acryloylaminoalkyl)sulfonium bis(fluorosulfonyl)imide, dialkyl((meth)acryloylaminoalkyl)sulfonium bis(trifluoromethanesulfonyl)imide, Dialkyl ((meth)acryloylaminoalkyl) sulfides such as dialkyl((meth)acryloylaminoalkyl)sulfonium dicyanamide, dialkyl((meth)acryloylaminoalkyl)sulfonium thiocyanate, etc. And ionic liquids containing phonium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

As a quaternary phosphonium cationic ion liquid,

Trialkyl (vinyl) phosphonium bis (fluorosulfonyl) imide, trialkyl (vinyl) phosphonium bis (trifluoromethanesulfonyl) imide, trialkyl (vinyl) phosphonium dicyanamide, trialkyl ( Ionic liquids containing trialkyl (vinyl) phosphonium cations such as vinyl) phosphonium thiocyanate,

Trialkyl((meth)acryloyloxyalkyl)phosphoniumbis(fluorosulfonyl)imide, trialkyl((meth)acryloyloxyalkyl)phosphoniumbis(trifluoromethanesulfonyl)imide, Trialkyl((meth)acryloyloxyalkyl)phosphites such as trialkyl((meth)acryloyloxyalkyl)phosphonium dicyanamide, trialkyl((meth)acryloyloxyalkyl)phosphoniumthiocyanate Ionic liquid containing phonium cations,

Trialkyl((meth)acryloylaminoalkyl)phosphoniumbis(fluorosulfonyl)imide, trialkyl((meth)acryloylaminoalkyl)phosphoniumbis(trifluoromethanesulfonyl)imide, Trialkyl((meth)acryloylaminoalkyl)phosphites such as trialkyl((meth)acryloylaminoalkyl)phosphonium dicyanamide and trialkyl((meth)acryloylaminoalkyl)phosphoniumthiocyanate And ionic liquids containing phonium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

Further, as a quaternary ammonium cation-based ionic liquid,

N,N,N-trialkyl-N-vinylammonium tetrafluoroborate, N,N,N-trialkyl-N-vinylammonium trifluoroacetate, N,N,N-trialkyl-N-vinylammonium hepta Fluorobutyrate, N,N,N-trialkyl-N-vinylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-vinylammonium perfluorobutanesulfonate, N,N,N- Trialkyl-N-vinylammoniumbis(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammoniumbis(pentafluoroethanesulfonyl)imide, N,N,N- Trialkyl-N-vinylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium hexafluorophosphate, N,N,N-trialkyl-N-vinylammonium (Trifluoromethanesulfonyl) N such as trifluoroacetamide, N,N,N-trialkyl-N-vinylammonium dicyanamide, N,N,N-trialkyl-N-vinylammoniumthiocyanate ,N,N-trialkyl-N-vinylammonium cation-containing ionic liquid,

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 trifluoromethanesulfo Nate, 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-tri Alkyl-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-(meth)acrylo N,N,N-trialkyl-N-(meth)acryloyl such as monooxyalkylammonium dicyanamide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium thiocyanate Ionic liquid containing oxyalkylammonium cations,

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 trifluoromethanesulfo Nate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium bis (Trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammoniumbis(pentafluoroethanesulfonyl)imide, N,N,N-tri Alkyl-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-(meth)acrylo N,N,N-trialkyl-N-(meth)acryloyl such as monoaminoalkylammonium dicyanamide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammoniumthiocyanate And ionic liquids containing aminoalkylammonium cations.

Moreover, as said alkyl substituent, it is preferable that it is a C1-C16 alkyl group, Especially preferably, it is C1-C12, More preferably, it is C1-C6.

Moreover, as said reactive ionic liquid, although it can be used without restriction|limiting in particular, It is more preferable that it is a reactive ionic liquid represented by any one of following formula (1)-(4). By containing a (meth)acrylic polymer containing a reactive ion liquid as a monomer unit in an antistatic agent composition, the antistatic layer formed by the antistatic agent composition contains the reactive ion liquid exhibiting an antistatic effect in a polymer skeleton. Since it is possible, the bleed-out of the antistatic component can be suppressed. In addition, since the reactive ionic liquid is a liquid (liquid phase) anywhere in the range of 0 to 150°C, and is a non-volatile molten salt and has transparency, the resulting antistatic layer is antistatic (high conductivity) ), heat resistance (thermal stability), transparency and low contamination can be satisfied, it is useful. Moreover, since the antistatic agent component is a reactive ionic liquid of a liquid, when it is used as an antistatic agent composition (solution), it is preferable from the viewpoint of easy formation of a uniform coating film and excellent workability when applied to a base film.

^{_{CH 2 = C (R 1)}} COOZX + Y - (1)

^{_{CH 2 = C (R 1)}} CONHZX + Y - (2)

^{_{CH 2 = C (R 1)}} COOX + Y - (3)

^{_{CH 2 C (R 1) CONHX}} + Y - (4)

Further, in the 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 part (X ⁺ ) constituting the reactive ionic liquid represented by any one of the formulas (1) to (4), a quaternary ammonium group, imidazolium group, pyridinium group, piperidinium group, pyrrolidis And a nium group, a pyrrole group, a quaternary phosphonium group, a trialkylsulfonium group, a pyrazolium group, and a guanidium group. Among these, in particular, a quaternary ammonium group is excellent in transparency and is a preferred form for electro-optical applications. In addition, the quaternary ammonium group does not have an unsaturated bond other than a polymerizable functional group in the molecule, so it is difficult to inhibit a general radical polymerization reaction during ultraviolet (UV) curing, and it is presumed to have high curability, thereby forming an antistatic layer It is suitable for

Specifically as the above quaternary ammonium group, trimethylammonium group, triethylammonium group, tripropylammonium group, methyldiethylammonium group, ethyldimethylammonium group, methyldipropylammonium group, dimethylbenzylammonium group, diethylbenzylammonium group, methyldibenzylammonium group, ethyl Dibenzyl ammonium group and the like can be mentioned, but among them, trimethylammonium group and methylbenzylammonium group are preferred forms because they are easy to obtain inexpensive industrial materials.

Further, formula (1) to (4) anion (parts) constituting the reactive ionic liquid represented by any of the formula (Y ^-) of, as the anion, SCN ^-, BF ₄ ^-, PF ₆ ^-, NO _{^{3 -, CH 3 COO -,}} CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (FSO 2) 2 N -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 _{^{C -, AsF 6 -, SbF}} 6 -, NbF 6 -, TaF 6 -, HF 2 -, (CN) 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, ^{_{C 3 F 7 COO -, (}} CF 3 SO 2) (CF 3 CO) N -, B (CN) 4 -, C (CN) 3 -, N (CN) 2 -, CH 3 OSO 3 -, C 2 _{^{H 5 OSO 3 -, C 4}} H 9 OSO 3 -, C 6 H 13 OSO 3 -, C 8 H 17 OSO 3 -, p- toluenesulfonate anion, a 2- (2-methoxyethyl) ethyl sulfate anion, (C ₂ F ₅ ) ₃ PF ₃ ^- and the like. Particularly, the anion component (fluorine-containing anion) containing a fluorine atom can obtain a low-melting ionic liquid and has excellent antistatic properties. desirable. In addition, it is preferable not to use chlorine ions, bromine ions, and the like as anions because they have corrosive properties.

As a combination of the cations (sites) and anions (sites) constituting the reactive ionic liquid represented by any one of the formulas (1) to (4), particularly preferred is acryloylaminopropyl trimethylammonium bis (tri Fluoromethanesulfonyl)imide, methacryloylaminopropyltrimethylammoniumbis(trifluoromethanesulfonyl)imide, acryloylaminopropyldimethylbenzylammoniumbis(trifluoromethanesulfonyl)imide, acrylic Loyloxyethyltrimethylammoniumbis(trifluoromethanesulfonyl)imide, acryloyloxyethyldimethylbenzylammoniumbis(trifluoromethanesulfonyl)imide, methacryloyloxyethyltrimethylammoniumbis(trifluoro Romethanesulfonyl)imide, acryloylaminopropyltrimethylammoniumbis(fluorosulfonyl)imide, methacryloylaminopropyltrimethylammoniumbis(fluorosulfonyl)imide, acryloylaminopropyldimethylbenzyl Ammonium bis(fluorosulfonyl)imide, acryloyloxyethyltrimethylammoniumbis(fluorosulfonyl)imide, acryloyloxyethyldimethylbenzylammoniumbis(fluorosulfonyl)imide, methacryloyl Oxyethyltrimethylammonium bis(fluorosulfonyl)imide, acryloylaminopropyltrimethylammoniumtrifluoromethanesulfonic acid, methacryloylaminopropyltrimethylammoniumtrifluoromethanesulfonic acid, acryloylaminopropyldimethylbenzylammoniumtri Fluoromethanesulfonic acid, acryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, acryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonic acid, methacryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, and the like.

It is preferable to contain 15 to 99 mass% of the said reactive ionic liquid in all the structural units (all monomeric units (component): 100 mass %) of the said (meth)acrylic-type polymer, and it is more preferable to contain 20 to 98 mass %. It is particularly preferable to contain 30 to 97% by mass. When the compounding 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.

As a general method for synthesizing a reactive ionic liquid, if the target ionic liquid is obtained, it is not particularly limited, but the literature "Ion Liquid-the Front Line and Future of Development" (published by CMC Corporation), the literature "Polymer, Vol. 52, P.1469-1482 (2011)", quaternization, ion exchange method, direct quaternization method, carbonic acid, as described in document "High-tech material system One Point 2 ionic liquid" (public publication) Ester quaternization method, hydroxide method, acid ester method, complexing method and neutralization method are used.

In addition, as the monomer unit constituting the (meth)acrylic polymer contained in the antistatic agent composition used in the present invention, (meth)acrylic acid alkyl ester is added to the monomer unit (component) having other polymerizability than the reactive ionic liquid. It is more preferable to use a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms. 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, and 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)acrylic Rate, 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, and the like.

It is preferable to contain 0-65 mass% of the said (meth)acrylic-acid alkylester as a monomer unit (component) among all the structural units (all monomer units (component): 100 mass %) of the said (meth)acrylic-type polymer, It is more preferable to contain 0 to 60 mass%. When the monomer unit (component) is within the above range, it is preferable from the viewpoint of obtaining ion conductivity and cohesive force suitable for the antistatic composition.

In addition, as a monomer unit constituting the (meth)acrylic polymer contained in the antistatic agent composition used in the present invention, monomer units (components) having other polymerizable properties other than the reactive ionic liquid are represented by the following formula (5). It is preferable to use an oxyalkylene group-containing monomer having an average added molar number of oxyalkylene units of 3 to 100. Like the reactive ionic liquid used in the present invention, when a cation portion (positive charge) and anion (negative charge) are included, the electrostatic force (coulombic force) generated between both charges is inversely proportional to the relative dielectric constant of the medium of both charges ( Coulomb's law). And, in the present invention, the oxyalkylene group-containing monomer (high relative dielectric constant) acts as a medium for the reactive ionic liquid, lowers the electrostatic force between the charges, and promotes ion dissociation of the reactive ionic liquid, In addition, with the oxyalkylene chain molecular motion of the oxyalkylene group-containing monomer, the ions are easily transported, and ion dissociation and ion transport of the reactive ionic liquid are promoted, thereby improving ion conductivity and preventing better charging. It is assumed that sex can be exercised.

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 from 2 to 4, n and q are 0 or integers from 2 to 100, n And q is never zero at the same time. Further, when R ₂ is an organic group, it is preferably a methyl group, lauryl group, phenyl group, stearyl group, octyl group, m and p are preferably 2, and n and q are preferably integers of 2 to 20. . When it is in the above-mentioned range, it is preferable because the oxyalkylene chain of the oxyalkylene group-containing monomer and the reactive ionic liquid easily interact, and the ions constituting the reactive ionic liquid are liable to dissociate.

As specific examples of the oxyalkylene group-containing monomer, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol ( Meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, butoxypolyethylene glycol (meth)acrylate, jade Methoxypolyethylene glycol (meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol (meth) Acrylate, methoxy polypropylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxyethylene glycol-polypropylene glycol (meth)acrylic Rate, octoxypolyethylene glycol-polypropylene glycol (meth)acrylate, polytetramethylene glycol (meth)acrylate, polytetramethylene glycol-polyethylene glycol (meth)acrylate, polytetramethylene glycol-polypropylene glycol (meth) And acrylate, polytetramethylene glycol-polybutylene glycol (meth)acrylate, and propylene glycol-polybutylene glycol (meth)acrylate. One type or two or more types of these oxyalkylene group-containing monomers can be used.

Of all the structural units of the (meth)acrylic polymer (total monomer units (components): 100% by mass), the oxyalkylene group-containing monomer is preferably 0 to 60% by mass, more preferably 5 to 50% by mass It is preferable, and it is most preferably 10 to 40% by mass. If it is in the said range, it is preferable because the oxyalkylene chain of the oxyalkylene group containing monomer is easy to perform molecular motion, and the transporting|action function of the ion which comprises a reactive ionic liquid improves.

Moreover, as other polymerizable monomers other than the (meth)acrylic acid alkyl ester, for the purpose of modification such as cohesive strength, heat resistance, and crosslinking, if necessary, other polymerizable polymerizable copolymerizable with the (meth)acrylic acid alkyl ester The monomer unit (component) (copolymerizable monomer) may be included. Moreover, it can be used in the range which does not impair the balance of cohesion force and ion conductivity as a monomer unit (component) which has other polymerizability. In particular, unlike the pressure-sensitive adhesive layer, it is preferable to use a glass transition temperature higher than that of the monomer unit used in the pressure-sensitive adhesive layer in order not to exhibit tackiness. By using such a monomer unit, as an antistatic layer (film), handling property can be improved and effective. These monomer compounds may be used alone or in combination of two or more.

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

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

In addition, the glass transition temperature (Tg _i ) of the monomer i is a nominal value described in the literature (eg, polymer handbook, adhesive hand log, etc.).

In addition, in this specification, "the glass transition temperature at the time of forming the homopolymer" means "the glass transition temperature of the homopolymer of the corresponding monomer", and any one monomer (sometimes referred to as "monomer X") It means the glass transition temperature (Tg) of the polymer formed only as a monomer component. Specifically, numerical values are exemplified in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989).

In addition, the glass transition temperature (Tg) of the homopolymer not described in the said document means the value obtained by the following measuring method, for example.

That is, 100 parts by mass of monomer X, 2,2'-azobisisobutyronitrile and 0.2 parts by mass of ethyl acetate and 200 parts by mass of ethyl acetate were added to a reactor equipped with a thermometer, stirrer, nitrogen introduction tube, and reflux cooling tube. , Stir for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymerization system in this way, the temperature was raised to 63°C and reacted for 10 hours. Subsequently, the mixture is cooled to room temperature to obtain a homopolymer solution having a solid content concentration of 33% by mass. Subsequently, this homopolymer solution was softly applied onto a release liner and dried to prepare a test sample (sheet-shaped homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of this test sample was weighed into an open cell made of aluminum, and the temperature was raised under a nitrogen atmosphere of 50 ml/min using a temperature modulated DSC (trade name "Q-2000", manufactured by T-A Instruments). At a rate of 5° C./min, the reversing heat flow behavior of the homopolymer was obtained.

With reference to JIS-K-7121, the curves of the step line change part of the glass transition and the straight line equidistant from the straight line extending from the low-side base line and the high-side base line of the obtained reversing heat flow to the vertical axis direction are obtained. The temperature of the crossing point is referred to as the glass transition temperature (Tg) when the homopolymer is used.

Specific examples of the other polymerizable monomer unit (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;

2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, Hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylates such as (meth)acrylic acid 10-hydroxydecyl, (meth)acrylic acid 12-hydroxylauryl, and (4-hydroxymethylcyclohexyl)methyl methacrylate. ;

Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride;

Sulfonic acid groups such as styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl(meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic 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 )N,N-dialkyl(meth)acrylamides such as acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide, N -Ethyl (meth)acrylamide, N-isopropyl (meth)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 (meth)acrylamide, N-butoxymethyl (meth)acrylamide, (N-substituted) amide-based monomers such as N-acryloyl morpholine;

N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, etc. Succinimide-based monomer;

Maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, and N-phenyl maleimide;

N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitacone Itaconimide-based monomers such as mid and N-lauryl itaconimide;

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, Nitrogen-containing heterocyclic monomers such as N-vinyl-3,5-morpholindione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, and N-vinylpyridazine ;

N-vinyl carboxylic acid amides;

Lactam monomers such as N-vinyl caprolactam;

Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile;

(Meth)acrylic acid aminoalkyl monomers such as (meth)acrylic acid aminoethyl, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid t-butylaminoethyl ;

(Meth)acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and ethoxypropyl (meth)acrylate;

Styrene-based monomers such as styrene and α-methylstyrene;

An epoxy group-containing acrylic monomer such as (meth)acrylic acid glycidyl;

Glycol-based acrylic ester monomers such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate;

(Meth)acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth)acrylate, silicone (meth)acrylate, and other heterocyclic rings, halogen atoms, and acrylic acid ester monomers having silicon atoms;

Olefin monomers such as isoprene, butadiene, and isobutylene;

Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether;

Vinyl esters such as vinyl acetate and vinyl propionate;

Aromatic vinyl compounds such as vinyl toluene and styrene;

Olefins or dienes such as ethylene, butadiene, isoprene, and isobutylene;

Vinyl ethers such as vinyl alkyl ethers;

Vinyl chloride;

Sulfonic acid group-containing monomers such as sodium vinylsulfonate;

Imide group-containing monomers such as cyclohexyl maleimide and isopropyl maleimide;

Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth)acrylate;

Acryloyl morpholine;

(Meth)acrylic acid esters having alicyclic hydrocarbon groups such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid esters having aromatic hydrocarbon groups such as phenyl (meth)acrylate and phenoxyethyl (meth)acrylate;

(Meth)acrylic acid ester obtained from terpene compound derivative alcohol;

And the like.

In particular, as the monomer unit, it is preferable to use the hydroxyl group-containing monomer (hydroxyl group-containing (meth)acrylic monomer) together with the reactive ionic liquid. By using the hydroxyl group-containing (meth)acrylic monomer, crosslinking and the like of the antistatic agent composition can be easily controlled, or an appropriate cohesive force can be obtained. In addition, unlike carboxyl groups or sulfonate groups that can generally act as a crosslinking site, hydroxyl groups are ionic compounds (alkali metal salts, ionic liquids, etc.) that can be added (combined) as a conductive agent (antistatic agent). Since it has a moderate interaction with, it can also be suitably used in antistatic properties.

In the total structural units (total monomer units (components): 100 mass%) of the (meth)acrylic polymer, the hydroxyl group-containing (meth)acrylic monomer is preferably 1 to 15 mass%, and 2 to 12 mass % Is more preferable, and 3 to 10 mass% is most preferred. If it is in the above range, it is preferable because it is easy to control the reaction with the crosslinking agent and cohesion.

In the present invention, it is preferable that other polymerizable monomers other than the hydroxyl group-containing (meth)acrylic monomer are 0 to 65% by mass in the total constituent units (all monomer units (components)) of the (meth)acrylic polymer. It is more preferably 0 to 60 mass%, and particularly preferably 0 to 55 mass%. By using the other polymerizable monomer within the above range, cohesion and adhesion to the base 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 known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization. In the case where the antistatic pressure-sensitive adhesive sheet of the present embodiment is used for the surface protection application 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, and a graft copolymer.

Moreover, it is preferable that the said antistatic agent composition also contains a conductive agent. In particular, as the above-mentioned conductive agent (antistatic agent), it is more preferable to contain an ionic compound, an ion conductive polymer, and the like, and more preferably an ionic compound such as an alkali metal salt or an ionic liquid. The ionic compound does not react with the reactive ionic liquid, and can be contained as a separate additive, and thus exhibits superior antistatic properties, and thus is a preferred form. In addition, the ionic compound is preferable because it has high interaction with the reactive ionic liquid embedded in the skeleton of the (meth)acrylic polymer, and also suppresses bleeding out, and has excellent low contamination.

It is preferable that content of the electrically conductive agent used for this invention is contained in 0-40 mass parts with respect to 100 mass parts of the said (meth)acrylic-type polymer contained in the said antistatic agent composition, and it contains 0.5-35 mass parts. It is more preferable, and it is still more preferable that it contains 1-30 mass parts. When the content exceeds 40 parts by mass, bleed out may occur, which is not preferable.

The antistatic layer in the present invention is characterized by being formed by crosslinking the antistatic composition. The antistatic layer (antistatic adhesive sheet) having better heat resistance can be obtained by appropriately adjusting and crosslinking the structural units, composition ratio, crosslinking agent selection and addition ratio of the (meth)acrylic polymer.

As a crosslinking agent used when forming the antistatic layer, an isocyanate compound, an epoxy compound, a melamine-based resin, an aziridine derivative, an oxazoline crosslinking agent, a silicone crosslinking agent, a silane crosslinking agent, and a metal chelate compound are used. Especially, an isocyanate compound or an epoxy compound is more preferably used from a viewpoint of obtaining moderate cohesive force, and it is an isocyanate compound (isocyanate type crosslinking agent) especially preferably. 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, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. , Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene isocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name Coronate L, Nippon Polyurethane) High school company), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name Coronate HL, Nippon Polyurethane high school company), isocyanurate body of hexamethylene diisocyanate (brand name Coronate HX, Nippon polyurethane) Isocyanate adducts, such as manufactured by Kogyo Co., Ltd.) and the like. Alternatively, a compound having at least one or more isocyanate groups in one molecule and one or more unsaturated bonds, specifically 2-isocyanatoethyl (meth)acrylate, etc., can also be used as the isocyanate crosslinking agent. 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 glycidylamine, N,N,N',N'-tetraglycidyl-m-xylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Corporation, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Corporation). These compounds may be used alone or in combination of two or more.

Hexamethylolmelamine etc. are mentioned as said melamine-type resin. Examples of the aziridine derivatives include, for example, commercially available product names HDU (manufactured by Soko Chemical Co.), trade name TAZM (manufactured by Soko Chemical Co.), and trade name TAZO (manufactured by Soko Chemical Co.). 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 the metal component, and acetylene, methyl acetoacetate, and ethyl lactate as the chelate component. These compounds may be used alone or in combination of two or more.

It is preferable that content of the said crosslinking agent is contained in 0.01-30 mass parts with respect to 100 mass parts of the said (meth)acrylic-type polymers contained in the said antistatic agent composition, It is more preferable that it contains 0.1-20 mass parts, 0.5 It is more preferable that it contains 15 to 15 parts by mass, and particularly preferably contains 0.5 to 10 parts by mass. When the content is less than 0.01 parts by mass, crosslinking by the crosslinking agent is insufficient, and the cohesive force of the antistatic agent composition becomes small, so that sufficient heat resistance may not be obtained. On the other hand, when the content exceeds 30 parts by mass, a cross-linking reaction proceeds in a short time to generate a gel foreign matter in the antistatic agent composition, which tends to cause appearance defects.

The antistatic agent composition may also contain a compound that causes keto-enol tautomerism. By containing the said compound, the effect of suppressing excessive viscosity increase and gelation of the antistatic composition after crosslinking agent formulation can be suppressed, and the effect of extending the pot life of the antistatic 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, for example, when the antistatic composition is in the form of an organic solvent solution or solvent-free.

As the compound which causes keto-enol tautomerism, various β-dicarbonyl compounds can be used. As specific examples, acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3 Β-diketones such as ,5-dione; Acetoacetic acid esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, and tert-butyl acetoacetate; Propionyl acetate esters such as ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, and tert-butyl propionyl acetate; Isobutyryl acetate esters such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, and tert-butyl isobutyryl acetate; Malonic acid esters such as methyl malonate and ethyl malonate; And the like. Among them, acetylacetone and acetoacetic acid esters are mentioned as suitable compounds. The compounds which cause such keto-enol tautomerism may be used alone or in combination of two or more.

The content of the compound that causes keto-enol tautomerism can be, for example, 0.1 to 20 parts by mass based on 100 parts by mass of the (meth)acrylic polymer, and is usually 0.5 to 15 parts by mass (for example, 1 to 10 parts by mass) It is advisable to do it). When the content of the compound is less than 0.1 parts by mass, sufficient use effect may be difficult to be exhibited. On the other hand, if the compound exceeds 20 parts by mass, it may remain in the antistatic layer, thereby lowering the antistatic property.

Further, in the present invention, as the crosslinking agent, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds can be added. In this case, the antistatic agent composition is crosslinked by irradiating radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, crosslinking treatment (curing) is possible by irradiation of radiation such as a vinyl group, acryloyl group, methacryloyl group, vinylbenzyl group, etc. 1 And polyfunctional monomer components having two or more species or two or more radiation reactive groups. Moreover, as said polyfunctional monomer, what has 10 or less radiation-reactive unsaturated bonds is normally used suitably. These compounds may be used alone or in combination of two or more.

As specific examples of the polyfunctional monomer, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, divinylbenzene, N,N And'-methylene bisacrylamide.

The blending amount of the polyfunctional monomer is appropriately selected by balance with the (meth)acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance, it is generally preferable to blend in an amount of 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 with 10 mass parts or less with respect to 100 mass parts of (meth)acrylic-type polymers from a point of flexibility.

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

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

As the photo-radical polymerization initiator, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, and α-methylbenzoin Human, benzyldimethyl ketal, trichloracetophenone, 2,2-diethoxy acetophenone, acetophenones such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy Propionphenones such as -4'-isopropyl-2-methylpropiophenone, benzophenones such as benzophenone, methylbenzophenone, p-chlorbenzophenone, and p-dimethylaminobenzophenone, 2-chlorthioxanthone Thioxanthones such as, 2-ethylthioxanthone and 2-isopropylthioxanthone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine And acylphosphine oxides such as pin oxide, (2,4,6-trimethylbenzoyl)-(ethoxy)-phenylphosphine oxide, benzyl, dibenzosuberone, and α-acyloxime ester. These compounds may be used alone or in combination of two or more.

Further, as the photo-cationic polymerization initiator, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, organic metals such as iron-allen complexes, titanocene complexes, arylsilaneol-aluminum complexes, etc. Complexes, nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaptoquinones, N-hydroxyimidosulfonates, and the like. These compounds may be used alone or in combination of two or more.

It is preferable to mix|blend 0.1 to 10 mass parts of said photoinitiator normally with respect to 100 mass parts of (meth)acrylic-type polymers, and to mix in 0.2 to 7 mass parts. If it is in the said range, it is easy to control a polymerization reaction, and it is preferable from a viewpoint of obtaining an appropriate molecular weight.

Moreover, it is also possible to use together photoinitiation polymerization adjuvants, such as amines. Examples of the photoinitiator are 2-dimethylaminoethyl benzoate, dimethylamino acetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester. These compounds may be used alone or in combination of two or more. It is preferable to mix|blend 0.05-10 mass parts with respect to 100 mass parts of (meth)acrylic-type polymers, and it is more preferable to mix|blend in the range of 0.1-7 mass parts. If it is in the said range, it is easy to control a polymerization reaction, and it is preferable from a viewpoint of obtaining an appropriate molecular weight.

As described above, in the case where a photopolymerization initiator having an optional component is added, the antistatic layer can be obtained by applying the above antistatic agent composition to one side or both sides of the base film and then irradiating it with light. In general, an antistatic layer is obtained by irradiating ultraviolet light 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 to photopolymerize.

Further, the antistatic composition may contain other known additives, for example, powders such as colorants and pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, surface lubricants, leveling agents, antioxidants, Corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particulates, foils and the like can be appropriately added depending on the application.

The antistatic layer is a liquid composition (antistatic agent composition) in which 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 a suitable solvent. It is a preferable form obtained by forming an antistatic agent solution) on at least one side of the base film. For example, a method in which the antistatic composition (antistatic agent solution) is applied to one side of the base film and dried to perform a curing treatment (heat treatment, ultraviolet treatment, etc.) as needed can be preferably employed.

As a solvent constituting the liquid composition (antistatic agent composition, antistatic agent solution), it is preferable that components (raw materials) used when forming the antistatic layer can be stably dissolved or dispersed. As such a 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 acetyl acetone; 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; Aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, and cyclohexanol; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether; Glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; One or two or more selected from the like can be used.

For the coating method in the formation of the antistatic layer, a known coating method is suitably used, specifically, for example, roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating, impregnation and curtain And a coating method.

The thickness of the antistatic layer of the present invention is usually 0.005 to 10 μm, more preferably about 0.01 to 5 μm, more preferably about 0.02 to 3 μm, particularly preferably about 0.03 to 1 μm, and most preferably It is about 0.05 to 0.5 µm. When it is in the said range, since it is less likely to damage the heat resistance, solvent resistance, and flexibility of the base film which forms the said antistatic layer, it becomes a preferable form.

<Base film>

As the base film constituting the pressure-sensitive adhesive sheet of the present invention, a known one can be used, and is not particularly limited, but is preferably a plastic film having heat resistance and solvent resistance and 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 up in a roll shape.

The plastic film is not particularly limited as long as it can be formed into a sheet or film, for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene/propylene Polyolefin films such as copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl alcohol copolymers, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate Polyester film, polyacrylate film, polystyrene film, nylon 6, nylon 6,6, partially aromatic polyamide, polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film, etc. Can be lifted.

In addition, the base film may be, if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder, acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, It is also possible to perform anti-adhesive treatments such as adhesion treatment, coating type, mixing type, and evaporation type, such as ultraviolet treatment.

Moreover, when using the adhesive sheet of this invention as a film for surface protection use, it is preferable form that the said base film uses the plastic film by which an antistatic treatment is performed. By using the above-described base film, since the charging of the surface protection film itself when peeled is more effectively suppressed, antistatic surface protection film in the technical field related to optical and electronic parts where charging or contamination becomes a particularly serious problem. As it becomes very useful. In addition, the base film is a plastic film, and the plastic film is subjected to an antistatic treatment, thereby reducing the charging of the surface protective film itself, and further improving the antistatic ability of the adherend (protected object). Is obtained.

In the present invention, the antistatic treatment performed on the plastic film is not particularly limited, but separately from the antistatic layer formed of the antistatic agent composition described above, an antistatic layer is separately provided on at least one side of the commonly used film. A method, a method of mixing a mixed type antistatic agent in a plastic film, or the like is used. As a method of forming an antistatic layer on at least one side of the film, a method of applying an antistatic resin containing an antistatic agent and a resin component, a conductive polymer, or a conductive resin containing a conductive material, or a method of depositing or plating a conductive material The adhesive sheet of the present invention includes structures such as a base film (plastic film and antistatic layer), an antistatic layer and an adhesive layer.

Examples of the antistatic agent (conductive agent) include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, first, second, and third amino groups, sulfonate salts, sulfate salts, and phos. Anionic antistatic agents having anionic functional groups such as phosphonates and phosphate ester salts, alkylbetaines and derivatives thereof, imidazolines and derivatives thereof, positive antistatic agents such as alanine and derivatives thereof, amino alcohols and derivatives thereof, glycerin and And nonionic antistatic agents such as derivatives thereof, polyethylene glycol, and derivatives thereof, and further, ionic conductive polymers obtained by polymerizing or copolymerizing monomers having the above-mentioned cationic, anionic and amphoteric ionically conductive groups. These compounds may be used alone or in combination of two or more.

Examples of the cationic antistatic agent include quaternary ammonium groups such as, for example, alkyltrimethylammonium salt, acylylamidopropyl trimethylammonium methosulfate, alkylbenzylmethylammonium salt, choline acyl chloride, and polydimethylaminoethyl methacrylate. And (meth)acrylate copolymers, styrene copolymers having a quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride, diallylamine copolymers having a quaternary ammonium group such as polydiallyldimethylammonium chloride, and the like. These compounds may be used alone or in combination of two or more.

Examples of the anionic antistatic agent include alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, alkyl phosphate ester salts, and sulfonic acid group-containing styrene copolymers. These compounds may be used alone or in combination of two or more.

Examples of the positive ion type antistatic agent include alkyl betaine, alkyl imidazolium betaine, and carbo betaine graft copolymerization. These compounds may be used alone or in combination of two or more.

As the nonionic antistatic agent, for example, fatty acid alkylolamide, di(2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, Polyoxysorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, copolymer containing polyether and polyester and polyamide, methoxy polyethylene glycol (meth) acrylic Rate etc. are mentioned. These compounds may be used alone or in combination of two or more.

As a conductive polymer, polyaniline, polypyrrole, polythiophene, etc. are mentioned, for example.

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, iodide Copper and alloys or mixtures thereof.

As the resin component used for the antistatic resin and the conductive resin, general-purpose resins such as polyester, acrylic, polyvinyl, urethane, melamine, and epoxy are used. Moreover, in the case of a polymer type antistatic agent, it is not necessary to contain a resin component. In addition, it is also possible to contain, as the cross-linking agent, compounds such as melamine-based, urea-based, glyoxal-based, acrylamide-based compounds, epoxy compounds, and isocyanate-based compounds in the antistatic resin component.

As a method for forming the antistatic layer, for example, the antistatic resin, the conductive polymer, and the conductive resin are diluted with a solvent such as an organic solvent or water, and the coating solution is applied to a plastic film and dried.

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, and n-propanol. And isopropanol. These solvents may be used alone or in combination of two or more.

As for the coating method in the formation of 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 coating methods Can be heard.

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

Moreover, as a compounding quantity of the said antistatic agent, 20 mass% or less with respect to the total weight of the said base film (plastic film), Preferably it is used in the range of 0.05-10 mass %. If it is within the above range, it is preferable because the possibility of impairing the heat resistance, solvent resistance and flexibility of the base film (plastic film) is small. The mixing method is not particularly limited as long as it is a method capable of uniformly mixing the antistatic agent with the resin used for the base film (plastic film), and includes, for example, a heating roll, a Banbury mixer, a pressurized kneader, and a biaxial shaft. A kneader or the like is used.

The thickness of the base film constituting the pressure-sensitive adhesive sheet of the present invention (in the case of having an antistatic layer on the plastic film, the thickness including the antistatic layer) is usually 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 it has excellent bonding workability to the adherend and peelability from the adherend.

<Adhesive composition and adhesive layer>

As the pressure-sensitive adhesive layer constituting the antistatic pressure-sensitive adhesive sheet of the present invention, known ones can be used, and are not particularly limited, and pressure-sensitive adhesives such as (meth)acrylic polymers, rubber polymers, silicone polymers, polyurethane polymers, polyester polymers, etc. As it can use various polymers generally used. In particular, it is preferably formed of 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). In addition, the (meth)acrylic polymer in the present invention refers to an acrylic polymer and/or methacryl-based polymer, and (meth)acrylate refers to acrylate and/or methacrylate. In addition, the said "main component" means the monomer with the highest structural ratio among the monomer units (components) which comprise the said (meth)acrylic polymer.

As the monomer unit (component) constituting the (meth)acrylic polymer of the present invention, it is preferable to use a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms from the viewpoint of obtaining adhesive properties. , More preferably, it is a (meth)acrylic-acid alkylester which has a C6-C14 alkyl group. As said (meth)acrylic-acid alkylester, 1 type(s) or 2 or more types can be used.

As the (meth)acrylic polymer having a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a main component, the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit (component) is 50 It is preferable to contain 99.9 mass %, and it is more preferable to contain 60 to 97 mass %. When the monomer unit (ingredient) is within the above range, it is preferable from the viewpoint of obtaining the wettability and cohesive force suitable for 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, and 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)acrylic Rate, 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, and the like.

Especially, when using the adhesive sheet of this invention as a surface protection film, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylic Rate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl As (meth)acrylate, n-tetradecyl (meth)acrylate, etc., (meth)acrylic-acid alkylester which has a C6-C14 alkyl group is mentioned as a suitable thing. By using a (meth)acrylic acid alkyl ester having an alkyl group having 6 to 14 carbon atoms, it is easy to control the adhesion to the adherend low, and it becomes an excellent re-release property.

In addition, as a monomer unit (component) having other polymerizability, the glass transition temperature (Tg) is set to 0° C. or less (typically -100° C. or more) for reasons of easy balance of adhesion performance, and (meth)acrylic polymer A polymerizable monomer or the like for adjusting the glass transition temperature (Tg) or peelability of can be used within a range that does not impair the effects of the present invention.

As other polymerizable monomers used in the (meth)acrylic polymers, (meth)acrylates having hydroxyl groups (hydroxyl group-containing (meth)acrylic monomers) are particularly preferable because crosslinking can be easily controlled. Is used. In addition, for the purpose of modification such as cohesive strength, heat resistance, and crosslinking property, in addition to the hydroxyl group-containing (meth)acrylic monomer capable of copolymerizing with the (meth)acrylic acid alkyl ester, if necessary, other monomer components (copolymerizable monomers) ) May be included. These monomer compounds may be used alone or in combination of two or more.

By using the hydroxyl group-containing (meth)acrylic monomer, crosslinking and the like of the pressure-sensitive adhesive composition can be easily controlled, and furthermore, it is easy to control the balance between improvement in wettability due to flow and reduction of adhesion in peeling. In addition, unlike the above-described carboxyl groups or sulfonate groups, which can generally act as crosslinking sites, hydroxyl groups are suitable as antistatic agents and suitable for ionic compounds (alkali metal salts, ionic liquids, etc.) that can be added (compounded). Since it has an interaction, it can be suitably used also in terms of antistatic properties. Examples of the hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl ( Meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methylacrylic Rate, N-methylol (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.

In the case where the hydroxyl group-containing (meth)acrylic monomer is included, the hydroxyl group-containing (meth)acrylic monomer is based on the total structural units (total monomer units (components): 100% by mass) of the (meth)acrylic polymer. Is preferably 0.1 to 15% by mass, more preferably 0.5 to 12% by mass, and most preferably 1 to 10% by mass. It is preferable to be in the above range, because it is easy to control the balance of the wettability and cohesive force of the pressure-sensitive adhesive composition.

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;

Contains sulfonic acid groups such as styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl(meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid Monomer;

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 )N,N-dialkyl(meth)acrylamides such as acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide, N -Ethyl (meth)acrylamide, N-isopropyl (meth)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 (meth)acrylamide, N-butoxymethyl (meth)acrylamide, (N-substituted) amide-based monomers such as N-acryloyl morpholine;

N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, etc. Succinimide-based monomer;

Maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, and N-phenyl maleimide;

N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitacone Itaconimide-based monomers such as mid and N-lauryl itaconimide;

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, Nitrogen-containing heterocyclic monomers such as N-vinyl-3,5-morpholindione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, and N-vinylpyridazine ;

N-vinylcarboxylic acid amides;

Lactam monomers such as N-vinyl caprolactam;

Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile;

(Meth)acrylic acid aminoalkyl monomers such as (meth)acrylic acid aminoethyl, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid t-butylaminoethyl ;

(Meth)acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and ethoxypropyl (meth)acrylate;

Styrene-based monomers such as styrene and α-methylstyrene;

An epoxy group-containing acrylic monomer such as (meth)acrylic acid glycidyl;

Glycol-based acrylic ester monomers such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate;

(Meth)acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth)acrylate, silicone (meth)acrylate, and other heterocyclic rings, halogen atoms, and acrylic acid ester monomers having silicon atoms;

Olefin monomers such as isoprene, butadiene, and isobutylene;

Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether;

Vinyl esters such as vinyl acetate and vinyl propionate;

Aromatic vinyl compounds such as vinyl toluene and styrene;

Olefins or dienes such as ethylene, butadiene, isoprene, and isobutylene;

Vinyl ethers such as vinyl alkyl ethers;

Vinyl chloride;

Sulfonate group-containing monomers such as sodium vinylsulfonate;

Imide group-containing monomers such as cyclohexyl maleimide and isopropyl maleimide;

Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth)acrylate;

Acryloyl morpholine;

(Meth)acrylic acid esters having alicyclic hydrocarbon groups such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid esters having aromatic hydrocarbon groups such as phenyl (meth)acrylate and phenoxyethyl (meth)acrylate;

(Meth)acrylic acid ester obtained from terpene compound derivative alcohol;

And the like. Moreover, 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 monomers may be used singly or in combination of two or more, but the entire structural unit of the (meth)acrylic polymers may be used. It is preferable that it is 0-40 mass% in (total monomer unit (component)), it is more preferable that it is 0-35 mass %, and it is especially preferable that it is 0-30 mass %. 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, more preferably 300,000 to 300 However, it is particularly preferable that it is 300,000 to 1,000,000. When the weight average molecular weight is less than 100,000, the cohesive force of the pressure-sensitive adhesive composition tends to be small, so that the pressure-sensitive adhesive residue tends to occur. On the other hand, when the weight average molecular weight exceeds 5 million, the fluidity of the polymer decreases, for example, there is a case where the wettability of the adherend becomes insufficient and the adhesive strength may be insufficient. In addition, the weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).

Further, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0°C or less, more preferably -10°C or less, more preferably -41°C or less, particularly preferably -51°C or less, Most preferably, it is -61°C or lower (normally -100°C or higher). When the glass transition temperature is higher than 0°C, the polymer is difficult to flow, for example, there is a case where wetting to the adherend becomes insufficient, and adhesive strength may be insufficient. In particular, by setting the glass transition temperature to -61°C or lower, an adhesive composition excellent in wettability and light peelability to an adherend (polarizing plate, etc.) is easily obtained. In addition, the glass transition temperature of the (meth)acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio to be used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization. When the antistatic pressure-sensitive adhesive sheet of the present embodiment is used for a surface protection application to be 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, and a graft copolymer.

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

As the crosslinking agent used in the present invention, isocyanate compounds, epoxy compounds, melamine-based resins, aziridine derivatives, oxazoline crosslinking agents, silicone crosslinking agents, silane crosslinking agents and metal chelate compounds are used. Especially, an isocyanate compound or an epoxy compound is more preferably used from a viewpoint of obtaining moderate cohesive force, and it is an isocyanate compound (isocyanate type crosslinking agent) especially preferably. 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, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. , Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene isocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name Coronate L, Nippon Polyurethane) High school), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name Coronate HL, Nippon Polyurethane), isocyanurate body of hexamethylene diisocyanate (trade name Coronate HX, Nippon Polyurethane) Isocyanate adducts, such as manufactured by Kogyo Co., Ltd.) and the like. Alternatively, a compound having at least one or more isocyanate groups in one molecule and one or more unsaturated bonds, specifically 2-isocyanatoethyl (meth)acrylate, etc., can also be used as the isocyanate crosslinking agent. 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 glycidylamine, N,N,N',N'-tetraglycidyl-m-xylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Corporation, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Corporation). These compounds may be used alone or in combination of two or more.

Hexamethylolmelamine etc. are mentioned as said melamine-type resin. Examples of the aziridine derivatives include, for example, commercially available product names HDU (manufactured by Soko Chemical Co.), trade name TAZM (manufactured by Soko Chemical Co.), and trade name TAZO (manufactured by Soko Chemical Co.). 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 the metal component, and acetylene, methyl acetoacetate, and ethyl lactate as the chelate component. 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, more preferably 0.5 to 15 parts by mass, and more preferably 0.5 to 15 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. It is more preferable that it contains 10 to 10 parts by mass. When the content is less than 0.01 part by mass, crosslinking by the crosslinking agent is insufficient, the cohesive force of the pressure-sensitive adhesive composition is small, and sufficient heat resistance may not be obtained, and there is a tendency to cause residual pressure-sensitive adhesive. On the other hand, when the content exceeds 20 parts by mass, the cohesive force of the polymer is large, the fluidity decreases, and for example, the wettability of the adherend becomes insufficient, and the adhesive force may be insufficient.

The pressure-sensitive adhesive composition disclosed herein may further contain a compound that causes keto-enol tautomerism. For example, in the pressure-sensitive adhesive composition containing a cross-linking agent or a pressure-sensitive adhesive composition that can be used in combination with a cross-linking agent, a form containing a compound that causes the keto-enol tautomerism can be preferably employed. Thereby, the effect of suppressing excessive viscosity increase and gelation of the pressure-sensitive adhesive composition after the crosslinking agent is blended can be realized to extend the useful time of the composition. 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, for example, when the pressure-sensitive adhesive composition is in the form of an organic solvent solution or a solvent-free solution.

As the compound causing the keto-enol tautomerism, various β-dicarbonyl compounds can be used. As specific examples, acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3 Β-diketones such as ,5-dione; Acetoacetic acid esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, and tert-butyl acetoacetate; Propionyl acetate esters such as ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, and tert-butyl propionyl acetate; Isobutyryl acetate esters such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, and tert-butyl isobutyryl acetate; Malonic acid esters such as methyl malonate and ethyl malonate; And the like. Among them, acetylacetone and acetoacetic acid esters are mentioned as suitable compounds. The compounds which cause such keto-enol tautomerism may be used alone or in combination of two or more.

The amount of the compound causing the keto-enol tautomerism can be, for example, 0.1 to 20 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer, and is usually 0.5 to 15 parts by mass (for example, 1 to 10 parts by mass) (Parts by mass) is suitable. When the amount of the compound is too small, sufficient use effect may not be exerted. On the other hand, if the compound is used more than necessary, it may remain in the pressure-sensitive adhesive layer to lower the cohesion.

Further, in the present invention, as the crosslinking agent, a polyfunctional monomer having two or more radiation-reactive unsaturated bonds can be added. In this case, the pressure-sensitive adhesive composition is crosslinked by irradiation with radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, crosslinking treatment (curing) is possible by irradiation of radiation such as a vinyl group, acryloyl group, methacryloyl group, vinylbenzyl group, etc. 1 And polyfunctional monomer components having two or more species or two or more radiation reactive groups. Moreover, as said polyfunctional monomer, what has 10 or less radiation-reactive unsaturated bonds is normally used suitably. These compounds may be used alone or in combination of two or more.

As specific examples of the polyfunctional monomer, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, divinylbenzene, N,N And'-methylene bisacrylamide.

The blending amount of the polyfunctional monomer is appropriately selected depending on the use of the pressure-sensitive adhesive sheet by balance with the (meth)acrylic polymer to be crosslinked. In order to obtain sufficient heat resistance by the cohesive force of the acrylic pressure-sensitive adhesive, it is generally preferable to blend in an amount of 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 with 10 mass parts or less with respect to 100 mass parts of (meth)acrylic-type polymers from a point of flexibility and adhesiveness.

As the radiation, for example, ultraviolet rays, laser rays, α rays, β rays, γ rays, X rays, electron beams, etc. are mentioned, but ultraviolet rays are suitably used from the viewpoints of good controllability and handling, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using a suitable light source such as a high pressure mercury lamp, microwave excitation lamp, or chemical lamp. Moreover, when using ultraviolet rays as radiation, the photopolymerization initiator shown below can be added to an acrylic adhesive.

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

As the photo-radical polymerization initiator, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, and α-methylbenzoin Human, benzyldimethyl ketal, trichloracetophenone, 2,2-diethoxy acetophenone, acetophenones such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy Propionphenones such as -4'-isopropyl-2-methylpropiophenone, benzophenones such as benzophenone, methylbenzophenone, p-chlorbenzophenone, and p-dimethylaminobenzophenone, 2-chlorthioxanthone Thioxanthones such as, 2-ethylthioxanthone and 2-isopropylthioxanthone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine And acylphosphine oxides such as pin oxide, (2,4,6-trimethylbenzoyl)-(ethoxy)-phenylphosphine oxide, benzyl, dibenzosuberone, and α-acyloxime ester. These compounds may be used alone or in combination of two or more.

Further, as the photo-cationic polymerization initiator, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, organic metals such as iron-allen complexes, titanocene complexes, arylsilaneol-aluminum complexes, etc. Complexes, nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaptoquinones, N-hydroxyimidosulfonates, and the like. These compounds may be used alone or in combination of two or more.

It is preferable to mix|blend 0.1 to 10 mass parts of said photoinitiator normally with respect to 100 mass parts of (meth)acrylic-type polymers, and to mix in 0.2 to 7 mass parts. If it is in the said range, it is easy to control a polymerization reaction, and it is preferable from a viewpoint of obtaining an appropriate molecular weight.

Moreover, it is also possible to use together photoinitiation polymerization adjuvants, such as amines. Examples of the photoinitiator are 2-dimethylaminoethyl benzoate, dimethylamino acetophenone, p-dimethylaminobenzoic acid ethyl ester, and p-dimethylaminobenzoic acid isoamyl ester. These compounds may be used alone or in combination of two or more. It is preferable to mix|blend 0.05-10 mass parts with respect to 100 mass parts of (meth)acrylic-type polymers, and it is more preferable to mix|blend in the range of 0.1-7 mass parts. If it is in the said range, it is easy to control a polymerization reaction, and it is preferable from a viewpoint of obtaining an appropriate molecular weight.

When the photopolymerization initiator having an optional component is added as described above, the pressure-sensitive adhesive composition is applied directly onto the adherend (protected body), or after being applied to a predetermined coated body such as a separator or The adhesive layer can be obtained by coating and applying to one surface on the antistatic layer, followed by light irradiation. Usually, a pressure-sensitive adhesive layer is obtained by irradiating ultraviolet light 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 to photopolymerize.

Further, the above-mentioned pressure-sensitive adhesive composition may contain other known additives, for example, conductive agents (antistatic agents), colorants, powders such as pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, surface lubricants, leveling Agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particulates, foils and the like can be appropriately added depending on the application. In particular, as the conductive agent (antistatic agent), it is preferred to use an ionic compound such as an alkali metal salt or an ionic liquid (including the reactive ionic liquid), for example.

The pressure-sensitive adhesive sheet of the present invention is formed by forming the pressure-sensitive adhesive layer on the antistatic layer. At this time, crosslinking of the pressure-sensitive adhesive composition is generally performed after application of the pressure-sensitive adhesive composition, but the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition after crosslinking is transferred onto the antistatic layer. It is also possible to do.

The method of forming the pressure-sensitive adhesive layer on the antistatic layer is not particularly concerned, for example, by applying the pressure-sensitive adhesive composition (solution) on the antistatic layer, drying and removing the polymerization solvent, etc., thereby forming the pressure-sensitive adhesive layer on the antistatic layer. It is produced. Thereafter, curing may be performed for the purpose of adjusting the component migration of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction. Moreover, when manufacturing an antistatic layer by apply|coating an adhesive composition (solution) on an antistatic layer, you may newly add 1 or more types of solvent other than a polymerization solvent in an adhesive composition so that it may apply uniformly on an antistatic layer.

In addition, as a method of forming the pressure-sensitive adhesive layer when manufacturing the pressure-sensitive adhesive sheet of the present invention, a known method used in the production of pressure-sensitive adhesive tapes is used. Specifically, roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating method, extrusion coating method by a die coater, etc. are mentioned, for example.

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

In the pressure-sensitive adhesive sheet (surface protective film) of the present invention, it is possible to bond the separator to the surface of the pressure-sensitive adhesive layer, if necessary, for the purpose of protecting the pressure-sensitive adhesive surface.

Although a paper or a plastic film is used as a material constituting the separator, a plastic film is suitably used because of its excellent surface smoothness. The film is not particularly limited as long as it is a film that can protect the pressure-sensitive adhesive layer. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride And copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, and ethylene-vinyl acetate copolymer films.

The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm, and more preferably about 15 to 50 μm. If it is in the above-mentioned range, it is preferable because it has excellent bonding workability to the pressure-sensitive adhesive layer and peelability from the pressure-sensitive adhesive layer. If necessary, the separator may be subjected to a silicone-based, fluorine-based, long-chain alkyl- or fatty acid amide-based release agent, a release and antifouling treatment with silica powder, or an antistatic treatment such as a coating type, mixing type, and vapor deposition type.

Since the antistatic pressure-sensitive adhesive sheet having the antistatic layer of the present invention has an antistatic layer having excellent antistatic properties, it can be used in surface protection applications and applications in electronic component manufacturing and shipping processes. In the above-mentioned use, it is possible to suppress dust or electronic components due to static electricity and to destroy electronic components due to static electricity, and thus, it is possible to suppress them and is useful.

The antistatic pressure-sensitive adhesive sheet having the antistatic layer of the present invention can be used as an optical film with an antistatic pressure-sensitive adhesive sheet attached to an optical film. The surface of the optical film can be protected by attaching the antistatic adhesive sheet to the optical film, which is useful. In particular, the antistatic pressure-sensitive adhesive sheet can be used in plastic products and the like, which are prone to static electricity, and thus is very useful as an antistatic in the technical field related to optical and electronic components, where charging is a particularly serious problem.

In addition, the antistatic adhesive sheet is adhered by forming the antistatic layer of the present invention on at least one side of the base film and adhering (immobilizing) the antistatic adhesive sheet with the adhesive layer on the antistatic layer to the optical film. It can be used as an optical film. By attaching the antistatic adhesive sheet, it is possible to prevent dropping of the optical properties due to damage to the optical film while preventing the antistatic layer from falling off. In addition, the adhesive layer is used in the case of the purpose of permanent or semi-permanent bonding by bonding (immobilizing) to the optical film, not requiring re-peelability (light peelability) and the like, as in the adhesive layer. Is to do. Moreover, as said adhesive layer (adhesive composition), a well-known thing can be used.

Example

Hereinafter, several examples related to the present invention will be described, but the present invention is not intended to be limited to those shown in these specific examples. In addition, "part" and "%" in the following description are a mass basis unless otherwise specified.

<Preparation of reactive ionic liquid (DMAEA-TFSI)>

Potassium bis(trifluoromethanesulfonyl)imide 114 while stirring 100 parts of a 79% aqueous solution of 2-(acryloyloxy)ethyltrimethylammonium chloride (DMAEA-Q, manufactured by Gouzinsha) in a 1L three-neck flask 114 The part diluted in 80 parts of ion-exchanged water was added under 60 degreeC heating. After 2 hours, the oil layer portion of the lower layer separated from the two layers was taken out, washed three times with ion-exchanged water, and then the remaining trace moisture was removed under reduced pressure to obtain 2-(acryloyloxy)ethyltrimethylammonium bis( Trifluoromethanesulfonyl)imide (DMAEA-TFSI) was obtained.

<Preparation of reactive ionic liquid (DMAPAA-TFSI)>

Ionized 116 parts of potassium bis(trifluoromethanesulfonyl)imide while stirring 100 parts of a 75% aqueous solution of (3-acrylamidepropyl)trimethylammonium chloride (DMAPAA-Q, manufactured by Gouzinsha) in a 1L three-necked flask Diluted 80 parts of exchange water was added under heating at 60°C. After 2 hours, the oil layer portion of the lower layer separated from the two layers was taken out, washed three times with ion-exchanged water, and the remaining trace moisture was removed under reduced pressure to obtain (3-acrylamidepropyl)trimethylammonium bis(trifluoro) Lomethanesulfonyl)imide (DMAPAA-TFSI) was obtained.

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

Methyl ethyl ketone 400 parts, 2-(acryloyloxy)ethyl trimethylammonium bis(trifluoromethanesulfonyl)imide (DMAEA-TFSI) 40 parts, methyl methacrylate 55 parts, 2-hydroxyethyl meta 5 parts of acrylate was put into a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, followed by reaction at 70°C for 4 hours, and then continued reaction at 80°C for 4 hours. . Then, 0.1 part of 2,2'-azobisisobutyronitrile was added and reacted at 80 DEG C for 1 hour. Thereafter, 0.17 part of 2,2'-azobisisobutyronitrile was added at 70°C to react for 4 hours, and then reacted at 80°C for 4 hours to obtain a (meth)acrylic polymer (A) for an antistatic layer. .

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

Methyl ethyl ketone 400 parts, 2-(acryloyloxy) ethyl trimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI) 95 parts, 2-hydroxyethyl methacrylate 5 parts, stirring blade , Thermometer, nitrogen gas introduction tube, cooler, was introduced into a four-necked flask equipped with a dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, and reacted at 70°C for 4 hours, followed by reaction at 80°C for 1 hour. . Then, 0.1 part of 2,2'-azobisisobutyronitrile was added and reacted at 80 DEG C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was added at 70°C to react for 4 hours, and then reacted at 80°C for 4 hours to obtain a (meth)acrylic polymer (B) for an antistatic layer. .

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

Methyl ethyl ketone 400 parts, (3-acrylamide propyl) trimethylammonium bis(trifluoromethanesulfonyl)imide (DMAPAA-TFSI) 95 parts, 2-hydroxyethyl methacrylate 5 parts, stirring blade, thermometer , Nitrogen gas was introduced into a four-necked flask equipped with a tube, a cooler, and a dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, and reacted at 70°C for 4 hours, followed by reaction at 80°C for 1 hour. . Then, 0.1 part of 2,2'-azobisisobutyronitrile was added and reacted at 80 DEG C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was added at 70°C to react for 4 hours, and then reacted at 80°C for 4 hours to obtain a (meth)acrylic polymer (C) for an antistatic layer. .

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

Methyl ethyl ketone 400 parts, 2-(acryloyloxy) ethyl trimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI) 85 parts, methoxy terminal polyethylene glycol methacrylate (average added moles 23 , Nichiyu Blemmer PME-1000) 10 parts, 2-hydroxyethyl methacrylate 5 parts, was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, and reacted at 70°C for 4 hours, followed by reaction at 80°C for 1 hour. . Then, 0.2 part of 2,2'-azobisisobutyronitrile was added and reacted at 80 DEG C for 3 hours. Thereafter, 0.2 part of 2,2'-azobisisobutyronitrile was added at 70°C to react for 4 hours, and then reacted at 80°C for 4 hours to obtain a (meth)acrylic polymer (D) for an antistatic layer. .

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

Methyl ethyl ketone 400 parts, 2-(acryloyloxy) ethyl trimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSI) 65 parts, methoxy terminal polyethylene glycol methacrylate (average added moles 23 , Nichiyu Blemmer PME-1000) 30 parts, 2-hydroxyethyl methacrylate 5 parts, was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, and reacted at 70°C for 4 hours, followed by reaction at 80°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. Moreover, the weight average molecular weight was 150,000.

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

In a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel, 200 parts of 2-ethylhexyl acrylate, 8 parts of 2-hydroxyethyl acrylate, and 2,2'-azo as a polymerization initiator 0.4 parts of bisisobutyronitrile and 312 parts of ethyl acetate were added, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was maintained at around 65°C for polymerization for 6 hours, and (meth)acrylic polymer for pressure-sensitive adhesive layer (F) A solution (40% by mass) 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 adhesive composition>

Coronanate L (trimethylolpropane/tolylene di) as a crosslinking agent in 500 parts (100 parts of polymer) of a solution of (meth)acrylic polymer (F) solution (40% by mass) for the pressure-sensitive adhesive layer diluted with ethyl acetate to 20% by mass. Solid content 75% by weight of isocyanate trimer adduct solution, ethyl acetate solution, manufactured by Nippon Polyurethane Kogyo Co., Ltd.) 5.3 parts, dioctyltin dilaurate (1% by mass of ethyl acetate solution) 3.0 parts as a crosslinking catalyst was added, and then at 25°C for about 5 minutes By mixing and stirring, an acrylic adhesive solution (1) was prepared.

[Example 1]

(Preparation of antistatic solution)

Coronate L (trimethylolpropane/tolylene diisocyanate trimer) as a crosslinking agent in 2381 parts (100 parts of polymer) of the (meth)acrylic polymer (A) solution (20% by mass) diluted with methyl ethyl ketone to 4.2% by mass The solid content of the body adduct was added 75 parts by weight of ethyl acetate solution, manufactured by Nippon Polyurethane High School) 4.0 parts, 5.0 parts of DMAEA-TFSI as a conductive agent, and 3.0 parts of dioctyltin dilaurate (1% by mass of ethyl acetate solution) as a crosslinking catalyst were added. , Mixing and stirring for about 5 minutes at 25 ℃ to prepare an antistatic agent solution (1).

(Preparation of antistatic treatment film)

The antistatic agent solution (1) was coated on a polyethylene terephthalate (PET) film (38 µm thick, manufactured by Toray Industries, Lumirr S10) using a Meyer bar, and dried at 130° C. for 1 minute to remove the solvent to prevent the antistatic layer ( A thickness of 0.5 µm) was formed to prepare an antistatic treatment film (1).

(Production of adhesive sheet)

The acrylic 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 an adhesive layer having a thickness of 20 μm.

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

[Example 2]

(Preparation of antistatic solution)

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

(Preparation of antistatic treatment 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 instead of the antistatic agent solution 1.

(Production of adhesive sheet)

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

[Example 3]

(Preparation of antistatic 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 treatment 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 instead of the antistatic agent solution 1.

(Production of adhesive sheet)

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

[Example 4]

(Preparation of antistatic solution)

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

(Preparation of antistatic treatment film)

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

(Production of adhesive sheet)

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

[Example 5]

(Preparation of antistatic solution)

The antistatic agent solution was prepared in the same manner as in Example 1, 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. 5) was prepared.

(Preparation of antistatic treatment film)

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

(Production of adhesive sheet)

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

[Example 6]

(Preparation of antistatic solution)

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

(Preparation of antistatic treatment 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.

(Production of adhesive sheet)

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

[Example 7]

(Preparation of antistatic solution)

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

(Preparation of antistatic treatment film)

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

(Production of adhesive sheet)

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

[Example 8]

(Preparation of antistatic solution)

Example 1 except that the (meth)acrylic polymer (C) was used instead of the (meth)acrylic polymer (A) and DMAPAA-TFSI 20.0 parts was used instead of 5.0 parts of DMAEA-TFSI as the conductive agent. Similarly, an antistatic agent solution 8 was prepared.

(Preparation of antistatic treatment film)

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

(Production of adhesive sheet)

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

[Example 9]

(Preparation of antistatic solution)

The antistatic agent solution was prepared in the same manner as in Example 1, except that the (meth)acrylic polymer (D) was used instead of the (meth)acrylic polymer (A) and 5.0 parts of DMAEA-TFSI was not used as the conductive agent. 9) was prepared.

(Preparation of antistatic treatment film)

Instead of the antistatic agent solution (1), the antistatic agent solution (9) was used and coated on a polyethylene terephthalate (PET) film (38 µm thick, Lumirr S10 manufactured by Toray Industries) using a Meyer bar, 130° C. The solvent was removed by drying for 1 minute to form an antistatic layer (0.1 µm thick) to prepare an antistatic treatment film (9).

(Production of adhesive sheet)

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

[Example 10]

(Preparation of antistatic solution)

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

(Preparation of antistatic treatment film)

Instead of the antistatic agent solution (1), the antistatic agent solution (10) was used, coated on a polyethylene terephthalate (PET) film (38 µm thick, Lumirr S10 manufactured by Toray Industries) using a Meyer bar, 130° C. The solvent was removed by drying for 1 minute to form an antistatic layer (0.25 µm thick) to prepare an antistatic treatment film 10.

(Production of adhesive sheet)

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

[Example 11]

(Preparation of antistatic treatment film)

Instead of the antistatic agent solution (1), the antistatic agent solution (10) was used, coated on a polyethylene terephthalate (PET) film (38 µm thick, Lumirr S10 manufactured by Toray Industries) using a Meyer bar, 130° C. The solvent was removed by drying for 1 minute to form an antistatic layer (0.1 µm thick) to prepare an antistatic treatment film 11.

(Production of adhesive sheet)

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

(Comparative Example 1)

(Preparation of antistatic solution)

The acrylic resin copolymerized by quaternary ammonium chloride (manufactured by Konishi, this dip PA-200 (32 mass%), ion-conducting polymer) was adjusted to 2.1 mass% with a mixed solvent of isopropyl alcohol:soft water = 2:1. To 100 parts of this solution, 25 parts of an epoxy-based resin (manufactured by Konishi, Bon Dip PA-100 (8.2% by mass)) was added, followed by mixing and stirring at 25°C for about 5 minutes, and a 2.5% by mass antistatic agent solution ( 11) was prepared.

(Preparation of antistatic treatment film)

Instead of the antistatic agent solution 1, the antistatic agent solution 11 was used, and instead of a polyethylene terephthalate (PET) film (38 µm thick, manufactured by Toray Industries, Lumirr S10), corona treated polyethylene terephthalate ( PET) An antistatic treatment film 12 was produced in the same manner as in Example 1 except that a film (38 µm thick, manufactured by Mitsubishi Corporation, Dia. Foil T100C) was used.

(Production of adhesive sheet)

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

(Comparative Example 2)

(Preparation of antistatic treatment film)

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

(Production of adhesive sheet)

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

<Measurement of weight average molecular weight (Mw)>

The weight average molecular weight (Mw) of the (meth)acrylic polymer (E) for the antistatic layer was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. Measurement conditions are as follows. In addition, the weight average molecular weight was calculated|required by the polymethylmethacrylate conversion value.

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

Sample injection volume: 20μl

Eluent: HFIP+10mM sodium trifluoroacetate

Flow rate: 0.3 ml/min

Measurement temperature: 40℃

column:

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

Detector: Differential Refractometer (RI)

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

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

Sample injection volume: 10 μl

Eluent: THF

Flow rate: 0.6ml/min

Measurement temperature: 40℃

column:

Sample column; TSKguardcolumn SuperHZ-H (1 pc.)+TSKgel SuperHZM-H (2 pcs.)

Reference column; TSKgel SuperH-RC (1 pc.)

Detector: Differential Refractometer (RI)

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

After cutting the pressure-sensitive adhesive sheet according to each of Examples and Comparative Examples to a size of 25 mm in width and 100 mm in length, and peeling the release liner, the surface of a triacetyl cellulose polarizing plate (manufactured by Nitto Denko, SEG1425DU, width: 70 mm, length: 100 mm) Then, after pressing with a hand roller, it was laminated under a pressing condition of 0.25 MPa and 0.3 m/min to prepare an evaluation sample (optical film with antistatic adhesive sheet).

After the lamination, after standing for 30 minutes in an environment of 23° C.×50% RH, the opposite side of the triacetyl cellulose polarizing plate was fixed to the acrylic plate with double-sided adhesive tape, and with an all-purpose tensile testing machine, one end of the adhesive sheet was The adhesive force when peeling at a tensile rate 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 x 50% RH. As the adhesive force at the time of low-speed peeling, from the viewpoint of suppressing the lifting or peeling of the adhesive tape, it was said that it was good at 0.07 N/25 mm or more, and that it was defective at less than 0.07 N/25 mm. In addition, Table 2 shows the measurement results.

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

After cutting the pressure-sensitive adhesive sheet according to each of Examples and Comparative Examples to a size of 25 mm in width and 100 mm in length, and peeling the release liner, the surface of a triacetyl cellulose polarizing plate (manufactured by Nitto Denko, SEG1425DU, width: 70 mm, length: 100 mm) Then, after pressing with a hand roller, it was laminated under a pressing condition of 0.25 MPa and 0.3 m/min to prepare an evaluation sample (optical film with antistatic adhesive sheet).

After the above-mentioned lamination, after standing for 30 minutes in an environment of 23° C.×50% RH, the opposite side of the triacetyl cellulose polarizing plate was fixed to the acrylic plate with double-sided adhesive tape, and one end of the adhesive sheet was pulled with a universal tensile testing machine. The adhesive force at 30 m/min (high-speed peeling) and the peeling angle at 180° was measured. The measurement was performed in an environment of 23°C x 50% RH. It was said that the adhesive strength at the time of high-speed peeling was less than 6.0 N/25 mm, and it was said that it was 6.0 N/25 mm or more. Table 2 shows the measurement results.

<Measurement of peeling high voltage>

As shown in Fig. 2, the pressure-sensitive adhesive sheet 2 according to each of the Examples and Comparative Examples was cut to a size of 70 mm in width and 130 mm in length, and after the separator was peeled off, an acrylic plate 4 previously removed (Mitsubishi Rayon) (3) (made by Nitto Denko Corporation, SEG1425DU, width: 70mm, length: 100mm) bonded to a manufactured product, acrylic light, thickness: 1mm, width: 70mm, length: 100mm). It squeezed out with a hand roller.

After standing for one day in an environment of 23°C x 50% RH, the sample is set at a predetermined position on the sample holder 5 as shown in FIG. One end of 30 mm was fixed to an automatic winding machine, and peeled to a peeling angle of 150° and a tensile speed of 30 m/min (high-speed peeling). At this time, the potential of the surface of the polarizing plate generated was measured by a potential measuring instrument 1 (KSD-0103 manufactured by Gas Electric Industries, Inc.) fixed at a predetermined position, and used as the value of the peeling voltage. The measurement was performed in an environment of 23°C x 50% RH. Moreover, as peeling large voltage, it is preferable that the absolute value is 1.0 kV or less, and it is more preferable that it is 0.5 kV or less. If it is within the above range, it is possible to prevent dust collection by static electricity and static electricity interference of electronic components, which is useful.

<Evaluation of contamination>

After measuring the peeling high voltage, the peeled pressure-sensitive adhesive sheet was hand-bonded again so that air bubbles were mixed with the polarizing plate after measurement, to prepare an evaluation sample.

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

・If contamination is not confirmed: ○

When contamination is confirmed: ×

<Measurement of surface resistivity (state)>

The adhesive sheet according to each of the Examples and Comparative Examples was left for 2 hours in an environment of 23° C.×50% RH, and then the separator was peeled off, and the surface resistivity of the pressure-sensitive adhesive surface was measured by a surface resistivity measuring device (Mitsubishi Chemical Corporation, High Resta). UP MCP-HT450 type). The applied voltage was 100 V and the applied time was 30 seconds. Moreover, it is preferable that surface resistivity is 10 ¹³ or less, and it is more preferable that it is 10 ¹² or less. If it is within the above range, it is possible to prevent dust collection by static electricity and static electricity interference of electronic components, which is useful.

<Measurement of surface resistivity (heat resistance)>

The separator of the pressure-sensitive adhesive sheet according to each of Examples and Comparative Examples was peeled off, left at 170°C for 30 minutes, and then left for 2 hours in an environment of 23°C x 50% RH to measure the surface resistivity of the pressure-sensitive adhesive surface. It was measured by Mitsubishi Chemical Corporation, High Resta UP MCP-HT450 type). The applied voltage was 100 V and the applied time was 30 seconds. Moreover, it is preferable that surface resistivity is 10 ¹³ or less, and it is more preferable that it is 10 ¹² or less.

<Thrillingness>

After cutting the pressure-sensitive adhesive sheet according to each of Examples and Comparative Examples to a size of 25 mm in width and 100 mm in length, and peeling the release liner, the surface of a triacetyl cellulose polarizing plate (manufactured by Nitto Denko, SEG1425DU, width: 70 mm, length: 100 mm) Then, after pressing with a hand roller, it was laminated under a pressing condition of 0.25 MPa and 0.3 m/min to prepare an evaluation sample (optical film with antistatic adhesive sheet). After the lamination, after standing for 30 minutes in an environment of 23° C.×50% RH, the opposite side of the triacetylcellulose polarizing plate was fixed to an acrylic plate with double-sided adhesive tape, and with an all-purpose tensile tester, one end of the adhesive sheet, When the tensile speed was 30 m/min (high-speed peeling) and the peeling angle was peeled at 180°, it was visually judged whether or not the adhesive remained on the surface of the triacetyl cellulose polarizing plate (adhesive residue).

When there is no adhesive residue: ○

When adhesive residue occurs: ×

<Transparency: Hayes>

After cutting the adhesive sheets of Examples and Comparative Examples to a size of 50 mm in width and 50 mm in length, the release liner was peeled off, and the haze was measured with a haze meter (manufactured by Murakami Shikisai Kijutsu Kenkyusho). A thing with a haze of less than 10% was called good, and a thing with 10% or more was called bad. Table 2 shows the measurement results.

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

According to the results of Table 2, in all of Examples 1 to 11 using the antistatic adhesive sheet produced according to the present invention, the surface resistivity after state and heating was 10 ¹³ or less, and the peeling voltage was also within ±1.0 kV, It was confirmed that the antistatic property was satisfied. Moreover, haze value was also 10% or less, and transparency was satisfied, and low contamination and anchoring property were also satisfied. Moreover, it was also confirmed that the adhesive force (low-speed peeling and high-speed peeling) which can be used as an adhesive sheet for re-peeling (surface protection, etc.) was maintained.

On the other hand, in Comparative Example 1, an antistatic pressure-sensitive adhesive sheet was formed in which an antistatic layer using an antistatic agent containing an acrylic resin copolymerized with quaternary ammonium chloride was formed on a corona-treated base film, but the peeling electrification voltage was ±. Results exceeding 1.0 kV and the surface resistivity after heating exceeded 10 ¹³ (exceeding the detection limit) were found. In addition, in Comparative Example 2, as a result of not performing corona treatment in the base film for Comparative Example 1, it was confirmed that the anchorability was insufficient, and the adhesive sheet itself capable of evaluation could not be obtained. Therefore, it was confirmed that, in any case of Comparative Examples 1 and 2, it was not possible to obtain antistatic properties (peeling high voltage, surface resistivity), adhesion properties, low fouling properties, transparency and transparency.

From the above results, the antistatic adhesive sheet provided with an antistatic layer formed of an antistatic agent composition containing a (meth)acrylic polymer containing a reactive (polymerizable) ionic liquid as a monomer unit as an intermediate layer is satisfactory in any evaluation. As a result, it was confirmed that it is possible to obtain an excellent effect that was not previously available.

1: Potentiometer 2: Adhesive sheet
3: Polarizing plate 4: Acrylic plate
5: fixture
10: antistatic adhesive sheet (adhesive sheet)
11: separator 12: adhesive layer
13: antistatic layer 14: base film

Claims (14)

It is an antistatic layer formed from the (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit and an antistatic agent composition containing a crosslinking agent,
The antistatic layer, wherein the reactive ionic liquid is a reactive ionic liquid represented by any one of the following formulas (1) to (4).
^{_{CH 2 = C (R 1)}} COOZX + Y - (1)
^{_{CH 2 = C (R 1)}} CONHZX + Y - (2)
^{_{CH 2 = C (R 1)}} COOX + Y - (3)
^{_{CH 2 = C (R 1)}} CONHX + Y - (4)
In Formulas (1) to (4), R ¹ is a hydrogen atom or a methyl group, X ⁺ is a cation moiety, and Y ^- is an anion excluding chlorine and bromine ions. Z represents an alkylene group having 1 to 3 carbon atoms] delete According to claim 1,
The anti-static layer, characterized in that the cation portion is a quaternary ammonium group. According to claim 1,
The antistatic layer, characterized in that the anion is a fluorine-containing anion. According to claim 1,
An antistatic layer, wherein the (meth)acrylic polymer comprises an oxyalkylene group-containing monomer having an average added mole number of 3 to 100 of the oxyalkylene unit represented by the following formula (5) as a monomer unit.
CH ₂ =C(R ₁ )-COO-(C _m H _2m O) _n -(C _p H _2p O) _q -R ₂ (5)
In Formula (5), R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a monovalent organic group, m and p are integers from 2 to 4, n and q are 0 or integers from 2 to 100, n And q is never 0 at the same time] According to claim 1,
An antistatic layer, wherein the (meth)acrylic polymer contains a hydroxyl group-containing (meth)acrylic monomer as a monomer unit. According to claim 1,
The antistatic layer, characterized in that the crosslinking agent is an isocyanate-based crosslinking agent. According to claim 1,
The antistatic layer, characterized in that the antistatic composition contains a conductive agent. An antistatic pressure-sensitive adhesive sheet, characterized in that the antistatic layer according to any one of claims 1 and 3 to 8 is formed on at least one side of the base film, and has an adhesive layer on the antistatic layer. The method of claim 9,
Anti-static adhesive sheet, characterized in that the base film is a plastic film. The method of claim 9,
An antistatic adhesive sheet characterized by being used for surface protection purposes. The method of claim 9,
An antistatic adhesive sheet characterized by being used in the process of manufacturing and shipping electronic components. An optical film with an antistatic adhesive sheet, which is characterized in that the antistatic adhesive sheet according to claim 11 is attached to an optical film. Forming the antistatic layer according to any one of claims 1 and 3 to 8 on at least one side of the base film, forming an adhesive layer on the antistatic layer, and adhering the adhesive layer to the optical film. An optical film with an antistatic adhesive sheet characterized by the above-mentioned.

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