TWI736546B - Antistatic agent for adhesives - Google Patents

Abstract

The object of the present invention is to provide an antistatic agent for adhesives that is excellent in durability even under high temperature and high humidity conditions. The antistatic agent for adhesives of the present invention is characterized by containing an ionic compound, wherein the cation site of the ionic compound is a cation represented by any one of the following formulas (1) to (3):

In the above formulas (1) to (3), R ¹ represents a hydrocarbon group with a carbon number of 1 or more and 18 or less, and may also include a heteroatom; R ² represents a hydrocarbon group with a carbon number of 2 or more and 4 or less, and a plurality of R ¹ or R ^2. Each can be the same or different.

Description

Antistatic agent for adhesives

The present invention relates to an antistatic agent for adhesives.

Generally speaking, the so-called static electricity refers to the phenomenon in which electric charges accumulate in an object and become charged; or, the charged electric charge itself. Static electricity, in addition to the accumulation of electric charges generated by the friction of the two dielectric materials, is also generated by contact with charged objects, etc., and accumulates on the surface of the object. The aforementioned static electricity may also cause the inhalation of foreign objects such as dust, electrostatic discharge of components, failure of measurement equipment, or fire. In addition, modern electromagnetic devices have a very high tendency to be temporarily or permanently damaged due to the discharge of static electricity.

For example, in a liquid crystal panel, an adhesive layer formed of an adhesive composition is often used to adhere a polarizing plate or a retardation plate to a glass substrate of a liquid crystal cell. Optical components such as polarizers and retardation plates are usually made of plastic materials and therefore have high electrical insulation. Therefore, static electricity is likely to be generated when the adhesive layer is peeled off. Therefore, if the polarizing plate or the retardation plate is stuck on the liquid crystal cell in the state where the static electricity generated thereby is left, there is a concern that the alignment direction of the liquid crystal molecules will be disturbed.

In addition, because the polarizing plate is manufactured at high speed, when the protective film of the polarizing plate is peeled off, the static electricity that should not have been generated in the existing steps will cause thin film transistors (TFT) and integrated circuits (ICs). ) The destruction phenomenon of the element and the possibility of inducing defects of the liquid crystal display panel.

Therefore, in order to suppress the generation of static electricity, there are proposals to provide an antistatic function to the adhesive layer, and as a means to impart an antistatic function to the adhesive layer, an ionic compound should be blended into the adhesive composition forming the adhesive layer (Patent Document 1).

In addition, even in semiconductor processing steps (for example, wafer dicing steps, back grinding steps), static electricity is generated due to peeling, friction, or contact of the adhesive. Therefore, it is proposed that as a method of suppressing the generation of static electricity in the same manner as described above, In the adhesive composition forming the adhesive layer, an ionic compound is blended (Patent Document 2).

However, the adhesive prepared by blending ionic compounds, when stored under high temperature and high humidity conditions, has the following problems due to the diffusion and movement of the ionic compounds: the surface resistance increases over time, or the ionic compounds move to the surface Layer oozes.

[Prior Technical Literature] (Patent Document)

Patent Document 1: Japanese Patent Application Publication No. 2011-037927

Patent Document 2: Japanese Patent Application Publication No. 2015-003988

The object of the present invention is to provide an antistatic agent for adhesives which is excellent in durability even under high temperature and high humidity conditions.

As a result of diligent research in order to solve the aforementioned problems, the inventors found that the aforementioned problems can be achieved by using an ionic compound having a specific cationic site, thereby completing the present invention.

The present invention relates to the following items [1] to [3].

[1] An antistatic agent for adhesives, which contains an ionic compound, wherein the cation site of the ionic compound is a cation represented by any one of the following formulas (1) to (3):

(前述式(1)~(3)中，R¹表示碳數1以上且18以下的烴基，亦可以包含雜原子；R²表示碳數2以上且4以下的烴基，並且複數個R¹或R²，各自可以相同亦可以不同。)

(In the aforementioned formulas (1) to (3), R ¹ represents a hydrocarbon group with 1 or more carbon atoms and 18 or less, and may also contain heteroatoms; R ² represents a hydrocarbon group with 2 or more carbon atoms and 4 or less, and a plurality of R ¹ or R ² , each may be the same or different.)

[2] The antistatic agent for adhesives as described in [1], wherein the anion site of the ionic compound is a compound containing a fluorine atom.

[3] The antistatic agent for adhesives as described in [1] or [2], wherein the anion site of the ionic compound is selected from the group consisting of bis(fluorinated sulfonyl) imide and bis(trifluoro) At least one of the group consisting of methanesulfonylimine.

According to the present invention, it is possible to provide an antistatic agent for adhesives which is excellent in durability even under high temperature and high humidity conditions.

Hereinafter, embodiments of the present invention will be described.

The ionic compound contained in the antistatic agent for adhesives of the present invention is composed of a cation site and an anion site, and can be either solid or liquid at room temperature (23°C/50% RH) By.

The cation site of the aforementioned ionic compound is represented by any one of the aforementioned formulas (1) to (3).

In formulas (1) to (3), R ¹ represents a hydrocarbon group having a carbon number of 1 or more and 18 or less, and may include a hetero atom. R ² represents a hydrocarbon group having a carbon number of 2 or more and 4 or less, preferably a hydrocarbon group having a carbon number of 2 or more and 3 or less, and more preferably a carbon number of 2 hydrocarbon group. A plurality of R ¹ or R ² may be the same or different.

The cation represented by formula (1) is not particularly limited. Specifically, it can include: 2-hydroxyethyltrimethylammonium cation, 2-hydroxyethyldimethylethylammonium cation, 2-hydroxyethyldimethylammonium cation Propylammonium cation, 2-hydroxyethyldimethylbutylammonium cation, 2-hydroxyethyldimethylhexylammonium cation, 2-hydroxyethyldimethyloctylammonium cation, 2-hydroxyethyldimethyldecylammonium cation Cation, 2- Hydroxyethyldimethyldodecylammonium cation, 2-hydroxyethyldimethylbenzylammonium cation, 2-hydroxyethyldiethylmethylammonium cation, 2-hydroxyethyltriethylammonium cation, 2-hydroxyethyl Diethylpropylammonium cation, 2-hydroxyethyldiethylbutylammonium cation, 2-hydroxyethyldiethylhexylammonium cation, 2-hydroxyethyldiethyloctylammonium cation, 2-hydroxyethyldiethyl Ethyldecylammonium cation, 2-hydroxyethyldiethyldodecylammonium cation, 2-hydroxyethyldiethylbenzylammonium cation, 2-hydroxyethyldibutylmethylammonium cation, 2-hydroxyethyldibutyl cation Ethylammonium cation, 2-hydroxyethyldibutylpropylammonium cation, 2-hydroxyethyltributylammonium cation, 2-hydroxyethyldibutylhexylammonium cation, 2-hydroxyethyldibutyloctylammonium cation, 2-hydroxyethyldibutyldecylammonium cation, 2-hydroxyethyldibutyldodecylammonium cation, 2-hydroxyethyldibutylbenzylammonium cation, 2-hydroxypropyltrimethylammonium cation, 4-hydroxy Butyltrimethylammonium cation, 2-hydroxypropyltriethylammonium cation, 4-hydroxybutyltriethylammonium cation, 2-hydroxypropyltributylammonium cation, 4-hydroxybutyltributylammonium cation, 2-hydroxypropyl 2-hydroxypropyl diethyl propyl ammonium cation, 2-hydroxypropyl diethyl propyl ammonium cation, 2-hydroxypropyl diethyl butyl ammonium cation, 2-hydroxypropyl diethyl hexyl ammonium cation, 2-hydroxypropyl diethyl ammonium cation Ethyloctylammonium cation, 2-hydroxypropyldiethyldecylammonium cation, 2-hydroxypropyldiethyldodecylammonium cation, 2-hydroxypropyldiethylbenzylammonium cation, etc. These cations may be used singly, or two or more of them may be used.

The cation represented by formula (2) is not particularly limited. Specifically, examples include bis(2-hydroxyethyl)dimethylammonium cation, bis(2-hydroxyethyl)ethylmethylammonium cation, bis(2-hydroxyethyl)ethylmethylammonium cation, 2-hydroxyethyl)propylmethylammonium cation, bis(2-hydroxyethyl)butylmethylammonium cation, bis(2-hydroxyethyl)hexylmethylammonium cation Bis(2-hydroxyethyl)octylmethylammonium cation, bis(2-hydroxyethyl)decylmethylammonium cation, bis(2-hydroxyethyl)dodecylmethylammonium cation, bis(2-hydroxyethyl)dodecylmethylammonium cation, Hydroxyethyl)octadecenylmethylammonium cation, bis(2-hydroxyethyl)benzylmethylammonium cation, bis(2-hydroxyethyl)diethylammonium cation, bis(2-hydroxyethyl)ethyl propyl Ammonium cation, bis(2-hydroxyethyl)ethylbutylammonium cation, bis(2-hydroxyethyl)ethylhexylammonium cation, bis(2-hydroxyethyl)ethyloctylammonium cation, bis(2-hydroxyethyl) Ethyl) ethyl decyl ammonium cation, bis (2-hydroxyethyl) ethyl dodecyl ammonium cation, bis (2-hydroxyethyl) ethyl benzyl ammonium cation, bis (2-hydroxyethyl) butyl propyl Ammonium cation, bis(2-hydroxyethyl)dibutylammonium cation, bis(2-hydroxyethyl)butylhexylammonium cation, bis(2-hydroxyethyl)butyloctylammonium cation, bis(2-hydroxyethyl) Cation , Bis(2-hydroxypropyl)diethylammonium cation, bis(2-hydroxypropyl)dibutylammonium cation, bis(2-hydroxypropyl)octadecenylmethylammonium cation, bis(4-hydroxybutyl) Dimethylammonium cation, bis(4-hydroxybutyl)diethylammonium cation, bis(4-hydroxybutyl)dibutylammonium cation, bis(2-hydroxybutyl)octadecenylmethylammonium cation, polyoxyethylene Dodecyl methyl ammonium cation, polyoxyethylene dodecyl ethyl ammonium cation, polyoxyethylene dodecyl butyl ammonium cation, polyoxyethylene dodecyl hexyl ammonium cation, polyoxyethylene ten Dialkyloctylammonium cation, polyoxyethylene octadecenyl methyl ammonium cation, polyoxyethylene octadecenyl ethyl ammonium cation, polyoxyethylene octadecenyl butyl ammonium cation, polyoxyethylene octadecene Hexylammonium cation, polyoxyethylene octadecenyl octyl ammonium cation, polyoxyethylene octadecyl methyl ammonium cation, polyoxyethylene octadecyl ethyl ammonium cation, polyoxyethylene octadecyl butyl ammonium cation Ions, polyoxyethylene octadecyl hexyl ammonium cation, polyoxyethylene octadecyl octyl ammonium cation, etc. These cations may be used singly, or two or more of them may be used.

The cation represented by formula (3) is not particularly limited. Specifically, it can include: tris(2-hydroxyethyl)methylammonium cation, tris(2-hydroxyethyl)ethylammonium cation, tris(2-hydroxyethyl) Ethyl)propylammonium cation, tris(2-hydroxyethyl)butylammonium cation, tris(2-hydroxyethyl)hexylammonium cation, tris(2-hydroxyethyl)octylammonium cation, tris(2-hydroxyethyl) )Decylammonium cation, tris(2-hydroxyethyl)dodecylammonium cation, tris(2-hydroxyethyl)octadecylammonium cation, tris(2-hydroxyethyl)octadecenium cation, tris(2 -Hydroxyethyl)benzylammonium cation, tris(2-hydroxypropyl)methylammonium cation, tris(2-hydroxypropyl)ethylammonium cation, tris(2-hydroxypropyl)propylammonium cation, tris(2-hydroxypropyl) Propyl) butylammonium cation, tris(2-hydroxypropyl)hexylammonium cation, tris(2-hydroxypropyl)octylammonium cation, tris(2-hydroxypropyl)decylammonium cation, tris(2-hydroxypropyl) ) Dodecylammonium cation, tris(2-hydroxypropyl)octadecylammonium cation, tris(2-hydroxypropyl)octadecenylammonium cation, tris(2-hydroxypropyl)benzylammonium cation, tris(4 -Hydroxybutyl) methylammonium cation, tris(4-hydroxybutyl)ethylammonium cation, tris(4-hydroxybutyl)propylammonium cation, tris(4-hydroxybutyl)butylammonium cation, tris(4-hydroxybutyl) Butyl)hexylammonium cation, tris(4-hydroxybutyl)octylammonium cation, tris(4-hydroxybutyl)decylammonium cation, tris(4-hydroxybutyl)dodecylammonium cation, tris(4-hydroxybutyl) Butyl)octadecylammonium cation, tris(4-hydroxybutyl)octadecenylammonium cation, tris(4-hydroxybutyl)benzylammonium cation, N-bis(2-hydroxyethyl)-N-(2 -Hydroxypropyl)methylammonium cation, N-bis(2-hydroxyethyl)-N-(2-hydroxybutyl)methylammonium cation, N-bis(2-hydroxypropyl)-N-(2-hydroxy Butyl) methylammonium cation, N-(2-hydroxymethyl)-N-(2-hydroxypropyl)-N-(2-hydroxybutyl)methylammonium cation and the like. These cations may be used singly, or two or more of them may be used.

Anionic portion of the ionic compound, as long as it can meet an anionic ionic compound is not particularly limited, and may be used, for ^{example: F -, Cl -, Br} -, I -, AlCl 4 -, Al 2 Cl 7 -, BF _{^{4 -, PF 6 -, SCN}} -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, _{(F 2 SO 2) 2 N} -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 N -, ^{_{C 4 F 9 SO 3 -,}} (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO - , and _{(CF 3 SO 2) (CF} 3 CO) N - and the like. These anions may be used singly, or two or more may be used.

Wherein the anionic component containing a fluorine atom, the preferred compound can be obtained from the ionic point of view a low melting point, and more preferably used _{is: (F 2 SO 2) 2} N - ( bis (sulfo acyl fluoride) (PEI) ) and _{(CF 3 SO 2) 2 N} - ( bis (trifluoromethane sulfonic acyl) (PEI)).

Specific examples of ionic compounds that can be used in the antistatic agent for adhesives of the present invention can be appropriately selected and used from the combination of the aforementioned cationic site and anionic site, and examples include: 2-hydroxyethyltrimethylammonium=hexafluorophosphate, 2-hydroxyethyltrimethylammonium=tetrafluoroborate, 2-hydroxyethyltrimethylammonium=trifluoromethanesulfonate, 2-hydroxyethyltrimethylammonium=bis(trifluoromethanesulfonyl)imide, 2 -Hydroxyethyltrimethylammonium = bis(fluorinated sulfonyl) imide, 2-hydroxyethyl dimethyl ethyl ammonium = bis(trifluoromethane sulfonyl) imide, 2-hydroxyethyl dimethyl ammonium Ethyl ammonium = bis(fluorinated sulfonyl) imide, 2- Hydroxyethyl dimethyl butyl ammonium = bis(trifluoromethanesulfonyl) imide, 2-hydroxyethyl dimethyl butyl ammonium = bis(fluorinated sulfonyl) imide, 2-hydroxyethyl Dimethyl octyl ammonium = bis (trifluoromethanesulfonyl) iminium, 2-hydroxyethyl dimethyl octyl ammonium = bis (fluorinated sulfonyl) iminium, 2-hydroxyethyl dimethyl Dodecyl ammonium = bis(trifluoromethanesulfonyl) imide, 2-hydroxyethyl dimethyl dodecyl ammonium = bis(fluorinated sulfonyl) imide, 2-hydroxyethyl diethyl Base methyl ammonium = hexafluorophosphate, 2-hydroxyethyl diethyl methyl ammonium = tetrafluoroborate, 2-hydroxyethyl diethyl methyl ammonium = trifluoromethanesulfonate, 2-hydroxyethyl diethyl Methyl ammonium = bis (trifluoromethanesulfonyl) imide, 2-hydroxyethyl diethyl methyl ammonium = bis (fluorinated sulfonyl) imide, 2-hydroxyethyl diethyl butyl ammonium = Bis(trifluoromethanesulfonyl) amide, 2-hydroxyethyl diethyl butyl ammonium = bis(fluorinated sulfonyl) amide, 2-hydroxyethyl diethyl octyl ammonium = bis( Trifluoromethanesulfonyl) imide, 2-hydroxyethyl diethyl octyl ammonium = bis(fluorinated sulfonyl) imide, 2-hydroxyethyl dibutyl methyl ammonium = bis(trifluoromethanesulfonyl) Base) amide, 2-hydroxyethyl dibutyl methyl ammonium = bis (fluorinated sulfonyl) amide, 2-hydroxyethyl tributyl ammonium = bis (trifluoromethane sulfonyl) amide, 2 -Hydroxyethyl tributyl ammonium = bis (fluorinated sulfonyl) amide, 2-hydroxyethyl dibutyl octyl ammonium = bis (trifluoromethane sulfonyl) amide, 2-hydroxyethyl two Butyl octyl ammonium = bis (sulfonyl fluoride) imide, 2-hydroxypropyl trimethyl ammonium = bis (trifluoromethane sulfonyl) imide, 2-hydroxypropyl trimethyl ammonium = bis (fluorinated Sulfonyl) imide, 4-hydroxybutyl trimethyl ammonium = bis(trifluoromethanesulfonyl) imide, 4-hydroxybutyl trimethyl ammonium = bis(fluorinated sulfonyl) imide, double (2-Hydroxyethyl)dimethylammonium=hexafluorophosphate, bis(2-hydroxyethyl)dimethylammonium=tetrafluoroborate, bis(2-hydroxyethyl)dimethylammonium=trifluoromethanesulfonic acid Salt, bis(2-hydroxyethyl) Dimethylammonium = bis(trifluoromethanesulfonyl)imid, dimethylammonium = bis(fluorosulfonyl)imid, bis(2-hydroxyethyl)butylmethylammonium = bis(trifluoromethanesulfon) Amino) amide, bis(2-hydroxyethyl)butylmethylammonium = bis(sulfonyl fluoride) amide, bis(2-hydroxyethyl)octylmethylammonium = bis(trifluoromethanesulfonyl) Base) amide, bis(2-hydroxyethyl) octyl methyl ammonium = bis (sulfonyl fluoride) amide, bis (2-hydroxyethyl) octadecenyl methyl ammonium = bis (trifluoro Methanesulfonyl) imide, bis(2-hydroxyethyl)octadecenylmethylammonium=bis(fluorinated sulfonyl)imid, bis(2-hydroxyethyl)butyloctylammonium=bis (Trifluoromethanesulfonyl) iminium, bis(2-hydroxyethyl) butyloctyl ammonium = bis(fluorinated sulfonyl) iminium, bis(2-hydroxypropyl) dimethylammonium = bis (Trifluoromethanesulfonyl) iminium, bis (2-hydroxypropyl) dimethyl ammonium = bis (fluorinated sulfonyl) iminium, bis (4-hydroxybutyl) dimethyl ammonium = bis ( Trifluoromethanesulfonyl) imide, bis(4-hydroxybutyl) dimethyl ammonium = bis(fluorinated sulfonyl) imide, polyoxyethylene dodecyl methyl ammonium = bis(trifluoromethane) Sulfonyl) amide, polyoxyethylene lauryl methyl ammonium = bis (fluorinated sulfonyl) amide, polyoxyethylene stearyl methyl ammonium = bis (trifluoromethane sulfonyl) amide Imine, polyoxyethylene stearyl methyl ammonium = bis (fluorinated sulfonyl) amide, polyoxyethylene stearyl methyl ammonium = bis (trifluoromethane sulfonyl) amide, polyoxy Ethylene octadecyl methylammonium = bis (sulfonyl fluoride) imide, tris (2-hydroxyethyl) methyl ammonium = hexafluorophosphate, tris (2-hydroxyethyl) methyl ammonium = tetrafluoroborate Salt, tris(2-hydroxyethyl)methylammonium=trifluoromethanesulfonate, tris(2-hydroxyethyl)methylammonium=bis(trifluoromethanesulfonyl)imide, tris(2-hydroxyethyl) Base) methyl ammonium = bis(fluorinated sulfonyl) amide, tris(2-hydroxypropyl) methyl ammonium = bis(trifluoromethane sulfonyl) amide, tris(2-hydroxypropyl) methyl Ammonium = bis(sulfonyl fluoride) imine, tris(4-hydroxybutyl) methylammonium = Bis(trifluoromethanesulfonyl)imid, tris(4-hydroxybutyl)methylammonium=bis(fluorosulfonyl)imid, etc. The plasmonic compound may be used singly, or two or more kinds may be used.

In addition, as the aforementioned ionic compound, a commercially available product can be used, or it can be synthesized in the following manner. As a synthesis method such as ionic compounds, as long as the desired ionic compound can be obtained, it is not particularly limited, and can be used as described in the document "Ionic Liquids-The Forefront and Future of Development" (published by CMC Co., Ltd.) Halide method, hydroxide method, acid ester method, complex formation method and neutralization method, etc.

The antistatic agent for an adhesive of the present invention contains an ionic compound as an effective ingredient, and the ionic compound has a cationic site as described in any one of the aforementioned formulas (1) to (3); and the adhesive The antistatic agent for the agent can be used alone, or it can be used by mixing additives such as stabilizers or solvents as necessary.

The addition amount of the antistatic agent for the adhesive of the present invention is 0.01 parts by mass or more relative to 100 parts by mass of the adhesive polymer, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and 40 parts by mass or less , Preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

The antistatic agent for adhesives of the present invention can be widely applied to adhesive polymers used in this technical field. Examples of the aforementioned adhesive polymer include (meth)acrylic polymers, rubber-based polymers, silicone-based polymers, and polyurethane-based polymers. Among these, it is preferable to be able to use a (meth)acrylic polymer.

The aforementioned (meth)acrylic polymer is, for example, a polymer containing alkyl (meth)acrylate as a monomer unit (component), and the alkyl (meth)acrylate has a linear or branched chain with 1 to 20 carbon atoms. Chain alkyl. Moreover, the said (meth)acrylic-type polymer can be set as the structure which used the alkyl (meth)acrylate which has a C1-C20 alkyl group individually or in combination of 2 or more types.

As the aforementioned alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate Base) isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate Ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) Isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, Dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, Heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. C1-20 alkyl (meth)acrylate (Preferably C2-14 alkyl (meth)acrylate, more preferably C2-10 alkyl (meth)acrylate) and the like. In addition, the so-called alkyl (meth)acrylate means alkyl acrylate and/or alkyl methacrylate, and "(meth)..." all have the same meaning.

The ratio of the aforementioned alkyl (meth)acrylate having an alkyl group with 1 to 20 carbon atoms is 50 parts by mass relative to 100 parts by mass of the total monomer units (components) used to prepare the (meth)acrylic polymer Parts or more, more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more. On the other hand, the aforementioned ratio is 99.9 parts by mass or less, preferably 98 parts by mass or less, and more preferably 96 parts by mass or less. If it is within the aforementioned range, it will become a better aspect because it can obtain better adhesive properties in an adhesive sheet used for re-peeling purposes.

In addition, the aforementioned (meth)acrylic polymer may contain other monomer units (components) (copolymerizable monomers) if necessary for modification of cohesive force, heat resistance, crosslinkability, etc. , This other monomer unit can be copolymerized with the aforementioned alkyl (meth)acrylate. Therefore, the (meth)acrylic polymer may contain a copolymerizable monomer in addition to the aforementioned alkyl (meth)acrylate as the main component. As the copolymerizable monomer, a monomer having a polar group can be suitably used. Furthermore, the so-called main component refers to the monomer with the highest blending ratio among the total monomer components.

Specific examples of the aforementioned copolymerizable monomers include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, methylene succinic acid, maleic acid, fumaric acid, Monomers containing carboxyl groups such as crotonic acid and methacrylic acid; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, (4-hydroxymethylcyclohexyl) )Methyl methacrylate, etc. (meth) hydroxyalkyl acrylate, etc. contain a hydroxyl group Monomers; maleic anhydride, methylene succinic anhydride and other monomers containing acid anhydride groups; styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropane Sulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)acrylic acid propyl sulfonate, (meth)acryloxynaphthalenesulfonic acid and other monomers containing sulfonic acid groups; phosphoric acid 2-hydroxy Monomers containing phosphoric acid groups such as ethyl acrylate; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide , N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-bis(n-butyl)(meth)acrylamide, N,N-Di(tertiarybutyl)(meth)acrylamide and other N,N-dialkyl(meth)acrylamide; N-ethyl(meth)acrylamide, N-isopropyl (Meth)acrylamide, N-butyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxyl Ethyl (meth)acrylamide, N-methylolpropane (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (methyl) (N-substituted) amide-based monomers such as acrylamide, N-butoxymethyl (meth)acrylamide, N-acrylamide morpholine; N-(meth)acryloxy Methyl succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene Succinimide monomers such as succinimide; N-cyclohexyl maleimide, N-isopropyl maleimide, N-dodecyl maleimide Maleimines, N-phenylmaleimide and other maleimine monomers; N-methylmethylene succinimide, N-ethylmethylene succinimide Imine, N-butylmethylene succinimide, N-octylmethylene succinimide, N-2-ethylhexylmethylene succinimide, N-cyclohexylimine Methyl succinimide, N- Methylene succinimide monomers such as dodecylmethylene succinimide; 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-vinyl N-imidazole, 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-oxa Azin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, N- Nitrogen-containing heterocyclic monomers such as pyridazine; N-vinyl carboxylic acid amines; N-vinyl caprolactam and other internal amine monomers; acrylonitrile, methacrylonitrile, etc. Cyanoacrylate monomers; (meth)aminoethyl acrylate, (meth)acrylate N,N-dimethylaminoethyl, (meth)acrylate tertiary butylaminoethyl, etc. (meth) Amine alkyl acrylate monomer; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate (Meth)acrylic acid alkoxyalkyl ester monomers such as ester, (meth)acrylate ethoxypropyl ester; styrene, α-methylstyrene and other styrene monomers; (meth)acrylic epoxy Propyl ester and other epoxy-containing propylene monomers; methyl tetrahydrofuran (meth)acrylate, fluorine-containing (meth)acrylate, silicone (meth)acrylate, etc. have heterocycles, halogen atoms, and silicon atoms Acrylate-based monomers such as isoprene, butadiene, isobutylene, etc.; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate Vinyl esters such as esters 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 Class; Chlorinated vinyl; Sodium vinyl sulfonate and other monomers containing sulfonic acid groups; Monomers containing sulfonic acid groups such as cyclohexyl maleimide and isopropyl maleimide; 2 -Isocyanatoethyl (meth)acrylate and other isocyanate group-containing monomers; acrylomorpholine; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isocamphor (meth)acrylate (Meth)acrylate esters, dicyclopentenyl (meth)acrylate and other alicyclic hydrocarbon groups; phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and other aromatic hydrocarbons (Meth) acrylate; (meth) acrylate obtained from terpene compound derivative alcohol, etc. These polymerizable monomers may be used singly or in two or more types.

When the aforementioned (meth)acrylic polymer contains a copolymerizable monomer together with the aforementioned alkyl (meth)acrylate as a main component, the aforementioned hydroxyl group-containing monomer or carboxyl group-containing monomer can be suitably used. Among them, as the aforementioned hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are suitable, and as the aforementioned carboxyl group-containing monomers, acrylic acid can be suitably used.

Although the reason why the antistatic agent for adhesives of the present invention is excellent in durability even under high temperature and high humidity conditions is not clear, it can be estimated as follows. That is, it can be inferred that when the aforementioned (meth)acrylic polymer has a hydroxyl group, a carboxyl group, etc., the ionic compound contained in the antistatic agent for adhesives of the present invention has a hydroxyl group at the cationic site, thereby improving the present invention. The ionic compound contained in the antistatic agent for adhesives is the same as the aforementioned The compatibility of the (meth)acrylic polymer and the improvement of durability can be exhibited.

In order to adjust the molecular weight of the aforementioned (meth)acrylic polymer, a chain transfer agent can be used in the polymerization. Examples of chain transfer agents used include: octyl mercaptan, dodecyl mercaptan, tertiary dodecyl mercaptan, mercaptoethanol, α-mercaptoglycerol, and other compounds having mercapto groups; thioacetic acid, methyl thioacetate Ester, ethyl thioacetate, propyl thioacetate, butyl thioacetate, tertiary butyl thioacetate, 2-ethylhexyl thioacetate, octyl thioacetate, decyl thioacetate, dodecyl thioacetate, Thioacetate esters such as thioacetate of ethylene glycol, thioacetate of neopentyl glycol, and thioacetate of pentaerythritol; α-methylstyrene dimer, etc. One kind of these chain transfer agents may be used alone, or two or more kinds may be used.

When preparing the aforementioned (meth)acrylic polymer, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) is used to utilize the curing reaction by heat or ultraviolet rays, which can easily To form a (meth)acrylic polymer. In particular, thermal polymerization can be suitably used from the viewpoint of the advantage of being able to shorten the polymerization time. A polymerization initiator can be used individually or in combination of 2 or more types.

Examples of the thermal polymerization initiator include azo polymerization initiators (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-Azo (2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azo Bis(2-carboxamidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2 '-Azobis(2-Methylpropionate amidine) bis Sulfate; 2,2'-azobis(N,N'-dimethylene isobutamidine) dihydrochloride, etc.); peroxide polymerization initiator (for example, dibenzyl peroxide, three Grade butyl peroxy maleate (t-butyl peroxide maleate, dodecyl peroxide, etc.); redox system polymerization initiator, etc.

The blending amount of the thermal polymerization initiator is not particularly limited. For example, it is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the total amount of monomer units (components) for preparing the (meth)acrylic polymer. It is formulated in an amount within the range of 5 parts by mass, more preferably 0.05 to 3 parts by mass.

The aforementioned photopolymerization initiator is not particularly limited. For example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, and chlorinated aromatics can be used. Group sulfonamide-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, diphenylethylenedione-based photopolymerization initiator, benzophenone-based photopolymerization initiator Agents, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, phosphine oxide-based photopolymerization initiators, and the like.

Specifically, as the aforementioned benzoin ether-based photopolymerization initiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- Dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF), anisole methyl ether, and the like. As the acetophenone-based photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-tertiary Butyl-dichloroacetophenone, 1-[4-(2-hydroxyethyl (Oxy)-phenyl] 2-hydroxy-2-methyl-1-propane-1-one (trade name: IRGACURE 2959, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (trade name: DAROCUR 1173, manufactured by BASF Corporation), methoxyacetophenone, and the like. Examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methyl Propane-1-one and so on. As a chlorinated aromatic sulfonyl-based photopolymerization initiator, for example, chlorinated 2-naphthalenesulfonyl and the like can be mentioned. As a photoactive oxime-type photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime etc. are mentioned, for example.

In addition, the aforementioned benzoin-based photopolymerization initiator includes, for example, benzoin and the like. The diphenylethylenedione-based photopolymerization initiator includes, for example, diphenylethylenedione and the like. The benzophenone-based photopolymerization initiator includes benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, and polyvinyl diphenyl ketone. Ketone, α-hydroxycyclohexyl phenyl ketone, etc. The ketal-based photopolymerization initiator includes, for example, benzildimethyl ketal and the like. The thioxanthone-based photopolymerization initiator includes, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethyl Thioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone Xanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc.

As the aforementioned phosphine oxide-based photopolymerization initiator, for example, bis(2,6-dimethoxybenzyl)phenyl phosphine oxide, bis(2,6-dimethoxybenzyl) (2,4,4-Trimethylpentyl)phosphine oxide, bis(2,6- Dimethoxybenzyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzyl)-(2-methylpropane-1-yl)phosphine oxide, bis(2,6- Dimethoxybenzyl)-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzyl)tertiary butylphosphine oxide, bis(2,6- Dimethoxybenzyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzyl)octylphosphine oxide, bis(2-methoxybenzyl)(2-methylpropane- 1-yl)phosphine oxide, bis(2-methoxybenzyl)(1-methylpropane-1-yl)phosphine oxide, bis(2,6-diethoxybenzyl)(2-methyl Propan-1-yl)phosphine oxide, bis(2,6-diethoxybenzyl)(1-methylpropane-1-yl)phosphine oxide, bis(2,6-dibutoxybenzyl) (2-methylpropane-1-yl)phosphine oxide, bis(2,4-dimethoxybenzyl)(2-methylpropane-1-yl)phosphine oxide, bis(2,4, 6-trimethylbenzyl)(2,4-dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzyl)benzylphosphine oxide, bis(2,6-di Methoxybenzyl)-2-phenylpropyl phosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenethylphosphine oxide, bis(2,6-dimethoxybenzene) (Methyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzylbenzylbutyl Phosphine oxide, 2,6-dimethoxybenzyl benzyl octyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,5-dicumyl phosphine oxide, double (2,4,6-trimethylbenzyl)-2-tolyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-4-tolyl phosphine oxide, bis(2,4 ,6-trimethylbenzyl)-2,5-diethylphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,3,5,6-tetramethyl Phenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,4-di-n-butoxyphenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl Pentyl phosphine oxide, bis(2,4,6-trimethylbenzyl)isobutyl phosphine oxide, 2,6-dimethoxybenzyl-2,4,6-trimethylbenzyl N-butyl phosphine oxide, bis(2,4,6-trimethylbenzyl) phenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-2,4-dibutoxy Phenyl phosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzyl)phosphine oxide]decane, tris(2-methylbenzyl)phosphine oxide, etc.

The compounding amount of the aforementioned photopolymerization initiator is not particularly limited. For example, it is preferably in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the total amount of monomer components for preparing the aforementioned (meth)acrylic polymer. The amount within is more preferably 0.05 to 3 parts by mass. Here, if the compounding amount of the photopolymerization initiator is less than 0.01 part by mass, the polymerization reaction may become insufficient. If the blending amount of the photopolymerization initiator exceeds 5 parts by mass, the photopolymerization initiator absorbs ultraviolet rays, which may prevent the ultraviolet rays from reaching the inside of the adhesive layer. At this time, a decrease in the polymerization rate occurs, and the molecular weight of the produced polymer becomes small.

The method for obtaining the aforementioned (meth)acrylic polymer is not particularly limited. As a synthesis method, various polymerization methods generally used can be applied to obtain the polymer. The various polymerization methods generally used are solution polymerization and emulsion polymerization. , Block polymerization, suspension polymerization, radiation hardening polymerization, etc.

When the aforementioned (meth)acrylic polymer is used in an adhesive sheet and the aforementioned adhesive sheet is used as a surface protection sheet, from the viewpoint of the productivity of the adhesive sheet, solution polymerization can be suitably used. Synthetic and emulsification polymerization. In addition, the obtained polymer may be any of random copolymers, block copolymers, interactive copolymers, graft copolymers, and the like.

The aforementioned (meth)acrylic copolymer preferably contains a curing agent. There are no particular limitations on the aforementioned curing agent. Specifically, it preferably contains one or more selected from the group consisting of isocyanate-based curing agents, epoxy-based curing agents, ethyleneimine-based curing agents, metal chelate-based curing agents, and amine-based curing agents .

The (meth)acrylic polymer formed by using the aforementioned crosslinking agent, because the antistatic agent for the adhesive of the present invention passes through the crosslinking agent and covalently bonds with the (meth)acrylic polymer Since bonding is performed, it can be estimated that the durability under higher temperature and high humidity conditions can be improved.

As the aforementioned isocyanate-based curing agent, specifically, a compound that preferably contains a bifunctional or more isocyanate group in the molecule, and more preferably a compound that contains a trifunctional or more functional isocyanate group in the molecule is exemplified.

Examples of the aforementioned isocyanate-containing compound include: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate Polyisocyanate compounds such as phenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, etc.; and, The adduct or biuret or isocyanurate of these isocyanate compounds and polyols such as trimethylolpropane; further, these isocyanate compounds are combined with known polyether polyols. Alcohol or polyester polyol, acrylic polyol, polybutadiene polyol Adducts such as alcohols, polyisoprene polyols, etc. These isocyanate-containing compounds may be used singly, or two or more kinds may be used.

As the isocyanate-based curing agent used as the aforementioned curing agent, preferably: trimethylolpropane adduct of phenylmethylene diisocyanate, trimer isocyanate of phenylmethylene diisocyanate, and isophorone diisocyanate The trimeric isocyanate body is particularly preferably the trimethylolpropane adduct of phenylmethylene diisocyanate. These hardeners may be used singly, or two or more of them may be used.

Examples of ethyleneimine hardeners include: N,N'-diphenylmethane-4,4'-bis(1-ethyleneimine carbonyl), N,N'-toluene-2,4 -Bis (1-ethyleneimine carbonyl compound), bis-m-phthalimide-1-(2-methylethyleneimine), tri-1-ethyleneimine phosphine oxide, N,N' -Hexamethylene-1,6-bis(1-ethyleneimine carbonyl), 2,2'-bishydroxymethylbutanol-tris[3-(1-ethyleneimine)propyl ester] , Trimethylolpropane tri-β-ethyleneimine propyl ester, tetramethylolpropane tri-β-ethyleneimine propyl ester, tri-2,4,6-(1-ethyleneimine Base) -1,3,5-triazabenzene and the like.

Examples of epoxy-based hardeners include: bisphenol A-epichlorohydrin type epoxy-based resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerin Diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N,N',N'-tetraepoxypropyl metaxylylenediamine, 1,3-bis(N,N'-diepoxypropylaminomethyl)cyclohexane, N,N,N ',N'-Tetraglycidylaminophenylmethane, triglycidol (triglycidyl) and so on. These hardeners may be used singly, or two or more of them may be used.

As an example of a metal chelate hardener, a coordination compound of a polyvalent metal and acetone or ethyl acetone can be cited. The polyvalent metal is aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, Magnesium, vanadium, chromium and zirconium, etc. These hardeners may be used singly, or two or more of them may be used.

Examples of amine hardeners include: hexamethylene diamine, triethyl diamine, polyethyleneimine, hexamethylene tetramine, divinyl triamine, triethyl tetramine, isophor Ketone diamine, amino resin and methylene resin, etc. These hardeners may be used singly, or two or more of them may be used.

With respect to 100 parts by mass of the (meth)acrylic polymer, these hardeners are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass.

In addition to the aforementioned components, the aforementioned adhesive polymer may also contain selected from the group consisting of polymerization inhibitors, adhesion-imparting agents, plasticizers, crosslinking accelerators, antioxidants, light One or two or more of stabilizers, metal corrosion inhibitors, (meth)acrylic polymers other than the aforementioned adhesive polymers, and rework agents.

The aforementioned adhesive polymer preferably contains an organic solvent in order to adjust its coatability. The organic solvent is not particularly limited. Specifically, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, Cyclohexane, Alicyclic hydrocarbons such as cycloheptane and cyclooctane; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane , Anisole, phenyl ethyl ether, diphenyl ether and other ethers; trichloromethane, tetrachloromethane, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, propyl acetate , Butyl acetate, methyl propionate and other esters; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; N,N-dimethylformamide , N,N-dimethylacetamide, N-methylpyrrolidone and other amides; acetonitrile, benzonitrile and other nitriles; dimethyl sulfinium, cyclobutane and other sulfinates. These polymerization solvents may be used singly, or two or more kinds may be used.

In the aforementioned adhesive polymer, the content of the organic solvent is usually 50 to 90% by mass, preferably 60 to 85% by mass.

The adhesive composition using the antistatic agent for adhesives of the present invention can be obtained by mixing the antistatic agent for adhesives, the adhesive polymer, and the crosslinking agent and other components as required by a previously known method. Make modulation. For example, the following method can be mentioned: in a polymer solution containing a copolymer, an ionic compound, a crosslinking agent and other components as required are blended; the copolymer is a synthetic adhesive polymer that is (meth)acrylic Obtained when polymer.

[Example]

Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, if there is no special mention, "parts" means "parts by mass".

[Measurement and Evaluation Method]

In the following Examples and Comparative Examples, the measurement methods and evaluation methods of various properties are as follows.

<Molecular weight: weight average molecular weight (Mw)>

The molecular weight of the (meth)acrylic copolymer was measured using a GPC device HLC-8220GPC manufactured by TOSOH Co., Ltd., and was calculated using a polystyrene conversion value.

The measurement conditions are as follows. Sample concentration: 0.2wt% (THF solution); sample injection volume: 10μl; eluent: THF; flow rate: 0.6 mL/min; measurement temperature: 40°C; column: sample column, TSK guard column Super HZ-H 1 + TSK gel Super HZM-H 2; Reference column: TSK gel Super H-RC 1; Detector: refractive index detector.

<Durability evaluation>

For the evaluation adhesive sheets obtained in the Examples and Comparative Examples, the surface resistance values were measured in an environment of 20°C/65% RH. The surface resistance value was measured at an applied voltage of 500V using R8340A manufactured by Advantest Co., Ltd. Let this be the initial surface resistance value (Ω/square).

In addition, after leaving this adhesive sheet for evaluation in a 60° C./90% RH environment for 500 hours, the surface resistance value was measured in the same manner. Let this be the surface resistance value after the endurance test.

<Preparation of (meth)acrylic copolymer>

((Meth) acrylic copolymer A)

In a reaction device equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, after filling with nitrogen gas, 70 parts of ethyl acetate, 15 parts of acetone, 62.5 parts of butyl acrylate, and 19.0 parts of acrylic phenoxy are added. Ethyl ester, 16.0 parts of methyl acrylate, 1.5 parts of acrylic acid, 1.0 part of 2-hydroxyethyl acrylate, and 0.1 part of 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industry Co., Ltd.) , Trade name V-60). While stirring, the reaction was carried out for 8 hours at the reflux temperature of the solvent in a nitrogen gas stream. After the completion of the reaction, 315 parts of toluene was added and then cooled to room temperature to prepare a polymer solution with a solid content of 20% by weight. The obtained (meth)acrylic copolymer A had a viscosity of 7000mPa‧s and a weight average molecular weight (Mw) of 1.35 million.

<Preparation of ionic compounds>

(Ionic compound C-1)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 139.6 g of 2-hydroxyethyl trimethylammonium chloride, 219.2 g of potassium bis(sulfonyl fluoride) imide and 359 g of acetonitrile, and stir at room temperature 2 hours.

After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 262 g of 2-hydroxyethyltrimethylammonium=bis(sulfonyl chloride)imide (92% yield).

The obtained 2-hydroxyethyltrimethylammonium=bis(sulfonyl chloride) imide was ^{measured by NMR (nuclear magnetic resonance) (1} H, ¹³ C) and FT-IR (Fourier infrared spectroscopy). Identify and confirm.

(Ionic compound C-2)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 169.6g of bis(2-hydroxyethyl)dimethylammonium chloride, 219.2g of bis(fluorinated sulfonyl)imidine, and 389g of acetonitrile. Stir at room temperature for 2 hours. After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 292 g of bis(2-hydroxyethyl)dimethylammonium=bis(fluorosulfonyl)imid potassium (yield 93%).

The obtained bis(2-hydroxyethyl)dimethylammonium=bis(fluorosulfonyl)imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-3)

In a four-necked flask equipped with a stirrer, a thermometer and a cooler, measure 267.8g of bis(2-hydroxyethyl)octylmethylammonium chloride, 219.2g of potassium bis(sulfonyl fluoride) imide and 595g of acetonitrile , Stir at room temperature for 2 hours.

After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 375 g of bis(2-hydroxyethyl)octylmethylammonium=bis(fluorinated sulfonyl)imide (yield 91%).

The obtained bis(2-hydroxyethyl)octylmethylammonium=bis(fluorinated sulfonyl)imidine was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-4)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 406g of bis(2-hydroxyethyl)octadecenylmethylammonium chloride, 219.2g of potassium bis(sulfonyl fluoride) imide and 938g Acetonitrile, stir at room temperature for 2 hours.

After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 496 g of bis(2-hydroxyethyl)octadecenylmethylammonium=bis(fluorinated sulfonyl)imide (yield 90%) .

The obtained bis(2-hydroxyethyl)octadecenylmethylammonium=bis(fluorinated sulfonyl)imidine was ^{identified by NMR (1} H, ¹³ C) measurement and FT-IR measurement. confirm.

(Ionic compound C-5)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 200g of tris(2-hydroxyethyl)methylammonium chloride, 219.2g of potassium bis(sulfonyl fluoride) imide and 420g of acetonitrile. Warm stirring for 2 hours.

After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 310 g of tris(2-hydroxyethyl)methylammonium=bis(fluorinated sulfonyl)imidine (yield 90%).

The obtained tris(2-hydroxyethyl)methylammonium=bis(fluorinated sulfonyl)imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-6)

In a four-necked flask equipped with a stirrer, thermometer, and cooler, measure 169.6g of bis(2-hydroxyethyl)dimethylammonium chloride, 287.1g of lithium bis(trifluoromethanesulfonyl)imide, and 457g of acetonitrile , Stir at room temperature for 2 hours.

After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 385 g of bis(2-hydroxyethyl)dimethylammonium=bis(trifluoromethanesulfonyl)imidine (yield 93%).

The obtained bis(2-hydroxyethyl)dimethylammonium=bis(trifluoromethanesulfonyl)imidine was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-7)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 286g of 1-octyl-4-methylpyridine bromide, 219.2g of potassium bis(fluorinated sulfonyl)imide, and 505g of distilled water. Warm stirring for 2 hours, and let stand for 3 hours. The supernatant of the obtained reaction liquid was removed to obtain a liquid product.

The obtained liquid product was washed 3 times in 200 g of distilled water, and then concentrated and filtered to obtain 348 g of 1-octyl-4-methylpyridine = bis(fluorinated sulfonyl) imide (product Rate 90%).

The obtained 1-octyl-4-methylpyridine=bis(fluorinated sulfonyl)imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-8)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 236g of 1-ethyl-3-methylimidazolium ethyl sulfate, 219.2g of potassium bis(fluorosulfonyl)imide and 455g of distilled water, Stir at room temperature for 2 hours, and let stand for 3 hours. The supernatant of the obtained reaction liquid was removed to obtain a liquid product.

The obtained liquid product was washed three times in 140 g of distilled water, and then concentrated and filtered to obtain 233 g of 1-ethyl-3-methylimidazole=bis(fluorinated sulfonyl)imide (yield 80%).

The obtained 1-ethyl-3-methylimidazole=bis(fluorinated sulfonyl)imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-9)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 207.8g of octyltrimethylammonium chloride, 219.2g of potassium bis(sulfonyl fluoride) imide and 427g of distilled water, and stir at room temperature for 2 hours. And let it stand for 3 hours. The supernatant of the obtained reaction liquid was removed to obtain a liquid product.

The obtained liquid product was washed three times in 176 g of distilled water, and then concentrated and filtered to obtain 324 g of octyltrimethylammonium=bis(fluorinated sulfonyl)imide (92% yield).

The obtained octyltrimethylammonium=bis(sulfonyl fluoride) imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

(Ionic compound C-10)

In a four-necked flask equipped with a stirrer, a thermometer, and a cooler, measure 236g of 1-ethyl-3-methylimidazole ethyl sulfate, 287.1g of lithium bis(trifluoromethanesulfonyl)imide and 523g of distilled water , Stir at room temperature for 2 hours, and let stand for 3 hours. The supernatant of the obtained reaction liquid was removed to obtain a liquid product.

The obtained liquid product was washed 3 times in 196 g of distilled water, and then concentrated and filtered to obtain 329 g of 1-ethyl-3-methylimidazole=bis(trifluoromethanesulfonyl)imide (product Rate 84%).

The obtained 1-ethyl-3-methylimidazole=bis(trifluoromethanesulfonyl)imide was ^{identified and confirmed by NMR (1} H, ¹³ C) measurement and FT-IR measurement.

[Example 1]

<Preparation of adhesive composition for evaluation>

With respect to 100 parts by weight (solid content conversion value) of the (meth)acrylic copolymer A solution, 1.5 parts by weight (solid content conversion value) of the ionic compound C-1 was added and stirred. Furthermore, 0.08 parts by weight of crosslinking agent B (bisuret type of hexamethylene diisocyanate (manufactured by Asahi Kasei Industrial Co., Ltd., trade name DURANATE 24A-100)) was mixed to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the polyethylene terephthalate film (PET film) that has been peeled off, the adhesive composition for evaluation prepared as described above is applied so that the dry film thickness becomes 20 μm, so that This was dried at 90°C for 4 minutes, transferred to a triacetylated cellulose film (TAC film), and cured in an atmosphere of 20°C and 65% RH for 7 days to obtain an adhesive sheet for evaluation.

Using the obtained adhesive sheet for evaluation, durability evaluation was performed. The results are shown in Table 1.

[Examples 2 to 6, Comparative Examples 1 to 4]

Except that the type of ionic compound in Example 1 was changed to that described in Table 1, the same procedure as in Example 1 was carried out to prepare and create an adhesive set for evaluation. The finished product and the adhesive sheet for evaluation were evaluated for durability. The results are shown in Table 1.

[Example 7]

<Preparation of adhesive composition for evaluation>

With respect to 100 parts by weight (solid content conversion value) of the (meth)acrylic copolymer A solution, 1.5 parts by weight (solid content conversion value) of the aforementioned ionic compound C-1 was added and stirred to obtain an adhesive for evaluation Composition.

<Production of adhesive sheet for evaluation>

On the polyethylene terephthalate film (PET film) that has been peeled off, the adhesive composition for evaluation prepared as described above is applied so that the dry film thickness becomes 20 μm, so that This was dried at 90°C for 4 minutes, transferred to a triacetylated cellulose film (TAC film), and cured in an atmosphere of 20°C and 65% RH for 1 day to obtain an adhesive sheet for evaluation.

Using the obtained adhesive sheet for evaluation, durability evaluation was performed. The results are shown in Table 1.

[Examples 8-11, Comparative Examples 5-7]

Except that the type of ionic compound in Example 7 was changed as described in Table 1, the same procedure as in Example 7 was carried out to prepare an evaluation adhesive composition and an evaluation adhesive sheet, and the durability was evaluated. The results are shown in Table 1.

[Example 12]

<Preparation of adhesive composition for evaluation>

With respect to 100 parts by weight (solid content conversion value) of the (meth)acrylic copolymer A solution, 1.5 parts by weight (solid content conversion value) of the ionic compound C-1 was added and stirred. Furthermore, 0.08 parts by weight of crosslinking agent B (bisuret type of hexamethylene diisocyanate (manufactured by Asahi Kasei Industrial Co., Ltd., trade name DURANATE 24A-100)) was mixed to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the polyethylene terephthalate film (PET film) that has been peeled off, the adhesive composition for evaluation prepared as described above is applied so that the dry film thickness becomes 20 μm, so that This was dried at 90° C. for 4 minutes, transferred to a PET film without peeling treatment, and cured in an atmosphere of 20° C. and 65% RH for 7 days to obtain an adhesive sheet for evaluation.

The PET film obtained by peeling off the obtained adhesive sheet for evaluation was peeled off, and durability evaluation was performed in this state. The results are shown in Table 1.

[Examples 13-17, Comparative Examples 8-11]

Except for changing the type of the ionic compound in Example 12 to be as described in Table 1, the same procedure as in Example 12 was carried out to prepare an evaluation adhesive composition and an evaluation adhesive sheet to perform durability evaluation. The results are shown in Table 1.

[Example 18]

<Preparation of adhesive composition for evaluation>

With respect to 100 parts by weight (solid content conversion value) of the (meth)acrylic copolymer A solution, 1.5 parts by weight (solid content conversion value) of the aforementioned ionic compound C-1 was added and stirred to obtain an adhesive for evaluation Composition.

<Production of adhesive sheet for evaluation>

On the polyethylene terephthalate film (PET film) that has been peeled off, the adhesive composition for evaluation prepared as described above is applied so that the dry film thickness becomes 20 μm, so that This was dried at 90° C. for 4 minutes, transferred to a PET film without peeling treatment, and cured in an atmosphere of 20° C. and 65% RH for 1 day to obtain an adhesive sheet for evaluation.

The PET film obtained by peeling off the obtained adhesive sheet for evaluation was peeled off, and durability evaluation was performed in this state. The results are shown in Table 1.

[Examples 19-22, Comparative Examples 12-14]

Except that the type of ionic compound in Example 18 was changed to that described in Table 1, the same procedure as in Example 18 was carried out to prepare an evaluation adhesive composition and an evaluation adhesive sheet, and the durability was evaluated. The results are shown in Table 1.

[Evaluation results]

[Table 1]

From the foregoing examples and comparative examples, it can be seen that when the antistatic agent for adhesives of the present invention is used, no change in the surface resistance value is found after the durability test, and it is excellent in durability even under high temperature and high humidity conditions. Antistatic agent for adhesives.

[Industrial availability]

According to the present invention, it is useful as an antistatic agent for adhesives that is excellent in durability even under conditions of high temperature and high humidity.

Although the present invention has been described with reference to detailed or specific aspects, as long as it does not depart from the spirit and scope of the present invention, a person with ordinary knowledge in the technical field to which the present invention belongs can easily add various changes or modifications.

This specification is based on the content of Japanese Patent Application 2015-148214 for which a patent was filed on July 28, 2015, and is incorporated into this specification with reference to the content.

Claims (1)

An antistatic agent for adhesives, which contains an ionic compound, wherein the cation site of the ionic compound is a cation represented by the following formula (2) or (3), and the anion site is a bis(fluorinated sulfonate) Base) imine,

In the above formula (2) or (3), R ¹ represents a hydrocarbon group with a carbon number of 1 or more and 18 or less, and may also include a heteroatom; R ² represents a hydrocarbon group with a carbon number of 2 or more and 4 or less, and a plurality of R ¹ or R ^2. Each can be the same or different; the addition amount of the antistatic agent for the adhesive is 0.01 parts by mass or more and 10 parts by mass or less, but not including 5 parts by mass or more and 10 parts by mass relative to 100 parts by mass of the adhesive polymer Servings or less.