KR102604947B1 - Antistatic agent for pressure sensitive adhesive - Google Patents

Abstract

[화학식 2]

[화학식 3]

(하기 식 (1) 내지 (3) 중, R¹은 탄소수 1 이상 18 이하의 탄화 수소기를 나타내고, 헤테로 원자를 포함해도 좋다. R²는 탄소수 2 이상 4 이하의 탄화 수소기를 나타내고, 복수의 R¹ 또는 R²는, 각각 동일하거나 상이해도 좋다.)The purpose of the present invention is to provide an antistatic agent for adhesives that has excellent durability even under high temperature and high humidity conditions.
The antistatic agent for dowel material of the present invention contains an ionic compound, and the cation moiety of the ionic compound is a cation represented by any of the following formulas (1) to (3).
[Formula 1]

[Formula 2]

[Formula 3]

(In the following formulas (1) to (3), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms and may contain a hetero atom. R ² represents a hydrocarbon group having 2 to 4 carbon atoms, and a plurality of R ¹ or R ² may be the same or different, respectively.)

Description

Antistatic agent for adhesive {ANTISTATIC AGENT FOR PRESSURE SENSITIVE ADHESIVE}

The present invention relates to an antistatic agent for adhesives.

In general, static electricity refers to the phenomenon of electric charges accumulating on an object, or the charged electric charge itself. Static electricity is generated not only by the accumulation of electric charges caused by friction between two types of dielectrics, but also by contact with a charged object, etc., and accumulates on the surface of the object. The static electricity may cause inhalation of foreign substances such as dust, electrostatic destruction of devices, malfunction of measuring devices, or fire. Additionally, modern electronic devices are highly prone to temporary or permanent damage due to the discharge of static electricity.

For example, in liquid crystal panels, an adhesive layer formed from an adhesive composition is often used to adhere a polarizer or a retardation plate to the glass substrate of the liquid crystal cell. Since optical members such as polarizers and retardation plates are usually made of plastic materials, they have high electrical insulation properties and are prone to generating static electricity, such as when peeling off an adhesive layer. Therefore, if a polarizing plate or a retardation plate is bonded to a liquid crystal cell with the static electricity generated in this way remaining, there is a risk that the alignment of the liquid crystal molecules may be disturbed.

In addition, because the polarizer is manufactured at high speed, when the polarizer protective film is peeled off, the TFT and IC elements may be destroyed by static electricity, which did not occur in the existing process, and may cause defects in the liquid crystal display panel.

Therefore, in order to suppress the generation of static electricity, it is required to provide an antistatic function to the adhesive layer, and as a means of providing an antistatic function to the adhesive layer, an ionic compound is blended in the adhesive composition forming the adhesive layer. This has been proposed (patent document 1).

In addition, even in semiconductor processing processes (e.g., dicing process, back grind process), static electricity is generated due to peeling, friction, contact, etc. of the adhesive, so as above, as a method of suppressing the generation of static electricity, the adhesive forming the adhesive layer is used. It has been proposed to mix an ionic compound in the composition (Patent Document 2).

However, in the adhesive containing an ionic compound, when stored under high temperature and high humidity conditions, there is a problem that the surface resistance value increases over time due to diffusion movement of the ionic compound, or the ionic compound bleeds into the surface layer.

Japanese Patent Publication No. 2011-037927 Japanese Patent Publication No. 2015-003988

The purpose of the present invention is to provide an antistatic agent for adhesives that has excellent durability even under high temperature and high humidity conditions.

As a result of intensive studies to solve the above problem, the present inventors have found that the above problem can be achieved by using an ionic compound having a predetermined cationic site, and have completed the present invention.

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

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

[Formula 1]

[Formula 2]

[Formula 3]

(In the above formulas (1) to (3), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms and may contain a hetero atom. R ² represents a hydrocarbon group having 2 to 4 carbon atoms, and a plurality of R ¹ or R ² may be the same or different, respectively.)

[2] The antistatic agent for an adhesive according to [1], wherein the anion portion of the ionic compound is a compound containing a fluorine atom.

[3] In [1] or [2], the anion moiety of the ionic compound is at least one selected from the group consisting of bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide. , antistatic agent for adhesives.

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

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described.

The ionic compound contained in the antistatic agent for adhesives of the present invention consists of a cationic moiety and an anionic moiety, and may be either solid or liquid at room temperature (23°C/50%RH).

The cationic moiety of the ionic compound is represented by any of the formulas (1) to (3).

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

The cation represented by formula (1) is not particularly limited, but specifically includes 2-hydroxyethyltrimethylammonium cation, 2-hydroxyethyldimethylethylammonium cation, 2-hydroxyethyldimethylpropylammonium cation, 2- Hydroxyethyldimethylbutylammonium cation, 2-hydroxyethyldimethylhexylammonium cation, 2-hydroxyethyldimethyloctylammonium cation, 2-hydroxyethyldimethyldecylammonium cation, 2-hydroxyethyldimethyllaurylammonium cation, 2 -Hydroxyethyldimethylbenzylammonium cation, 2-hydroxyethyldiethylmethylammonium cation, 2-hydroxyethyltriethylammonium cation, 2-hydroxyethyldiethylpropylammonium cation, 2-hydroxyethyldiethylbutylammonium Cation, 2-hydroxyethyldiethylhexylammonium cation, 2-hydroxyethyldiethyloctylammonium cation, 2-hydroxyethyldiethyldecylammonium cation, 2-hydroxyethyldiethylaurylammonium cation, 2-hyde Roxyethyldiethylbenzylammonium cation, 2-hydroxyethyldibutylmethylammonium cation, 2-hydroxyethyldibutylethylammonium cation, 2-hydroxyethyldibutylpropylammonium cation, 2-hydroxyethyltributylammonium cation. , 2-hydroxyethyldibutylhexylammonium cation, 2-hydroxyethyldibutyloctylammonium cation, 2-hydroxyethyldibutyldecylammonium cation, 2-hydroxyethyldibutyllaurylammonium cation, 2-hydroxy Ethyldibutylbenzylammonium cation, 2-hydroxypropyltrimethylammonium cation, 4-hydroxybutyltrimethylammonium cation, 2-hydroxypropyltriethylammonium cation, 4-hydroxybutyltriethylammonium cation, 2-hydroxypropyl Tributylammonium cation, 4-hydroxybutyltributylammonium cation, 2-hydroxypropyldiethylmethylammonium cation, 2-hydroxypropyldiethylpropylammonium cation, 2-hydroxypropyldiethylbutylammonium cation, 2- Hydroxypropyldiethylhexylammonium cation, 2-hydroxypropyldiethyloctylammonium cation, 2-hydroxypropyldiethyldecylammonium cation, 2-hydroxypropyldiethylaurylammonium cation, 2-hydroxypropyldiethyl Benzyl ammonium cations, etc. can be mentioned. These may be used individually as one type, or two or more types may be used.

The cation represented by formula (2) is not particularly limited, but specifically includes bis(2-hydroxyethyl)dimethylammonium cation, bis(2-hydroxyethyl)ethylmethylammonium cation, and bis(2-hydroxy Ethyl)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)laurylmethylammonium cation, bis(2-hydroxyethyl)oleylmethylammonium cation, bis(2-hydroxyethyl)benzylmethylammonium cation, Bis(2-hydroxyethyl)diethylammonium cation, bis(2-hydroxyethyl)ethylpropylammonium cation, bis(2-hydroxyethyl)ethylbutylammonium cation, bis(2-hydroxyethyl)ethylhexyl ammonium Cation, bis(2-hydroxyethyl)ethyloctylammonium cation, bis(2-hydroxyethyl)ethyldecylammonium cation, bis(2-hydroxyethyl)ethyllaurylammonium cation, bis(2-hydroxyethyl) Ethylbenzylammonium cation, bis(2-hydroxyethyl)butylpropylammonium cation, bis(2-hydroxyethyl)dibutylammonium cation, bis(2-hydroxyethyl)butylhexylammonium cation, bis(2-hydroxy Ethyl)butyloctylammonium cation, bis(2-hydroxyethyl)butyldecylammonium cation, bis(2-hydroxyethyl)butyllauryl ammonium cation, bis(2-hydroxyethyl)butylbenzylammonium cation, bis(2) -Hydroxypropyl)dimethylammonium cation, bis(2-hydroxypropyl)diethylammonium cation, bis(2-hydroxypropyl)dibutylammonium cation, bis(2-hydroxypropyl)oleylmethylammonium cation, bis (4-hydroxybutyl)dimethylammonium cation, bis(4-hydroxybutyl)diethylammonium cation, bis(4-hydroxybutyl)dibutylammonium cation, bis(2-hydroxybutyl)oleylmethylammonium cation , polyoxyethylenelaurylmethylammonium cation, polyoxyethylenelaurylethylammonium cation, polyoxyethylenelaurylbutylammonium cation, polyoxyethylenelaurylhexylammonium cation, polyoxyethylenelauryloctylammonium cation, polyoxyethylene oleate Monomethylammonium cation, polyoxyethyleneoleylethylammonium cation, polyoxyethyleneoleylbutylammonium cation, polyoxyethyleneoleylhexylammonium cation, polyoxyethyleneoleyloctylammonium cation, polyoxyethylenestearylmethylammonium cation, Examples include polyoxyethylenestearylethylammonium cation, polyoxyethylenestearylbutylammonium cation, polyoxyethylenestearylhexylammonium cation, and polyoxyethylenestearyloctylammonium cation. These may be used individually as one type, or two or more types may be used.

The cation represented by formula (3) is not particularly limited, but specifically includes tris(2-hydroxyethyl)methylammonium cation, tris(2-hydroxyethyl)ethylammonium cation, and tris(2-hydroxyethyl). ) Propylammonium cation, tris(2-hydroxyethyl)butylammonium cation, tris(2-hydroxyethyl)hexylammonium cation, tris(2-hydroxyethyl)octylammonium cation, tris(2-hydroxyethyl)decyl Ammonium cation, tris(2-hydroxyethyl)laurylammonium cation, tris(2-hydroxyethyl)stearylammonium cation, tris(2-hydroxyethyl)oleyl ammonium cation, tris(2-hydroxyethyl) Benzyl ammonium cation, tris(2-hydroxypropyl)methylammonium cation, tris(2-hydroxypropyl)ethylammonium cation, tris(2-hydroxypropyl)propylammonium cation, tris(2-hydroxypropyl)butylammonium Cation, tris(2-hydroxypropyl)hexylammonium cation, tris(2-hydroxypropyl)octylammonium cation, tris(2-hydroxypropyl)decylammonium cation, tris(2-hydroxypropyl)lauryl ammonium cation. , Tris(2-hydroxypropyl)stearylammonium cation, Tris(2-hydroxypropyl)oleyl ammonium 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)hexylammonium cation, Tris (4-hydroxybutyl)octylammonium cation, tris(4-hydroxybutyl)decylammonium cation, tris(4-hydroxybutyl)laurylammonium cation, tris(4-hydroxybutyl)stearylammonium cation, tris (4-hydroxybutyl)oleylammonium 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-hydroxybutyl)methylammonium cation, N-(2 -Hydroxymethyl)-N-(2-hydroxypropyl)-N-(2-hydroxybutyl)methylammonium cation, etc. can be mentioned. These may be used individually as one type, or two or more types may be used.

The anionic portion of the ionic compound is not particularly limited as long as it satisfies the requirement to become an ionic compound, 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 ^- can be used. These may be used individually as one type, or two or more types may be used.

Among them, the anionic component containing a fluorine atom is preferable because an ionic compound with a low melting point is obtained, and (F ₂ SO ₂ ) ₂ N ^- (bis(fluorosulfonyl)imide), and (CF ₃ SO ₂ ) ₂ N ^- (bis(trifluoromethanesulfonyl)imide) is more preferably used.

Specific examples of the ionic compound used in the antistatic agent for adhesives of the present invention are appropriately selected from the combination of the above cationic moiety and anionic moiety, and are used as follows: 2-hydroxyethyltrimethylammonium = hexafluorophosphate, 2-hydroxyethyltrimethyl Ammonium = tetrafluoroborate, 2-hydroxyethyltrimethylammonium = trifluoromethanesulfonate, 2-hydroxyethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide, 2-hydroxyethyltrimethylammonium = Bis(fluorosulfonyl)imide, 2-hydroxyethyldimethylethylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldimethylethylammonium=bis(fluorosulfonyl)imide, 2-Hydroxyethyldimethylbutylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldimethylbutylammonium=bis(fluorosulfonyl)imide, 2-hydroxyethyldimethyloctylammonium=bis (trifluoromethanesulfonyl)imide, 2-hydroxyethyldimethyloctylammonium=bis(fluorosulfonyl)imide, 2-hydroxyethyldimethyllaurylammonium=bis(trifluoromethanesulfonyl)imide de, 2-hydroxyethyldimethyllaurylammonium = bis (fluorosulfonyl) imide, 2-hydroxyethyldiethylmethylammonium = hexafluorophosphate, 2-hydroxyethyldiethylmethylammonium = tetrafluoro Borate, 2-hydroxyethyldiethylmethylammonium=trifluoromethanesulfonate, 2-hydroxyethyldiethylmethylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldiethylmethylammonium =bis(fluorosulfonyl)imide, 2-hydroxyethyldiethylbutylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldiethylbutylammonium=bis(fluorosulfonyl) Imide, 2-hydroxyethyldiethyloctylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldiethyloctylammonium=bis(fluorosulfonyl)imide, 2-hydroxyethyl Dibutylmethylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxyethyldibutylmethylammonium=bis(fluorosulfonyl)imide, 2-hydroxyethyltributylammonium=bis(trifluoro) lomethanesulfonyl)imide, 2-hydroxyethyltributylammonium=bis(fluorosulfonyl)imide, 2-hydroxyethyldibutyloctylammonium=bis(trifluoromethanesulfonyl)imide, 2 -Hydroxyethyldibutyloctylammonium=bis(fluorosulfonyl)imide, 2-hydroxypropyltrimethylammonium=bis(trifluoromethanesulfonyl)imide, 2-hydroxypropyltrimethylammonium=bis(fluoro) Rosulfonyl)imide, 4-hydroxybutyltrimethylammonium=bis(trifluoromethanesulfonyl)imide, 4-hydroxybutyltrimethylammonium=bis(fluorosulfonyl)imide, bis(2-hyde) Roxyethyl)dimethylammonium=hexafluorophosphate, bis(2-hydroxyethyl)dimethylammonium=tetrafluoroborate, bis(2-hydroxyethyl)dimethylammonium=trifluoromethanesulfonate, bis(2-hydride) Roxyethyl)dimethylammonium=bis(trifluoromethanesulfonyl)imide, dimethylammonium=bis(fluorosulfonyl)imide, bis(2-hydroxyethyl)butylmethylammonium=bis(trifluoromethanesulfonyl) Ponyl)imide, bis(2-hydroxyethyl)butylmethylammonium=bis(fluorosulfonyl)imide, bis(2-hydroxyethyl)octylmethylammonium=bis(trifluoromethanesulfonyl)imide , Bis(2-hydroxyethyl)octylmethylammonium=bis(fluorosulfonyl)imide, bis(2-hydroxyethyl)oleylmethylammonium=bis(trifluoromethanesulfonyl)imide, bis( 2-hydroxyethyl)oleylmethylammonium=bis(fluorosulfonyl)imide, bis(2-hydroxyethyl)butyloctylammonium=bis(trifluoromethanesulfonyl)imide, bis(2-hyde) Roxyethyl)butyloctylammonium=bis(fluorosulfonyl)imide, bis(2-hydroxypropyl)dimethylammonium=bis(trifluoromethanesulfonyl)imide, bis(2-hydroxypropyl)dimethylammonium =bis(fluorosulfonyl)imide, bis(4-hydroxybutyl)dimethylammonium=bis(trifluoromethanesulfonyl)imide, bis(4-hydroxybutyl)dimethylammonium=bis(fluorosulfonyl) Ponyl) imide, polyoxyethylene lauryl methyl ammonium = bis (trifluoromethanesulfonyl) imide, polyoxyethylene lauryl methyl ammonium = bis (fluorosulfonyl) imide, polyoxyethylene oleyl methyl ammonium =bis(trifluoromethanesulfonyl)imide, polyoxyethyleneoleylmethylammonium=bis(fluorosulfonyl)imide, polyoxyethylenestearylmethylammonium=bis(trifluoromethanesulfonyl)imide , polyoxyethylenestearylmethylammonium=bis(fluorosulfonyl)imide, tris(2-hydroxyethyl)methylammonium=hexafluorophosphate, tris(2-hydroxyethyl)methylammonium=tetrafluoroborate. , Tris(2-hydroxyethyl)methylammonium=trifluoromethanesulfonate, Tris(2-hydroxyethyl)methylammonium=bis(trifluoromethanesulfonyl)imide, Tris(2-hydroxyethyl) Methylammonium=bis(fluorosulfonyl)imide, tris(2-hydroxypropyl)methylammonium=bis(trifluoromethanesulfonyl)imide, tris(2-hydroxypropyl)methylammonium=bis(fluoro) Rosulfonyl)imide, tris(4-hydroxybutyl)methylammonium=bis(trifluoromethanesulfonyl)imide, tris(4-hydroxybutyl)methylammonium=bis(fluorosulfonyl)imide etc. can be mentioned. These may be used individually as one type, or two or more types may be used.

In addition, commercially available ionic compounds such as those described above may be used, but they can also be synthesized as follows. The method for synthesizing ionic compounds, etc. is not particularly limited as long as the target ionic compound, etc. can be obtained, but can be found in the literature "Ionic Liquids - Frontiers and Future of Development -" [CMC Publishing Co., Ltd. As described in [Published], halide method, hydroxide method, acid ester method, complex formation method, neutralization method, etc. can be used.

The antistatic agent for adhesives of the present invention is composed of an ionic compound having a cationic moiety represented by any of the above formulas (1) to (3) as an active ingredient, and may be used alone, but may be used alone, with a stabilizer, etc. as needed. It can also be used by mixing additives or solvents.

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

The antistatic agent for adhesives of the present invention can be widely applied to adhesive polymers used in the relevant technical field. Examples of the adhesive polymer include (meth)acrylic polymer, rubber polymer, silicone polymer, and polyurethane polymer. Among these, it can be preferably used for (meth)acrylic polymers.

The (meth)acrylic polymer is a polymer containing, for example, a (meth)acrylic acid alkyl ester having a straight or branched alkyl group having 1 to 20 carbon atoms as a monomer unit (component). In addition, the (meth)acrylic polymer may be composed of an alkyl (meth)acrylic acid ester having an alkyl group having 1 to 20 carbon atoms alone or in combination of two or more types.

Examples of the (meth)acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate ) Octyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Undecyl, (meth)acrylic acid dodecyl, (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl, (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl, (meth)acrylic acid heptadecyl, (meth)acrylic acid octa. (meth)acrylic acid C1-20 alkyl esters such as decyl, nonadecyl (meth)acrylate, eicosyl (meth)acrylate [preferably (meth)acrylic acid C2-14 alkyl ester, particularly preferably (meth)acrylic acid C2- 10 alkyl ester] and the like. Additionally, (meth)acrylic acid alkyl ester refers to acrylic acid alkyl ester and/or methacrylic acid alkyl ester, and “(meth)…” 」 all have the same meaning.

The ratio of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is 50 parts by mass or more, and 60 parts by mass or more with respect to 100 parts by mass of the total amount of monomer units (components) for preparing the (meth)acrylic polymer. is more preferable, and 70 parts by mass or more is particularly preferable. On the other hand, the above 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 above range, desirable adhesive properties can be obtained for an adhesive sheet that can be used for re-peelability, so it becomes a preferred form.

In addition, the (meth)acrylic polymer is intended to improve cohesion, heat resistance, crosslinking, etc., and, if necessary, other monomer units (components) that can be copolymerized with the (meth)acrylic acid alkyl ester (copolymerizable monomer) It may be included. Therefore, the (meth)acrylic polymer may contain a copolymerizable monomer together with the (meth)acrylic acid alkyl ester as the main component. As the copolymerizable monomer, a monomer having a polar group can be preferably used. In addition, the main component means the monomer with the highest mixing ratio among the total amount of monomer components.

Specific examples of the copolymerizable monomer include 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)acrylic acid, 3-hydroxypropyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, 6-hydroxyhexyl (meth)acrylic acid, 8-hydroxyoctyl (meth)acrylic acid, hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylate such as 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl methacrylate; monomers containing acid anhydride groups such as maleic anhydride and itaconic acid 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; Phosphate group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth) ) Acrylamide, N,N-dialkyl (meth)acrylamide such as 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, N-n-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-acryloylmorpholine; N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, etc. succinimide monomer; Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide Itaconimide-based monomers such as mead 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-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, and N-vinylpyridazine. ; N-vinylcarboxylic acid amides; Lactam monomers such as N-vinylcaprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; (meth)acrylic acid aminoalkyl monomers such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; (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; Acrylic monomers containing epoxy groups such as glycidyl (meth)acrylate; acrylic acid ester-based monomers having a heterocycle, a halogen atom, a silicon atom, etc., such as tetrahydrofurfuryl (meth)acrylate, fluorine atom-containing (meth)acrylate, and silicon (meth)acrylate; Olefin-based 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 ether; vinyl chloride; monomers containing sulfonic acid groups such as sodium vinyl sulfonate; Imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; Isocyanate group-containing monomers such as 2-isocyanate ethyl (meth)acrylate; Acryloylmorpholine; (meth)acrylic acid esters having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclofentanyl (meth)acrylate; (meth)acrylic acid esters having an aromatic hydrocarbon group such as phenyl (meth)acrylate and phenoxyethyl (meth)acrylate; (meth)acrylic acid ester obtained from terpene compound derivative alcohol; etc. can be mentioned. These may be used individually as one type, or two or more types may be used.

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

The reason why the antistatic agent for adhesives of the present invention has excellent durability even under high temperature and high humidity conditions is not clear, but can be inferred as follows. That is, when the (meth)acrylic polymer has a hydroxyl group, a carboxyl group, etc., the ionic compound contained in the antistatic agent for an adhesive of the present invention has a hydroxyl group at the cation site, so the antistatic agent for an adhesive of the present invention It can be inferred that the compatibility between the ionic compound contained therein and the (meth)acrylic polymer has increased, resulting in improved durability.

In order to adjust the molecular weight of the (meth)acrylic polymer, a chain transfer agent may be used during polymerization. Chain transfer agents used include, for example, compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-dodecyl mercaptan, mercaptoethanol, and α-thioglycerol; Thioglycolic acid, methyl thioglycolic acid, ethyl thioglycolic acid, propyl thioglycolic acid, butyl thioglycolic acid, t-butyl thioglycolic acid, 2-ethylhexyl thioglycolic acid, octyl thioglycolic acid, decyl thioglycolic acid, thioglycolic acid thioglycolic acid esters such as dodecyl glycolate, thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, and thioglycolic acid ester of pentaerythritol; α-methylstyrene dimer, etc. can be mentioned. These may be used individually as one type, or two or more types may be used.

When preparing the (meth)acrylic polymer, the (meth)acrylic polymer can be easily formed by using a curing reaction by heat or ultraviolet rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator). . In particular, thermal polymerization can be preferably used due to the advantage of shortening the polymerization time. The polymerization initiator can be used individually or in combination of two or more types.

Examples of the thermal polymerization initiator include azo-based polymerization initiators (e.g., 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis( 2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2 '-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis(2-methylpropionamidine) disulfate, 2,2' -Azobis(N,N'-dimethyleneisobutylamidine)dihydrochloride, etc.); peroxide-based polymerization initiators (e.g., dibenzoyl peroxide, t-butyl peroxymaleate, lauroyl peroxide, etc.); Redox-based polymerization initiators, etc. can be mentioned.

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

The photopolymerization initiator is not particularly limited and includes, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, and a benzoin-based photopolymerization initiator. , a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, etc. can be used.

Specifically, the benzoin ether-based photopolymerization initiator is, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1, 2-diphenylethan-1-one [brand name: RGACURE 651, manufactured by BASF], anisole methyl ether, etc. Acetophenone-based photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone [trade name: RGACURE 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4 -(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Product name: RGACURE 2959, manufactured by BASF], 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one [Brand name: DAROCUR 1173, manufactured by BASF], methoxyacetophenone, etc. are mentioned. As an α-ketol photopolymerization initiator, for example, 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1- You can lift your whole back. Examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

Additionally, the benzoin-based photopolymerization initiator includes, for example, benzoin. Benzyl-based photopolymerization initiators include, for example, benzyl and the like. Benzophenone-based photopolymerization initiators include, for example, benzophenone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone. Ketal-based photopolymerization initiators include, for example, benzyldimethyl ketal. Thioxanthone-based photopolymerization initiators include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone. Includes acidthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc.

The acylphosphine oxide-based photopolymerization initiator includes, for example, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine. Oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6) -Dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexyl Phosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)( 1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1- Methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropane -1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis ( 2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenyl Propylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, Bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6 -Trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3 ,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl- 2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxy Phenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide, etc. can be mentioned.

The amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, for 100 parts by mass of the total amount of monomer components for preparing the (meth)acrylic polymer. It is mixed in the amount within. Here, if the amount of photopolymerization initiator is less than 0.01 parts by mass, the polymerization reaction may become insufficient. If the amount of the photopolymerization initiator exceeds 5 parts by mass, the photopolymerization initiator absorbs ultraviolet rays, and the ultraviolet rays may not reach the inside of the adhesive layer. In this case, the polymerization rate decreases or the molecular weight of the produced polymer decreases.

The method of obtaining the (meth)acrylic polymer is not particularly limited, and the polymer can be obtained by applying various polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization that are generally used as synthesis methods. You can.

When the (meth)acrylic polymer is used in a pressure-sensitive adhesive sheet and when the pressure-sensitive adhesive sheet is used as a surface protection sheet, solution polymerization or emulsion polymerization can be preferably used from the viewpoint of productivity of the pressure-sensitive adhesive sheet. Additionally, the obtained polymer may be any of random copolymers, block copolymers, alternating copolymers, and graft copolymers.

The (meth)acrylic polymer preferably contains a curing agent. The curing agent is not particularly limited, but specifically, preferably includes one or two or more selected from isocyanate-based curing agents, epoxy-based curing agents, ethyleneimine-based curing agents, metal chelate-based curing agents, and amine-based curing agents.

In the (meth)acrylic polymer using the above crosslinking agent, since the antistatic agent for an adhesive of the present invention is bonded to the (meth)acrylic polymer by a covalent bond through the crosslinking agent, it can be assumed that durability under high temperature and high humidity conditions is improved. .

Specifically, as the isocyanate-based curing agent, a compound containing a bifunctional or higher isocyanate group in the molecule is preferable, and a compound containing a trifunctional or higher isocyanate group is more preferable.

Examples of compounds containing the isocyanate group include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and tetramethylxylyl. Polyisocyanate compounds such as lene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenylisocyanate, and adduct or biuret forms, or isocyanurate forms, of these isocyanate compounds with polyol compounds such as trimethylolpropane. , further examples include adducts of these isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. These may be used individually as one type, or two or more types may be used.

As the isocyanate-based curing agent used as the above-mentioned curing agent, the trimethylolpropane adduct form of tolylene diisocyanate, the isocyanurate form of tolylene diisocyanate, and the isocyanurate form of isophorone diisocyanate are preferable, especially trimethyl of tolylene diisocyanate. An all-propane adduct body is more preferable. These may be used individually as one type, or two or more types may be used.

Ethyleneimine-based curing agents include, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxide), N,N'-toluene-2,4-bis(1-aziridinecarboxide), boxide), bisisophthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridine carcopy) id), 2,2'-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], trimethylolpropanetri-β-aziridinylpropionate, tetramethylolmethanetri- β-aziridinyl propionate, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, etc.

Epoxy-based curing agents include, for example, bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3- Bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidylaminophenylmethane, triglycidyl, etc. are mentioned. These may be used individually as one type, or two or more types may be used.

Metal chelate curing agents include, for example, coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium with acetylacetone or ethyl acetoacetate. These may be used individually as one type, or two or more types may be used.

Amine-based curing agents include, for example, hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophorone diamine, amino resin, and methylene resin. These may be used individually as one type, or two or more types may be used.

These curing agents 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, per 100 parts by mass of the (meth)acrylic polymer.

The adhesive polymer includes, in addition to the above components, a polymerization inhibitor, a tackifier, a plasticizer, a crosslinking accelerator, an antioxidant, a light stabilizer, a metal corrosion inhibitor, and (meta) other than the adhesive polymer, to the extent that the effect of the present invention is not impaired. ) It may contain one or two or more types selected from acrylic polymers and rework agents.

The adhesive polymer preferably contains an organic solvent in order to improve its applicability. The organic solvent is not particularly limited, but specifically includes aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, and diphenyl ether; Halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; Ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; Amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; Nitriles such as acetonitrile and benzonitrile; Sulfoxides such as dimethyl sulfoxide and sulfolane can be mentioned. Such polymerization solvents may be used individually or in combination of two or more.

In the 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 prepared by mixing the antistatic agent for adhesives, the adhesive polymer, a crosslinking agent if necessary, and other components by a conventionally known method. For example, there is a method of mixing an ionic compound, a crosslinking agent if necessary, and other components into a polymer solution containing the copolymer obtained when synthesizing a (meth)acrylic polymer, which is an adhesive polymer.

Example

Next, the present invention will be described in detail based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, unless otherwise specified, “part” refers to “part by mass.”

[Measurement/evaluation method]

In the following examples and comparative examples, the measurement 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 CORPORATION, and calculated as a polystyrene conversion value.

The measurement conditions are as follows. Sample concentration: 0.2 wt% (THF solution), sample injection volume: 10 μl, eluent: THF, flow rate: 0.6 ml/min, measurement temperature: 40°C, column: sample column; 1 TSKguardcolumnSuperHZ-H + 2 TSKgelSuperHZM-H, reference column; 1 x TSKgel SuperH-RC, detector: differential refractometer.

<Durability evaluation>

For the adhesive sheets for evaluation obtained in Examples and Comparative Examples, the surface resistance value was measured in an environment of 20°C/65%RH. The surface resistance value was measured at an applied voltage of 500 V using R8340A manufactured by ADVANTEST CORPORATION. This was taken as the initial surface resistance value (Ω/□).

Additionally, after this pressure-sensitive adhesive sheet for evaluation was left in a 60°C/90%RH environment for 500 hours, the surface resistance value was measured in the same manner. This was taken as the surface resistance value after the durability test.

<Preparation of (meth)acrylic copolymer>

((meth)acrylic copolymer A)

After nitrogen gas was sealed in a reaction device equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube, 70 parts of ethyl acetate, 15 parts of acetone, 62.5 parts of butyl acrylate, 19.0 parts of phenoxyethyl acrylate, 16.0 parts of methyl acrylate, 1.5 parts of acrylic acid, 1.0 part of 2-hydroxyethyl acrylate, and 0.1 part of azo polymerization initiator 2,2'-azobisisobutyronitrile (WAKO PURE CHEMICAL INDUSTRIES, LTD. product name V-60) I put it in. While stirring, the reaction proceeded for 8 hours at the reflux temperature of the solvent in a nitrogen gas stream. After completion of the reaction, 315 parts of toluene was added, cooled to room temperature, and a polymer solution with a solid content of 20% by weight was prepared. The viscosity of the obtained (meth)acrylic copolymer A was 7,000 mPa·s, and the weight average molecular weight (Mw) was 1.35 million.

<Preparation of ionic compounds>

(ionic compound C-1)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 139.6 g of 2-hydroxyethyltrimethylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide potassium, and 359 g of acetonitrile were weighed and stirred at room temperature for 2 hours. did.

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

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

(ionic compound C-2)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 169.6 g of bis(2-hydroxyethyl)dimethylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide, and 389 g of acetonitrile were weighed and incubated at room temperature for 2 hours. Stirred. After filtering the obtained reaction liquid, the filtrate was concentrated and dried to obtain 292 g of bis(2-hydroxyethyl)dimethylammonium=potassium bis(fluorosulfonyl)imide (yield 93%).

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

(ionic compound C-3)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 267.8 g of bis(2-hydroxyethyl)octylmethylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide potassium, and 595 g of acetonitrile were weighed and stored at room temperature. Stirred 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(fluorosulfonyl)imide (yield 91%).

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

(ionic compound C-4)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 406 g of bis(2-hydroxyethyl)oleylmethylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide potassium, and 938 g of acetonitrile were weighed and stored at room temperature. Stirred for 2 hours.

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

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

(ionic compound C-5)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 200 g of tris(2-hydroxyethyl)methylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide potassium, and 420 g of acetonitrile were weighed and incubated at room temperature for 2 hours. Stirred.

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

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

(ionic compound C-6)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 169.6 g of bis(2-hydroxyethyl)dimethylammonium chloride, 287.1 g of lithium bis(trifluoromethanesulfonyl)imide, and 457 g of acetonitrile were weighed and stored at room temperature. and stirred 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)imide (yield 93%).

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

(ionic compound C-7)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 286 g of 1-octyl-4-methylpyridinium bromide, 219.2 g of bis(fluorosulfonyl)imide potassium, and 505 g of distilled water were weighed, and stirred at room temperature for 2 hours. , 3 hours of politics. The supernatant of the obtained reaction solution was removed, and a liquid product was obtained.

The obtained liquid product was washed three times with 200 g of distilled water, concentrated and dried to obtain 348 g of 1-octyl-4-methylpyridinium=bis(fluorosulfonyl)imide (yield 90%).

The obtained 1-octyl-4-methylpyridinium=bis(fluorosulfonyl)imide was identified and confirmed by NMR ( ^1H , ^13C ) measurement and FT-IR measurement.

(ionic compound C-8)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 236 g of 1-ethyl-3-methylimidazolium ethyl sulfate, 219.2 g of bis(fluorosulfonyl)imide potassium, and 455 g of distilled water were weighed and incubated at room temperature for 2 hours. It was stirred and left to stand for 3 hours. The supernatant of the obtained reaction solution was removed, and a liquid product was obtained.

The obtained liquid product was washed three times with 140 g of distilled water, concentrated, and dried to obtain 233 g of 1-ethyl-3-methylimidazolium=bis(fluorosulfonyl)imide (80% yield).

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

(ionic compound C-9)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 207.8 g of octyltrimethylammonium chloride, 219.2 g of bis(fluorosulfonyl)imide potassium, and 427 g of distilled water were weighed, stirred at room temperature for 2 hours, and left to stand for 3 hours. . The supernatant of the obtained reaction solution was removed, and a liquid product was obtained.

The obtained liquid product was washed three times with 176 g of distilled water, concentrated and dried to obtain 324 g of octyltrimethylammonium = bis(fluorosulfonyl)imide (yield 92%).

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

(ionic compound C-10)

In a four-necked flask equipped with a stirrer, thermometer, and condenser, 236 g of 1-ethyl-3-methylimidazolium ethyl sulfate, 287.1 g of lithium bis(trifluoromethanesulfonyl)imide, and 523 g of distilled water were weighed and stored at room temperature. It was stirred for 2 hours and left to stand for 3 hours. The supernatant of the obtained reaction solution was removed, and a liquid product was obtained.

The obtained liquid product was washed three times with 196 g of distilled water, concentrated and dried to obtain 329 g of 1-ethyl-3-methylimidazolium=bis(trifluoromethanesulfonyl)imide (yield 84%).

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

[Example 1]

<Preparation of adhesive composition for evaluation>

1.5 parts by weight (converted to solid content) of the ionic compound C-1 was added to 100 parts by weight (converted to solid content) of the (meth)acrylic copolymer A solution and stirred. Additionally, 0.08 parts by weight (solid content conversion value) of crosslinking agent B [buret type of hexamethylene diisocyanate (manufactured by ASAHI KASEI CORPORATION, brand name DURANATE 24A-100)] was mixed to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the peeled polyethylene terephthalate film (PET film), the adhesive composition for evaluation prepared above was applied to a dry film thickness of 20㎛, dried at 90°C for 4 minutes, and applied on the triacetylcellulose film (TAC film). It was transferred and cured for 7 days in an atmosphere of 20°C and 65%RH to obtain an adhesive sheet for evaluation.

Durability evaluation was performed using the obtained adhesive sheet for evaluation. The results are shown in Table 1.

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

In Example 1, an adhesive composition for evaluation and an adhesive sheet for evaluation were prepared and manufactured in the same manner as in Example 1, except that the type of ionic compound was changed as shown in Table 1, and durability evaluation was performed. . The results are shown in Table 1.

[Example 7]

<Preparation of adhesive composition for evaluation>

1.5 parts by weight (converted to solid content) of the ionic compound C-1 was added to the (meth)acrylic copolymer A solution relative to 100 parts by weight (converted to solid content) and stirred to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the peeled polyethylene terephthalate film (PET film), the adhesive composition for evaluation prepared above was applied to a dry film thickness of 20㎛, dried at 90°C for 4 minutes, and applied on the triacetylcellulose film (TAC film). It was transferred and cured for 1 day in an atmosphere of 20°C and 65%RH to obtain an adhesive sheet for evaluation.

Durability evaluation was performed using the obtained adhesive sheet for evaluation. The results are shown in Table 1.

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

In Example 7, an adhesive composition for evaluation and an adhesive sheet for evaluation were prepared and manufactured in the same manner as in Example 7, except that the type of ionic compound was changed as shown in Table 1, and durability evaluation was performed. . The results are shown in Table 1.

[Example 12]

<Preparation of adhesive composition for evaluation>

1.5 parts by weight (converted to solid content) of the ionic compound C-1 was added to 100 parts by weight (converted to solid content) of the (meth)acrylic copolymer A solution and stirred. Additionally, 0.08 parts by weight (solid content conversion value) of crosslinking agent B [buret type of hexamethylene diisocyanate (manufactured by ASAHI KASEI CORPORATION, brand name DURANATE 24A-100)] was mixed to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the peeled polyethylene terephthalate film (PET film), the adhesive composition for evaluation prepared above was applied to a dry film thickness of 20㎛, dried at 90°C for 4 minutes, and transferred onto the non-peeled PET film. and cured for 7 days in an atmosphere of 20°C and 65%RH to obtain an adhesive sheet for evaluation.

Durability evaluation was carried out in a state in which the peel-treated PET film of the obtained pressure-sensitive adhesive sheet for evaluation was peeled off. The results are shown in Table 1.

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

In Example 12, an adhesive composition for evaluation and an adhesive sheet for evaluation were prepared and manufactured in the same manner as in Example 12, except that the type of ionic compound was changed as shown in Table 1, and durability evaluation was performed. . The results are shown in Table 1.

[Example 18]

<Preparation of adhesive composition for evaluation>

1.5 parts by weight (converted to solid content) of the ionic compound C-1 was added to 100 parts by weight (converted to solid content) of the (meth)acrylic copolymer A solution and stirred to obtain an adhesive composition for evaluation.

<Production of adhesive sheet for evaluation>

On the polyethylene terephthalate film (PET film) that has been peeled, the adhesive composition for evaluation prepared above is applied to a dry film thickness of 20㎛, dried at 90°C for 4 minutes, and transferred onto the PET film that has not been peeled. , cured for 1 day in an atmosphere of 20°C and 65%RH to obtain an adhesive sheet for evaluation.

Durability evaluation was performed in a state in which the PET film subjected to the peeling treatment of the obtained pressure-sensitive adhesive sheet for evaluation was peeled off. The results are shown in Table 1.

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

In Example 18, an adhesive composition for evaluation and an adhesive sheet for evaluation were prepared and manufactured in the same manner as in Example 18, except that the type of ionic compound was changed as shown in Table 1, and durability was evaluated. . The results are shown in Table 1.

[Evaluation results]

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

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

Although the present invention has been described in detail and with reference to specific embodiments, it is obvious to those skilled in the art that various further changes and modifications can be made without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application (2015-148214) filed on July 28, 2015, the contents of which are incorporated herein by reference.

Claims (3)

Contains an ionic compound, and the cation portion of the ionic compound is a cation represented by any of the following formulas (2) to (3),
[Formula 2]

[Formula 3]

(In the following formulas (2) to (3), R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms and may contain a hetero atom. R ² represents a hydrocarbon group having 2 to 4 carbon atoms, and a plurality of R ¹ or R ² may be the same or different, respectively.)
An antistatic agent for an adhesive, characterized in that the anionic portion of the ionic compound is (F ₂ SO ₂ ) ₂ N ^- (bis(fluorosulfonyl)imide). delete delete