JP7036892B2 - Adhesive layer and adhesive film - Google Patents

Description

The present invention relates to a pressure-sensitive adhesive composition containing an antistatic agent and a pressure-sensitive adhesive film. More specifically, with respect to a pressure-sensitive adhesive composition containing an alkoxysilyl group-containing ionic compound as an antistatic agent, the pressure-sensitive adhesive composition is excellent in antistatic property without impairing the adhesive performance, and since it contains an alkoxysilyl group, it has adhesiveness to a glass plate. The present invention relates to providing a pressure-sensitive adhesive composition having excellent reworkability with respect to an adherend and a pressure-sensitive adhesive film using the same.

Conventionally, in the manufacturing process / assembly process of precision parts such as electronic equipment parts, optical equipment parts, image display panels, etc., the surface of these precision parts and members is temporarily protected to prevent the working environment atmosphere. A surface protective film is attached to the surface of precision parts and members in order to prevent the adhesion of particles and gaseous contaminants and the generation of scratches and dents.
For example, the surface protective film used in the process of manufacturing optical members such as polarizing plates and retardation plates, which are members constituting a liquid crystal display, is formed on one side of an optically transparent polyethylene terephthalate (PET) resin film. Although the pressure-sensitive adhesive layer is formed, a release-treated release film for protecting the pressure-sensitive adhesive layer is bonded onto the pressure-sensitive adhesive layer until it is bonded to the optical member.

In addition, optical members such as polarizing plates and retardation plates are inspected with optical evaluations such as display capability, hue, contrast, and foreign matter contamination of the liquid crystal display plate with the surface protective film bonded. As the required performance for the surface protective film, it is required that no air bubbles or foreign substances adhere to the pressure-sensitive adhesive layer.
Further, in recent years, when the surface protective film is peeled off from an optical member such as a polarizing plate or a retardation plate, the peeling charge generated by the static electricity generated when the adherend peels off the adhesive layer is electrically controlled by the liquid crystal display. There is a concern that it may affect circuit failure, and excellent antistatic properties are required for the pressure-sensitive adhesive layer.
Further, the optical member often has a surface made of glass (inorganic glass, particularly non-alkali glass), and is required to have excellent adhesiveness to a glass plate.
Further, when the surface protective film is attached to an optical member such as a polarizing plate or a retardation plate, the surface protective film may be peeled off and then reattached for various reasons. In addition, it is required that it can be easily peeled off from the optical member of the adherend (reworkability).
As described above, in recent years, the surface protective film has been used because of the required performance for the pressure-sensitive adhesive layer constituting the surface protective film, such as adhesiveness to a glass plate, excellent antistatic property, and reworkability to an adherend. It is required from the viewpoint of ease of use.
However, the required performances for the pressure-sensitive adhesive layer constituting the surface protective film, such as adhesiveness to the glass plate, excellent antistatic property, and reworkability to the adherend, are separately satisfied. Although it was possible, it was a difficult task to meet the required performance required for the pressure-sensitive adhesive layer of the surface protective film at the same time at a low cost.

Regarding excellent antistatic properties, a method of kneading an antistatic agent into a base film is shown as a method for imparting antistatic properties to a surface protective film, and examples of the antistatic agent include (a). Various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, (b) a sulfonic acid base, a sulfate ester base, a phosphoric acid ester base, and a phosphonic acid base. Anionic antistatic agents having anionic groups such as, (c) amphoteric antistatic agents such as amino acid-based and aminosulfate esters, (d) nonionic antistatic agents such as aminoalcohol-based, glycerin-based and polyethylene glycol-based. , (E) A high-molecular-weight antistatic agent obtained by increasing the amount of the antistatic agent as described above is disclosed (Patent Document 1).

Further, in recent years, it has been proposed to contain such an antistatic agent in the base film, or to directly contain the antistatic agent in the pressure-sensitive adhesive layer instead of applying it to the surface of the base film (). Patent Document 2).
In Patent Document 2, a polymerizable mixture containing (1) (a) urethane acrylate, (b) (meth) acrylate having a polyalkylene oxide chain, and (c) an adhesive force-imparting monomer as main components is irradiated with radiation. Disclosed is an antistatic pressure-sensitive adhesive composition containing a copolymer obtained by polymerization and (2) an ionic compound, and a pressure-sensitive adhesive sheet using the same. As a specific method for producing an adhesive composition, a urethane acrylate such as polyester urethane acrylate, a (meth) acrylate monomer having a polyoxyalkylene chain such as methoxypolyethylene glycol acrylate, and an adhesion such as hydroxypropyl acrylate are bonded. An ionic compound such as lithium perchlorate is mixed with a polymerizable mixture containing a force-imparting monomer and, if necessary, an additional comonomer such as isooctyl acrylate, and a photopolymerization initiator is added if necessary. It is said that the pressure-sensitive adhesive composition can be obtained by stirring until it is completely dissolved and then irradiating it with ultraviolet rays or the like to cure it.
However, since lithium perchlorate used as an ionic compound has metal corrosiveness, there is a problem that the place where the obtained antistatic pressure-sensitive adhesive composition can be used is limited.

Regarding the reworkability of the liquid crystal panel with respect to the polarizing plate, for example, a curing agent for an isocyanate-based compound and a specific silicate oligomer are added in an acrylic resin in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin. A blended pressure-sensitive adhesive composition has been proposed (Patent Document 3).
In Patent Document 3, an acrylic acid alkyl ester having an alkyl group having about 2 to 12 carbon atoms, a methacrylate alkyl ester having an alkyl group having about 4 to 12 carbon atoms, or the like is used as a main monomer component, and for example, a carboxyl group-containing monomer or the like is used. It is said that the functional group-containing monomer component of the above can be contained. Generally, it is preferable to contain the above main monomer in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, and more preferably. It is said that it is desired to be 0.01 to 25% by weight. Such a pressure-sensitive adhesive composition described in Patent Document 3 has a small change in cohesive force and adhesive force with time even under high temperature or high temperature and high humidity, and exhibits an excellent effect on curved surface adhesive force. It is said to have sex.
In general, when the pressure-sensitive adhesive layer has a soft property, adhesive residue is likely to occur, and the reworkability is likely to decrease. That is, when they are erroneously pasted together, they are difficult to peel off and are likely to be difficult to reattach. From this, it is considered necessary to crosslink a monomer having a functional group such as a carboxyl group with the main agent to make the pressure-sensitive adhesive layer have a certain hardness in order to have reworkability.

Japanese Unexamined Patent Publication No. 11-070629 Japanese Unexamined Patent Publication No. 2000-129235 Japanese Unexamined Patent Publication No. 8-199130

Antistatic functions are often required as adhesive sheets, and various types of antistatic agents have been tried. However, especially in the application of optical films, although it can have an antistatic function, it has drawbacks such as poor transparency, and further, due to insufficient compatibility of the antistatic agent with the adhesive, the adherend. There are problems such as poor adhesive strength to the glass plate and poor durability, and further drawbacks such as poor antistatic agent bleed-out and poor reworkability to the adherend when the adhesive sheet is peeled off. There were many. Even if these performances can be satisfied, there are problems such as high cost, and an adhesive containing an antistatic agent that can overcome these drawbacks at low cost has been required.

The present invention has been made in view of the above circumstances, and is an antistatic agent having excellent antistatic properties without impairing adhesive performance, excellent adhesiveness to a glass plate, and excellent reworkability to an adherend. It is an object of the present invention to provide a pressure-sensitive adhesive composition containing the above, and a pressure-sensitive adhesive film using the same.

In order to solve the above problems, the present invention is a pressure-sensitive adhesive composition containing an antioxidant, which comprises a (meth) acrylic polymer as a main component, and the ionic compound represented by the formula 1 as the antioxidant. Provided is a pressure-sensitive adhesive composition comprising the above, wherein the ionic compound has an organic cation containing a hydrolyzable silicon-containing group.

(However, in Equation 1, Z ⁺ indicates a cation and X ⁻ indicates an anion.)
The cation Z ⁺ of the ionic compound is preferably one or more kinds of alkoxysilyl group-containing cations represented by the formula 2.

(However, in Equation 2, R ¹ and R ² represent alkyl groups that are the same or different from each other, n represents an integer of 1 to 3, Q ¹ represents an alkylene group having 1 to 10 carbon atoms, and E. Represents NH or S, Q ² represents a single bond or an alkylene group having 1 to 10 carbon atoms, Q ³ represents an alkylene group having 1 to 10 carbon atoms, and V ⁺ represents an ammonium group or a pyridinium group. , Pyrrolidinium group, imidazolium group, guanidinium group, isouronium group, thiouronium group, piperidinium group, pyrazolium group, morpholinium group, phosphonium group, sulfonium group. However, it may have a substituent.)
The hydrolyzable silicon-containing group is an alkoxysilyl group selected from a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group and an ethyldiethoxysilyl group. Is preferable.

The (meth) acrylic polymer is a copolymerizable vinyl containing (A) at least one alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms, and (B) a hydroxyl group and / or a carboxyl group. It is a copolymer composition composed of at least one kind of monomer, and the antistatic agent is (C) 0 ionic compounds represented by the above formula 1 with respect to 100 parts by weight of the copolymer composition. It is preferable to contain 1 to 20 parts by weight as an essential component.
The (meth) acrylic polymer comprises at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms and at least one of a copolymerizable vinyl monomer having a (B') vinyl group. It is a copolymer composition composed of seeds, and the antistatic agent is (C) 0.1 to 20 ionic compounds represented by the above formula 1 with respect to 100 parts by weight of the copolymer composition. It is preferable to contain parts by weight as an essential component.
The (meth) acrylic polymer is a copolymer composition composed of at least two kinds of alkyl (meth) acrylate monomers having (A) alkyl groups having C1 to C14 carbon atoms, and is 100 weight by weight of the copolymer composition. It is preferable that the antistatic agent contains (C) 0.1 to 20 parts by weight of the ionic compound represented by the above formula 1 as an essential component.

The surface resistivity of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is preferably 1.0 × 10 ⁺¹² Ω / □ or less.
The anion X ^- of the ionic compound includes hexafluorophosphate anion, bis (fluorosulfonyl) imide anion, tris (pentafluoroethyl) trifluorophosphate anion, bis (trifluoromethanesulfonyl) imide anion, thiosian acid anion, and alkylbenzene. It is preferably one or more selected from an inorganic or organic anion group consisting of a sulfonic acid anion, a perchlorate anion salt, and a boron tetrafluoride anion.

The present invention also provides a pressure-sensitive adhesive film in which the pressure-sensitive adhesive composition is laminated on one side of a base material.
The present invention also provides a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated on one side of a base material.
The present invention also provides a surface protective film using the pressure-sensitive adhesive film.
The present invention also provides a surface protective film for a polarizing plate using the pressure-sensitive adhesive film.
The present invention also provides an optical surface protective film using the pressure-sensitive adhesive film.
The present invention also provides an optical film with a pressure-sensitive adhesive, in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated on at least one surface of the optical film.
It is preferable that the optical film of the optical film with an adhesive is a polarizing plate.
The present invention also provides an image display device in which the pressure-sensitive optical film is bonded to each other via the pressure-sensitive adhesive layer.

According to the present invention, by using a pressure-sensitive adhesive containing a hydrolyzable silicon-containing group, particularly an antistatic agent having an alkoxysilyl group, the adhesiveness to a glass plate is excellent, and the antistatic property and adhesion are obtained. It is possible to improve problems such as defects such as reworkability for the body.

Hereinafter, the present invention will be described based on a preferred embodiment.
The pressure-sensitive adhesive composition of the present invention has a pressure-sensitive adhesive polymer as a main component of the pressure-sensitive adhesive and an antistatic agent that imparts antistatic properties, and as the antistatic agent, a hydrolyzable silicon-containing group, particularly alkoxysilyl. It is characterized by containing an ionic compound having a group.
This makes it possible to improve the adhesiveness to the glass plate, and to improve the problems such as antistatic property and reworkability to the adherend.

As the pressure-sensitive adhesive polymer used in the present invention, an acrylic polymer is preferable, and in particular, a copolymer composition containing at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 as a main component. Is preferable.
(A) As the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) Examples thereof include acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.

As the pressure-sensitive adhesive polymer used in the present invention, a copolymerization composition comprising (A) at least one kind of alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms and at least one kind of other copolymerizable monomer. You can also adopt things. In this case, examples of the other copolymerizable monomer include a copolymerizable vinyl monomer having a (B') vinyl group and (B) a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group.
Examples of the copolymerizable vinyl monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyl-containing (meth) acrylic acid esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl ( Examples thereof include hydroxyl group-containing (meth) acrylamides such as meta) acrylamide, and at least one selected from these compound groups is preferable.
Examples of the copolymerizable vinyl monomer containing a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. At least one selected from these compound groups is preferable.
Copolymerizable vinyl monomers other than the above include aromatic group-containing (meth) acrylic acid esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, as well as styrene, acrylamide, acrylonitrile, methyl vinyl ether, and ethyl vinyl ether. , Vinyl acetate, vinyl chloride and other various vinyl monomers.

Further, as the pressure-sensitive adhesive polymer used in the present invention, a copolymer composition composed of at least two kinds of (A) alkyl (meth) acrylate monomers having an alkyl group having C1 to C14 carbon atoms can be adopted. In this case, the copolymerization composition can be obtained without using a copolymerizable vinyl monomer other than the alkyl (meth) acrylate monomer having (A) an alkyl group having C1 to C14 carbon atoms.

The ionic compound used as an antistatic agent in the present invention is represented by the formula 1, and the cation Z ⁺ is an organic cation having a hydrolyzable silicon-containing group. The ionic compound may be an ionic liquid that becomes a liquid at room temperature (for example, 30 ° C.), or may be a solid at room temperature.

Z ⁺ X- ⁽ Equation 1)

(However, in Equation 1, Z ⁺ indicates a cation and X ⁻ indicates an anion.)

The anion X ^- of the ionic compound includes hexafluorophosphate anion, bis (fluorosulfonyl) imide anion, tris (pentafluoroethyl) trifluorophosphate anion, bis (trifluoromethanesulfonyl) imide anion, thiosian acid anion, and alkylbenzene. It is preferably one or more selected from an inorganic or organic anion group consisting of a sulfonic acid anion, a perchlorate anion salt, and a boron tetrafluoride anion.

The cation Z ⁺ of the ionic compound is a pyridinium cation, an imidazolium cation, a sulfonium cation, a phosphonium cation, a pyrrolidinium cation, a guanidinium cation, an ammonium cation, an isouronium cation, a thiouronium cation, and a piperidinium cation. , Pyrazolium cations, morpholinium cations and the like, preferably one or more selected from the cation group.
The cation Z ⁺ is an organic cation having a hydrolyzable silicon-containing group.

As the hydrolyzable silicon-containing group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidesilyl group and the like are preferably used. Of these, the alkoxysilyl group represented by the formula 1a is preferable.

(R ¹ O) _n (R ² ) _3-n Si- (Equation 1a)

However, in the formula 1b, R ¹ and R ² represent the same or different alkyl groups from each other, and n represents an integer of 1 to 3.

Examples of the alkoxysilyl group include an alkoxydialkylsilyl group (n = 1), an alkyldialkoxysilyl group (n = 2), and a trialkoxysilyl group (n = 3). Alkoxydialkoxysilyl groups (n = 2) or trialkoxysilyl groups (n = 3) are preferred.
Examples of the alkoxy group ( ^R1 O) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group and the like.
Examples of the alkyl group (R ² ) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and the like.

Specific examples of the alkoxysilyl group include a trimethoxysilyl group (formula 1a-1), a triethoxysilyl group (formula 1a-2), and a methyldimethoxysilyl represented by the following formulas 1a-1 to 1a-6. Examples thereof include a group (formula 1a-3), a methyldiethoxysilyl group (formula 1a-4), an ethyldimethoxysilyl group (formula 1a-5), an ethyldiethoxysilyl group (formula 1a-6) and the like.

(CH ₃ O) ₃ Si- (Equation 1a-1)
(C ₂ H ₅ O) ₃ Si- (Equation 1a-2)
(CH ₃ ) (CH ₃ O) ₂ Si- (Equation 1a-3)
(CH ₃ ) (C ₂ H ₅ O) ₂ Si- (Equation 1a-4)
(C ₂ H ₅ ) (CH ₃ O) ₂ Si- (Equation 1a-5)
(C ₂ H ₅ ) (C ₂ H ₅ O) ₂ Si- (Equation 1a-6)

Among other hydrolyzable silicon-containing groups, the hydrolyzable group that can be used in place of the alkoxy group (R1O) includes a vinyloxy group, a ¹ -methylvinyloxy group, a 1-ethylvinyloxy group and the like. Alkenyloxy group; Asyloxy group such as acetyloxy group, propanoyloxy group, benzoyloxy group; Amino group such as dimethylamino group, methylethylamino group, diethylamino group; dimethylaminooxy group, methylethylaminooxy group, diethylaminooxy Aminooxy groups such as groups; (CH ₃ ) ₂ C = NO- and (C ₂ H ₅ ) ₂ C = NO- and other oxime groups; CH ₃ CON (CH ₃ )-and C ₂ H ₅ CON (CH ₃ ). )-Or other amide groups. These hydrolyzable groups L have hydrolyzability when bonded to the Si atom of the silyl group.

The silyl group in the hydrolyzable silicon-containing group may be a siloxane group. Examples of the hydrolyzable silicon-containing group having a siloxane group include those represented by the formula 1a'and those having the hydrolyzable group such as an alkenyloxy group instead of the alkoxy group ( ^R1O ). Can be mentioned.

(R ² ) ₃ SiO (R ¹ O) ₂ Si- (Equation 1a')

The cation Z ⁺ of the ionic compound is preferably one or more kinds of alkoxysilyl group-containing cations represented by the formula 1b.

(R ¹ O) _n (R ² ) _3-n Si-Q-V ⁺ (Equation 1b)

However, in the formula 1b, R ¹ and R ² represent the same or different alkyl groups from each other, and n represents an integer of 1 to 3.
Q represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be a linear group or a branched group, and may be a non-converting group or a substituent. Further, an ether bond (-O-), a sulfide bond (-S-), an imino group (-NH-), a carbonyl group (-CO-), and an ester bond (-COO- or -OCO-) are attached to the main chain of the alkylene group. Hetero that constitutes a functional group such as-), amide bond (-CONH- or -NHCO-), carbonate bond (-OCOO-), urethane bond (-NHCOO- or -OCONH-), urea bond (-NHCONH-), etc. It may contain one or more atoms (atoms of elements other than carbon and hydrogen such as O, S, N).
However, when the main chain of the alkylene group Q has a heteroatom, the number of the heteroatoms is not included in the number of carbon atoms of the alkylene group. Further, in the alkylene group Q, the atom adjacent to Si of the silicon-containing group is not a heteroatom but a carbon atom.
V ⁺ is a monovalent cation group selected from an ammonium group, a pyridinium group, a pyrrolidinium group, an imidazolium group, a guanidinium group, an isouronium group, a thiouronium group, a piperidinium group, a pyrazonium group, a morpholinium group, a phosphonium group and a sulfonium group. As shown, the cation group V ⁺ may have a non-converting group or a substituent.

Examples of the substituent that may be contained in the alkylene group Q include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; a phenyl group, a naphthyl group, a 4-methylphenyl group and a 4-methoxyphenyl group. Aryl group which may have a substituent of: methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, trifluoromethoxy group, benzyloxy group. An alkoxy group may have a substituent such as; a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 3-phenoxyphenoxy group and the like. Good aryloxy groups; halogen atoms such as fluorine and chlorine atoms are exemplified. If the alkylene group has a substituent, the carbon number of the substituent is not included in the carbon number of the alkylene group.

The alkylene group Q may be a linking group that links a hydrolyzable silicon-containing group (alkoxysilyl group or the like) and a cationic group (V ⁺ ), and may be, for example, -C _i H _2i- , -C _i . H _2i OC _j H _2j- , -C _i H _2i SC _j H _2j- , -C _i H _2i NHC _j H _2j- , -C _i H _2i COC _j H _2j- , -C _i H _2i COOC _j H _2j -, -C _i H _2i OCOC _j H _2j- , -C _i H _{2i NHCOC j} H _2j- , -C _i H _2i CONHC _j H _2j- , -C _i H _2i OCOC _j H 2j-, -C _i H _2i NHCOOC _j H _2j- , -C _i H _2i OCONNHC _j H _2j- , -C _i H _2i NHCONHC _j H _2j- , -C _i H _2i OC _j H _2j OC _k H _2k- , -C _i H _2i OC _j H _2j COOC _k H _2k- , -C _i H _2i NHC _j H _2j COOC _k H _2k- , -C _i H _2i SC _j H _2j COOC _k H _2k- , etc. (However, i, j, k is an integer greater than or equal to 1).
Examples of the alkylene group represented by C _i H _2i , C _j H _2j , and C _k H _2k include -CH _2- , -CH ₂ CH _2- , -C (CH ₃ )-, and -CH ₂ CH. ₂ CH _2- , -CH ₂ C (CH ₃ )-, -C (CH ₃ ) CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , etc. Hydrocarbon groups can be mentioned.
When the linking group Q has a heteroatom in the main chain of the alkylene group, it is preferable that the heteroatom constitutes a chemical bond that is not easily cleaved by hydrolysis or the like. As a result, the linking group Q can exert a function as a linking group for linking a hydrolyzable silicon-containing group (alkoxysilyl group or the like) and a cationic group (V ⁺ ).

The cation Z ⁺ of the ionic compound is preferably one or more kinds of alkoxysilyl group-containing cations represented by the formula 2.

(R ¹ O) _n (R ² ) _3-n Si-Q ¹ -E-Q ² -COO-Q ³ -V ⁺ (Equation 2)

(However, in Equation 2, R ¹ and R ² represent alkyl groups that are the same or different from each other, n represents an integer of 1 to 3, Q ¹ represents an alkylene group having 1 to 10 carbon atoms, and E. Represents NH or S, Q ² represents a single bond or an alkylene group having 1 to 10 carbon atoms, Q ³ represents an alkylene group having 1 to 10 carbon atoms, and V ⁺ represents an ammonium group or a pyridinium group. , Pyrrolidinium group, imidazolium group, guanidinium group, isouronium group, thiouronium group, piperidinium group, pyrazolium group, morpholinium group, phosphonium group, sulfonium group. However, it may have a substituent.)

Examples of the ammonium group include a trialkylammonium group (-N ⁺ R ₃ ) and a dialkylammonium group (-N ⁺ HR ₂ ). Examples of the phosphonium group include a trialkylphosphonium group (−P ⁺ R ₃ ) and a dialkylphosphonium group (−P ⁺ HR ₂ ). Examples of the sulfonium group include a dialkyl sulfonium group (−S ⁺ R ₂ ) and the like. R in these formulas represents the same or different alkyl groups from each other.

Pyridinium group, pyrrolidinium group, imidazolium group, guanidinium group, isouronium group, thiouronium group, piperidinium group, pyrazolium group, morpholinium group include pyridinium, pyrrolidinium, imidazolium, guanidinium, isouronium, thiouronium, piperidinium, pyrazolium, respectively. In the nitrogen atom or carbon atom contained in, or the oxygen atom of isouronium or the sulfur atom of thiouronium, a group capable of binding to ^Q3 can be mentioned.

The substituent which may be contained in the cationic group (V ⁺ ) includes an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; a phenyl group, a naphthyl group, a 4-methylphenyl group and a 4-methoxy group. An aryl group which may have a substituent such as a phenyl group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a trifluoromethoxy group, An alkoxy group which may have a substituent such as a benzyloxy group; a substituent such as a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 3-phenoxyphenoxy group and the like. An aryloxy group which may be used; a halogen atom such as a fluorine atom and a chlorine atom is exemplified.

Examples of the cation Z ⁺ used in the present invention include trialkyl (alkoxysilylalkyl) ammonium, trialkyl ([({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl]) ammonium, and trialkyl ([({{ [(Alkoxysilyl) alkyl] amino} acyl) oxy] alkyl}) ammonium, trialkyl ([({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl}) ammonium and other hydrolyzable silicon-containing Ammonium cation with a group;
1-[(alkoxysilyl) alkyl] pyridinium, 1-[({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] pyridinium, 1-[({[(alkoxysilyl) alkyl] amino} acyl) oxy] alkyl } Pyridinium, a pyridinium cation having a hydrolyzable silicon-containing group, such as 1-[({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl} pyridinium;

1-alkyl-1-[(alkoxysilyl) alkyl] pyrrolidinium, 1-alkyl-1-[({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] pyrrolidinium, 1-alkyl-1-[({[((alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] Hydrolyzable silicon-containing groups such as alkoxysilyl) alkyl] amino} acyl) oxy] alkyl} pyrrolidinium, 1-alkyl-1-[({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl} pyrrolidinium. Pyrrolidinium cation with
1-alkyl-3-[(alkoxysilyl) alkyl] imidazolium, 1,2-dialkyl-3-[(alkoxysilyl) alkyl] imidazolium, 1-alkyl-3-[({[(alkoxysilyl) alkyl]] Carbamoyl} oxy) alkyl] imidazolium, 1-alkyl-3-[({[(alkoxysilyl) alkyl] amino} acyl) oxy] alkyl} imidazolium, 1-alkyl-3-[({[(alkoxysilyl)) Alkoxy] sulfanyl} acyl) oxy] alkyl} imidazolium cations with hydrolyzable silicon-containing groups such as imidazolium;

Hydrolyzable, such as 1-[(alkoxysilyl) alkyl] guanidinium, 2-[(alkoxysilyl) alkyl] guanidinium, 1,1,3,3-tetraalkyl-2-[(alkoxysilyl) alkyl] guanidinium. Guanidinium cation with silicon-containing group;
2-alkyl-1-[(alkoxysilyl) alkyl] isouronium, 2-[(alkoxysilyl) alkyl] isouronium, 1,1,3,3-tetraalkyl-2-[(alkoxysilyl) alkyl] isouronium, etc. Isouronium cations with hydrolyzable silicon-containing groups;
2-alkyl-1-[(alkoxysilyl) alkyl] thiouronium, 1-alkyl-2-[(alkoxysilyl) alkyl] thiouronium, 1,1,3,3-tetraalkyl-2-[(alkoxysilyl) alkyl] A thiouronium cation having a hydrolyzable silicon-containing group, such as thiouronium;

1-alkyl-1-[(alkoxysilyl) alkyl] piperidinium, 1-alkyl-1-[({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] piperidinium, 1-alkyl-1-[({[((alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] Hydrolyzable silicon-containing groups such as alkoxysilyl) alkyl] amino} acyl) oxy] alkyl} piperidinium, 1-alkyl-1-[({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl} piperidinium. Piperidinium cation with
1-alkyl-2-[(alkoxysilyl) alkyl] pyrazolium, 1-alkyl-2-[({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] pyrazolium, 1-alkyl-2-[({[((alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] Hydrolyzable silicon-containing groups such as alkoxysilyl) alkyl] amino} acyl) oxy] alkyl} pyrazolium, 1-alkyl-2-[({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl} pyrazolium. Pyrazolium cation with
4-alkyl-4-[(alkoxysilyl) alkyl] morpholinium, 4-alkyl-4-[({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] morpholinium, 4-alkyl-4-[({[((alkoxysilyl) alkyl] carbamoyl} oxy) alkyl] Hydrolyzable silicon-containing groups such as alkoxysilyl) alkyl] amino} acyl) oxy] alkyl} morpholinium, 4-alkyl-4-[({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl} morpholinium. Morphorinium cation with

Trialkyl [(alkoxysilyl) alkyl] phosphonium, trialkyl ([({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl]) phosphonium, trialkyl ([({[(alkoxysilyl) alkyl] amino} acyl)) Oxy] alkyl}) phosphonium, trialkyl ([({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl}) phosphonium and other phosphonium cations with hydrolyzable silicon-containing groups;
Dialkyl [(alkoxysilyl) alkyl] sulfonium, dialkyl ([({[(alkoxysilyl) alkyl] carbamoyl} oxy) alkyl]) sulfonium, dialkyl ([({[(alkoxysilyl) alkyl] amino} acyl) oxy] alkyl }) Sulfonium, sulfonium cations with hydrolyzable silicon-containing groups such as [({[(alkoxysilyl) alkyl] sulfanyl} acyl) oxy] alkyl}) sulfonium;
And so on.

Specific examples of the cation Z ⁺ used in the present invention include, for example,
Trimethyl ([2- ({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium, trimethyl ([2-({[3- (triethoxysilyl) propyl] carbamoyl} oxy) ethyl]) Ammonium, trimethyl ([2-({[3- (methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium, trimethyl ([2-({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy)) Ethyl]) ammonium, trimethyl ([2-({[3- (ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium, trimethyl ([2-({[3- (ethyldiethoxysilyl) propyl] carbamoyl] } Oxy) Ethyl]) Ammonium,
1- [2-({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium, 1- [2-({[3- (triethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium, 1- [2-({[3- (Methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium, 1- [2-({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium , 1- [2-({[3- (Ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium, 1- [2-({[3- (ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] Pyridinium,
Trimethyl ({2-[(3-{[3- (trimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(3-{[3- (triethoxysilyl) propyl) ] Amino} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(3-{[3- (methyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[( 3-{[3- (Methyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(3-{[3- (ethyldimethoxysilyl) propyl] amino} propanoyl) oxy) ] Ethyl}) ammonium, trimethyl ({2-[(3-{[3- (ethyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium,
Trimethyl ({2-[(2-methyl-3-{[3- (trimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(2-methyl-3-{[] 3- (Triethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(2-methyl-3-{[3- (methyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] Ethyl}) ammonium, trimethyl ({2-[(2-methyl-3-{[3- (methyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(2-2-]) Methyl-3-{[3- (ethyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium, trimethyl ({2-[(2-methyl-3-{[3- (ethyldiethoxysilyl) propyl) ] Sulfanyl} propanoyl) oxy] ethyl}) ammonium,
And so on.

The compound represented by the above formula 2 can be synthesized by using a known synthesis method.
For example, the compound represented by (R ¹ O) _n (R ² ) _3-n Si—Q—V ⁺ is (R ¹ O) _n (R ² ) _3-n Si—Q—Hal (where Hal). Can be synthesized by reacting a compound represented by (representing a halogen such as Cl, Br, I) with an amine, imidazole, or the like.
The compound represented by (R ¹ O) _n (R ² ) _3-n Si-Q ¹ -NH-COO-Q ³ -V ⁺ is (R ¹ O) _n (R ² ) _3-n Si. It can also be synthesized by reacting a compound represented by ^−Q1 −NCO with a compound represented by HO— ^Q3 −V ⁺ .

Specific examples of the anion X ⁻ used in the present invention include borate tetrafluoride [BF _4- ], phosphoric acid hexafluoride [PF ₆ ⁻ ], ^and tris (pentafluoroethyl) trifluorophosphate [PF ₃ (C). ₂ F ₅ ) _3- ^] , bis (fluorosulfonyl) imide [(FSO ₂ ) ₂ N- ^] , bis (trifluoromethanesulfonyl) imide [(CF ₃ SO ₂ ) ₂ N- ^] , bis (pentafluoroethanesulfonyl) Iimide [(C ₂ F ₅ SO ₂ ) ₂ N- ^] , Bis (Heptafluoropropanesulfonyl) imide [(C ₃ F ₇ SO ₂ ) ₂ N- ^] , (Trifluoromethanesulfonyl) (Pentafluoroethanesulfonyl) imide [ (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) N- ^] , (Trifluoromethanesulfonyl) (Heptafluoropropanesulfonyl) imide [(CF ₃ SO ₂ ) (C ₃ F ₇ SO ₂ ) N- ^] , ( Examples thereof include trifluoromethanesulfonyl) (nonafluorobutanesulfonyl) imide [(CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) N- ^] .
Of these, BF _4- ^, PF _6- ^, PF ₃ (C ₂ F ₅ ) _3- ^, (FSO ₂ ) ₂ N- ^, and (CF ₃ SO ₂ ) ₂ N ^- are preferable.

Specific examples of the ionic compound (Z ⁺ · X ⁻ ) used in the present invention include a combination of the above-mentioned preferable cation Z ⁺ and a preferred anion X ⁻ , for example.
Trimethyl ([2- ({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (trimethoxysilyl) propyl]] Carbamoyl} oxy) ethyl]) ammonium hexafluorophosphate, trimethyl ([2-({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tetrafluoride borate, trimethyl ([ 2-({[3- (Trimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ([2- ({[3- (triethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (triethoxysilyl) propyl]] Carbamoyl} oxy) ethyl]) Ammonium hexafluorophosphate, trimethyl ([2-({[3- (triethoxysilyl) propyl] Carbamoyl} oxy) ethyl]) Ammonium tetrafluoride phosphate, trimethyl ([ 2-({[3- (Triethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ([2- ({[3- (methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (methyldimethoxysilyl) propyl]] Carbamoyl} oxy) ethyl]) ammonium hexafluorophosphate, trimethyl ([2-({[3- (methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tetrafluoride borate, trimethyl ([ 2-({[3- (Methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ([2- ({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (methyldiethoxysilyl)) Propyl] carbamoyl} oxy) ethyl]) ammonium hexafluorophosphate, trimethyl ([2-({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tetrafluoride borate, Trimethyl ([2-({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ([2- ({[3- (ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (ethyldimethoxysilyl) propyl]] Carbamoyl} oxy) ethyl]) ammonium hexafluorophosphate, trimethyl ([2-({[3- (ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tetrafluoride borate, trimethyl ([ 2-({[3- (Ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ([2- ({[3- (ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium bis (fluorosulfonyl) imide salt, trimethyl ([2-({[3- (ethyldiethoxysilyl)) Propyl] carbamoyl} oxy) ethyl]) ammonium hexafluorophosphate, trimethyl ([2-({[3- (ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tetrafluoride borate, Trimethyl ([2-({[3- (ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl]) ammonium tris (pentafluoroethyl) trifluorophosphate salt,

1- [2-({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (trimethoxysilyl) propyl] carbamoyl] } Oxy) ethyl] pyridinium hexafluorophosphate, 1- [2-({[3- (trimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluoride borate, 1- [2-( {[3- (Trimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,
1- [2-({[3- (triethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (triethoxysilyl) propyl] carbamoyl] } Oxy) Ethyl] pyridinium hexafluorophosphate, 1- [2-({[3- (triethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluoride borate, 1- [2-( {[3- (Triethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,
1- [2-({[3- (Methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (methyldimethoxysilyl) propyl] carbamoyl] } Oxy) ethyl] pyridinium hexafluorinated phosphate, 1- [2-({[3- (methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluorinated borate, 1- [2-( {[3- (Methyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,
1- [2-({[3- (Methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (methyldiethoxysilyl) propyl) ] Carbamoyl} oxy) ethyl] pyridinium hexafluorophosphate, 1- [2-({[3- (methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluoride borate, 1- [ 2-({[3- (Methyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,
1- [2-({[3- (Ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (ethyldimethoxysilyl) propyl] carbamoyl] } Oxy) Ethyl] pyridinium hexafluorophosphate, 1- [2-({[3- (ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluoride borate, 1- [2-( {[3- (Ethyldimethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,
1- [2-({[3- (Ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium bis (fluorosulfonyl) imide salt, 1- [2-({[3- (ethyldiethoxysilyl) propyl) ] Carbamoyl} oxy) ethyl] pyridinium hexafluorophosphate, 1- [2-({[3- (ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tetrafluoride borate, 1- [ 2-({[3- (Ethyldiethoxysilyl) propyl] carbamoyl} oxy) ethyl] pyridinium tris (pentafluoroethyl) trifluorophosphate salt,

Trimethyl ({2-[(3-{[3- (trimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[3) -(Trimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (trimethoxysilyl) propyl] amino} propanoyl) oxy) ] Ethyl}) Ammonium tetrafluoroborate, trimethyl ({2-[(3-{[3- (trimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium Tris (pentafluoroethyl) trifluorophos Fate salt,
Trimethyl ({2-[(3-{[3- (triethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[3) -(Triethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (triethoxysilyl) propyl] amino} propanoyl) oxy) ] Ethyl}) Ammonium tetrafluoride borate, trimethyl ({2-[(3-{[3- (triethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophos Fate salt,
Trimethyl ({2-[(3-{[3- (methyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[3) -(Methyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (methyldimethoxysilyl) propyl] amino} propanoyl) oxy) ] Ethyl}) Ammonium tetrafluoride borate, trimethyl ({2-[(3-{[3- (methyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophos Fate salt,
Trimethyl ({2-[(3-{[3- (methyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[ 3- (Methyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (methyldiethoxysilyl) propyl] amino}) Propyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(3-{[3- (methyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium tris (pentafluoro) Ethyl) trifluorophosphate salt,
Trimethyl ({2-[(3-{[3- (ethyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[3) -(Ethyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (ethyldimethoxysilyl) propyl] amino} propanoyl) oxy) ] Ethyl}) Ammonium tetrafluoride borate, trimethyl ({2-[(3-{[3- (ethyldimethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophos Fate salt,
Trimethyl ({2-[(3-{[3- (ethyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(3-{[ 3- (Ethyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(3-{[3- (ethyldiethoxysilyl) propyl] amino}) Propanoyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(3-{[3- (ethyldiethoxysilyl) propyl] amino} propanoyl) oxy] ethyl}) ammonium tris (pentafluoro) Ethyl) trifluorophosphate salt,

Trimethyl ({2-[(2-methyl-3-{[3- (trimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(2) -Methyl-3-{[3- (trimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[3-] (Trimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(2-methyl-3-{[3- (trimethoxysilyl) propyl] sulfanyl}) Propyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ({2-[(2-methyl-3-{[3- (triethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(2) -Methyl-3-{[3- (triethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[3-] (Triethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(2-methyl-3-{[3- (triethoxysilyl) propyl] sulfanyl}) Propyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ({2-[(2-methyl-3-{[3- (methyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(2) -Methyl-3-{[3- (methyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[3-] (Methyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(2-methyl-3-{[3- (methyldimethoxysilyl) propyl] sulfanyl}} Propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ({2-[(2-methyl-3-{[3- (methyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[( 2-Methyl-3-{[3- (methyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[] 3- (Methyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluorinated borate, trimethyl ({2-[(2-methyl-3-{[3- (methyldiethoxysilyl)) Propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ({2-[(2-methyl-3-{[3- (ethyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[(2) -Methyl-3-{[3- (ethyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[3-] (Ethyldimethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluoride borate, trimethyl ({2-[(2-methyl-3-{[3- (ethyldimethoxysilyl) propyl] sulfanyl}} Propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
Trimethyl ({2-[(2-methyl-3-{[3- (ethyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium bis (fluorosulfonyl) imide salt, trimethyl ({2-[( 2-Methyl-3-{[3- (ethyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium hexafluorinated phosphate, trimethyl ({2-[(2-methyl-3-{[] 3- (Ethyldiethoxysilyl) propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tetrafluorinated borate, trimethyl ({2-[(2-methyl-3-{[3- (ethyldiethoxysilyl)) Propyl] sulfanyl} propanoyl) oxy] ethyl}) ammonium tris (pentafluoroethyl) trifluorophosphate salt,
And so on.

With respect to 100 parts by weight of the copolymer composition of the pressure-sensitive adhesive polymer used in the present invention, the antistatic agent is (C) 0.1 to 20 parts by weight of the ionic compound represented by the above formula 1, more preferably. Is preferably contained in an amount of 0.1 to 10 parts by weight.

The surface resistivity of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is preferably 1.0 × 10 ⁺¹² Ω / □ or less. If the surface resistivity is large, the performance to release the static electricity generated by charging during peeling is inferior. Therefore, by making the surface resistivity sufficiently small, the peeling band generated by the static electricity generated when the adherend peels off the adhesive layer. The voltage is reduced, and it is possible to suppress the influence on the electric control circuit of the adherend and the like.

The pressure-sensitive adhesive composition of the present invention preferably crosslinks the pressure-sensitive adhesive polymer when forming the pressure-sensitive adhesive layer. For cross-linking, the pressure-sensitive adhesive composition may contain a known cross-linking agent, or may be cross-linked by optical cross-linking such as ultraviolet rays (UV). Examples of the cross-linking agent include a bifunctional or higher functional isocyanate compound, a bifunctional or higher functional epoxy compound, a bifunctional or higher acrylate compound, and a metal chelate compound.
Further, as other components, known additives such as silane coupling agents, antioxidants, surfactants, curing accelerators, plasticizers, fillers, curing retarders, processing aids, antiaging agents, etc. shall be appropriately added. Can be done. These can be used alone or in combination of two or more.

The pressure-sensitive adhesive film of the present invention is obtained by laminating a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a base film. The pressure-sensitive adhesive film of the present invention can be suitably used for a surface protection film, a surface protection film for a polarizing plate, a surface protection film for optics, an optical film with a pressure-sensitive adhesive, a polarizing plate with a pressure-sensitive adhesive, and the like.
As the base film of the pressure-sensitive adhesive layer and the release film (separator) for protecting the pressure-sensitive adhesive surface, a resin film such as a polyester film can be used.
On the base film, on the side opposite to the side where the adhesive layer of the resin film is formed, antifouling treatment with silicone-based or fluorine-based mold release agent or coating agent, silica fine particles, etc., application of antistatic agent, etc. Antistatic treatment such as kneading can be applied.
The release film is subjected to a mold release treatment with a silicone-based or fluorine-based mold release agent or the like on the surface of the pressure-sensitive adhesive layer that is combined with the adhesive surface.
In the case of an optical surface protective film such as a surface protective film for a polarizing plate, it is preferable that the base film and the pressure-sensitive adhesive layer have sufficient transparency.

In the optical film with an adhesive, as the base film, an optical film such as a polarizing plate film, a retardation plate film, a lens film, a polarizing plate film that also serves as a retardation plate, and a polarizing plate film that also serves as a lens film can be used. ..
The optical film with an adhesive is formed by laminating an adhesive layer on one side or both sides of the optical film, and can be used for bonding to a glass plate or the like of an image display device. These optical films with an adhesive can be bonded to a glass substrate or the like via an adhesive layer and incorporated into an image display device or the like. The pressure-sensitive adhesive layer used for the pressure-sensitive optical film such as a polarizing plate with a pressure-sensitive adhesive preferably has sufficient transparency.
Further, the polarizing plate used as the base film generally has a three-layer structure sandwiched between both sides of a polyvinyl alcohol-based polarizing element and a triacetyl cellulose-based protective film.
A stretched triacetyl cellulose-based film, a stretched polycycloolefin-based film, or a stretched cellulose acetate propionate film instead of a polarizing plate or a triacetyl cellulose-based film in which the surface of the protective film is coated with a discotic liquid crystal. The structure is such that they are pasted together. Further, these polarizing plate films are bonded to a glass substrate, which is a surface base material of a liquid crystal display panel, via an adhesive layer.

INDUSTRIAL APPLICABILITY The present invention uses an antistatic agent, which is an ionic compound represented by the formula 1, as an adhesive, thereby providing an antistatic function and further improving the adhesive force to a glass plate. Durability can be improved, and the advantages of both can be utilized at a lower cost than when both an antistatic agent and a silane coupling agent are conventionally used in combination, and the above-mentioned problems can be improved.

Hereinafter, the present invention will be specifically described with reference to Examples.

<Manufacturing of acrylic copolymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the air in the reactor was replaced with nitrogen gas. Then, 100 parts by weight of 2-ethylhexyl acrylate and 1.5 parts by weight of 6-hydroxyhexyl acrylate and 100 parts of solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65 ° C. for 8 hours to obtain an acrylic copolymer solution 1 of Example 1 having a weight average molecular weight of 500,000. Got
[Examples 2 to 7 and Comparative Examples 1 to 2]
Each of the monomers is used in Examples 2 to 7 and Comparative Examples 1 and 2 in the same manner as the acrylic copolymer solution 1 used in Example 1 above, except that the composition of each monomer is as shown in Table 1. An acrylic copolymer solution was obtained.

<Manufacturing of adhesive composition, surface protective film, and polarizing plate film>
[Example 1]
1.0 part by weight of antistatic agent C-1 (see Tables 3 and 4) and coronate HX (hexa) with respect to acrylic copolymer solution 1 (of which 100 parts by weight is acrylic copolymer) produced as described above. 1.5 parts by weight of isocyanurate of methylene diisocyanate (HDI) compound) was added and mixed by stirring to obtain the pressure-sensitive adhesive composition of Example 1. This pressure-sensitive adhesive composition is applied onto a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ° C. to remove the solvent, and the pressure-sensitive adhesive layer has a thickness of 25 μm. I got a sheet.
After that, the adhesive sheet is transferred to the surface opposite to the antistatic and antifouling treated polyethylene terephthalate (PET) film on one surface, and "antistatic and antifouling treated". A surface protective film of Example 1 having a laminated structure of "PET film / adhesive layer / release film (PET film coated with silicone resin)" was obtained.
[Examples 2 to 4 and Comparative Examples 1 to 2]
The surface protective films of Examples 2 to 4 and Comparative Examples 1 and 2 were obtained in the same manner as the surface protective film of Example 1 above, except that the composition of each of the additives was as shown in Table 1. ..
[Examples 5 to 7]
The composition of each additive is as shown in Table 1, and the same as in Example 1 above, except that the substrate to be transferred is a polarizing plate, is described in the same manner as in Example 1 above. A polarizing plate film of Examples 5 to 7 having a laminated structure of "coated PET film)" was obtained.

In Table 1, the blending ratio of each component is based on 100 parts by weight of the total of alkyl acrylate monomers (in the case of using a copolymerizable vinyl monomer, the total of the alkyl acrylate monomer and the copolymerizable vinyl monomer). The numbers are shown in parentheses. The compound names of the abbreviations of each component used in Table 1 are shown in Table 2. The chemical formulas of the antistatic agents used in Table 1 are shown in Table 3.
Coronate (registered trademark) HX, HL and L-45 are trade names of Nippon Polyurethane Industry Co., Ltd., and TETRAD (registered trademark) -X is a trade name of Mitsubishi Gas Chemical Company, Inc. Trademark) 24A-100 is a trade name of Asahi Kasei Chemicals Co., Ltd.

<Test method and evaluation>
The surface protective films of Examples 1 to 4 and Comparative Examples 1 to 2 and the polarizing plate films of Examples 5 to 7 were aged for 7 days in an atmosphere of 23 ° C. and 50% RH, and then a release film (silicone resin coating) was applied. The PET film) was peeled off to expose the pressure-sensitive adhesive layer, which was used as a sample for measuring the surface resistance.
Further, the surface protective film on which the pressure-sensitive adhesive layer was exposed and the polarizing plate film were attached to the surface of the non-alkali glass plate via the pressure-sensitive adhesive layer, left for one day, and then at 50 ° C., 5 atm, 20. A sample that was autoclaved for 1 minute and left at room temperature for another 12 hours was used as a sample for measuring adhesive strength.
Further, the surface protective film and the polarizing plate film on which the pressure-sensitive adhesive layer was exposed were bonded to the surface of the non-alkali glass plate via the pressure-sensitive adhesive layer to prepare a sample for measuring durability and reworkability.

<Surface resistivity>
After aging, before bonding to a non-alkali glass plate, the release film (PET film coated with silicone resin) is peeled off to expose the adhesive layer, and the resistance meter Hiresta UP-HT450 (manufactured by Mitsubishi Chemical Analytech) is used. The surface resistance of the pressure-sensitive adhesive layer was measured using.

<Durability>
The durability measurement sample obtained above was left at 60 ° C. and 90% RH for 250 hours, then taken out to room temperature, and peeling from the adherend, foaming and the like were visually confirmed. The evaluation criteria were "○" when no peeling / foaming was confirmed, "Δ" when peeling / foaming was slightly confirmed, and "×" when peeling / foaming was clearly confirmed.

<Reworkability>
The reworkability measurement sample obtained above was left at 70 ° C. in a DRY atmosphere for 24 hours, then taken out to room temperature, and the adherend when the surface protection film and the polarizing plate film were peeled off from the non-alkali glass plate. The adhesive residue on the surface was visually confirmed. The evaluation criteria were evaluated as "○" when no adhesive residue was confirmed, "Δ" when a slight adhesive residue was confirmed, and "×" when the adhesive residue was clearly confirmed.

<Adhesive strength to glass plate>
A sample for measuring the adhesive strength obtained above (a 25 mm wide surface protective film and a polarizing plate film bonded to the surface of a non-alkali glass plate) was used in a 180 ° direction using a tensile tester. The peeling strength measured by peeling at a tensile speed of 3 m / min was taken as the adhesive strength.

Table 4 shows the evaluation results. The surface resistivity is expressed by a method in which "m × 10 ^{+ n} " is set to "mE + n" (where m is an arbitrary real number and n is a positive integer).

The surface protective films of Examples 1 to 4 and the polarizing plate films of Examples 5 to 7 had a surface resistivity of 1.0 × 10 ⁺¹² Ω / □ or less, and had an appropriate adhesive strength. That is, it has become possible to improve the problems such as the antistatic property and the reworkability for the adherend.
The surface resistivity of the surface protective films of Comparative Examples 1 and 2 exceeded 1.0 × 10 ⁺¹² Ω / □, and there was a problem in antistatic property. Further, the surface protective films of Comparative Examples 1 and 2 have problems in durability and reworkability with respect to the adherend.

Claims (5)

A pressure-sensitive adhesive layer obtained by cross-linking a pressure-sensitive adhesive composition containing a (meth) acrylic polymer, an antistatic agent, and a cross-linking agent by UV curing.
The (meth) acrylic polymer copolymerizes at least one of the alkyl (meth) acrylate monomers having (A) alkyl groups having C1 to C14 and at least one of the other copolymerizable monomers. It is a copolymer
The antistatic agent contains an ionic compound represented by the formula 1, the ionic compound has an organic cation containing a hydrolyzable silicon-containing group, and the organic cation Z ⁺ is represented by the formula 2. It is one or more types of alkoxysilyl group-containing cations, and the ionic compound is contained in a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Characteristic adhesive layer.

(However, in Equation 1, Z ⁺ indicates a cation and X ⁻ indicates an anion.)

(However, in Equation 2,
R ¹ and R ² represent alkyl groups that are the same or different from each other.
n represents an integer of 1 to 3 and represents
^Q1 represents an alkylene group having 1 to 10 carbon atoms.
E stands for NH or S
^Q2 represents a single bond or an alkylene group having 1 to 10 carbon atoms.
^Q3 represents an alkylene group having 1 to 10 carbon atoms.
V ⁺ is a monovalent cation group selected from an ammonium group, a pyridinium group, a pyrrolidinium group, an imidazolium group, a guanidinium group, an isouronium group, a thiouronium group, a piperidinium group, a pyrazonium group, a morpholinium group, a phosphonium group and a sulfonium group. As shown, the cation group may have a non-converting group or a substituent. ) The anion X ^- of the ionic compound includes hexafluorophosphate anion, bis (fluorosulfonyl) imide anion, tris (pentafluoroethyl) trifluorophosphate anion, bis (trifluoromethanesulfonyl) imide anion, thiosian acid anion, and alkylbenzene. The pressure-sensitive adhesive layer according to claim 1, wherein the pressure-sensitive adhesive layer is one or more selected from an inorganic or organic anion group consisting of a sulfonic acid anion, a perchlorate anion salt, and a boron tetrafluoride anion. A surface protective film in which the pressure-sensitive adhesive layer according to claim 1 or 2 is laminated on one side of a base material. An optical film with an adhesive, wherein the adhesive layer according to claim 1 or 2 is laminated on at least one surface of the optical film. An image display device in which the optical film with an adhesive according to claim 4 is bonded to each other via the adhesive layer.