TW201516123A - Adhesive layer for chemical liquid treatment, adhesive sheet for chemical liquid treatment, surface protective sheet, and glass substrate - Google Patents

Abstract

This invention aims to provide an adhesive layer for chemical liquid treatment that can both prevent chemical liquid immersion and inhibit the stripping electrostatic voltage (antistatic property) of the stripped adhered body that has not been subjected to antistatic treatment, an adhesive sheet for chemical liquid treatment containing the aforementioned adhesive layer, a surface protective sheet, and a glass substrate attached with the aforementioned surface protective sheet. The adhesive layer for chemical liquid treatment according to this invention is characterized in that it is formed with an adhesive composition containing polymer (A) that has a glass transition temperature not exceeding 0 DEG C, the solvent-insoluble component ratio is 50-90 mass%, and the surface resistivity is 103-1013 [Omega]/□.

Description

Adhesive layer for chemical treatment, adhesive sheet for chemical treatment, surface protection sheet, and glass substrate

The present invention relates to an adhesive layer for treating a liquid medicine. Specifically, it relates to an adhesive layer having a chemical solution immersion property and an antistatic property, and is used to form an adhesive sheet in the form of a sheet or a belt, a surface protective sheet, and the above surface. A glass substrate made of a protective sheet. More specifically, the present invention relates to a surface protective sheet for treating a chemical liquid which can cover a non-treated object portion (a portion to be excluded from the influence of the chemical liquid) when the adherend is treated with the chemical liquid.

An adhesive sheet (protective sheet) for covering a non-treated object portion (the portion to be affected by the influence of the chemical liquid) of the above-mentioned adherend when the material to be treated (the material to be treated) is treated with the chemical liquid, and typically includes a film The adhesive (adhesive layer) and the substrate supporting the adhesive are attached, and the adhesive is applied to the adherend. The adhesive sheet (protective sheet) for treating such a chemical solution can be preferably used, for example, for dissolving glass by a chemical solution (etching liquid) for adjusting the thickness of the glass or removing the burrs formed on the cut end surface of the glass. Etching treatment, partial etching of the surface of the metal by the chemical solution (etching solution), plating treatment of the connection terminal portion of the circuit board (printed substrate, flexible printed circuit (FPC), etc.) by the chemical liquid (electroplating solution) in. Patent Documents 1 and 2 can be cited as documents related to such a technique.

The protective sheet is required to have a chemical liquid from the surface thereof (the interface directly exposed to the chemical liquid, that is, the surface opposite to the side attached to the side of the adherend), or the outer edge (hereinafter also referred to as an end surface or side) The nature of the immersion, that is, the immersion resistance (sealing property).

Here, the infiltration of the chemical liquid from the outer edge of the protective sheet also occurs from the interface between the adhesive of the protective sheet and the adherend. In order to prevent such a chemical solution from entering the interface, it is important that the adhesive (adhesive layer) constituting the protective sheet adheres to the surface of the adherend without any gap (adhesiveness) and adhesion strength (adhesion).

Also, the protective sheet is peeled off at a stage that is no longer needed. In general, the protective sheet or the plastic material constituting the adherend and the glass have high electrical insulation, and static electricity is generated during friction or peeling. Therefore, static electricity is also generated when the protective sheet is peeled off from the adherend. Therefore, in addition to the adsorption of dust or dust in the air or the discomfort caused by electric shock, there are various electrostatic hazards such as damage to the circuit board or the connection terminal due to static electricity. Therefore, in order to prevent such an unfavorable situation, the protective sheet is subjected to various antistatic treatments.

For example, a method of adding a surfactant having a low molecular weight to an adhesive and transferring the surfactant from the adhesive to the adherend to prevent static electricity has been disclosed (for example, see Patent Document 3). However, in this method, the surfactant easily bleeds out to the surface of the adhesive, and when applied to the protective sheet, there is a problem that the adherend is contaminated. Therefore, when an adhesive to which a surfactant having a low molecular weight is added is applied to a protective sheet, it is difficult to exhibit sufficient antistatic properties without impairing the characteristics of the adherend.

Further, a method of adding an antistatic agent containing a polyether polyol and an alkali metal salt to an acrylic adhesive to suppress the exudation of the antistatic agent to the surface of the adhesive is disclosed (for example, refer to Patent Document 4). However, in the method, the bleed out of the antistatic agent cannot be avoided. As a result, when it is actually applied to the protective sheet, if the treatment at a high temperature is performed, contamination of the adherend due to the occurrence of bleed may occur.

Further, a technique of an antistatic acrylic adhesive containing an acrylic copolymer having an alkylene oxide chain and an ionic compound in a side chain (Patent Document 5) is disclosed, and both antistatic property and low pollution property are achieved. However, in this method, there are floating, peeling, etc. The problem with the issue of adhesion.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-53346

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-82299

[Patent Document 3] Japanese Patent Laid-Open No. Hei 9-165460

[Patent Document 4] Japanese Patent Laid-Open No. Hei 6-128539

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-206776

In view of the above, it is an object of the present invention to provide an adhesive layer for a chemical treatment which can prevent the peeling static voltage (antistatic property) from being detached from the adherend without the antistatic treatment. An adhesive sheet for treating a liquid medicine layer of an adhesive layer, a surface protective sheet, and a glass substrate with a surface protective sheet attached to the surface protective sheet.

The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 ° C, and the solvent insoluble component ratio is 50 to 90% by mass. And the surface resistivity is 10 ³ ~ 10 ¹³ Ω / □.

Preferably, the adhesive composition of the present invention contains the (meth)acrylic polymer (B), and the (meth)acrylic polymer (B) has a weight average molecular weight of 1,000. The above is less than 30,000, and contains a (meth)acrylic monomer having an alicyclic structure represented by the following formula (1) as a monomer component.

CH ₂ =C(R ¹ )COOR ² (1)

[In the formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic hydrocarbon group having an alicyclic structure. ]

Preferably, the adhesive layer for treating a chemical solution of the present invention contains the above adhesive composition Ionic compound (C).

In the adhesive layer for treating a chemical solution of the present invention, it is preferable that the above-mentioned adhesive composition contains a compound (D) having a polyoxyalkylene chain.

In the adhesive layer for a chemical treatment of the present invention, the pressure-sensitive adhesive composition preferably contains 0.005 to 2 parts by mass of the (meth)acrylic polymer (B) per 100 parts by mass of the polymer (A). .

In the adhesive layer for a chemical liquid treatment of the present invention, the pressure-sensitive adhesive composition preferably contains 0.005 to 2 parts by mass of the ionic compound (C) per 100 parts by mass of the polymer (A).

In the adhesive layer for a chemical treatment of the present invention, the adhesive composition preferably contains 0.005 to 1 part by mass of the above compound having a polyoxyalkylene chain with respect to 100 parts by mass of the polymer (A). ).

In the adhesive layer for treating a chemical solution of the present invention, the polymer (A) is preferably a (meth)acrylic polymer (a).

In the adhesive layer for chemical liquid treatment of the present invention, it is preferable that the alicyclic hydrocarbon group of the (meth)acrylic monomer having an alicyclic structure has a bridged ring structure.

In the adhesive layer for chemical liquid treatment of the present invention, it is preferred that the (meth)acrylic polymer (B) has a glass transition temperature of 0 to 300 °C.

In the adhesive layer for treating a chemical solution of the present invention, the ionic compound (C) is preferably an alkali metal salt and/or an ionic liquid.

In the adhesive layer for treating a chemical liquid of the present invention, it is preferred that the alkali metal salt is a lithium salt.

In the adhesive layer for a chemical liquid treatment of the present invention, the ionic liquid is preferably one or more selected from the group consisting of a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt, and a phosphorus-containing phosphonium salt.

In the adhesive layer for treating a chemical solution of the present invention, the ionic liquid preferably contains one or more kinds of cations represented by the following general formulae (C1) to (C5).

[Chemical 1]

[R in the formula (C1) represents _a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _b and R _{c are the} same or different and represent hydrogen or a carbon number of 1 to 16. The hydrocarbon group, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. However, when the nitrogen atom contains a double bond, R _c does not exist. ]

In the [Formula (C2) R _d represents C 1-50 hydrocarbon group having 2 to 20, the portion of the hydrocarbon groups may be substituted with the as heteroatom functional group, R _e, the same or different R _f and R _g, represents hydrogen or a C The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]

[R _h in the formula (C3) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom, and R _i , R _j and R _{k are the} same or different and represent hydrogen or a carbon number of 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]

[Z in the formula (C4) represents a nitrogen, sulfur or phosphorus atom, and R _l , R _m , R _n and R _{o are the} same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, and a part of the above hydrocarbon group may be substituted by a hetero atom Functional group. However, when Z is a sulfur atom, R _o does not exist. ]

[R _P in the formula (C5) represents a hydrocarbon group having 1 to 18 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]

In the adhesive layer for treating a chemical solution of the present invention, the compound (D) having a polyoxyalkylene chain is preferably an organopolyoxane having a polyoxyalkylene chain.

In the adhesive layer for chemical treatment of the present invention, the organopolyoxyalkylene having a polyoxyalkylene chain is preferably an organopolyoxane represented by the following formulas (D1) to (D3).

[Chemical 2]

In the [Formula (D1) R ₁ is a monovalent organic group, R _2, R ₃ and R ₄ is alkylene, R ₅ is hydrogen or an organic group, m and n are integers of 0 to 1000. However, m and n are not 0 at the same time. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]

In the [Formula (D2) R ₁ is a monovalent organic group, R _2, R ₃ and R ₄ is alkylene, R ₅ is hydrogen or an organic group, m is an integer of 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]

In the [Formula (D3) R ₁ is a monovalent organic group, R _2, R ₃ and R ₄ is alkylene, R ₅ is hydrogen or an organic group, m is an integer of 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]

The pressure-sensitive adhesive layer for treating a chemical solution of the present invention preferably contains a hydroxyl group-containing monomer as a monomer component constituting the (meth)acrylic polymer (a).

The pressure-sensitive adhesive layer for treating a chemical solution of the present invention preferably contains an average of 5.0% by mass or less of an oxygen-extended alkyl unit based on the total amount of the monomer components constituting the (meth)acryl-based polymer (a). A reactive monomer having an oxygen-containing alkylene group having a molar number of 3 to 40.

The adhesive sheet for treating a liquid medicine of the present invention is preferably formed on at least one side of the support. There is the above adhesive layer.

Preferably, the support for treating a liquid medicine according to the present invention is that the support is an antistatic treated plastic film.

The surface protection sheet of the present invention preferably comprises the above-mentioned pressure-sensitive adhesive sheet for chemical liquid treatment.

In the glass substrate with a surface protection sheet of the present invention, it is preferable that the surface protection sheet is attached to the glass substrate.

According to the present invention, it is possible to provide an adhesive layer for a chemical solution which can prevent the peeling static voltage (antistatic property) from being detached from the adherend without antistatic treatment, and has the above adhesive. The adhesive sheet for a chemical liquid treatment layer, a surface protective sheet, and a glass substrate with a surface protection sheet to which the surface protection sheet is attached are useful.

1‧‧‧Support

2‧‧‧Adhesive layer

3‧‧‧Release liner

4‧‧‧Antistatic layer

10‧‧‧Adhesive sheet (surface protection sheet)

20‧‧‧ glass

30‧‧‧sample fixed table

40‧‧‧potentiometer

Fig. 1 is a cross-sectional view schematically showing a configuration example of a protective sheet for chemical liquid processing.

Fig. 2 is a cross-sectional view schematically showing another configuration example of a protective sheet for chemical treatment.

Fig. 3 is a cross-sectional view schematically showing another configuration example of the protective sheet for chemical treatment.

Fig. 4 is a cross-sectional view schematically showing another configuration example of the protective sheet for chemical treatment.

Fig. 5 is a schematic configuration diagram of a potential measuring unit used for measurement of a peeling static voltage in the examples and the like.

The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 ° C, and the solvent insoluble component ratio is 50 to 90% by mass. And the surface resistivity is 10 ³ ~ 10 ¹³ Ω / □. When the solvent-insoluble component ratio is in the range of 50 to 90% by mass, the reliability (adhesiveness, adhesion, and re-peelability) is good, and the penetration of the chemical solution can be prevented. Further, when the surface resistivity is in the range of 10 ³ to 10 ¹³ Ω/□, the generation of the peeling static voltage (the antistatic property is imparted) can be suppressed.

The following is an adhesive layer for forming a liquid chemical treatment of the present invention (sometimes referred to as "sticky" Adhesive composition used in the coating layer", an adhesive layer formed of the above adhesive composition, an adhesive sheet for chemical treatment having the above adhesive layer (sometimes referred to simply as "adhesive sheet"), A surface protective sheet (sometimes abbreviated as "protective sheet") and a glass substrate to which the surface protective sheet is attached will be described in detail.

<Overall composition of adhesive sheet for processing liquid (surface protection sheet)>

The adhesive sheet for processing a chemical solution (surface protective sheet) disclosed herein includes a support and an adhesive layer provided on at least one side of the support. The shape of the adhesive sheet may be a sheet shape, and may be, for example, a roll shape or a single plate shape with a separator.

A typical configuration example of the adhesive sheet is schematically shown in Fig. 1. The adhesive sheet 10 includes a sheet-shaped support (for example, a sheet-like substrate made of resin) 1 and an adhesive layer 2 provided on one side (one side) thereof. The adhesive sheet 10 is attached to a specific portion of the adherend before the treatment of the adherend (the material to be treated) with the chemical solution (the portion to be protected, typically the portion to be excluded from the influence of the chemical solution). The following is also referred to as "non-processing object portion"). Thereby, the above-mentioned non-treated object portion can be protected from the chemical liquid. Further, the adhesive sheet 10 before use (i.e., before being attached to the adherend) is typically as shown in Fig. 2, the surface of the adhesive layer 2 (attached to the surface of the adherend. Hereinafter also referred to as "adhesive surface" ") is a form protected by the release liner 3 having at least the release surface of the adhesive layer 2 side. Alternatively, the other surface of the support 1 (the back surface of the surface on which the adhesive layer 2 is provided) may be a peeling surface, and the adhesive sheet 10 may be wound into a roll to protect the other surface from the adhesive layer 2. The shape of the surface (adhesive surface). Further, the adhesive sheet 10 may be a double-sided adhesive sheet in which the adhesive layer 2 is provided on each surface of the support 1 . In this case, the attachment surface (adhesive surface) of each of the adhesive layers and the adherend may be protected by the release liner 3 having at least the adhesive layer side as the release surface, or may be The release liner 3 of the peeling surface is wound into a roll shape. Further, as shown in FIG. 3, the antistatic layer 4 may be provided on the other surface of the support 1 (the back surface of the surface on which the adhesive layer 2 is provided). Further, as shown in FIG. 4, the antistatic layer 4 may be provided between the support 1 and the adhesive layer 2. In addition, the "sheet" in the present invention includes a thickness phase compared to the sheet. For thinner films, or tapes commonly referred to as adhesive tapes.

<Polymer (A)>

The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 °C. The polymer (A) is not particularly limited as long as the glass transition temperature is less than 0 ° C, and for example, an acrylic polymer, a rubber-based polymer, an anthrone-based polymer, a polyurethane-based polymer, and a polyester can be used. A polymer or the like which is usually used as an adhesive. It is particularly preferable to use a (meth)acrylic polymer which is compatible with the following (meth)acrylic polymer (B) which is preferably used in the adhesive layer of the present invention and which has high transparency.

The glass transition temperature (Tg) of the above polymer (A) is less than 0 ° C, preferably less than -10 ° C, more preferably less than -40 ° C, and usually -80 ° C or more. When the glass transition temperature (Tg) of the polymer (A) is 0° C. or more, the polymer may not easily flow, and the wetting of the adherend (protected body) may be insufficient, and the adhesion may be lowered. Further, the glass transition temperature of the above polymer (A) is not too low, and it is advantageous in preventing the infiltration of the chemical solution (typically, the chemical solution which is mainly caused by the swelling of the adhesive by the chemical solution).

In addition, in the present specification, "the glass transition temperature at the time of forming a homopolymer" means "the glass transition temperature of the homopolymer of the monomer", meaning that only a certain monomer (sometimes referred to as "monomer" X") The glass transition temperature (Tg) of the polymer formed as a monomer component. Specifically, numerical values are listed in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989).

Further, the glass transition temperature (Tg) of the homopolymer which is not described in the above document means, for example, a value obtained by the following measurement method.

In other words, 100 parts by mass of the monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and ethyl acetate 200 as a polymerization solvent are charged into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, and a reflux condenser. The mass fraction was stirred while introducing nitrogen gas for 1 hour. After removing oxygen in the polymerization system as above, the temperature was raised to 63 ° C and reacted for 10 hours. Following On the other hand, the mixture was cooled to room temperature to obtain a homopolymer solution having a solid content concentration of 33% by mass. Then, the homopolymer solution was cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of the test sample was weighed into an open cell made of aluminum, and a temperature-adjusted DSC (trade name "Q-2000" TA Instruments) was used, and nitrogen gas at 50 ml/min was used. The reversing heat flow (Reversing Heat Flow) behavior of the homopolymer was obtained at a heating rate of 5 ° C/min.

Referring to JIS-K-7121, the temperature at the point where the straight line equidistant from the line on the low temperature side of the obtained reversible heat flow and the line extending on the high temperature side in the longitudinal direction intersects the curve of the stepwise change portion of the glass transition. The glass transition temperature (Tg) as a homopolymer.

Further, the weight average molecular weight (Mw) of the polymer (A) is, for example, preferably from 30,000 to 5,000,000, more preferably from 100,000 to 2,000,000, and still more preferably from 200,000 to 1,000,000. When the weight average molecular weight (Mw) is less than 30,000, the cohesive force of the adhesive (layer) may be insufficient, and the chemical solution may easily enter. On the other hand, when the weight average molecular weight (Mw) exceeds 5,000,000, the fluidity of the adhesive may be lowered, the wetting of the adherend may be insufficient, and the adhesion may be lowered.

<(Meth)acrylic polymer (a)>

Hereinafter, the (meth)acrylic polymer (a) which is a preferable specific example of the above polymer (A) will be described in detail.

The (meth)acrylic polymer (a) is preferably a monomer component containing 50% by mass or more of a linear alkyl group or a branched alkyl group having 1 to 20 carbon atoms as a monomer component. Polymer. Further, the (meth)acrylic polymer (a) may be composed of a single alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, or a combination of two or more kinds.

The method for obtaining the above (meth)acrylic polymer (a) is not particularly limited and may be Solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, radiation hardening polymerization, and the like are various polymerization methods generally used in the synthesis method of a (meth)acrylic polymer. Further, when the adhesive layer (adhesive sheet) for treating a chemical solution of the present invention is used in the case of the surface protective sheet described below, solution polymerization or emulsion polymerization is preferably used.

The ratio of the alkyl (meth)acrylate having the alkyl group having 1 to 20 carbon atoms to the total amount of the monomer component (100% by mass) for preparing the (meth)acrylic polymer (a) It is preferably 50% by mass or more, more preferably 50% by mass to 99.9% by mass, still more preferably 60% by mass to 98% by mass, and particularly preferably 70% by mass to 95% by mass. When it is in the above range, it is preferable to obtain a preferable adhesive property (adhesive sheet, surface protective sheet) for the chemical solution treatment (adhesiveness, adhesion, re-peelability).

Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A) Isooctyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (methyl) Cetyl acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate (meth) acrylic acid C _1-20 alkyl [Preferably (meth) acrylic acid C _2-14 alkyl ester, and further preferably (meth) acrylic acid C _2-10 alkyl esters] and the like. Further, the alkyl (meth)acrylate means an alkyl acrylate and/or an alkyl methacrylate, and "(meth)"" means the same meaning.

In addition, in order to improve cohesive force, heat resistance, crosslinkability, etc., the above (meth)acrylic acid The polymer (a) may contain other monomer components (copolymerizable monomers) copolymerizable with the above alkyl (meth)acrylate, as needed. Therefore, the (meth)acrylic polymer (a) may contain a copolymerizable monomer while containing an alkyl (meth)acrylate as a main component. As the copolymerizable monomer, a monomer having a polar group can be preferably used.

Specific examples of the copolymerizable monomer include carboxyl groups such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Monomer; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (A) (8-hydroxyoctyl acrylate), 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc. (methyl) a hydroxyl group-containing monomer such as a hydroxyalkyl acrylate; an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, and 2-(methyl)propenylamine-2- a sulfonic acid group-containing monomer such as methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethyl a phosphate group-containing monomer such as a acryloyl phosphatidyl phosphate; (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) propylene oxime Amine, N,N-dipropyl (methyl) propyl Indoleamine, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl) (A) N,N-dialkyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl, etc. (Meth) acrylamide, N-n-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxy Methylpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (A a (N-substituted) guanamine monomer such as acrylamide or N-propenylmorpholine; N-(methyl) propylene oxime methylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl- Amber quinone imine monomer such as 8-oxo octamethylene succinimide; N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide , a maleimide monomer such as N-phenylmaleimide; N-methyl itaconimine, N-ethyl itaconimine, N-butyl itaconimine, N-octyl ketamine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-lauryl ketimine, etc. Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinyl Pyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(methyl)propenyl-2-pyrrolidone, N -(Meth)acryloylpiperidine, N-(methyl)propenylpyrrolidine, N-vinylmorpholine, N-vinyl-2-piperidone, N-vinyl-3- Linoleone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrrolidone a nitrogen-containing heterocyclic monomer such as azole, N-vinyl isoxazole, N-vinylthiazole, N-vinylisothiazole or N-vinylpyridazine; N-vinyl carboxamide; N- An internal amide monomer such as vinyl caprolactam; a cyano group-containing monomer such as acrylonitrile or methacrylonitrile; an aminoethyl (meth) acrylate or a N, N-dimethyl methacrylate Aminoalkyl (meth) acrylate monomer such as aminoethyl ester or tert-butylaminoethyl (meth)acrylate; methoxyethyl (meth)acrylate; ethoxylated (meth) acrylate Alkoxyalkyl (meth)acrylate such as ethyl ethyl acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate or ethoxypropyl methacrylate Body; styrene monomer such as styrene or α-methylstyrene; An epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; fluorine atom (meth)acrylate; anthrone (meth)acrylate; An acrylate monomer such as a ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; and vinyl acetate Vinyl esters such as vinyl propionate; aromatic vinyl compounds such as vinyl toluene and styrene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; and vinyl ethers such as vinyl alkyl ethers a monomer containing a sulfonic acid group such as vinyl chloride or sodium vinyl sulfonate; a monomer containing a quinone imine group such as cyclohexylmaleimide or isopropyl maleimide; (meth)acrylic acid 2 - an isocyanate group-containing monomer such as isocyanatoethyl ester; propylene morpholine; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate having an alicyclic hydrocarbon group such as dicyclopentanyl methacrylate; phenyl (meth) acrylate or (meth) acrylate Group, ethyl (methyl) acrylate of an aromatic hydrocarbon; terpene compound is obtained from the derivative of an alcohol (meth) acrylate. In addition, these copolymerizable monomers may be used alone or in combination of two or more.

When the (meth)acrylic polymer (a) contains a copolymerizable monomer while containing an alkyl (meth)acrylate as a main component, it is preferably used as the above copolymerizable monomer. The above hydroxyl group-containing monomer or the above carboxyl group-containing monomer. Among them, as the hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate can be preferably used, and as the carboxyl group-containing monomer, acrylic acid is preferably used. .

The content of the above copolymerizable monomer is not particularly limited, and is usually relative to The total amount (100% by mass) of the monomer component of the acrylic polymer (a) is preferably 0.01% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, based on the copolymerizable monomer. It is preferably 0.5% by mass to 20% by mass. By containing 0.01% by mass or more of the above copolymerizable monomer, it is possible to prevent the cohesive force of the adhesive (layer) from being lowered, and it is possible to prevent contamination from peeling of the adherend. In addition, by setting the content of the copolymerizable monomer to 40% by mass or less, it is possible to prevent the cohesive force from being excessively high and to improve the adhesiveness at normal temperature (25 ° C).

The (meth)acrylic polymer (a) may further contain 5.0% by mass or less of an oxygen-extended alkyl unit having an average addition molar amount of 3 to 40, and an oxygen-containing alkyl group as a reactive monomer. Body composition.

The average addition mole number of the oxygen-extended alkyl unit in the above-mentioned oxygen-containing alkyl group-reactive monomer is preferably from 3 to 40, more preferably from the viewpoint of compatibility with the ionic compound. It is 4 to 35, and particularly preferably 5 to 30. When the average addition molar number is 3 or more, there is a tendency that the contamination reducing effect of the adherend (protected body) can be efficiently obtained. Further, when the average addition molar number is more than 40, the interaction with the ionic compound acting as an antistatic agent is enhanced, and the adhesive composition is gel-like and difficult to coat, so good. Further, the terminal of the oxygen alkyl group may be directly a hydroxyl group, or may be substituted with another functional group or the like.

The reactive monomer having an oxygen-containing alkylene group may be used singly or in combination of two or more kinds thereof, and the total amount of the monomer component (100% by mass) based on the (meth)acryl-based polymer (a). It is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.0% by mass or less, and particularly preferably 1.0% by mass or less. When the content of the above-mentioned oxygen-containing alkyl group-containing reactive monomer exceeds 5.0% by mass, the interaction with the ionic compound acting as an antistatic agent is enhanced, the ion conduction is hindered, and the antistatic property is lowered, which is not preferable.

Examples of the oxygen-extended alkyl unit of the above-mentioned oxygen-containing alkyl group-reactive monomer include a unit having an alkylene group having 1 to 6 carbon atoms, and examples thereof include an oxymethylene group, an oxygen-extended ethyl group, and an oxygen group. Propylene, oxygen and butyl groups. The hydrocarbyl group of the oxygen alkyl chain may be straight or branched.

Further, it is more preferred that the above-mentioned oxygen-containing alkylene group-reactive monomer is a reactive monomer having an oxiranyl group. By using a (meth)acrylic polymer containing a reactive monomer having an oxiranyl group as a base polymer, the compatibility of the base polymer with the ionic compound can be improved, and the bleed out is preferably suppressed. By the adherend, a highly polluting adhesive (layer) can be obtained.

Examples of the reactive monomer of the oxygen-containing alkylene group include a (meth)acrylic acid alkylene oxide adduct and a reactive substituent having a propylene group, a methacryloyl group or an allyl group in the molecule. Reactive surfactants and the like.

Specific examples of the (meth)acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (A). Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, B Oxypolyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, dodecyloxy polyethylene glycol (Meth) acrylate, octadecyloxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, xin Oxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

Further, specific examples of the reactive surfactant include an anionic reactive surfactant having a (meth)acryl fluorenyl group or an allyl group, a nonionic reactive surfactant, and a cationic reaction. Sexual surfactants, etc.

Examples of the anionic reactive surfactant include those represented by the formulae (A1) to (A10).

[Chemical 3]

[R ₁ in the formula (A1) represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group or a fluorenyl group having 1 to 30 carbon atoms, X represents an anionic hydrophilic group, and R ₃ and R _{4 are the} same or different and represent a carbon number of 1 to The alkyl group of 6 has an average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].

[R ₁ in the formula (A2) represents hydrogen or a methyl group, and R ₂ and R _{7 are the} same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R ₃ and R _{5 are the} same or different and represent hydrogen or an alkyl group; R ₄ and R _{6 are the} same or different and represent hydrogen, an alkyl group, a benzyl group or a styryl group, and X represents an anionic hydrophilic group. The average addition molar number m and n represent 0 to 40, but (m+n) Indicates the number from 3 to 40. ].

[In the formula (A3), R ₁ represents hydrogen or a methyl group, R ₂ represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and an average addition molar number n represents a number of 3 to 40. ].

[Chemical 6]

[In the formula (A4), R ₁ represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group having 1 to 30 carbon atoms or a fluorenyl group, and R ₃ and R _{4 are the} same or different and each represents an alkylene group having 1 to 6 carbon atoms, X. It represents an anionic hydrophilic group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].

[In the formula (A5), R ₁ represents a hydrocarbon group, an amine group, a carboxylic acid residue, R ₂ represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and an average addition molar number n represents 3~ An integer of 40. ].

[In the formula (A6), R ₁ represents a hydrocarbon group having 1 to 30 carbon atoms, R ₂ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, R ₃ represents hydrogen or a propenyl group, and R ₄ represents a hydrocarbon having 1 to 6 carbon atoms; Base, X represents an anionic hydrophilic group, and the average addition molar number n represents a number from 3 to 40. ].

[In the formula (A7), R ₁ represents hydrogen or a methyl group, and R ₂ and R _{4 are the} same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ₃ represents a hydrocarbon group having 1 to 30 carbon atoms; and M represents hydrogen; The alkali metal, ammonium or alkanolammonium group has an average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].

[R ₁ and R ₅ in the formula (A8) are the same or different and each represents hydrogen or a methyl group, and R ₂ and R _{4 are the} same or different and each represents an alkylene group having 1 to 6 carbon atoms, and R ₃ represents a carbon number of 1 to 30. The hydrocarbon group, M represents hydrogen, an alkali metal, an ammonium group or an alkanolammonium group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ]

[In the formula (A9), R ₁ represents an alkylene group having 1 to 6 carbon atoms, R ₂ represents a hydrocarbon group having 1 to 30 carbon atoms, and M represents a hydrogen, an alkali metal, an ammonium group or an alkanolammonium group, and the average addition is mo The number of ears n represents the number from 3 to 40. ]

[化12]

[R ₁ , R ₂ and R ₃ in the formula (A10) are the same or different and represent hydrogen or a methyl group, and R ₄ represents a hydrocarbon group having a carbon number of 0 to 30 (in the case where the carbon number is 0, R ₄ does not exist) R ₅ and R _{6 are the} same or different and represent an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents 3~40 number. ].

X in the above formulae (A1) to (A6) and (A10) represents an anionic hydrophilic group. Examples of the anionic hydrophilic group include those represented by the following formulas (a1) to (a2).

[Chemical 13]-SO ₃ M ₁ (a1)

[M ₁ in the formula (a1) represents a hydrogen, an alkali metal, an ammonium group or an alkanolammonium group. ]

[M ₂ and M ₃ in the formula (a2) are the same or different and each represents a hydrogen, an alkali metal, an ammonium group, or an alkanolammonium group. ]

Examples of the nonionic reactive surfactant include those represented by the formulae (N1) to (N6).

[化15]

[In the formula (N1), R ₁ represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group having 1 to 30 carbon atoms or a fluorenyl group, and R ₃ and R _{4 are the} same or different, and represent an alkylene group having a carbon number of 1 to 6, an average The addition moiré m and n represent 0 to 40, but (m+n) represents the number of 3 to 40. ]

[In the formula (N2), R ₁ represents hydrogen or a methyl group, and R ₂ , R ₃ and R _{4 are the} same or different, and represent an alkylene group having 1 to 6 carbon atoms, and the average addition molar number n, m and l represents 0~40, but (n+m+l) means 3~40. ]

[In the formula (N3), R ₁ represents hydrogen or a methyl group, and R ₂ and R _{3 are the} same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R ₄ represents a hydrocarbon group or a mercapto group having 1 to 30 carbon atoms, and an average The addition moiré m and n represent 0 to 40, but (m+n) represents the number of 3 to 40. ]

[化18]

[In the formula (N4), R ₁ and R _{2 are the} same or different and each represents a hydrocarbon group having 1 to 30 carbon atoms, R ₃ represents hydrogen or a propenyl group, and R ₄ represents an alkylene group having 1 to 6 carbon atoms, and the average addition is Mo. The number of ears n represents the number from 3 to 40. ]

[wherein R ₁ and R ₃ in the formula (N5) are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R ₂ and R _{4 are the} same or different and each represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms or a mercapto group; The average addition mole number m and n represent 0 to 40, but (m+n) represents the number from 3 to 40. ]

[R ₁ , R ₂ and R ₃ in the formula (N6) are the same or different and represent hydrogen or a methyl group, and R ₄ represents a hydrocarbon group having a carbon number of 0 to 30 (in the case where the carbon number is 0, R ₄ does not exist) R ₅ and R _{6 are the} same or different and represent an alkylene group having 1 to 6 carbon atoms. The average addition molar number m and n represent 0 to 40. However, (m+n) represents a number of 3 to 40. ]

Further, as a specific commercial product of the above oxygen-containing alkyl group-reactive monomer, for example, For example, BLEMMER PME-400, BLEMMER PME-1000, BLEMMER 50POEP-800B (all manufactured by Nippon Oil & Fats Co., Ltd.), LATEMUL PD-420, LATEMUL PD-430 (all of which are manufactured by Kao Corporation), ADEKA REASOAP ER-10 ADEKA REASOAP NE-10 (all of which are manufactured by Asahi Denki Kogyo Co., Ltd.).

Further, in the above (meth)acryl-based polymer (a), in order to adjust the cohesive force of the obtained adhesive layer, a polyfunctional monomer may be contained as needed.

Examples of the polyfunctional monomer include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate , allyl (meth) acrylate, vinyl (meth) acrylate, divinyl benzene, epoxy acrylate, polyester acrylate, urethane acrylate, butane diol di (meth) acrylate Ester, hexanediol di(meth)acrylate, and the like. Among them, trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate can be preferably used. These polyfunctional monomers may be used singly or in combination of two or more.

The content of the above polyfunctional monomer varies depending on the molecular weight, the number of functional groups, and the like, relative to the total amount of the monomer component (100 mass) for preparing the above (meth)acrylic polymer (a). %) is preferably added in an amount of 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, still more preferably 0.03 to 1% by mass. When the content of the above polyfunctional monomer exceeds 3% by mass, for example, the cohesive force of the obtained adhesive layer is too high, and the adhesive strength may be lowered. On the other hand, if it is less than 0.01% by mass, for example, the cohesive force of the obtained adhesive layer is lowered, and when one part of the adhesive layer is peeled off from the adherend (protected body), it remains in the adherend and is contaminated. Happening.

When the (meth)acrylic polymer (a) is prepared (polymerized), it is used by heat polymerization. An acrylic polymer can be easily formed by heat or radiation-induced hardening reaction of a polymerization initiator such as a starter or a photopolymerization initiator (photoinitiator). In particular, thermal polymerization can be preferably used in terms of the advantage of being able to shorten the polymerization time and the like. The polymerization initiators may be used singly or in combination of two or more.

Examples of the thermal polymerization initiator include an azo polymerization initiator (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2 , 2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisoprene, 2,2'-azo double (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'-dimethyleneisobutylphosphonium) dihydrochloride, etc.; peroxide polymerization An initiator (for example, benzamidine peroxide, tert-butyl peroxymaleate, laurel, etc.); a redox polymerization initiator or the like.

The content of the thermal polymerization initiator is not particularly limited. For example, it is preferably 0.01 to 5 by mass based on 100 parts by mass of the total of the monomer components for preparing the (meth)acryl-based polymer (a). More preferably, it is 0.05 to 3 parts by mass.

The photopolymerization initiator is not particularly limited, and for example, a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-keto alcohol photopolymerization initiator, an aromatic sulfonium sulfonate can be used. Chlorine photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal light A polymerization initiator, a thioxanthone-based photopolymerization initiator, a mercaptophosphine oxide-based photopolymerization initiator, and the like.

Specific examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1. 2-Diphenylethane-1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisole methyl ether or the like. Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF Corporation], 4- Phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1 -propan-1-one [trade name: Irgacure 2959, manufactured by BASF Corporation], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [trade name: Darocur 1173, manufactured by BASF Corporation], A Oxyacetophenone and the like. Examples of the α-keto alcohol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2- Methylpropan-1-one and the like. Examples of the aromatic sulfonium chloride-based photopolymerization initiator include 2-naphthalenesulfonium chloride and the like. The photoactive oxime-based photopolymerization initiator may, for example, be 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-ruthenium or the like.

Further, the benzoin-based photopolymerization initiator includes, for example, benzoin or the like. The benzyl photopolymerization initiator includes, for example, a benzyl group or the like. The benzophenone photopolymerization initiator includes, for example, benzophenone, benzhydrylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone , α-hydroxycyclohexyl phenyl ketone, and the like. The ketal-based photopolymerization initiator includes, for example, benzyldimethylketal or the like. The thioxanthone photopolymerization initiator includes, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

Examples of the fluorenylphosphine oxide-based photopolymerization initiator include bis(2,6-dimethoxybenzylidene)phenylphosphine oxide and bis(2,6-dimethoxybenzylidene). (2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzylidene) n-butylphosphine oxide, bis(2,6-dimethoxybenzoate) Mercapto)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzylidene)-(1-methylpropan-1-yl)phosphine oxide, double 2,6-dimethoxybenzimidyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzylidene)cyclohexylphosphine oxide, bis(2,6-dimethoxy Benzoyl fluorenylphosphine, bis(2-methoxybenzimidyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzhydryl) ( 1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzhydryl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethyl) (1-Methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzylidene) (2-methylpropan-1-yl) oxidation Phosphine, bis(2,4-dimethoxybenzylidene)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzylidene) (2, 4-dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzylidene)benzylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2- Phenylpropylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzylidene)benzyl oxidation Phosphine, bis(2,6-dimethoxybenzylidene)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2-phenylethyl oxide Phosphine, 2,6-dimethoxybenzimidylbenzyl butylphosphine oxide, 2,6-dimethoxybenzimidylbenzyloctylphosphine oxide, bis(2,4,6-trimethyl) Benzobenzhydryl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2-methylphenylphosphine oxide, bis(2, 4,6-trimethylbenzylidene)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,5-diethylphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzamide Diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide Isobutylphosphine oxide, 2,6-dimethoxybenzhydryl-2,4,6-trimethylbenzimidyl-n-butylphosphine oxide, bis(2,4,6-trimethyl) Benzobenzino)phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[double (2 , 4,6-trimethylbenzimidyl)phosphine oxide]decane, tris(2-methylbenzhydryl)phosphine oxide, and the like.

The content of the photopolymerization initiator is not particularly limited. For example, it is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the monomer components for preparing the (meth)acryl-based polymer (a). More preferably, it is 0.05 to 3 parts by mass. Here, when the content of the photopolymerization initiator is less than 0.01 parts by mass, the polymerization reaction may be insufficient. When the content of the photopolymerization initiator exceeds 5 parts by mass, the photopolymerization initiator absorbs ultraviolet rays and the ultraviolet rays cannot reach the inside of the pressure-sensitive adhesive layer. In this case, the polymerization rate is lowered or the molecular weight of the produced polymer is decreased. Further, there is a case where the cohesive force of the adhesive layer formed thereby is lowered, and a part of the adhesive layer remains in the adherend when the adhesive layer is peeled off from the adherend, and the adherend cannot be reused. In addition, photopolymerization The starting agents may be used singly or in combination of two or more.

In the present embodiment, the (meth)acrylic polymer (a) may be prepared by irradiating a mixture of the monomer component and the polymerization initiator with radiation (ultraviolet rays or the like) to partially form a monomer component. Part of the polymer (acrylic polymer slurry) polymerized. The following (meth)acrylic polymer (B) may be blended in an acrylic polymer slurry to prepare an adhesive composition, and the adhesive composition may be applied to a specific coated body to irradiate radiation. (ultraviolet rays, etc.) to complete the polymerization.

Examples of the radiation include ultraviolet rays (UV), thunder rays, α rays, β rays, γ rays, X rays, and electron beams, and are preferable in terms of controllability and workability, and cost. Use ultraviolet light. It is better to use ultraviolet rays having a wavelength of 200 to 400 nm. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp.

Further, a photopolymerization initiation aid such as an amine may be used in combination with the above photopolymerization initiator. Examples of the photopolymerization initiation aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, and p-dimethylaminobenzene. Isoamyl formate and the like. These compounds may be used singly or in combination of two or more. The photopolymerization initiation aid is preferably formulated in an amount of from 0.05 to 10 parts by mass, more preferably from 0.1 to 7 parts by mass, based on 100 parts by mass of the polymer (A). When it is in the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

Further, in the case where the above photopolymerization initiator is formulated, the above-mentioned adhesive composition is directly applied to the adherend (protected body) or to a specific coated body such as a separator. After the above, or after coating on one side of the support (substrate) having antistatic properties, light irradiation is performed, whereby an adhesive layer can be obtained. In general, an adhesive layer can be obtained by photopolymerizing ultraviolet rays having an illuminance of from 1 to 200 mW/cm ² at a wavelength of from 300 to 400 nm at a light amount of about 200 to 4000 mJ/cm ² .

The weight average molecular weight (Mw) of the above (meth)acrylic polymer (a) is preferably, for example, preferably It is 30,000 to 5 million, more preferably 100,000 to 2 million, and more preferably 200,000 to 1 million. When the weight average molecular weight (Mw) is too smaller than the above range, the cohesive force of the adhesive (layer) may be insufficient, and the chemical solution may be easily infiltrated. On the other hand, when the weight average molecular weight (Mw) is too larger than the above range, the fluidity of the adhesive may be lowered, the wetting of the adherend may be insufficient, and the adhesion may be lowered.

Further, the glass transition temperature (Tg) of the (meth)acrylic polymer (a) is less than 0 ° C, preferably less than -10 ° C, more preferably less than -40 ° C, and usually -80 ° C or more. . When the glass transition temperature (Tg) of the (meth)acrylic polymer (a) is 0° C. or higher, the polymer may not easily flow, and the wetting of the adherend may be insufficient, and the adhesion may be lowered. Further, the glass transition temperature (Tg) of the (meth)acrylic polymer (a) described above is not too low to prevent the infiltration of the chemical solution (typically, the chemical solution which is mainly caused by the swelling of the adhesive due to the chemical solution).

In the case where the (meth)acrylic polymer (a) is a copolymer, the glass transition temperature (Tg) is a value calculated according to the following formula (2) (Fox formula).

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +‧‧‧+Wn/Tg _n (2)

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

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

<(Meth)acrylic polymer (B)>

The adhesive composition used in the formation of the adhesive layer for treating a chemical solution of the present invention preferably contains a (meth)acrylic polymer (B), and the weight average of the above (meth)acrylic polymer (B) The (meth)acrylic monomer having an alicyclic structure represented by the following formula (1) is a monomer component having a molecular weight of 1,000 or more and less than 30,000.

CH ₂ =C(R ¹ )COOR ² (1)

[In the formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic hydrocarbon group having an alicyclic structure. ]

The (meth)acrylic polymer (B) functions as a tackifying resin. In the case where the adhesive composition used in forming the pressure-sensitive adhesive layer for chemical solution treatment of the present invention is an acrylic pressure-sensitive adhesive composition, for example, it is easily compatible with the above (meth)acrylic polymer (a). Particularly preferred.

The alicyclic hydrocarbon group R ² in the above formula (1) may, for example, be an alicyclic hydrocarbon group such as a cyclohexyl group, an isobornyl group or a dicyclopentyl group. Examples of the (meth) acrylate having such an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate having a cyclohexyl group, isobornyl (meth)acrylate having an isobornyl group, and a bicyclic ring. An ester of (meth)acrylic acid such as dipentyl (meth)acrylate or an alicyclic alcohol. By using the acrylic monomer having a structure having a large volume in the (meth)acrylic polymer (B) as a monomer component, the bonding strength (adhesive strength) can be improved.

Further, the alicyclic hydrocarbon group constituting the (meth)acryl-based polymer (B) preferably has a bridged ring structure. The bridged ring structure refers to an alicyclic structure of three or more rings. By making the (meth)acrylic polymer (B) have a bulky structure such as a bridged ring structure, the adhesion strength (adhesive sheet, surface protective sheet) of the chemical treatment layer can be further improved (adhesion) force).

Examples of the alicyclic hydrocarbon group R ² having the above-mentioned bridge ring structure include a dicyclopentanyl group represented by the following formula (3a), a dicyclopentenyl group represented by the following formula (3b), and the following formula (3c). And the adamantyl group represented by the following formula (3d), the tricyclopentenyl group represented by the following formula (3e), and the like. Further, when the (meth)acrylic polymer (B) is synthesized or when the UV-polymerization is used in the production of the adhesive composition, the polymerization is less likely to occur, and the ring has a bridge ring structure. Among the above (meth)acrylic monomers having an alicyclic structure, a dicyclopentyl group represented by the following formula (3a) or an adamantyl group represented by the following formula (3c) can be particularly preferably used. A (meth)acrylic monomer having a saturated structure such as a tricyclopentyl group represented by the following formula (3d) is a monomer constituting the (meth)acrylic polymer (B).

Further, examples of the (meth)acrylic monomer having an alicyclic structure having three or more rings having a bridged ring structure include dicyclopentyl methacrylate and dicyclopentyl acrylate. Dicyclopentyloxyethyl methacrylate, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 1-gold acrylate Alkyl ester, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2- (Meth) acrylate such as ethyl-2-adamantyl ester. These (meth)acrylic monomers may be used singly or in combination of two or more.

The (meth)acrylic polymer (B) may be a homopolymer of a (meth)acrylic monomer having an alicyclic structure, or may be a (meth)acrylic monomer having an alicyclic structure. a copolymer of a body with another (meth) acrylate monomer or a copolymerizable monomer.

Examples of such a (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. Butyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Dibutyl acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) (meth)acrylic acid alkyl ester such as decyl acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate; (methyl) An aryl (meth)acrylate such as phenyl acrylate or benzyl (meth) acrylate; a (meth) acrylate obtained from a terpene compound derivative alcohol. Such (meth) acrylate may be used singly or in combination of two or more.

Further, the (meth)acrylic polymer (B) may copolymerize other monomer components (copolymerizable monomers) copolymerizable with (meth) acrylate in addition to the above (meth) acrylate component unit. And get.

Examples of other monomers copolymerizable with the above (meth) acrylate include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, a carboxyl group-containing monomer such as isocrotonic acid; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxy (meth)acrylate (meth)acrylic acid alkoxyalkyl ester monomer such as ethyl methacrylate or ethoxypropyl methacrylate; salt of (meth)acrylic acid alkali metal salt; Acrylate, di(meth)acrylate of diethylene glycol, di(meth)acrylate of triethylene glycol, di(meth)acrylate of polyethylene glycol, di(methyl) of propylene glycol a bis(meth) acrylate monomer such as acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate or the like (poly)alkyl diol; trishydroxyl a poly (meth) acrylate monomer such as a propane tri(meth) acrylate; Vinyl esters such as vinyl acetate and vinyl propionate; halogenated vinyl compounds such as vinylidene chloride and 2-chloroethyl (meth)acrylate; 2-vinyl-2-oxazoline, 2-vinyl a oxazoline group-containing polymerizable compound such as 5-methyl-2-oxazoline or 2-isopropenyl-2-oxazoline; (meth)acryloyl aziridine, (methyl) a polymerizable compound containing aziridine group such as 2-aziridine ethyl acrylate; allyl glycidyl ether, glycidyl (meth)acrylate, ethyl glycidyl (meth)acrylate Ethylene group-containing ethylene monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactone and 2-hydroxyethyl (meth)acrylate a hydroxyl group-containing ethylene monomer such as an ester adduct; a polypropylene glycol, a polyethylene glycol, a polytetramethylene glycol, a polytetramethylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, and a polybutylene a copolymer of an alcohol and a polyethylene glycol, or a macromonomer having an unsaturated group such as a (meth) acrylonitrile group, a styryl group or a vinyl group bonded to a terminal of the polyalkylene glycol; Alkyl (meth)acrylate a fluorine-containing ethylene monomer; an anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; an aromatic vinyl compound monomer such as styrene, α-methylstyrene or vinyltoluene; 2-chloroethyl A vinyl monomer containing a reactive halogen such as a vinyl ether or a monochloroacetic acid ester; (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (methyl) Acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl Ethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (methyl) An amidino group-containing ethylene monomer such as acrylamide or N-propylene decylmorpholine; N-(methyl) propylene oxymethylene succinimide, N-(meth) acrylonitrile -6-oxygen Amber quinone imine monomer such as hexamethylene succinimide, N-(methyl) propylene decyl-8-oxy octamethylene succinimide; N-cyclohexylmaleimide, N - maleic imine monomer such as isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide; N-methyl itaconimine, N -ethyl ketimine, N-butyl ketimine, N-octyl ketimine, N-2-ethylhexyl ketimine, N-cyclohexyl ketamine Amine, N-Lauryl ketimine, etc.; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidine Ketone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(methyl)acrylonitrile -2-pyrrolidone, N-(meth)acrylopylpiperidine, N-(methyl)propenylpyrrolidine, N-vinylmorpholine, N-vinylpyrazole, N-vinylisoxazole a nitrogen-containing heterocyclic monomer such as N-vinylthiazole, N-vinylisothiazole or N-vinylpyridazine; N-vinyl carboxamide; N-vinyl group An indoleamine monomer such as indoleamine; a cyano group-containing monomer such as (meth)acrylonitrile; an aminoethyl (meth)acrylate; and N,N-dimethylaminoethyl (meth)acrylate An aminoalkylalkyl (meth) acrylate such as tributylaminoethyl (meth)acrylate; a quinone imine group such as cyclohexylmaleimide or isopropylmaleimide Monomer; isocyanate-containing monomer such as 2-isocyanatoethyl (meth)acrylate; vinyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, allyl An organic monomer containing trimethyl decane, trimethoxydecyl propylallylamine, 2-methoxyethoxytrimethoxydecane, or the like; hydroxyethyl (meth) acrylate; Hydroxypropyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxyl (meth)acrylate Lauryl ester, methacrylic acid (4-hydroxymethyl) a hydroxyl group-containing monomer such as a hydroxyalkyl (meth) acrylate such as cyclohexyl) methyl ester; tetrahydrofurfuryl (meth) acrylate, fluorine atom (meth) acrylate, fluorenone (meth) acrylate An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; and a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; An olefin or a diene such as ethylene, butadiene, isoprene or isobutylene; a vinyl ether such as a vinyl alkyl ether; a vinyl chloride; and a radically polymerizable vinyl group at the terminal of the monomer having a vinyl group polymerized; Macromonomers, etc. These monomers may be copolymerized with the above (meth) acrylate either singly or in combination.

Examples of the (meth)acryl-based polymer (B) include a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and cyclohexyl methacrylate (CHMA). Copolymer with isobornyl methacrylate (IBXMA), copolymer of methyl methacrylate (MMA) and isobornyl methacrylate (IBXMA), cyclohexyl methacrylate (CHMA) and propylene morpholine Copolymer of (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA), 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Copolymer, copolymer of dicyclopentyl methacrylate (DCPMA) with isobornyl methacrylate (IBXMA), copolymerization of dicyclopentyl methacrylate (DCPMA) and methyl methacrylate (MMA) , copolymer of cyclohexyl methacrylate (CHMA) and methyl methacrylate (MMA), copolymer of dicyclopentyl methacrylate (DCPMA) and acrylic acid (AA), dicyclopentyl methacrylate Base ester (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentyl acrylate (D) CPA), a homopolymer of 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), and the like.

Further, the (meth)acryl-based polymer (B) may be introduced with a functional group reactive with an epoxy group or an isocyanate group. Examples of such a functional group include a hydroxyl group, a carboxyl group, an amine group, a decylamino group, and a fluorenyl group. When the (meth)acrylic polymer (B) is produced, a single copolymer having such a functional group can be used. body.

When the (meth)acrylic polymer (B) is a copolymer of a (meth)acrylic monomer having an alicyclic structure and another (meth) acrylate monomer or a copolymerizable monomer, In the total amount of the monomer component (100% by mass) of the (meth)acrylic polymer (B), the content of the (meth)acrylic monomer having an alicyclic structure is preferably 5% by mass or more. More preferably, it is 10 mass% or more, further preferably 20 mass% or more, and particularly preferably 30 mass% or more (usually less than 100 mass%, preferably 90 mass% or less). When the (meth)acrylic monomer having an alicyclic structure is contained in an amount of 5 mass% or more, the bonding strength (adhesion) can be improved. Further, the (meth)acrylic polymer (B) and the compound (D) having a polyoxyalkylene chain have a moderate phase by containing the above (meth)acrylic monomer having an alicyclic structure. In the separation, the mobility of the ionic compound (C) transported by the polyoxyalkylene chain is improved by the (meth)acrylic polymer (B), and as a result, the antistatic property can be improved. On the other hand, when it is less than 5% by mass, there is a case where the adhesion is poor.

The weight average molecular weight (Mw) of the (meth)acrylic polymer (B) is preferably 1,000 or more and less than 30,000, more preferably 1,500 or more and less than 20,000, more preferably 2,000 or more and less than 10,000. When the weight average molecular weight is 30,000 or more, the strength (adhesion) is lowered. Further, when the weight average molecular weight is less than 1,000, it may be contaminated by the adherend due to the low molecular weight.

The measurement of the weight average molecular weight (Mw) of the polymer (A) ((meth)acrylic polymer (a)) or the (meth)acrylic polymer (B) or the like can be carried out by gel permeation chromatography ( The GPC method was obtained by converting polystyrene. Specifically, the measurement was carried out according to the methods and conditions described in the following examples.

The glass transition temperature (Tg) of the (meth)acrylic polymer (B) is preferably from 0 to 300 ° C, more preferably from 50 ° C to 280 ° C, still more preferably from 90 ° C to 280 ° C, particularly preferably 110 ° C ~ 250 ° C. When the glass transition temperature (Tg) of the (meth)acryl-based polymer (B) is less than 0 ° C, sufficient adhesion strength (adhesion) may not be obtained. When it is 300 ° C or more, since the cohesive force of the adhesive layer is too high, the wettability to the adherend is insufficient, which is not preferable. In the present embodiment, the glass transition temperature (Tg) of a representative material which can be used as the (meth)acryl-based polymer (B) is shown in Table 1 below. The glass transition temperature (Tg) shown in Table 1 is a nominal value described in the literature, the product list, or the like, or a value calculated based on the following formula (3) (Fox formula).

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +‧‧‧+Wn/Tg _n (3)

[In the formula (3), Tg represents a glass transition temperature (unit: K) of the (meth)acrylic polymer (B), and Tg _i (i = 1, 2, ..., n) represents a monomer i to form a homopolymer The glass transition temperature (unit: K), W _i (i = 1, 2, ... n) represents the mass fraction of monomer i in all monomer components. ]

The above formula (3) is a calculation formula when the (meth)acrylic polymer (B) is composed of n kinds of monomer components of the monomer 1, the monomer 2, ..., and the monomer n.

The abbreviations in Table 1 indicate the following compounds.

DCPMA: Dicyclopentyl methacrylate

DCPA: Dicyclopentyl acrylate

IBXMA: Isobornyl Methacrylate

IBXA: Isobornyl acrylate

CHMA: cyclohexyl methacrylate

CHA: cyclohexyl acrylate

IBMA: isobutyl methacrylate

MMA: Methyl methacrylate

ADMA: 1-adamantyl methacrylate

ADA: 1-adamantyl acrylate

The content of the above (meth)acrylic polymer (B) is not particularly limited, for example, phase The amount of the polymer (A) is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, even more preferably 0.05 to 0.5 parts by mass. When the amount of the (meth)acrylic polymer (B) exceeds 2.0 parts by mass, the antistatic property of the adhesive layer may be lowered. When the amount of the (meth)acrylic polymer (B) is less than 0.005 parts by mass, the adhesive strength (adhesive strength) may not be obtained. The situation of improving the effect is not good.

In the (meth)acrylic polymer (B), the (meth)acrylic monomer having the above-described structure can be solution-polymerized, emulsion-polymerized, and block-formed in the same manner as the above (meth)acryl-based polymer (a). Polymerization, suspension polymerization, radiation hardening polymerization, and the like are used as a synthesis method, and various polymerization methods generally used are applied.

In order to adjust the weight average molecular weight (Mw) of the above (meth)acryl-based polymer (B), a chain transfer agent may be used in the polymerization. Examples of the chain transfer agent to be used include octyl mercaptan, lauryl mercaptan, third (dodecyl) mercaptan, mercaptoethanol, α-thioglycerol and the like having a mercapto group; mercaptoacetic acid Methyl thioglycolate, ethyl decyl acetate, propyl thioglycolate, butyl thioglycolate, tert-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, thioglycolic acid A mercaptoacetate such as a dialkyl ester, a mercaptoacetate of ethylene glycol, a mercaptoacetate of neopentyl glycol, a mercaptoacetate of pentaerythritol, or the like, an α-methylstyrene dimer or the like.

The content of the chain transfer agent is not particularly limited, and it is preferably contained in an amount of 100 parts by mass based on 100 parts by mass of the total of the (meth)acrylic monomers constituting the (meth)acrylic polymer (B). The chain transfer agent is 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass. By adjusting the amount of the chain transfer agent added in this manner, a (meth)acrylic polymer (B) having a preferred molecular weight can be obtained. Further, the chain transfer agents may be used singly or in combination of two or more.

<Ionic compound (C)>

In the adhesive layer for treating a chemical solution of the present invention, it is preferred that the adhesive composition contains an ionic compound (C), and more preferably the ionic compound (C) is an alkali metal salt and/or an ionic liquid. body. The ionic compound is a compound which exhibits ionic dissociation at normal temperature, and can provide excellent antistatic properties by containing the ionic compound. In addition, even if the amount of the alkali metal salt is a small amount (adjusted amount), the ionic dissociation property is high, and therefore it is useful to suppress the antistatic property which is excellent in the contamination of the adherend. Further, since the ionic liquid itself exhibits excellent electrical conductivity, it is useful to provide sufficient antistatic energy only by allowing the adhesive layer to contain a trace amount of ionic liquid.

<alkali metal salt>

As the above alkali metal salt, for example, a cation containing Li ⁺ , Na ⁺ , K ⁺ and containing Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF can be preferably used. ₆ ^- , SCN ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , C ₉ H ₁₉ COO ^- , CF ₃ COO ^- , C ₃ F ₇ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , F(HF) _n ^- , (CN) ₂ N ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ (CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- and (FSO ₂ a metal salt composed of an anion of ₂ N ^- . More preferably, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C and other lithium salts, and further preferably LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₃ F ₇ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C. These alkali metal salts may be used singly or in combination of two or more.

<ionic liquid>

The above ionic liquid system refers to a liquid (liquid) non-volatile molten salt at any temperature in the range of 0 to 150 °C. Since the ionic liquid is liquid at any temperature within the above range, it is easier to add, disperse or dissolve in the adhesive than the solid salt. Furthermore, since the ionic liquid does not have a vapor pressure (non-volatile), it is not It will disappear in time and will continue to obtain antistatic properties.

Further, by using the above ionic liquid as an antistatic agent, an adhesive layer having a high antistatic effect can be obtained without impairing the adhesion property. Although the details of the reason why excellent antistatic properties can be obtained by using an ionic liquid are not clear, it is considered that since the ionic liquid has a low melting point (melting point of 150 ° C or less) as compared with a usual ionic compound, molecular motion is easy. Get excellent antistatic energy. Further, it is considered that particularly when the antistatic property to the adherend is achieved, by transferring a very small amount of the ionic liquid to the adherend, excellent peeling antistatic property of the adherend can be achieved. In particular, since the ionic liquid having a melting point of room temperature (25 ° C) or less can be more efficiently transferred to the adherend, excellent antistatic properties can be obtained.

The ionic liquid is preferably any one of a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt or a phosphorus-containing phosphonium salt, and more preferably an organic cationic component and an anionic component represented by the following general formulae (C1) to (C5). By. By using such a cation-containing ionic liquid, antistatic energy can be obtained and thus excellent.

R _a in the above formula (C1) represents _a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _b and R _{c are the} same or different and represent hydrogen or a carbon number of 1 to 16. The hydrocarbon group, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. However, when the nitrogen atom contains a double bond, R _c does not exist.

R _d in the above formula (C2) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _e , R _f and R _{g are the} same or different and represent hydrogen or carbon number 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.

R _h in the above formula (C3) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _i , R _j and R _{k are the} same or different and represent hydrogen or carbon number 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.

Z in the above formula (C4) represents a nitrogen, sulfur or phosphorus atom, and R _l , R _m , R _n and R _{o are the} same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms, and a part of the above hydrocarbon group may be substituted by a hetero atom. Functional group. However, when Z is a sulfur atom, R _o does not exist.

R _P in the above formula (C5) represents a hydrocarbon group having 1 to 18 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.

Examples of the cation represented by the formula (C1) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, a morpholinium cation, and the like.

Specific examples thereof include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl-4. -methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-B -1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidine Ruthenium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1 - butyl pyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propyl Piperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation 1-methyl-1-acetate Isopiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidine Ruthenium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropyl Isopiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2- Phenylhydrazine cation, 1,2-dimethylhydrazine cation, 1-ethylcarbazole cation, N-ethyl-N-methylmorpholinium cation, and the like.

Examples of the cation represented by the formula (C2) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-dodecyl 3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-di Methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3 -methylimidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidine Ruthenium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetra Hydroquinone cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl -1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3 , 4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.

Examples of the cation represented by the formula (C3) include a pyrazolium cation, a pyrazolinium cation, and the like.

Specific examples include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, and 1-ethyl-2,3. 5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1- Ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-three Methylpyrazolium cations and the like.

The cation represented by the formula (C4) may, for example, be a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the above alkyl group via an alkenyl group, an alkoxy group, or an epoxy group. a cation or the like substituted by a base.

Specific examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, tetraheptyl ammonium cation, and triethylmethylammonium cation. , tributylethylammonium cation, trimethylsulfonium ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethyl Ammonium cation, trimethyl phosphonium cation, triethyl phosphonium cation, tributyl phosphonium cation, trihexyl phosphonium cation, diethyl methyl phosphonium cation, dibutyl ethyl phosphonium cation, dimethyl fluorenyl cation, Tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethylmethyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl fluorenyl a phosphonium cation, a diallyldimethylammonium cation, a tributyl-(2-methoxyethyl)phosphonium cation, and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethylsulfonium ammonium cation, diethylmethyl phosphonium cation, dibutylethyl phosphonium cation, dimethyl fluorenyl group are preferably used. An asymmetric tetraalkylammonium cation such as a phosphonium cation, a triethylmethyl phosphonium cation, a tributylethyl phosphonium cation, a trimethylsulfonium cation, a trialkyl phosphonium cation, a tetraalkyl phosphonium cation, or N , N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, diallyldimethylammonium cation, N,N-di Methyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N- Amyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexyl ammonium cation, N,N-dimethyl-N- Ethyl-N-heptyl ammonium cation, N,N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl -N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N- Diethyl-N-butyl-N-heptyl ammonium cation, N,N-dimethyl-N-pentyl-N-hexyl ammonium cation, N,N-dimethyl-N,N-dihexylammonium a cation, a trimethylheptyl ammonium cation, a N,N-diethyl-N-methyl-N-propylammonium cation, an N,N-diethyl-N-methyl-N-amyl ammonium cation, N,N-Diethyl-N-methyl-N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-amyl ammonium cation, triethyl propyl ammonium cation, triethyl Yl amyl ammonium cation, triethylheptyl ammonium cation, N,N-dipropyl-N-methyl-N-ethyl ammonium cation, N,N-dipropyl-N-methyl-N-pentyl Alkyl ammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N- Methyl-N-amyl ammonium Cationic, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-amylammonium cation .

Examples of the cation represented by the formula (C5) include a phosphonium cation. Further, specific examples of R _P in the above formula (E) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, decyl group, dodecyl group, and tridecane. Base, tetradecyl, octadecyl and the like.

On the other hand, the anion component is not particularly limited as long as it can form an ionic liquid, and for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , SCN can be used. ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ 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 ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , C ₉ H ₁₉ COO ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₄ H ₉ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ ( CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- , (FSO ₂ ) ₂ N ^- , B(CN) ₄ ^- , C(CN) ₃ ^- , N (CN) ₂ ^- , p-toluenesulfonate anion, 2-(2-methoxyethyl) ethyl sulfate anion, and the like. Among them, in particular, an anionic component containing a fluorine atom can obtain an ionic liquid having a low melting point, or can be obtained by phase with a (meth)acrylic polymer (a) or a (meth)acrylic polymer (B). It is preferably used because it has an excellent ionic liquid.

Further, as the anion component, an anion or the like represented by the following formula (C6) can be further used.

In the [formula (C6) R ₁ ~ R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, the alkenyl group may have a substituent group, the alkynyl group may have a substituent group, the group may have a substituent group of the aryl And a heterocyclic group which may have a substituent. The hydrogen atom of the above substituent may be further substituted with another substituent (substituent such as an electron withdrawing group). ]

Further, as the anion component, an anion or the like represented by the following formula (C7) can also be used.

As the above anionic component, among them, an anion component containing a fluorine atom in particular, a ionic liquid having a low melting point or a (meth)acrylic polymer (a) or a (meth)acrylic polymer (B) can be obtained. It is preferably used because it is an ionic liquid excellent in compatibility.

Specific examples of the ionic liquid used in the present invention can be appropriately selected from the combination of the above cationic component and anionic component, and examples thereof include 1-butylpyridinium tetrafluoroborate and 1-butylpyridinium hexafluorophosphate. Phosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis ( Trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 1,1-di Methylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1- Propyl pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1- Amylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-glycol Pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butene Kipyrrole Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis ( Trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(trifluoro Methanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 ,1-Dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1,1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1-heptylpiper Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylperidine Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidine Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidine bismuth (Trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis (three Fluoromethanesulfonyl) quinone imine, 1,1-dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonate Indenylamine, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis ( Fluoroethinyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis (five Fluoroethinyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoro Ethylsulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonate Indole, quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Ethyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Butyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Hexyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1- 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-B -1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl - 1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1- Butyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 2-methyl-1-pyrroline Tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl 3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methyl Imidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl- 3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1- Butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl 3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl 3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2 - dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-methylpyrazolium tetrafluoroborate, 2-methylpyrazolium tetrafluoroborate, 1- Ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethyl) Sulfhydryl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-three Methylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonate Iridium imine, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethyl Pyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-2 ,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazoline bis(pentafluoroethanesulfonate) Iridium imine, 1-propyl-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethyl Pyrithione bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide , 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazole Ruthenium bis(trifluoromethanesulfonyl)trifluoroacetamide, tetraamyl ammonium triflate, tetraamylammonium bis(trifluoromethanesulfonyl) ruthenium, tetrahexylammonium trifluoride Methanesulfonate, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, tetraheptyl ammonium trifluoromethanesulfonate, tetraheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, two Allyldimethylammonium IV Borate, diallyldimethylammonium triflate, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium double (five Fluoroethinyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N- Methyl-N-(2-methoxyethyl)ammonium triflate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium double (three Fluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, glycidol Trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl)pyrene Amine, tetraoctylfluorene triflate, tetraoctylphosphonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-propyl ammonium bis ( Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl- N-ethyl-N-amyl ammonium bis(trifluoromethanesulfonyl) fluorene imine, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl) fluorene Imine N,N-Dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium (Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N -propyl-N-butyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-di Methyl-N-propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonate Iridium imine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N -heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N - dimethyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl --N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonate Iridium imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl- N-amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl amyl ammonium bis(trifluoromethanesulfonate) Iridium imine, triethylheptyl ammonium bis(trifluoromethanesulfonyl)pyrene , N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-amyl ammonium Bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl -N,N-dihexylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonyl) fluorene Amine, N,N-dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine , N-methyl-N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoro Acetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl)trifluoro Ethylamine, N-ethyl-N-methylmorpholinium thiocyanate, 4-ethyl-4-methylmorpholinium methyl carbonate, and the like.

As the ionic liquid described above, a commercially available product can be used, and it can also be synthesized in the following manner. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and a halide method or a hydroxide method as described in the literature "Iron Liquid - The Forefront and Future of Development -" [CMC Publishing] is generally used. , acid ester method, mismatch formation method and medium And law.

Hereinafter, for the halide method, the hydroxide method, the acid ester method, the mismatch formation method, and the neutralization method, the synthesis method of the nitrogen-containing phosphonium salt is exemplified, and other sulfur-containing phosphonium salts, phosphorus-containing phosphonium salts, etc. Other ionic liquids can also be obtained by the same method.

The halide method is a method which is carried out by a reaction represented by the following formulas (1) to (3). First, a tertiary amine is reacted with a halogenated alkyl group to obtain a halide (reaction formula (1), using chlorine, bromine, or iodine as a halogen). The obtained halide is reacted with an acid (HA) or a salt (MA, M is a cation which forms a salt with a target anion such as ammonium, lithium, sodium or potassium) having an anionic structure (A ^- ) of a target ionic liquid to obtain a target ion. Liquid (R ₄ NA).

(1) R ₃ N+RX→R ₄ NX(X:Cl, Br, I) (2) R ₄ NX+HA→R ₄ NA+HX (3)R ₄ NX+MA→R ₄ NA+MX (M: NH ₄ , Li, Na, K, Ag, etc.)

The hydroxide method is a method carried out by a reaction as shown in (4) to (8). First, for halide (R ₄ NX), electrolysis by ion exchange membrane method (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) The reaction formula (6)) obtains hydroxide (R ₄ NOH) (using chlorine, bromine, iodine as a halogen). The target ionic liquid (R ₄ NA) is obtained by reacting the obtained hydroxides with the reaction formulas (7) to (8) in the same manner as the above halogenation method.

(4) R ₄ NX+H ₂ O→R ₄ NOH+1/2H ₂ +1/2X ₂ (X:Gl,Br,l) (5)R ₄ NX+P-OH→R ₄ NOH+PX (P-OH: OH type ion exchange resin) (6) R ₄ NX+1/2Ag ₂ O+1/2H ₂ O→R ₄ NOH+AgX (7)R ₄ NOH+HA→R ₄ NA +H ₂ O (8)R ₄ NOH+MA→R ₄ NA+MOH(M:NH ₄ ,Li,Na,K,Ag, etc.)

The acid ester method is a method carried out by a reaction as shown in (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (reaction formula (9), using an ester of a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid, or methanesulfonic acid, A An ester of an organic acid such as phosphinic acid or formic acid as an acid ester). The target ionic liquid (R ₄ NA) is obtained by reacting the obtained acid ester with the reaction formulas (10) to (11) in the same manner as the above halogenation method. Further, an ionic liquid can be directly obtained by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester.

The mismatch formation method is a method carried out by a reaction as shown in (12) to (15). First, a quaternary ammonium halide (R ₄ NX), a quaternary ammonium hydroxide (R ₄ NOH), a quaternary ammonium carbonate (R ₄ NOCO ₂ CH ₃ ), etc., and hydrogen fluoride (HF), or Ammonium fluoride (NH ₄ F) is reacted to obtain a fluorinated quaternary ammonium salt (reaction formula (12) to (14)). An ionic liquid can be obtained by forming a reaction between the obtained fluorinated quaternary ammonium salt and a fluoride such as BF ₃ , AlF ₃ , PF ₅ , AsF ₅ , SbF ₅ , NbF ₅ or TaF ₅ (reaction formula (15) ).

(12) R ₄ NX+HF→R ₄ NF+HX(X:Cl,Br,I) (13)R ₄ NY+HF→R ₄ NF+HY(Y:OH, OCO ₂ CH ₃ (14) R ₄ NY+NH ₄ F→R ₄ NF+NH ₃ +HY(Y:OH, OCO ₂ CH ₃ ) (15)R ₄ NF+MF _n-1 →R ₄ NMF _n (MF _{n- 1} : BF ₃ , AlF ₃ , PF ₅ , AsF ₆ , SbF ₅ , NbF ₅ , TaF _{5 ,} etc.)

The neutralization method is carried out by a reaction as shown in (16). By subjecting the tertiary amine to HBF ₄ , HPF ₆ , CH ₃ COOH, CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₂ NH and other organic acids are obtained by reaction.

(16) R ₃ N+HZ→R ₃ HN ⁺ Z ^- [HZ:HBF ₄ ,HPF ₆ ,CH ₃ COOH,CF ₃ COOH,GF ₃ SO ₃ H,(CF ₃ SO ₂ ) ₂ NH , (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₆ SO ₂ ) ₂ NH and other organic acids]

R in the above formulas (1) to (16) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.

Further, the ionic liquid may be used singly or in combination of two or more.

Further, the content of the ionic compound (C) is not particularly limited, and is, for example, preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, based on 100 parts by mass of the polymer (A). Preferably, it is 0.05 to 1 part by mass, and most preferably 0.07 to 0.8 parts by mass. When it is in the above range, the obtained adhesive layer (adhesive sheet) can exhibit excellent adhesive strength (adhesion) and antistatic property, and is useful.

<Compound (D) having a polyoxyalkylene chain>

In the adhesive composition for treating a chemical solution of the present invention, the above-mentioned adhesive composition preferably contains the compound (D) having a polyoxyalkylene chain, and is not particularly limited as long as it is a compound having a polyoxyalkylene chain. For example, as the oxygen-extended alkyl unit, a carbon number of 1 to 6 can be cited. Examples of the unit of the alkyl group include an oxymethylene group, an oxygen-extended ethyl group, an oxygen-extended propyl group, and an oxygen-extended butyl group. The hydrocarbon group constituting the above oxygen alkyl chain may be a straight chain or a branched chain. For example, polyethylene glycol, polypropylene glycol (glycol type), polypropylene glycol (triol type), polytetramethylene ether glycol, methoxy polyethylene glycol, ethoxy polyethylene polyethylene An alcohol and a derivative or copolymer of the above polymer. These may be used singly or in combination of two or more. The polyoxyalkylene chain interacts with the ionic compound to promote ion detachment while transporting ions by molecular motion of the chain, thereby obtaining an effect of improving ion conductivity.

The molecular weight of the compound having a polyoxyalkylene chain is preferably a number average molecular weight of 100,000 or less, more preferably 200 to 50,000. If the molecular weight exceeds 100,000, the contamination of the adherend is increased, which is not preferable.

Further, in the above compound (D) having a polyoxyalkylene chain, it is preferred that the compound (D) having a polyoxyalkylene chain is an organopolyoxane having a polyoxyalkylene chain, more preferably The organopolyoxane having the polyoxyalkylene chain is an organopolyoxane having a polyoxyalkylene chain represented by the following formulas (D1) to (D3).

R ₁ in the above formula (D1) is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, and m and n are integers of 0 to 1000. However, m and n are not 0 at the same time. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.

In the above formula (D2), R ₁ is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, and m is an integer of from 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.

In the above formula (D3), R ₁ is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, and m is an integer of from 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.

As the above organopolyoxyalkylene having a polyoxyalkylene chain, for example, the following constitution can be used. Specifically, R ₁ in the formula is an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a tolyl group, or a monovalent organic group exemplified by an aralkyl group such as a benzyl group or a phenethyl group. Each may have a substituent such as a hydroxyl group. As R ₂ , R ₃ and R _{4 ,} a methylene group having a carbon number of 1 to 8 such as a methylene group, an exoethyl group or a propyl group can be used. Here, R ₃ and R ₄ are different alkylene groups, and R ₂ may be the same as or different from R ₃ or R ₄ . In order to increase the concentration of the ionic compound which can be dissolved in the polyoxyalkylene side chain, R ₃ and R _{4 are} preferably either an exoethyl or a propyl group. R ₅ may be a monovalent organic group exemplified by an alkyl group such as a methyl group, an ethyl group or a propyl group, or a fluorenyl group such as an ethyl group or a propyl group, and each may have a substituent such as a hydroxyl group. These compounds may be used singly or in combination of two or more. Further, the molecule may have a reactive substituent such as a (meth)acrylinyl group, an allyl group or a hydroxyl group.

As a commercial item of the above-mentioned organopolyoxane having a polyoxyalkylene chain, for example, trade names KF-351A, KF-353, KF-945, KF-6011, KF-889, KF-6004 (for example) The above are manufactured by Shin-Etsu Chemical Co., Ltd., FZ-2122, FZ-2164, FZ-7001, SH8400, SH8700, SF8410, SF8422 (above is manufactured by Toray Dow Corning), TSF-4440, TSF-4445, TSF-4452, TSF-4460 (manufactured by Momentive Performance Materials), BYK-333, BYK-377, BYK- UV3500, BYK-UV3570 (manufactured by BYK-Chemie Japan Co., Ltd.), and the like. These may be used singly or in combination of two or more.

The content of the above compound (D) having a polyoxyalkylene chain is not particularly limited, and is relative to the above polymer (A) 100 from the viewpoint of the adhesive strength (adhesion) and antistatic property of the adhesive layer. The mass part is preferably 0.005 to 1 part by mass, more preferably 0.01 to 0.8 part by mass, still more preferably 0.03 to 0.5 part by mass.

The adhesive composition used in the present invention is in addition to the above polymer (A), (meth)acrylic polymer (B), ionic compound (C), and compound (D) having a polyoxyalkylene chain. It is also possible to contain various additives which are usually used in the field of adhesives as optional components. As the optional component, in addition to the above additives, other tackifying resins, crosslinking agents, catalysts, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, and the like may be exemplified. Stabilizers, preservatives, antistatic agents, etc. Such an additive can be used in a conventional manner according to a conventional method.

<crosslinker>

In order to adjust the cohesive force of the adhesive layer of the present invention, the above adhesive composition may also contain a crosslinking agent. As the crosslinking agent, a crosslinking agent which is usually used in the field of adhesives can be used, and examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an anthrone crosslinking agent, an oxazoline crosslinking agent, and nitrogen. A propidium crosslinking agent, a decane crosslinking agent, a melamine crosslinking agent (such as an alkyl etherified melamine crosslinking agent), a metal chelate crosslinking agent, and the like. Further, the above-mentioned polyfunctional monomer which can be used as a monomer component of the above (meth)acrylic polymer (a) can also be used as a crosslinking agent. In particular, an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent can be preferably used. These compounds may be used singly or in combination of two or more.

Examples of the isocyanate-based crosslinking agent (isocyanate compound) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophora. Ketone diisocyanate, etc. Alicyclic isocyanates, aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzenedimethyl diisocyanate, trimethylolpropane/toluene diisocyanate terpolymer Adduct (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: CORONATE HL, manufactured by Japan Polyester Industries Co., Ltd.), Liuya An isocyanate adduct such as an isocyanurate body (trade name: CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) of methyl diisocyanate. Or a compound having at least one or more isocyanato groups and one or more unsaturated bonds in one molecule, and specifically, 2-isocyanatoethyl (meth)acrylate may be used as an isocyanate crosslinking agent. use. These compounds may be used singly or in combination of two or more.

Examples of the epoxy-based crosslinking agent (epoxy compound) include bisphenol A, an epichlorohydrin-based epoxy resin, ethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. Glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidylamine, N, N, N', N'-tetraglycidyl meta-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like. These compounds may be used singly or in combination of two or more.

Examples of the melamine-based crosslinking agent include hexamethylol melamine and the like. In addition, as the above-mentioned aziridine-based crosslinking agent (aziridine derivative), for example, the product name of the commercial product is HDU (manufactured by Mutual Pharmaceutical Co., Ltd.), the product name is TAZM (manufactured by Mutual Pharmaceutical Co., Ltd.), and the product is used. Named TAZO (manufactured by Mutual Pharmaceutical Co., Ltd.). These compounds may be used singly or in combination of two or more.

Examples of the metal chelate-based crosslinking agent (metal chelate compound) include aluminum, iron, tin, titanium, and nickel. Examples of the chelate component include acetylene and ethyl acetacetate. , ethyl lactate, and the like. These compounds may be used alone or in combination of two Used in combination.

The content of the crosslinking agent to be used in the present invention is not particularly limited. For example, it is preferably 0.001 to 0.8 parts by mass, more preferably 0.01 to 0.7 parts by mass, per 100 parts by mass of the polymer (A). When the content of the above-mentioned crosslinking agent is less than 0.001 part by mass, the cohesive force of the adhesive (layer) may be reduced, and the infiltration of the chemical solution may occur. On the other hand, when the content of the above-mentioned crosslinking agent exceeds 0.8 parts by mass, the cohesive force of the adhesive (layer) increases, the fluidity decreases, the wetting of the adherend is insufficient, and the strength (adhesion) Reduce the embarrassment.

Further, the content of the above polyfunctional monomer is appropriately selected depending on the balance with the polymer to be crosslinked, and further depending on the use of the adhesive layer (adhesive sheet, surface protective sheet). Further, in order to obtain sufficient heat resistance by the cohesive force of the adhesive (layer), in the case of using the above polymer (A) (for example, the above (meth)acrylic polymer (a)), the above polymer is used. (A) 100 parts by mass, preferably 0.001 to 1.0 part by mass. In addition, in terms of flexibility and adhesion, it is more preferably 0.5 parts by mass or less based on 100 parts by mass of the above polymer (A).

Further, when the above polyfunctional monomer is used as the crosslinking agent, radiation can be irradiated in order to carry out the crosslinking reaction. Examples of the radiation include ultraviolet rays, thunder rays, α rays, β rays, γ rays, X rays, and electron beams, and ultraviolet rays are preferably used in terms of controllability and workability, and cost. It is better to use ultraviolet rays having a wavelength of 200 to 400 nm. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. Further, when ultraviolet rays are used as the radiation, the photopolymerization initiator which can be used for preparing (polymerizing) the (meth)acryl-based polymer (a) can be similarly added and added to the adhesive composition ( Photoinitiator) and photopolymerization initiation aid. In the case where the above-mentioned polyfunctional monomer is used as the crosslinking agent, radiation irradiation can be performed, and the photopolymerization initiator used in this case can be used in accordance with the type of the radiation-reactive component and by irradiation. Causing the polymerization It is sufficient to generate a radical or a cation by ultraviolet rays of a suitable wavelength.

The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass, based on 100 parts by mass of the polymer (A). When it is in the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.

In the case where the above photopolymerization initiator is added, by applying the above-mentioned adhesive composition directly to the adherend (protected body) or after coating it on a specific coated body such as a separator After coating on one side of the support (substrate), light irradiation is performed to carry out a crosslinking reaction, and an adhesive layer can be obtained. In general, an adhesive layer can be obtained by photopolymerizing ultraviolet rays having an illuminance of from 1 to 200 mW/cm ² at a wavelength of from 300 to 400 nm at a light amount of about 200 to 4000 mJ/cm ² .

Further, the above-mentioned adhesive composition used in the present invention may further contain a crosslinking accelerator. The kind of the crosslinking accelerator can be appropriately selected depending on the kind of the crosslinking agent to be used. Further, in the present specification, the crosslinking accelerator means a catalyst for increasing the rate of crosslinking reaction by a crosslinking agent. Examples of the crosslinking accelerator include tin-containing dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetate, tetra-n-butyltin, trimethyltin hydroxide, and the like. (Sn) compound; N, N, N', N'-tetramethylhexanediamine, or an amine such as triethylamine, or a nitrogen-containing (N) compound such as an imidazole. Among them, a Sn-containing compound is preferred. The amount of the crosslinking accelerator to be contained in the above-mentioned adhesive composition is, for example, about 0.0001 to 1.0 part by mass (preferably about 0.001 to 0.5 part by mass) based on 100 parts by mass of the polymer (A).

The above adhesive composition used in the present invention may further contain a compound which produces keto-enol tautomerism. For example, in the adhesive composition used for the adhesive composition containing a crosslinking agent or the adjustable crosslinking agent, the aspect containing the above-described compound which produces the keto-enol tautomerization can be preferably used. Thereby, it is possible to achieve an effect of suppressing an excessive increase in viscosity or gelation of the adhesive composition after the crosslinking agent is blended, and prolonging the service life of the adhesive composition. In the case where at least an isocyanate compound is used as the above crosslinking agent, it contains a ketone- Enol tautomeric compounds are of particular interest. This technique can be preferably applied, for example, to the case where the above-mentioned adhesive composition is in an organic solvent solution or a solventless form.

As the above compound which produces keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane-2. Β-diketones such as 4-dione and 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl acetate, isopropyl acetate, acetonitrile Acetyl acetate such as tert-butyl ester; acetonitrile acetate such as ethyl acetate, isopropyl acetate, and butyl phthalate; ethyl acetate and isobutyl phthalate Examples include isobutyl phthalate esters such as ester, isopropyl isobutyl phthalate acetate and tributyl butyl acetoacetate; malonic esters such as methyl malonate and ethyl malonate. Among them, preferred examples of the compound include acetamidineacetone and acetamidine acetate. The keto-enol tautomerization compound may be used singly or in combination of two or more.

The content of the keto-enol tautomerizing compound may be, for example, 0.1 to 20 parts by mass, and usually 0.5 to 15 parts by mass (for example, 1 to 10 parts by mass) per 100 parts by mass of the polymer (A). appropriate. When the amount of the above compound is too small, it may be difficult to exhibit a sufficient use effect. On the other hand, if it is necessary to use the above compound, it may remain in the adhesive layer and the cohesive force may be lowered.

The above adhesive composition may contain a tackifying resin as needed. The (meth)acrylic copolymer (B) has a function as a tackifying resin in the adhesive layer of the present invention, and as the other tackifying resin, a conventionally known resin can be used without particular limitation. For example, a terpene type tackifying resin, a phenol type tackifying resin, a rosin type tackifying resin, an aliphatic petroleum resin, an aromatic petroleum resin, a copolymerization petroleum resin, an alicyclic petroleum resin, and a xylene resin are mentioned. , epoxy-based tackifying resin, polyamine-based tackifying resin, ketone-based tackifying resin, elastic system tackifying resin. These may be used alone or in combination of two or more. In the case of using a tackifying resin, it does not lower the properties of the above polymer (A), or (meth)acrylic polymer (B), and the effect of sufficiently obtaining a tackifying resin. The amount is preferably 20 parts by mass or less (typically 0.01 to 10 parts by mass) based on 100 parts by mass of the polymer (A).

The above adhesive composition may be prepared by blending other polymers (any polymer) as needed in the above polymer (A). Such an arbitrary polymer can be formulated, for example, in order to increase the cohesive force of the adhesive. The cohesive force of the adhesive helps to prevent the immersion of the chemical solution from the outer edge of the adhesive sheet (surface protection sheet) (typically preventing the infiltration of the liquid mainly due to the swelling of the adhesive due to the liquid medicine) ) improvement.

<Adhesive layer for drug solution treatment>

The adhesive layer of the present invention may be a hardened layer of the adhesive composition. For example, the above adhesive layer can be formed by appropriately applying a hardening treatment after imparting (for example, coating, coating) an adhesive composition to a suitable support. When the support is an antistatically treated plastic substrate, an adhesive layer may be formed on the antistatic layer, or an adhesive layer may be formed on the surface not subjected to the antistatic treatment. In the case where two or more kinds of hardening treatments (drying, crosslinking, polymerization, etc.) are carried out, these may be carried out simultaneously or in multiple stages. For the adhesive composition using a partial polymer (acrylic polymer slurry), the final copolymerization reaction (to further copolymerize a part of the polymer to form a complete polymer) is typically carried out as the above hardening treatment. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Hardening treatment such as crosslinking or drying can be carried out as needed. For example, when it is a photocurable adhesive composition and it needs to dry, it can be hard-hardened after drying. For the adhesive composition using a complete polymer, a treatment such as drying (heat drying), crosslinking, or the like is typically performed as the above-described hardening treatment as needed.

The coating and coating of the above adhesive composition (adhesive composition solution) may be, for example, a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, or a rod. It is implemented by a usual coater such as a coater, a knife coater, or a spray coater. Further, the adhesive composition may be directly applied to the support (substrate) to form an adhesive layer, and the adhesive layer formed on the release liner may be transferred to the support.

The thickness of the above-mentioned pressure-sensitive adhesive layer is not particularly limited and may be appropriately adjusted depending on the purpose. The thickness of the adhesive layer can be, for example, about 1 to 100 μm. Further, from the viewpoint of adhesion to the surface of the adherend, the thickness is preferably 2 μm or more, more preferably 3 μm or more (for example, 5 μm or more, and typically 7 μm or more). Further, from the viewpoint of peeling workability, the thickness of the adhesive layer is preferably 90 μm or less, more preferably 70 μm or less, and typically 50 μm or less. It is also preferable that the thickness of the adhesive layer is not too large from the viewpoint of suppressing the infiltration of the chemical solution caused by the swelling of the adhesive.

The arithmetic mean surface roughness of the surface of the adhesive layer (adhesive surface, that is, the attachment surface to the adherend) is preferably 1 μm or less, more preferably about 0.05 to 0.75 μm (for example, about 0.05 to 0.5 μm, typically It is a range of about 0.1 to 0.3 μm). When the smoothness of the adhesive surface is improved, the adhesion between the adhesive surface and the interface of the adherend is improved. Thereby, it is possible to better prevent the chemical solution from entering from the interface between the adhesive and the adherend. Further, since the unevenness of the stress distribution due to the peeling of the adhesive layer having a high smoothness from the surface of the adherend is small, it is possible to better prevent the partial adhesive from being broken and remaining on the side of the adherend due to local stress. phenomenon. Therefore, the adhesive sheet (surface protective sheet) having the adhesive layer on the support (substrate) can be smoothly peeled off from the adherend without causing contamination such as paste residue on the surface of the adherend.

Further, the arithmetic mean surface roughness of the adhesive surface can be measured using a usual surface roughness measuring device (for example, a non-contact three-dimensional surface shape measuring device manufactured by Veeco Co., Ltd., model "Wyko NT-3300").

Further, the solvent-insoluble component ratio (gel fraction) of the adhesive layer of the present invention is 50 to 90% by mass, preferably 55 to 87% by mass, more preferably 60 to 85% by mass. When the solvent-insoluble component ratio exceeds 90% by mass, the strength (adhesion) decreases, and when it is less than 50% by mass, the cohesive force of the adhesive (layer) is lowered, and the paste may remain. Further, the method for evaluating the solvent insoluble component ratio was measured according to the methods and conditions described in the following examples.

Further, the surface resistivity of the above adhesive layer is 10 ³ to 10 ¹³ Ω/□, preferably 10 ⁴ to 10 ¹³ Ω/□, more preferably 10 ⁶ to 10 ¹³ Ω/□. When it is in the above range, it is useful to suppress the peeling static voltage and to impart antistatic properties. Further, the method for evaluating the surface resistivity was measured according to the methods and conditions described in the following examples.

<Support>

The adhesive sheet for chemical treatment of the present invention preferably forms the above-mentioned adhesive layer on at least one side of the support. The adhesive sheet having the above adhesive layer is useful because it is excellent in chemical solution immersion property and antistatic property. In addition, as a support (base material) used for the above-mentioned adhesive sheet (surface protection sheet), a support such as a known film shape or a sheet shape can be appropriately selected and used. The material of the support is not particularly limited. For example, a support formed of a metal material (aluminum or the like), a support formed of a resin material, a support formed of the composite material (for example, a plastic film on which a metal is vapor-deposited on one side), or the like can be used.

Preferred examples of the support (substrate) in the technology disclosed herein include a support (plastic film) comprising the following resin materials: polyethylene (PE), polypropylene (PP), and ethylene propylene rubber ( Polyolefin resin such as EPR), ethylene-propylene-butene copolymer, ethylene-ethyl acrylate copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene Polyester resin such as ethylene dicarboxylate; polyamine resin (PA); polyimine resin (PI); polyphenylene sulfide resin (PPS); polycarbonate resin (PC); polyurethane Resin (PU); ethylene-vinyl acetate resin (EVA); fluororesin such as polytetrafluoroethylene (PTFE); acrylic resin. The support may be a support containing a resin material containing one type of the resin alone, or a support (plastic film) containing a resin material containing two or more of such resins.

Here, the plastic film generally refers to a non-porous plastic film, which is distinguished from the concept of a woven fabric or a non-woven fabric. As the support of the adhesive sheet (surface protective sheet) disclosed herein, any of the non-stretched plastic film and the stretch (uniaxially stretched or biaxially stretched) plastic film can be used.

Among these, a resin material which is preferable from the viewpoint of having moderate flexibility is a polyolefin resin (for example, one of polyolefin resins such as PP, PE, and EPR is contained alone or blended. There are two or more kinds of polyolefin resins) and polyester resins (for example, PET). Since the polyolefin resin or the polyester resin has moderate flexibility, the adhesive sheet (surface protective sheet) having the support made of such a resin material is easy even when there is a step difference on the surface of the adherend, for example. Follow the above steps (ie, surface shape followability is higher). Therefore, it is not easy to form a immersion path (void) of the chemical solution between the adhesive (layer) constituting the adhesive sheet and the adherend. Therefore, it is preferable as a support for an adhesive sheet (surface protective sheet) for chemical liquid treatment.

Further, the above-described step difference may be derived from a structure formed on the surface of the adherend. Examples of the adherend having such a structure include a flat type personal computer, a mobile phone, an organic LED (light emitting diode), and the like, and a surface is partially provided with a transparent conductive film (for example, ITO (indium oxide). Tin) film, or a glass substrate of a flexible printed substrate (FPC).

As a support (substrate) of the adhesive sheet (surface protective sheet) disclosed herein, a support comprising a resin material having a high acid resistance can be preferably used. The support is exposed to acidic acid liquid (for example, hydrofluoric acid solution used in etching of glass, or chromium plating solution, copper sulfate plating solution, nickel plating solution, acid electroless nickel plating solution, acid tin plating solution, etc.) The plating solution is also not prone to swelling. Therefore, it is advantageous to prevent the acidic chemical solution from swelling the support and immersing it in the adhesive sheet (surface protective sheet) and reaching the adherend (non-treated portion). From the viewpoint of excellent acid resistance and flexibility balance, a support comprising a polyolefin resin can be exemplified as a preferred support.

The support (substrate) may be a single layer or a multilayer structure of two or more layers (for example, a three-layer structure). For example, a resin film (multilayer film) including a multilayer structure of the above film can be used as a support. In the multilayer film, the resin material constituting each layer may be a resin material containing one of the above resins alone, or a resin material containing two or more kinds of resins.

In a preferred embodiment, the support (substrate) is a single layer or a plurality of layers of a polyolefin resin film. Here, the polyolefin resin film refers to a plastic film formed of a resin material containing a polyolefin resin (that is, a resin containing a polyolefin as a main component). The proportion of the polyolefin resin in the resin component (polymer component) in the polyolefin resin film is preferably more than 50% by mass, preferably 75% by mass or more, and more preferably 90% by mass or more. It may be a film in which the resin component substantially contains a polyolefin resin. Alternatively, it may be a film formed of a resin material containing a polyolefin resin as a resin component in addition to a polyolefin resin as a main component (for example, a component of more than 50% by mass in the resin component). Resin components other than PA (PC, PC, PU, EVA, etc.).

As the polyolefin resin, one type of polyolefin may be used alone or two or more types of polyolefins may be used in combination. The polyolefin may be, for example, a homopolymer of an α-olefin, a copolymer of two or more kinds of α-olefins, a copolymer of one or two or more kinds of α-olefins and another ethylene monomer, and the like. Specific examples thereof include an ethylene-propylene copolymer such as PE, PP, and EPR, an ethylene-propylene-butene copolymer, and an ethylene-ethyl acrylate copolymer. Any of low density (LD) polyolefin and high density (HD) polyolefin can be used. Examples of such a polyolefin resin film include a biaxially oriented polypropylene (OPP) film, a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, and a medium density polyethylene (MDPE) film. , high density polyethylene (HDPE) film, polyethylene (PE) film blended with two or more kinds of polyethylene (PE), PP/PE blended with polypropylene (PP) and polyethylene (PE) A polyolefin resin film such as a film or various soft polyolefin films.

The above-mentioned PP may be various polymers (propylene-based polymers) containing propylene as a main monomer (mainly constituting a monomer, that is, a component exceeding 50% by mass of the entire monomer). The concept of a propylene-based polymer herein includes, for example, the following polypropylene.

A homopolymer of propylene (ie, homopolypropylene). For example, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene.

Propylene and other alpha-olefins (typically selected from ethylene and alpha-olefins having 4 to 10 carbon atoms) One or two or more kinds of random copolymers (random polypropylene). For example, a random polypropylene obtained by randomly copolymerizing 96 to 99.9 mol% of propylene with 0.1 to 4 mol% of other α-olefins (preferably ethylene and/or butene).

A copolymer (block polypropylene) obtained by copolymerizing a propylene group with another α-olefin (typically one or more selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms). The block polypropylene may contain, as a by-product, a rubber component containing at least one of propylene and the other α-olefin as a component. For example, a polymer containing 0.1 to 10 mol% of other α-olefin (preferably ethylene and/or butene) copolymerized with 90 to 99.9 mol% of propylene, and propylene and others as a by-product. A block polypropylene having at least one rubber component as a component of the α-olefin.

The PP resin may be a resin in which the main component of the resin component is the propylene-based polymer and other polymers are blended as a subcomponent. The above-mentioned other polymer may be an a-olefin other than propylene, for example, agglomerates of an α-olefin having 2 or 4 to 10 carbon atoms as a main monomer (mainly constituting a monomer, that is, a component exceeding 50% by mass of the entire monomer) One type or two or more types of olefins. The PP resin may have a composition containing at least PE as the above-mentioned subcomponent. For example, the content of PE may be 3 to 50 parts by mass (typically 5 to 30 parts by mass) with respect to 100 parts by mass of PP. It may be a PP resin in which the resin component substantially contains PP and PE. Further, a PP resin having at least PE and EPR as an auxiliary component (for example, a PP resin in which a resin component substantially contains PP and PE and EPR) may be contained. In this case, for example, the EPR content may be 3 to 50 parts by mass (typically 5 to 30 parts by mass) based on 100 parts by mass of the PP.

The above PE may be a homopolymer of ethylene or a copolymer of ethylene as a main monomer and another α-olefin (for example, an α-olefin having 3 to 10 carbon atoms). Preferable examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Any of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE) can be used. For example, LDPE and/or LLDPE can be preferably used.

As the support (substrate), an olefin-based polymer alloy and a carbonyl group can also be used. A polyolefin resin film of a thermoplastic resin of a base unit. Here, the thermoplastic resin containing a carbonyl unit means a thermoplastic resin containing a carbonyl (C=O) unit in a molecular skeleton. Such a polyolefin resin film does not substantially contain a halogen atom, and has flexibility, heat resistance, and flame retardancy equivalent to those of polyvinyl chloride (PVC).

The olefin-based polymer alloy is mainly used for suppressing thermal deformation of a support (base material), and is preferably a polymer alloy containing an ethylene component and a propylene component. The form of the polymer alloy is not particularly limited. For example, a polymer dopant obtained by physically mixing two or more kinds of polymers may be used, and a block in which two or more kinds of polymers are covalently bonded is used. A copolymer or a graft copolymer, and various forms such as an IPN (Interpenetrating Polymer Network) structure in which two or more kinds of polymers are entangled with each other and are not covalently bonded. It may be any one of a compatible polymer alloy in which two or more kinds of polymers are compatible, and an incompatible polymer alloy in which two or more kinds of polymers are incompatible to form a phase-separated structure.

Examples of such an olefin-based polymer alloy include polymer dopants of polypropylene (homopolypropylene, atactic polypropylene) and polyethylene (copolymer containing ethylene and a small amount of α-olefin), propylene/ethylene. a copolymer, a terpolymer of propylene and ethylene with other α-olefins other than these (as other α-olefins, 1-butene, 1-pentene, 1-hexene, 4-methyl-1) -pentene, 1-heptene, 1-octene, etc., preferably 1-butene.).

When the olefin-based polymer alloy is a copolymer, a multistage polymerized olefin copolymer (preferably an ethylene/propylene copolymer) obtained by polymerization of a plurality of stages of two or more stages is preferred. The polymer alloy described in JP-A-2001-192629 is exemplified as the multi-stage polymerized olefin copolymer. That is, a polymerization of the first stage using a monomer mixture containing propylene as a main component, followed by a polypropylene (grade 1)/propylene-ethylene copolymer obtained by copolymerizing propylene and ethylene at the second stage and thereafter (second Polymer alloys of grades and after). The polymerization of the first stage is preferably carried out in the presence of a titanium compound catalyst and an organoaluminum compound catalyst. The second and subsequent polymerizations are preferably titanium-containing polyolefins formed in the polymerization of the first stage. It is carried out in the presence of a hydrocarbon and an organoaluminum compound catalyst. Examples of the titanium compound catalyst include pulverization of titanium trichloride with magnesium chloride and n-butyl orthotitanate, 2-ethylhexanol, ethyl p-toluate, ruthenium tetrachloride, and phthalic acid. A solid catalyst having a spherical shape and an average particle diameter of 1 to 30 μm, which is treated with diisobutyl ester or the like. The organoaluminum compound catalyst may, for example, be an alkyl aluminum such as triethylaluminum. Further, an antimony compound such as diphenyldimethoxydecane may be added to the polymerization layer, or an iodine compound such as iodine iodide may be added as an electron donor.

From the viewpoint of suppressing thermal deformation, the olefin-based polymer alloy preferably exhibits a dynamic storage modulus (E') at 80 ° C of 40 MPa or more and less than 180 MPa (for example, 45 MPa to 160 MPa) and exhibits at 120 ° C. The dynamic storage modulus (E') is 12 MPa or more and less than 70 MPa (for example, 15 MPa to 65 MPa). Further, in consideration of surface shape followability or workability in the vicinity of room temperature, it is preferable that the dynamic storage modulus (E') at 23 ° C is 200 MPa or more and less than 400 MPa. The dynamic storage modulus (E') is a value measured by preparing a test piece (thickness: 0.2 mm, width: 10 mm, length: 20 mm) formed of a polymer alloy, and using DMS200 (manufactured by Seiko Instruments Co., Ltd.) as a measuring instrument. The dynamic viscoelastic behavior of the test piece caused by temperature dispersion was measured under specific measurement conditions (for example, measurement method: tensile mode, temperature increase rate: 2 ° C/min, frequency: 1 Hz). Examples of such a polymer alloy include the trade names "Catalloy KS-353P", "Catalloy KS-021P", "Catalloy C200F", and "Catalloy Q-200F" manufactured by Sun Allomer Co., Ltd., and the like.

The thermoplastic resin containing a carbonyl group is a thermoplastic resin containing a carbonyl (C=O) unit in a molecular skeleton for imparting moderate flexibility and good elongation to a support (substrate). When the polyolefin resin film contains an inorganic flame retardant as described below, it may be used as a component for activating the flame retardancy imparted by the inorganic flame retardant. The thermoplastic resin is preferably a soft polyolefin-based resin containing a carbonyl unit in its molecular skeleton. For example, a vinyl copolymer obtained by using a vinyl ester and/or an α,β-unsaturated carboxylic acid or a derivative thereof as a monomer or a comonomer (ethylene/vinyl acetate copolymer, ethylene/ An unsaturated carboxylic acid copolymer or the like), a metal salt or the like. The melting point of the thermoplastic resin is not particularly limited, but is preferably 120 ° C or lower (typically 40 to 100 ° C). The above melting point can be measured by a usual differential scanning calorimeter (DSC).

The vinyl ester in the ethylene-based copolymer or the metal salt thereof may, for example, be a vinyl carboxylate such as vinyl acetate. Further, examples of the α,β-unsaturated carboxylic acid or a derivative thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. ; (methyl) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, cyclomethacrylate Ester, octadecyl (meth)acrylate, dodecyl (meth)acrylate, 1-methyl maleate, 1-ethyl maleate, diethyl maleate, fumaric acid Unsaturated carboxylic acid esters such as 1-methyl ester and glycidyl (meth)acrylate. These may be used alone or in combination of two or more. Among them, an alkyl (meth)acrylate is preferred, and ethyl acrylate is more preferred.

Preferred examples of the ethylene/vinyl ester copolymer and the ethylene/unsaturated carboxylic acid copolymer include an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/ethyl acrylate copolymer, and an ethylene/acrylic acid. /ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl acetate/ethyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/glycidyl methacrylate-ethyl acrylate Copolymers and such metal salts. These may be used alone or in combination of two or more.

The polyolefin resin film containing the olefin polymer alloy and the thermoplastic resin containing a carbonyl unit preferably contains an inorganic flame retardant. Examples of such an inorganic flame retardant include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide; and basic magnesium carbonate, calcium magnesium carbonate, and calcium carbonate. Metal carbonates such as barium carbonate and dolomite; metal hydrates such as hydrotalcite and borax (hydrates of metal compounds); inorganic metal compounds such as barium metaborate and magnesium oxide. These may be used alone or in combination of two or more. Among them, preferred are aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, and hydroxide. a metal hydroxide such as calcium or barium hydroxide, or basic magnesium carbonate or hydrotalcite.

Further, the inorganic flame retardant is preferably subjected to a surface treatment by a decane coupling agent. Thereby, various characteristics such as flexibility, heat resistance, and flame retardancy can be further improved. Specific examples of such a decane-based coupling agent include vinyltriethoxydecane, vinyl-tris(2-methoxy-ethoxy)decane, and γ-methylpropenyloxypropyltrimethyl. Oxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-β-(amino group Ethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltri Ethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane. These may be used alone or in combination of two or more.

The method of surface treatment of the inorganic metal compound using the decane-based coupling agent is not particularly limited, and a conventionally known method such as a dry treatment method or a wet treatment method can be suitably employed. The amount of the decane-based coupling agent to the surface of the inorganic metal compound varies depending on the type of the coupling agent, the type of the inorganic metal compound, the specific surface area, and the like. Therefore, it cannot be generalized, and is usually 0.1 to 0.1 part by mass of the inorganic metal compound. 5.0 parts by mass (for example, 0.3 to 3.0 parts by mass).

The mixing ratio of the olefin polymer alloy to the carbonyl group-containing thermoplastic resin is not particularly limited, and from the viewpoint of heat resistance and flame retardancy, for example, it is preferably 90:10 to 20:80 on a mass basis. . Further, in the case of blending an inorganic flame retardant, the polymer component (the total of the multistage polymerized olefin copolymer and the thermoplastic resin containing a carbonyl unit) is 100 in terms of improving flame retardancy and maintaining flexibility. The blending amount is preferably from 10 to 200 parts by mass (e.g., from 20 to 100 parts by mass).

Any of the above resin films may contain an appropriate component suitable for the use of the adhesive sheet (surface protective sheet) as needed. For example, a photo-trapping agent such as a radical scavenger or an ultraviolet absorber, an antioxidant, an antistatic agent, a coloring agent (dye, pigment, etc.) may be appropriately formulated. Additives such as fillers, slip agents, anti-blocking agents.

Examples of the light stabilizer include benzotriazoles, hindered amines, and benzoic acid esters as active ingredients.

Examples of the antioxidant include alkylphenols, alkylene bisphenols, thioacrylates, organic phosphites, amines, hydroquinones, hydroxylamines, and the like.

The above-mentioned additives may be used alone or in combination of two or more. The content of the above-mentioned additive can be set to a normal content of a resin film used as a support (substrate) of the surface protective sheet in the use according to the use of the surface protective sheet (for example, for glass etching or plating mask). The amount of blending is the same.

Such a support (substrate) (resin film) can be suitably produced by a conventionally known conventional film forming method (extrusion molding, inflation molding, etc.). The surface on which the adhesive layer side is provided in the support (the side surface of the adhesive layer, the surface on which the adhesive is applied) may be subjected to treatment for improving the adhesion to the adhesive layer (to obtain the anchoring property of the adhesive) Treatment), for example, surface treatment such as corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, primer (primer) coating, and the like. As a surface treatment (primer treatment) by primer coating, it is preferred to use a primer obtained by blending an isocyanate in an acrylic polymer. The surface (back surface) of the support opposite to the side surface of the above-mentioned adhesive layer side can be subjected to surface treatment such as antistatic treatment or peeling treatment as needed. In the peeling treatment, for example, a long-chain alkyl-based or an oxime-based release-treated layer is provided on the back surface of the support to reduce the unwinding force of the surface protective sheet wound into a roll shape.

The thickness of the support (substrate) can be appropriately selected depending on the flexibility (hardness) of the resin film to be used and the like. The thickness of the support is preferably 500 μm or less (preferably 400 μm or less, more preferably 300 μm or less, and typically 250 μm or less, from the viewpoint of followability or adhesion of the surface having a step difference. For example, it is 200 μm or less). In addition, the thickness of the support is from the viewpoint of peeling workability and other operability (handling property) Suitably, it is 10 μm or more (preferably 20 μm or more, more preferably 25 μm or more, for example, 30 μm or more). Further, when the thickness of the support is increased, there is a tendency that the chemical liquid is easily prevented from being swollen from the surface of the surface protection sheet.

The surface on the side where the adhesive layer is provided in the support preferably has a surface state (surface roughness of the adhesive surface) which does not affect the adhesive layer (that is, does not constitute a main cause of an increase in the arithmetic mean surface roughness of the adhesive surface). The degree of smoothness. For example, the support preferably has an arithmetic mean surface roughness of the side surface of the adhesive layer of 1 μm or less, more preferably 0.05 to 0.75 μm (e.g., about 0.05 to 0.5 μm, typically about 0.1 to 0.3 μm). By adopting this configuration, the smoothness of the adhesive surface is also improved.

The support may be subjected to mold release, antifouling treatment, or acid treatment using an anthrone-based, fluorine-based, long-chain alkyl-based or fatty amide-based release agent, cerium oxide powder, or the like, as needed. Antistatic treatment such as alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, etc., followed by easy treatment, coating type, kneading type, vapor deposition type, and the like.

Further, the support (plastic film) used in the adhesive sheet (surface protective sheet) of the present invention is preferably subjected to an antistatic treatment. By performing antistatic treatment, it is possible to prevent generation of static electricity, and it is particularly useful in the technical field related to optical and electronic components in which static electricity causes serious problems. The antistatic treatment applied to the plastic film is not particularly limited, and a method in which an antistatic layer is provided on at least one side of a film or a method in which a kneading antistatic agent is kneaded in a plastic film can be used. The method of providing an antistatic layer on at least one side of the film includes a method of applying an antistatic resin composed of an antistatic agent and a resin component, or a conductive polymer or a conductive resin containing a conductive material. Or a method of vaporizing or plating a conductive substance.

Examples of the antistatic agent contained in the antistatic resin include a quaternary ammonium salt, a pyridinium salt, and a cationic antistatic agent having a cationic functional group such as a primary amine group, a secondary amino group or a tertiary amino group. An anionic antistatic agent having an anionic functional group such as a sulfonate or a sulfonate, a phosphonate or a phosphate ester, an alkylbetaine and a derivative thereof, Amphoteric antistatic agent such as imidazoline and its derivatives, alanine and its derivatives, nonionic antistatic agent such as amino alcohol and its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, Further, an ion conductive polymer obtained by polymerizing or copolymerizing a monomer having the above cationic, anionic or zwitterionic ionic conductive group. These compounds may be used singly or in combination of two or more.

Specifically, examples of the cationic antistatic agent include an alkyltrimethylammonium salt, a mercaptoguanidinopropyltrimethylammonium methylsulfate, an alkylbenzylmethylammonium salt, and an anthracene. a (meth) acrylate copolymer having a quaternary ammonium group such as choline chloride or polydimethylaminoethyl methacrylate, and a quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride A styrene copolymer, a diallylamine copolymer having a quaternary ammonium group such as polydiallyldimethylammonium chloride or the like. These compounds may be used singly or in combination of two or more.

Examples of the anionic antistatic agent include an alkylsulfonate, an alkylbenzenesulfonate, an alkylsulfate, an alkylethoxysulfate, an alkyl phosphate, and a sulfonic acid. a styrene copolymer. These compounds may be used singly or in combination of two or more.

Examples of the amphoteric ion-type antistatic agent include an alkylbetaine, an alkylimidazolium betaine, and a carbobetaine graft copolymer. These compounds may be used singly or in combination of two or more.

Examples of the nonionic antistatic agent include fatty acid hydroxyalkyl decylamine, bis(2-hydroxyethyl)alkylamine, polyoxyethylideneamine, fatty acid glyceride, and polyoxyethylene. Alcohol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene ethyl sorbitan fatty acid esters, polyoxyethylene ethyl phenyl ethers, polyoxyethylene ethyl ethers, polyethylene glycols Polyoxyethylene ethyl diamine, a copolymer comprising a polyether and a polyester and a polyamine, a methoxy polyethylene glycol (meth) acrylate, or the like. These compounds may be used singly or in combination of two or more.

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

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

As the resin component used in the antistatic resin and the conductive resin, a general-purpose resin such as polyester, acrylic, polyethylene, urethane, melamine or epoxy resin can be used. Further, in the case of a polymer type antistatic agent, a resin component may not be contained. In addition, a compound such as melamine or hydroxyalkylated melamine, urea, glyoxal or acrylamide may be contained in the antistatic resin component, and an epoxy compound or an isocyanate may be contained. Compound.

The method for forming the antistatic layer can be formed, for example, by diluting the antistatic resin, the conductive polymer, and the conductive resin with an organic solvent or a solvent such as water to apply the coating liquid to the plastic. The film is dried and dried.

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

A known coating method can be suitably used for the coating method in the formation of the antistatic layer. Specific examples thereof include a roll coating method, a gravure coating method, a reverse coating method, and a roll brush coating method. Spraying method, air knife coating method, impregnation coating method and curtain coating method.

The thickness of the antistatic resin layer, the conductive polymer, and the conductive resin is usually 0.01 to 5 μm, preferably about 0.03 to 1 μm.

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

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

Further, as the kneading type antistatic agent, the above antistatic agent can be suitably used. The content (mixing amount) of the kneading-type antistatic agent is used in an amount of 20% by mass or less, preferably 0.05% to 10% by mass based on the total mass of the plastic film as the support. The kneading method is not particularly limited as long as it can uniformly mix the above antistatic agent in a resin for a plastic film, and for example, a heating roll, a Banbury mixer, a pressure kneader, and a biaxial kneading can be used. Machine and so on.

The adhesive sheet (surface protection sheet) of the present invention may be an adhesive sheet (surface protection sheet) with a release liner attached to the surface of the adhesive layer before use (before being attached to the adherend) Shape. When the release liner is disposed on the adhesive surface and the surface (peeling surface) facing the adhesive surface is excellent in smoothness, the smoothness of the adhesive surface (adhesive surface) can be more stably maintained until the adhesive sheet is used (surface protection) The film) is up to now.

The release liner (separator) is not particularly limited, and various papers (which may be paper having a resin laminated on the surface), a resin film, or the like can be used. In the case of using a resin film as a release liner, preferred examples of the resin component constituting the resin film include a polyolefin resin, a polyester resin such as PET, a polyamide resin, a polycarbonate resin, and a polyamine. Carbamate resin and the like. The release liner may be a release liner comprising a resin material containing one of the resins alone, or a release liner comprising a resin material in which two or more resins (for example, PE and PP) are blended. The resin film for such a release liner can be produced by a usual film forming method, similarly to the resin sheet for a support. The structure of the release liner may be a single layer or a multilayer structure of two or more layers.

In the case where the transfer method is employed as a method of providing an adhesive layer on a support, the same substance can be used for the transfer sheet and the release liner. For example, the support is bonded to the adhesive layer formed on the release surface of the transfer sheet, and the adhesive layer is transferred to the support, and the transfer sheet is directly left on the adhesive layer to serve as a release liner. Pad utilization. The transfer sheet doubles as a release liner in terms of improving productivity, reducing material costs, and reducing waste. The situation is better.

The thickness of the release liner is not particularly limited and may be about 5 to 500 μm (for example, about 10 to 200 μm, typically about 20 to 200 μm). The release surface of the release liner (the surface disposed in contact with the adhesive surface) may be subjected to a release treatment using a conventionally known release agent (for example, an ordinary anthrone type, a long-chain alkyl type, a fluorine type, or the like) as needed. The back surface of the peeling surface may be subjected to a peeling treatment, or a surface treatment other than the peeling treatment may be performed.

The arithmetic mean surface roughness of the surface of the release liner disposed on the side of the adhesive layer is preferably 0.05 to 0.75 μm (for example, about 0.05 to 0.5 μm, typically about 0.1 to 0.3 μm). Thereby, the smoothness of the surface (adhesive surface) of a high adhesive can be maintained until the surface protection sheet is used. The smoothness of the adhesive surface is higher than that of preventing the immersion of the chemical solution from the interface between the adhesive and the adherend. Further, it is also preferable from the viewpoint of preventing the residue of the paste. For the same reason, the surface of the adhesive layer is protected by abutting the surface (adhesive surface) of the adhesive layer against the back surface of the support to protect the adhesive surface until the surface protective sheet is used. The arithmetic mean surface roughness is preferably from 0.05 to 0.75 μm (e.g., from about 0.05 to 0.5 μm, typically from about 0.1 to 0.3 μm).

<Surface protection sheet>

The surface protection sheet of the present invention preferably comprises the above-mentioned pressure-sensitive adhesive sheet for chemical liquid treatment. The above adhesive sheet can be attached to a desired portion of the adherend to be used as a surface protective sheet for protecting the portion. Since the adhesive used in the surface protection sheet has high adhesion to the adherend, the chemical protection liquid (especially the aqueous liquid medicine, typically acidic liquid) is adhered to the outer edge of the surface protection sheet. The agent is excellent in immersing in the interface with the adherend. Thereby, it is possible to reliably prevent the chemical solution from infiltrating into a portion where it is not desired to be exposed to the chemical liquid, and to protect the surface thereof.

The surface protection sheet of the present invention can be preferably used for such a treatment, for example, in order to reduce the thickness of the glass, or to remove the burrs or microcracks formed on the cut end surface of the glass (the etching liquid) Etching treatment of dissolved glass; Etching or printing of a chemical liquid (etching liquid) to partially etch the surface of the metal; and to connect the terminal portion of the printed circuit board (printed substrate, flexible printed circuit (FPC), etc.) with a chemical solution (plating solution) Plating treatment, etc.

Further, for example, when the surface protective sheet is attached to the outer edge of the adherend and the chemical liquid treatment is performed, if the chemical liquid is partially from the outer edge of the adherend (the area where the surface protective sheet is attached) When the outer edge is immersed, there is a flaw in the smoothness of the edge of the adherend due to the influence of the chemical solution. If the smoothness of the outer edge of the adherend is impaired, in particular, the adhering body which is weak as a glass substrate may cause disadvantages such as a decrease in the strength of the adherend. The surface protection sheet disclosed herein is excellent in the performance of preventing the chemical solution from entering from the outer edge of the surface protection sheet, and therefore it is possible to effectively prevent the phenomenon that the smoothness of the outer edge of the adherend is lowered.

<glass substrate>

The glass substrate with a surface protection sheet of the present invention preferably has the surface protection sheet attached to the glass substrate. By attaching the surface protection sheet to the glass substrate, for example, in order to adjust the thickness of the glass or to remove the burrs formed on the cut end surface of the glass, the chemical solution (a highly acidic chemical solution such as hydrofluoric acid) is used to dissolve the glass. In the etching treatment or the like, the surface protective sheet has a property of preventing the chemical liquid from entering the surface of the glass which is not required to be treated by the chemical liquid (anti-drug immersion property, sealing property), that is, a glass surface as the adherend The property of no gap adhesion (no floating, or peeling, excellent adhesion) and the subsequent strength (excellent adhesion in the liquid) and the case where the above surface protection sheet is no longer needed can be easily It is useful for the property of peeling (repeelability). Further, since the surface protective sheet has excellent antistatic property, it is useful for suppressing static electricity generated on the surface of the glass as the adherend when the surface protective sheet is not required to be peeled off. The glass substrate may be, for example, a flat type personal computer, or a mobile phone, an organic LED (light emitting diode), or the like, partially provided with a transparent conductive film (for example, an ITO (Indium Tin Oxide) film) or a flexible printed substrate (for example). FPC) glass substrate.

[Examples]

In the following, several embodiments of the invention are described, but the invention is not intended to be limited to the specific examples. In addition, the "parts" and "%" in the following description are the quality standards unless otherwise specified.

The components of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 and 2 are shown in Table 2, and Table 3 shows the evaluation results.

The abbreviations in Table 2 above indicate the following compounds, and the parts represent the parts by mass of the solid content.

2EHA: 2-ethylhexyl acrylate

HEA: 2-hydroxyethyl acrylate

DCPMA: Dicyclopentyl Methacrylate

MMA: Methyl methacrylate

CHMA: cyclohexyl methacrylate

BMP-TFSI: 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone

EMI-FSI: 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine

KF6004: organopolyoxane with polyoxyalkylene chain

Pluronic 25R-2: polyoxypropylene propyl-polyoxyethylene ethyl-polyoxypropyl propyl block copolymer

Coronate L: Trimethylolpropane/toluene diisocyanate 3-polymer adduct

Coronate HX: isocyanurate body of hexamethylene diisocyanate

<Preparation of (meth)acrylic polymer (a) (2EHA/HEA=96/4) as component (A)>

96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator and 150 parts by mass of ethyl acetate, nitrogen gas was introduced while slowly stirring, and the liquid temperature in the flask was maintained at around 65 ° C. The polymerization reaction was carried out for an hour to prepare a (meth)acrylic polymer (a) solution (40% by mass). The glass transition temperature (Tg) of the (meth)acrylic polymer (a) calculated according to the Fox formula was -68 ° C, and the weight average molecular weight (Mw) was 550,000.

<Preparation of (meth)acrylic polymer 1 (DCPMA/MMA=60/40) as component (B)>

100 parts by mass of ethyl acetate, 60 parts by mass of dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 40 parts by mass of methyl methacrylate (MMA), and 3.5 parts by mass of α-thioglycerol of the chain transfer agent A four-necked flask of a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel was prepared. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 2 hours, followed by 80 ° C. The reaction was carried out for 5 hours. The glass transition temperature (Tg) calculated from the Fox equation of the obtained (meth)acryl-based polymer 1 was 144 ° C, and the weight average molecular weight (Mw) was 4,200.

<Preparation of (meth)acrylic polymer 2 (CHMA/MMA=60/40) as component (B)>

100 parts by mass of ethyl acetate, 60 parts by mass of cyclohexyl methacrylate (CHMA), 40 parts by mass of methyl methacrylate (MMA), and 3.5 parts by mass of α-thioglycerol as a chain transfer agent were supplied with stirring. A four-necked flask of a blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 2 hours, followed by 80 ° C. The reaction was carried out for 5 hours. The glass transition temperature (Tg) calculated from the Fox equation of the obtained (meth)acrylic polymer 2 was 81 ° C, and the weight average molecular weight (Mw) was 4,100.

(Example 1) (modulation of adhesive composition)

To 500 parts by mass of the solution (solid content: 100 parts by mass) of the solution obtained by diluting the (meth)acrylic polymer (a) solution (40% by mass) to 20% by mass with toluene, 0.25 parts by mass (methyl group) was added. Acrylic polymer 1, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) as an ionic compound (trade name: CIL-312, Japan Carlit) The company manufactures 0.5 parts by mass at 25 ° C, and is an organopolyoxane having a polyoxyalkylene chain as a compound having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 A mass fraction of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.33 parts by mass (solid form) Composition 0.25 mass 3 parts by mass of an ethyl acetate solution of 1% by mass of a solid content of dioctyltin dilaurate as a cross-linking catalyst, and mixing and stirring at 25 ° C for about 5 minutes to prepare an adhesive composition (1) ).

(production of adhesive sheets)

The adhesive composition (1) was applied to a corona-treated surface of a polyethylene film (trade name: NSO Film, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm, "PE #150" in Table 3) as a support. The film was heated at 80 ° C for 1 minute to form an adhesive layer having a thickness of 25 μm. Then, on the surface of the above-mentioned adhesive layer as a release liner, a surface of a polyethylene film (trade name: NSO FILM, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm) opposite to the corona-treated surface was bonded to each other to prepare an adhesive sheet.

(Example 2) (modulation of adhesive composition)

The adhesive composition (2) was prepared in the same manner as in Example 1 except that 0.15 parts by mass of the above (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (2) was used instead of the above-mentioned adhesive composition (1).

(Example 3) (modulation of adhesive composition)

The adhesive composition (3) was prepared in the same manner as in Example 1 except that 0.08 parts by mass of the above (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (3) was used instead of the above-mentioned adhesive composition (1).

(Example 4) (modulation of adhesive composition)

Instead of using 0.33 parts by mass of the above CORONATE L (trimethylolpropane/toluene diisocyanate trimer), 0.25 parts by mass of an isocyanurate body of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) was used. The adhesive composition (4) was prepared in the same manner as in Example 1 except that the solid content of the product was 75 mass% of an ethyl acetate solution (manufactured by Nippon Polyurethane Co., Ltd.).

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (4) was used instead of the above-mentioned adhesive composition (1).

(Example 5) (modulation of adhesive composition)

Using 0.75 parts by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C) instead of using 0.5 mass The above 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C), Otherwise, the adhesive composition (5) was prepared in the same manner as in Example 4.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (5) was used instead of the above-mentioned adhesive composition (1).

(Example 6) (modulation of adhesive composition)

0.1 parts by mass of an organopolysiloxane having a polyoxyalkylene chain as a compound having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.), instead of using 0.05 parts by mass as described above An organopolyoxane having a polyoxyalkylene chain of a compound having an alkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.), The adhesive composition (6) was prepared in the same manner as in Example 4 except the above.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (6) was used instead of the above-mentioned adhesive composition (1).

(Example 7) (modulation of adhesive composition)

Using 0.67 parts by mass of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.), instead of using 0.33 parts by mass of the above CORONATE L (Adhesive agent was prepared in the same manner as in Example 2 except that the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct was 75 mass% in ethyl acetate solution, manufactured by Japan Polyurethane Industrial Co., Ltd.) Composition (7).

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (7) was used instead of the above-mentioned adhesive composition (1).

(Example 8) (modulation of adhesive composition)

Using 0.67 parts by mass of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.), instead of using 0.33 parts by mass of the above CORONATE L (Adhesive agent was prepared in the same manner as in Example 3 except that the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct was 75 mass% in ethyl acetate solution, manufactured by Japan Polyurethane Industrial Co., Ltd.) Composition (8).

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (8) was used instead of the above-mentioned adhesive composition (1).

(Example 9) (modulation of adhesive composition)

The adhesive composition (9) was prepared in the same manner as in Example 2 except that 0.15 parts by mass of the (meth)acrylic polymer 2 was used instead of 0.15 parts by mass of the above (meth)acrylic polymer 1.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (9) was used instead of the above-mentioned adhesive composition (1).

(Embodiment 10) (modulation of adhesive composition)

The adhesive composition (10) was prepared in the same manner as in Example 3 except that 0.08 parts by mass of the (meth)acrylic polymer 2 was used instead of 0.15 parts by mass of the above (meth)acrylic polymer 1.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (10) was used instead of the above-mentioned adhesive composition (1).

(Example 11) (modulation of adhesive composition)

0.1 parts by mass of polyoxyl-propyl-polyoxyethylidene-polyoxypropyl propyl block copolymer (trade name: Pluronic 25R-2, manufactured by ADEKA Co., Ltd.), instead of using 0.05 parts by mass as described above as having a polyoxygen extension An adhesive composition (11) was prepared in the same manner as in Example 2 except that the organopolysiloxane having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the compound of the alkyl chain. ).

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (11) was used instead of the above-mentioned adhesive composition (1).

(Embodiment 12) (modulation of adhesive composition)

0.5 parts by mass of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine (EMI-FSI) (manufactured by First Industrial Pharmaceutical Co., Ltd., IL-110) was used instead of 0.5 part by mass of the above 1 -butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C), except The adhesive composition (12) was prepared in the same manner as in Example 2.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (12) was used instead of the above-mentioned adhesive composition (1).

(Example 13) (modulation of adhesive composition)

The adhesive composition (13) was prepared in the same manner as in Example 1 except that 0.25 parts by mass of the above (meth)acrylic polymer 1 was not used.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (13) was used instead of the above-mentioned adhesive composition (1).

(Example 14) (modulation of adhesive composition)

The adhesive composition (14) was prepared in the same manner as in Example 1 except that 1.0 part by mass of the (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (14) was used instead of the above-mentioned adhesive composition (1).

(Example 15) (production of adhesive sheets)

The corona treatment surface coated on a polyethylene terephthalate film (trade name: Lumirror S-105, manufactured by Toray Film Processing Co., Ltd., thickness 75 μm, "PET #75" in Table 3) was used instead of the above polyethylene. An adhesive sheet was produced in the same manner as in Example 7 except that a film (trade name: NSO FILM, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm) was heated at 80 ° C for 1 minute to form an adhesive layer having a thickness of 20 μm.

(Comparative Example 1) (modulation of adhesive composition)

The above (meth)acrylic polymer 1, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., 25) was not used. An organopolysiloxane having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) as a compound having a polyoxyalkylene chain, and other examples 1 The adhesive composition (15) was prepared in the same manner.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (15) was used instead of the above-mentioned adhesive composition (1).

(Comparative Example 2) (modulation of adhesive composition)

0.15 parts by mass of (meth)acrylic polymer 1 is used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1, and 1.0 part by mass of isocyanurate body of hexamethylene diisocyanate is used (trade name) :CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) in place of 0.33 parts by mass of CORONATE L (75% by mass of the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct as a crosslinking agent) The adhesive composition (16) was prepared in the same manner as in Example 1 except that the Japan Polyurethane Industry Co., Ltd. was used.

(production of adhesive sheets)

An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (16) was used instead of the above-mentioned adhesive composition (1).

(experiment method) <Measurement of molecular weight>

The weight average molecular weight (Mw) of the polymer and the (meth)acrylic copolymer was measured using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8220GPC). The measurement conditions were as follows, and the molecular weight was determined by standard polystyrene conversion. ‧ Sample concentration: 0.2% by mass (tetrahydrofuran (THF) solution) ‧ Sample injection amount: 10 μl ‧ Eluent: THF ‧ Flow rate: 0.6 ml / min ‧ Measurement temperature: 40 ° C ‧ Column: Sample column: TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2)

Reference column: TSK gel Super H-RC (1) ‧ Detector: Differential Refractometer (RI)

<Measurement of Solvent Insoluble Component Rate>

Solvent-insoluble component ratio (gel ratio) After the measurement sample of the weight W1 was wrapped with a porous sheet made of tetrafluoroethylene resin and immersed in ethyl acetate for 1 week at room temperature, the measurement sample was dried and the acetic acid B was measured. The weight W2 of the ester-insoluble component was determined by substituting W1 and W2 into the following formula: solvent insoluble component ratio (gel fraction) [% by mass] = W2 / W1 × 100.

More specifically, the solvent insoluble component ratio (gel fraction) can be measured by the following method. Specifically, about 0.1 g of the measurement sample was wrapped in a bundle of tetrafluoroethylene resin having an average pore diameter of 0.2 μm, and the mouth was tied with a kite string. The total mass Wa (mg) of the porous sheet made of tetrafluoroethylene resin and the kite line was measured in advance. And the mass of the packet (the total mass of the adhesive layer and the packet) Wb (mg) was measured. The packet was placed in a spiral tube having a capacity of 50 mL (one spiral was used for one packet), and the spiral tube was filled with ethyl acetate. After allowing to stand at room temperature (typically 23 ° C) for 7 days, the above-mentioned packet was taken out and dried at 120 ° C for 2 hours, and the mass Wc (mg) of the dried packet was measured. Solvent-insoluble component ratio (gel fraction) (% by mass) of the adhesive layer By substituting the above Wa, Wb, and Wc into the following equation: Solvent-insoluble component ratio (gel fraction) [% by mass] = (Wc - Wa) / (Wb - Wa) × 100.

As the porous sheet made of the above-mentioned tetrafluoroethylene resin, the trade name "NITOFLON (registered trademark) NTF1122" manufactured by Nitto Denko Corporation can be used. Further, the solvent-insoluble component ratio of the adhesive layer of the present invention is 50 to 90% by mass, preferably 55 to 87% by mass, more preferably 60 to 85% by mass. When the solvent-insoluble component ratio exceeds 90% by mass, the strength (adhesion) decreases, and when it is less than 50% by mass, the cohesive force of the adhesive (layer) may decrease and the paste may remain. Further, the method for evaluating the solvent insoluble component ratio was measured according to the methods and conditions described in the following examples.

<(measurement of surface resistivity)>

After the adhesive sheets of the respective examples and the comparative examples were allowed to stand in an environment of 23 ° C × 50% RH for 2 hours, the separator was peeled off, and adhesion was measured by a surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450 type). Surface resistivity of the surface of the agent (pasta). The application was carried out with a voltage of 100 V and an application time of 30 seconds. Further, the surface resistivity of the adhesive layer of the present invention is 10 ³ to 10 ¹³ Ω/□, preferably 10 ⁴ to 10 ¹³ Ω/□, more preferably 10 ⁶ to 10 ¹³ Ω/□. When it is in the above range, it is useful to suppress the peeling static voltage and to impart antistatic properties.

<Following reliability (fixed load peeling test)>

The adhesive sheets of the respective examples and comparative examples were cut into a size of 10 mm in width and 60 mm in length, and the release liner was peeled off, and then pressed against a glass with a 2 kg hand roller (the product name "MICROSLIDE GLASS" manufactured by Matsunaga Glass Co., Ltd." The surface of the width: 70 mm, length: 100 mm, thickness: 1.3 mm), and an evaluation sample was produced.

After the above lamination, after standing for 30 minutes in an environment of 23 ° C × 50% RH, a fixed load (3 g) was placed on the one end side of the adhesive sheet 1. The tape sample was peeled off at a fixed load so that the peeling angle became 90°. The length of 10 mm was used as the remaining length, and the time until the remaining portion of 50 mm in length was peeled off was measured. The measurement is at 23 ° C It is carried out under the environment of ×50% RH.

In the present invention, the evaluation of the peeling time under a fixed load of 2 minutes or more was good, and the evaluation of less than 2 minutes was bad. When the peeling time is 2 minutes or longer, it is useful to prevent adhesion (adhesion) of the chemical solution.

<Measurement of peeling static voltage>

The adhesive sheet 1 was cut into a size of 70 mm in width and 120 mm in length, and the release liner was peeled off, and then pressed by a hand-pressing roll to a glass 20 (Microslonide GLASS) manufactured by Songlang Glass Co., Ltd. The surface of the width: 70 mm, length: 100 mm, thickness: 1.3 mm) so that the end of one side protrudes by 20 mm.

After standing for one day in an environment of 23 ° C × 50% RH, the sample was placed at a specific position of the sample fixing table 30 as shown in FIG. The end portion of the one side protruding by 20 mm was fixed to an automatic winder, and peeling was performed at a peeling angle of 150° and a stretching speed of 10 m/min. The potential of the surface of the glass 20 produced at this time was measured by a potential measuring device 40 (KSD-0103, manufactured by Kasuga Electric Co., Ltd.) fixed at a specific position as a value of the peeling static voltage. The measurement was carried out in an environment of 23 ° C × 50% RH. Further, as the peeling static voltage, the absolute value is preferably 1.0 kV or less, more preferably 0.9 kV or less. If it is within the above range, it is useful to prevent dust collection or electrostatic damage caused by static electricity.

As shown in the above Table 3, it was confirmed that in all of the examples, the solvent insoluble component ratio and the surface resistivity of the adhesive layer were within a desired range, and it was possible to suppress the peeling static voltage, that is, excellent in antistatic property, and then be reliable. Excellent in properties, that is, excellent in immersion resistance.

On the other hand, in Comparative Example 1, it was confirmed that the surface resistivity exceeded 10 ¹³ Ω/□, and the peeling static voltage was not sufficiently suppressed, and the antistatic property was inferior. In Comparative Example 2, it was confirmed that the solvent insoluble component ratio of the adhesive layer exceeded 90% by mass. Then, the reliability is insufficient, and the immersion resistance of the chemical solution is poor.

Claims (22)

An adhesive layer for treating a chemical solution, which is formed by an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 ° C, and a solvent insoluble component ratio of 50 to 90% by mass. And the surface resistivity is 10 ³ ~ 10 ¹³ Ω / □. The adhesive layer for liquid chemical treatment according to claim 1, wherein the adhesive composition contains a (meth)acrylic polymer (B), and the weight average molecular weight of the (meth)acrylic polymer (B) is 1000. The above (but less than 30,000) and comprising a (meth)acrylic monomer having an alicyclic structure represented by the following formula (1) as a monomer component, CH ₂ =C(R ¹ )COOR ² (1) [In the formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic hydrocarbon group having an alicyclic structure]. The adhesive layer for liquid chemical treatment according to claim 1, wherein the above adhesive composition contains an ionic compound (C). The adhesive layer for liquid chemical treatment according to claim 1, wherein the above adhesive composition contains the compound (D) having a polyoxyalkylene chain. The adhesive layer for liquid chemical treatment according to claim 2, wherein the adhesive composition contains 0.005 to 2 parts by mass of the above (meth)acrylic polymer (B) based on 100 parts by mass of the polymer (A). . The adhesive layer for chemical treatment according to claim 3, wherein the adhesive composition contains 0.005 to 2 parts by mass of the ionic compound (C) per 100 parts by mass of the polymer (A). The adhesive layer for liquid chemical treatment according to claim 4, wherein the above-mentioned adhesive composition contains 0.005 to 1 part by mass of the above compound having a polyoxyalkylene chain with respect to 100 parts by mass of the polymer (A). ). The adhesive layer for liquid chemical treatment according to claim 1, wherein the polymer (A) is a (meth)acrylic polymer (a). The adhesive layer for liquid chemical treatment according to claim 2, wherein the alicyclic hydrocarbon group of the above (meth)acrylic monomer having an alicyclic structure has a bridged ring structure. The adhesive layer for chemical treatment according to claim 2, wherein the (meth)acrylic polymer (B) has a glass transition temperature of 0 to 300 °C. The adhesive layer for liquid chemical treatment according to claim 3, wherein the ionic compound (C) is an alkali metal salt and/or an ionic liquid. The adhesive layer for treating a liquid medicine according to claim 11, wherein the alkali metal salt is a lithium salt. The adhesive layer for liquid chemical treatment according to claim 11, wherein the ionic liquid is one or more selected from the group consisting of a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt, and a phosphorus-containing phosphonium salt. The adhesive layer for chemical treatment according to claim 11, wherein the ionic liquid contains one or more cations represented by the following general formulae (C1) to (C5), [R in the formula (C1) represents _a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _b and R _{c are the} same or different and represent hydrogen or a carbon number of 1 to 16. a hydrocarbon group, a part of the above hydrocarbon group may be a hetero atom-substituted functional group, but in the case where the nitrogen atom contains a double bond, R _c does not exist; [wherein R _d in the formula (C2) represents a carbon number of 2 to 20 a hydrocarbon group, a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _e , R _f and R _{g are the} same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the above hydrocarbon group may be substituted by a hetero atom. Functional group;] [ _Rh in the formula (C3) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R _i , R _j and R _{k are the} same or different and represent hydrogen. Or a hydrocarbon group having 1 to 16 carbon atoms, a part of the above hydrocarbon group may be a hetero atom-substituted functional group; [wherein Z in the formula (C4) represents a nitrogen, sulfur or phosphorus atom, R _l , R _m , R _n and R _o the same or different, represent a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon groups may be substituted with a portion of the heteroatom of the functional group is, but, when in the case where Z is a sulfur atom, the R & lt absent _o In the] [Formula (C5) R _P represents a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon groups may be a part of the hetero atoms is substituted by a functional group]. The adhesive layer for liquid chemical treatment according to claim 4, wherein the compound (D) having a polyoxyalkylene chain is an organopolyoxane having a polyoxyalkylene chain. The adhesive layer for treating a liquid medicine according to claim 15, wherein the organopolyoxane having a polyoxyalkylene chain is an organopolyoxane represented by the following formulas (D1) to (D3), In the [Formula (D1) R ₁ is a monovalent organic group, R _2, R ₃ and R ₄ is alkylene, R ₅ is hydrogen or an organic group, m and n are integers of 0 to 1000, but, m, n is not 0 at all, a and b are integers from 0 to 1000, and a and b are not 0 at the same time;] [R ₁ in formula (D2) is a monovalent organic group, and R ₂ , R ₃ and R ₄ are Alkyl, R ₅ is hydrogen or organic, m is an integer from 1 to 2000, a and b are integers from 0 to 1000, but a and b are not 0 at the same time;] [R ₁ in formula (D3) Is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, m is an integer from 1 to 2000, and a and b are integers from 0 to 1000, but a, b Not at the same time 0]. The adhesive layer for chemical treatment according to claim 8, which contains a hydroxyl group-containing monomer as a monomer component constituting the (meth)acrylic polymer (a). The adhesive layer for chemical treatment according to claim 8, wherein the average amount of the oxygen-extended alkyl unit is 5.0% by mass or less based on the total amount of the monomer components constituting the (meth)acryl-based polymer (a). A reactive monomer having an oxygen-containing alkylene group having a molar number of 3 to 40. An adhesive sheet for treating a liquid medicine, characterized in that it is formed with an adhesive layer according to any one of claims 1 to 18 on at least one side of the support. The adhesive sheet for treating a liquid medicine according to claim 19, wherein the support is an antistatic treated plastic film. A surface protection sheet comprising the adhesive sheet for liquid chemical treatment according to claim 19 or 20. A glass substrate with a surface protection sheet attached to a glass substrate with a surface protection sheet as claimed in claim 21.