CN110655882A - Adhesive composition, adhesive sheet, and optical member - Google Patents

Adhesive composition, adhesive sheet, and optical member Download PDF

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Publication number
CN110655882A
CN110655882A CN201910572736.9A CN201910572736A CN110655882A CN 110655882 A CN110655882 A CN 110655882A CN 201910572736 A CN201910572736 A CN 201910572736A CN 110655882 A CN110655882 A CN 110655882A
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China
Prior art keywords
pressure
sensitive adhesive
meth
mass
adhesive sheet
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Granted
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CN201910572736.9A
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Chinese (zh)
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CN110655882B (en
Inventor
片冈贤一
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings

Abstract

An object of the present invention is to provide an adhesive composition that can provide an adhesive sheet (adhesive layer) having the following properties: the pressure-sensitive adhesive sheet for surface protection has excellent antistatic properties when the pressure-sensitive adhesive sheet is peeled from the surface of an optical member (for example, a polarizing film) to which the pressure-sensitive adhesive sheet is attached, and has excellent adhesion (adhesiveness) between the surface of the optical member and a layer such as an interlayer filler when a layer such as an interlayer filler is newly provided on the surface of the optical member after the pressure-sensitive adhesive sheet is attached. The adhesive composition of the present invention contains an adhesive polymer, a polyether compound containing 3 or more polyoxyalkylene chains in the molecule and no siloxane chain, and an ionic compound.

Description

Adhesive composition, adhesive sheet, and optical member
Technical Field
The invention relates to an adhesive composition, an adhesive sheet and an optical member. The pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition is suitable for use in applications such as plastic products that are likely to generate static electricity (for example, liquid crystal display panels, Plasma Display Panels (PDPs), organic Electroluminescence (EL) displays, and the like), and is particularly useful as a surface protective film used for the purpose of protecting the surface of optical members (for example, polarizing films, wavelength plates, retardation plates, optical compensation films, reflection sheets, brightness enhancement films, and touch panel members used in liquid crystal displays, and the like).
Background
The pressure-sensitive adhesive sheet (surface protective film) generally has a structure in which a pressure-sensitive adhesive layer is provided on a film-like base film. The pressure-sensitive adhesive sheet is used for the purpose of protecting an adherend (protected object) from damage or contamination during processing, transportation, or the like by being adhered to the adherend via the pressure-sensitive adhesive layer. For example, a panel of a liquid crystal display is formed by bonding an optical member such as a polarizing film or a wavelength plate to a liquid crystal cell via an adhesive layer. In the manufacture of the liquid crystal display panel, the polarizing film attached to the liquid crystal cell is once manufactured in a roll form, and then unwound from the roll and cut into a desired size according to the shape of the liquid crystal cell. Here, in the process of processing or transporting the polarizing film, the polarizing film may be damaged by friction with a transport roller or the like, and therefore, in order to prevent this, a measure is taken to protect the polarizing film by bonding an adhesive sheet to one surface or both surfaces (typically one surface) of the polarizing film. Then, the pressure-sensitive adhesive sheet is peeled and removed at a stage where it becomes unnecessary.
Generally, since the adhesive sheet (surface protective film) and the optical member are made of plastic materials, they have high electrical insulation properties and generate static electricity due to friction and peeling. Therefore, static electricity is likely to be generated even when the adhesive sheet is peeled off from an optical member such as a polarizing film, and if a voltage is applied to the liquid crystal in a state where the static electricity remains, there is a concern that the alignment of the liquid crystal molecules is lost and the panel is broken. In addition, the presence of static electricity causes dust to be attracted and reduces workability. In view of the above, in order to impart antistatic properties to the adhesive layer itself constituting the adhesive sheet, a procedure has been performed in which a polyether-modified polysiloxane and an ionic compound that function as an antistatic agent are incorporated into an adhesive (adhesive composition) (see patent document 1).
In some cases, after the pressure-sensitive adhesive sheet (surface protective film) is peeled off from the surface of the optical member, a layer having another function is provided on the surface of the optical member. For example, a layer of an interlayer filler or the like may be provided for bonding the surface of an optical member such as a polarizing film or a layer having a touch panel function to a protective layer or the like made of glass, plastic or the like (see patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-236266
Patent document 2: japanese patent laid-open publication No. 2016-113467
Disclosure of Invention
Problems to be solved by the invention
However, when an adhesive sheet (adhesive layer) formed of an adhesive having polyether-modified polysiloxane is attached to an optical member such as a polarizing film and then peeled off at an unnecessary stage, the polyether-modified polysiloxane component contained in the adhesive sheet (adhesive layer) is transferred to the surface of the optical member, and a layer of an interlayer filler or the like provided on the surface of the optical member thereafter and the adhesiveness (adhesiveness) to the surface of the optical member from which the adhesive sheet is peeled off are deteriorated.
Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition that can give an adhesive sheet (adhesive layer) as follows: the pressure-sensitive adhesive sheet for surface protection has excellent antistatic properties when the pressure-sensitive adhesive sheet is peeled from the surface of an optical member (for example, a polarizing film) to which the pressure-sensitive adhesive sheet is attached, and excellent adhesion (adhesiveness) between the surface of the optical member and a layer such as an interlayer filler when a layer such as an interlayer filler is newly provided on the surface of the optical member after the pressure-sensitive adhesive sheet is peeled.
Means for solving the problems
That is, the adhesive composition of the present invention contains an adhesive polymer, a polyether compound containing 3 or more polyoxyalkylene chains in the molecule and not containing a siloxane chain, and an ionic compound.
In the adhesive composition of the present invention, the adhesive polymer is preferably a (meth) acrylic polymer and/or a urethane polymer.
In the adhesive composition of the present invention, the end of the polyoxyalkylene chain preferably contains at least one selected from the group consisting of a linear or branched alkyl group, a saturated fatty acid residue, and an unsaturated fatty acid residue.
The pressure-sensitive adhesive sheet of the present invention preferably has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on at least one side of a substrate film.
The optical member of the present invention is preferably one having the adhesive sheet bonded thereto.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention is useful in that an adhesive sheet having an adhesive layer formed from an adhesive composition containing an adhesive polymer, an ionic compound as an antistatic agent, and a specific polyether compound is excellent in antistatic properties when peeled off at a stage where the adhesive sheet is not required after being stuck to the surface of an optical member such as a polarizing film, and in adhesion (adhesiveness) between the surface of the optical member from which the adhesive sheet is peeled off and a layer such as an interlayer filler newly provided on the surface of the optical member.
Drawings
Fig. 1 is a schematic cross-sectional view showing one configuration example of the adhesive sheet (surface protective film) of the present invention.
FIG. 2 is a schematic diagram of the potential measuring section.
Description of the symbols
1: antistatic layer
2: substrate film
3: adhesive layer
4: diaphragm
10: adhesive sheet (surface protective film)
11: glass plate
12: adhered object (film with hard coating)
13: sample fixing table
14: electric potential measuring device
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
< Overall Structure of adhesive sheet (surface protective film) >
The pressure-sensitive adhesive sheet disclosed herein is in a form generally referred to as a pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, or the like, and is particularly suitable as a surface protective film for protecting the surface of an optical member (for example, an optical member used as a constituent element of a liquid crystal display panel such as a polarizing film or a wavelength plate) during processing or transportation of the optical member. The pressure-sensitive adhesive layer in the surface protective film is typically formed continuously, but is not limited to this form, and may be formed in a regular or irregular pattern such as dots or stripes, for example. The pressure-sensitive adhesive sheet (surface protective film) disclosed herein may be in the form of a roll or a sheet.
< substrate film >
The pressure-sensitive adhesive sheet (surface protective film) of the present invention preferably has a substrate film. In the technique disclosed herein, the resin material constituting the base film may be used without particular limitation, and for example, a material excellent in characteristics such as transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, flexibility, and dimensional stability is preferably used. In particular, since the base film has flexibility, the adhesive composition can be applied by a roll coater or the like and can be wound up in a roll form, which is useful.
The substrate film is preferably formed of, for example, a polyester-based polymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate; cellulose polymers such as diacetylcellulose and triacetylcellulose; a polycarbonate-series polymer; acrylic polymers such as polymethyl methacrylate; a plastic film made of a resin material containing a cyclic olefin polymer or the like as a main resin component (a main component in the resin component, typically, a component accounting for 50% by mass or more) is used as the base film. Other examples of the resin material include styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; olefin polymers such as polyethylene, polypropylene, cyclic or norbornene-structured polyolefins, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide polymers such as nylon 6, and aromatic polyamide; and the like as the resin material. Examples of the resin material include imide polymers, sulfone polymers, polyethersulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aromatic ester polymers, polyacetal polymers, and epoxy polymers. Or a substrate film formed of a blend of 2 or more of the above polymers.
As the base film, a plastic film made of a transparent thermoplastic resin material is preferably used. Among the above plastic films, a polyester film is more preferable. The polyester film as used herein refers to a film containing, as a main resin component, a polymer material (polyester resin) having a main skeleton based on ester bonds, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. The polyester film has properties preferable as a base film of an adhesive sheet (surface protective film) such as excellent optical properties and dimensional stability, and the polyester film itself has a property of being easily charged.
Various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (such as a pigment and a dye) may be added to the resin material constituting the base film as needed. For example, a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and coating with a primer can be performed. Such surface treatment may be, for example, treatment for improving adhesion between the base film and the pressure-sensitive adhesive layer (thickening property of the pressure-sensitive adhesive layer).
The pressure-sensitive adhesive sheet (surface protective film) of the present invention may also use an antistatic-treated plastic film as the substrate film. The use of the substrate film is preferable because electrification of the pressure-sensitive adhesive sheet itself can be suppressed at the time of peeling. The base film is a plastic film, and by applying antistatic treatment to the plastic film, the electrification of the pressure-sensitive adhesive sheet itself can be reduced, and a film excellent in antistatic ability to an adherend can be obtained. The method for imparting the antistatic function is not particularly limited, and conventionally known methods can be used, and examples thereof include: a method of applying an antistatic resin comprising an antistatic agent and a resin component, and a conductive resin comprising a conductive polymer and a conductive substance; a method of evaporating or plating a conductive material; and a method of mixing an antistatic agent or the like; a method of forming an antistatic layer, and the like.
The thickness of the base film is usually 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the base film is within the above range, the adhesion workability to an adherend and the peeling workability from an adherend are excellent, and therefore, the base film is preferable.
The pressure-sensitive adhesive sheet disclosed herein may be implemented to further include an antistatic layer and other layers in addition to the base material film and the pressure-sensitive adhesive layer. Examples of the other layer include an antistatic layer and a primer layer (adhesion-promoting layer) for increasing the adhesion of the adhesive layer.
< adhesive composition >
The pressure-sensitive adhesive composition of the present invention is not particularly limited as long as it contains a pressure-sensitive adhesive polymer having pressure-sensitive adhesiveness, and a pressure-sensitive adhesive layer can be formed from the pressure-sensitive adhesive composition. As the above adhesive composition, for example: acrylic adhesives, urethane adhesives, synthetic rubber adhesives, natural rubber adhesives, and the like. Among these, the adhesive polymer is more preferably a (meth) acrylic polymer and/or a urethane polymer, and further preferably an acrylic adhesive containing a (meth) acrylic polymer and/or a urethane adhesive containing a urethane polymer, and particularly preferably an acrylic adhesive using the adhesive polymer, that is, a (meth) acrylic polymer.
< acrylic pressure-sensitive adhesive >
When an acrylic pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer, a (meth) acrylic polymer, which is a pressure-sensitive adhesive polymer constituting the acrylic pressure-sensitive adhesive, can be used as a main monomer of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms as a raw material monomer constituting the polymer. As the (meth) acrylic monomer, 1 or 2 or more species can be used. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the peeling force (adhesive force) to an adherend (protected object) can be easily controlled to a low level, and a pressure-sensitive adhesive sheet (surface protective film) excellent in light peeling property and removability can be obtained. In the present invention, the (meth) acrylic polymer refers to an acrylic polymer and/or a methacrylic polymer, and the (meth) acrylate refers to an acrylate and/or a methacrylate.
Specific examples of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.
Among these, when the adhesive sheet of the present invention is used as a surface protective film, preferred monomers include (meth) acrylic monomers having an alkyl group having 4 to 14 carbon atoms, such as n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate. Particularly, by using a (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms, the peeling force (adhesive force) to an adherend can be easily controlled to a low level, and the removability is excellent.
The (meth) acrylic monomer containing an alkyl group having 1 to 14 carbon atoms is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, further preferably 85 to 99.9% by mass, and particularly preferably 90 to 99.5% by mass, based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer. If the content is less than 70% by mass, the adhesive composition will have an appropriate wettability and the cohesive force of the adhesive layer will be poor, which is not preferable.
In the adhesive composition of the present invention, the (meth) acrylic polymer preferably contains a hydroxyl group-containing (meth) acrylic monomer as a raw material monomer. As the hydroxyl group-containing (meth) acrylic monomer, 1 or 2 or more species can be used. By using the hydroxyl group-containing (meth) acrylic monomer, crosslinking and the like of the pressure-sensitive adhesive composition can be easily controlled. Therefore, it is easy to control the balance between the improvement of wettability by the flow and the reduction of peeling force (adhesive force) during peeling.
Examples of the hydroxyl group-containing (meth) acrylic monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, 4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, and the like. The use of a hydroxyl group-containing (meth) acrylic monomer having an alkyl group having 4 or more carbon atoms is particularly preferable because light peeling is facilitated at the time of high-speed peeling.
The hydroxyl group-containing (meth) acrylic monomer is contained in an amount of preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass, based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer. When the amount is within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the pressure-sensitive adhesive layer to be obtained can be easily controlled, and therefore, the preferable range is obtained.
Further, as the other polymerizable monomer component, in order to easily obtain the balance of adhesive properties, a polymerizable monomer or the like for adjusting the glass transition temperature and the peelability of the (meth) acrylic polymer may be used within a range not impairing the effect of the present invention by setting the Tg to 0 ℃ or lower (usually-100 ℃ or higher).
As the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms used in the (meth) acrylic polymer and the polymerizable monomer other than the hydroxyl group-containing (meth) acrylic monomer, a carboxyl group-containing (meth) acrylic monomer can be used. The use of the carboxyl group-containing (meth) acrylic monomer is preferable because it suppresses an increase in adhesive strength of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) with time, and is excellent in removability, prevention of an increase in adhesive strength, and workability, and also excellent in cohesive force and shear force of the pressure-sensitive adhesive layer.
Examples of the carboxyl group-containing (meth) acrylic monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
The carboxyl group-containing (meth) acrylic monomer is preferably 0 to 3% by mass, more preferably 0 to 2% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0.001 to 0.5% by mass, based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer. When the amount is within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the pressure-sensitive adhesive layer to be obtained can be easily controlled, and therefore, the preferable range is obtained.
When the hydroxyl group-containing (meth) acrylic monomer and the carboxyl group-containing (meth) acrylic monomer are used in combination, the carboxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 0.005 to 0.1% by mass based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer. By adjusting the content within the above range, a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having further excellent removability and prevention of increase in adhesive strength can be obtained, and this is effective.
The other polymerizable monomer may be used without particular limitation as long as the characteristics of the present invention are not impaired. For example: a cohesive force/heat resistance improving component such as a cyano group-containing monomer, a vinyl ester monomer, or an aromatic vinyl monomer, a peeling force (adhesive force) improving component such as an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloyl morpholine, or a vinyl ether monomer, or a component having a functional group that functions as a crosslinking base point. Among them, nitrogen-containing monomers such as a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and N-acryloylmorpholine are preferably used. The use of the nitrogen-containing monomer is useful because it can secure an appropriate peeling force (adhesive force) without causing lifting, peeling, or the like, and can obtain an adhesive sheet (surface protective film) having a more excellent shear force. These polymerizable monomers may be used in 1 or 2 or more species.
Examples of the cyano group-containing monomer include: acrylonitrile, methacrylonitrile.
Examples of the amide group-containing monomer include: acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N' -methylenebisacrylamide, N-dimethylaminopropylacrylamide, N-dimethylaminopropylmethacrylamide, diacetoneacrylamide and the like.
Examples of the imide group-containing monomer include: cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, and the like.
Examples of the amino group-containing monomer include: aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, and the like.
Examples of the vinyl ester monomer include: vinyl acetate, vinyl propionate, vinyl laurate, and the like.
Examples of the aromatic vinyl monomer include: styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrenes, and the like.
Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether, and the like.
Examples of the vinyl ether monomer include: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
In the present invention, the other polymerizable monomer is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on 100% by mass of the total amount of the monomer components constituting the (meth) acrylic polymer. The other polymerizable monomers can be appropriately adjusted to obtain desired characteristics.
The (meth) acrylic polymer may further contain an oxyalkylene group-containing reactive monomer as a monomer component. By using, as the base polymer, a (meth) acrylic polymer containing the oxyalkylene group-containing reactive monomer as a monomer component, the compatibility of the base polymer with the polyether compound is improved, bleeding out of an adherend can be suitably suppressed, and a pressure-sensitive adhesive composition having stain resistance (low staining property) can be obtained.
The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 10 to 200 ten thousand, more preferably 20 to 100 ten thousand, still more preferably 30 to 80 ten thousand, and particularly preferably 30 to 70 ten thousand. When the weight average molecular weight is less than 10 ten thousand, the cohesive force of the binder layer becomes small, and thus paste residue tends to occur. On the other hand, when the weight average molecular weight is more than 200 ten thousand, the fluidity of the polymer is lowered, the wetting of the adherend (for example, polarizing film) becomes insufficient, and there is a tendency that the swelling occurs between the adherend and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (surface protective film). The weight average molecular weight means a weight average molecular weight measured by GPC (gel permeation chromatography).
The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ℃ or lower, more preferably-20 ℃ or lower, still more preferably-40 ℃ or lower, and particularly preferably-50 ℃ or lower (usually-100 ℃ or higher). When the glass transition temperature is higher than 0 ℃, the polymer is difficult to flow, and wetting of a polarizing film as an optical member, for example, becomes insufficient, and expansion tends to occur between the polarizing film and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (surface protective film). Among them, by setting the glass transition temperature to-60 ℃ or lower, in particular, an adhesive layer excellent in wettability to an optical member (for example, a polarizing film) and light peelability can be easily obtained. The glass transition temperature of the (meth) acrylic polymer can be adjusted to fall within the above range by appropriately changing the monomer components and the composition ratio used.
The polymerization method of the (meth) acrylic polymer is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization, and particularly, solution polymerization is a more preferable mode from the viewpoint of handling properties and characteristics such as low contamination to an adherend (protected object). The polymer obtained may be any of random copolymers, block copolymers, alternating copolymers, graft copolymers, and the like.
< urethane adhesive >
When a urethane adhesive is used for the adhesive layer, any appropriate urethane adhesive can be used. As such a urethane adhesive, an adhesive comprising an adhesive polymer obtained by reacting a polyol with a polyfunctional isocyanate compound, that is, an adhesive comprising a urethane polymer, or an adhesive comprising an adhesive polymer obtained by reacting a urethane prepolymer with a polyfunctional isocyanate compound, that is, an adhesive comprising a urethane polymer, is preferably used.
Examples of the polyhydric alcohol include: polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, castor oil polyols, and the like. The number of the polyhydric alcohols may be only 1, or may be 2 or more.
The polyester polyol is obtained, for example, by esterification of a polyol component with an acid component.
Examples of the polyol component include: ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like. Examples of the acid component include: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, anhydrides thereof, and the like.
Examples of the polyether polyol include polyether polyols obtained by addition polymerization of an epoxide such as ethylene oxide, propylene oxide, or butylene oxide using water, a low-molecular-weight polyol (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), a bisphenol (bisphenol a, etc.), or dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.), etc., as an initiator. Specific examples thereof include: polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Examples of the polycaprolactone polyol include caprolactone polyesterdiols obtained by ring-opening polymerization of cyclic ester monomers such as e-caprolactone and e-valerolactone.
Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; polycarbonate polyols obtained by subjecting the polyol component to ester exchange condensation with carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate; a copolymerized polycarbonate polyol obtained by using 2 or more of the above polyol components in combination; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a carboxyl group-containing compound to an esterification reaction; polycarbonate polyols obtained by etherification of the above-mentioned various polycarbonate polyols with a hydroxyl group-containing compound; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and an ester compound to an ester exchange reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to an ester exchange reaction; polyester polycarbonate polyols obtained by polycondensation of the above polycarbonate polyols with dicarboxylic acid compounds; a copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with an epoxide; and so on.
Examples of the castor oil polyol include castor oil polyols obtained by reacting a castor oil fatty acid with the above polyol component. Specific examples thereof include castor oil polyols obtained by reacting castor oil fatty acids with polypropylene glycol.
The number average molecular weight (Mn) of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000. By adjusting the number average molecular weight (Mn) of the polyol to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore, the adhesive can be applied without involving air bubbles.
Examples of the polyfunctional isocyanate compound include: aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene Diisocyanate (HDI) and dimer acid diisocyanate, alicyclic isocyanates such as cyclopentene diisocyanate, cyclohexene diisocyanate, isophorone diisocyanate (IPDI) and 1, 3-bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and Xylylene Diisocyanate (XDI), and aromatic isocyanates such as allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonimine bond, and the like,
Figure BDA0002111297040000111
Modified polyisocyanates obtained by modifying the above isocyanate compounds with diazinetrione bonds or the like. For example, commercially available products include trade names of Takenate 300S, Takenate500, Takenate 600, Takenate D165N, and Takenate D178N (manufactured by Mitsui chemical Co., Ltd.), Sumidol T80, Sumidol L, Desmodur N3400 (manufactured by Mitsui Bayer Urethane Co., Ltd.), MILLONATE MR, MILLONATE MT, CORONATE L, CORONATE HL, and CORONATE HX (manufactured by Tosoh corporation). These isocyanate compounds may be used alone, or 2 or more kinds thereof may be mixed and used, or a 2-functional isocyanate compound and a 3-functional or more isocyanate compound may be used in combination.
The equivalent ratio of NCO groups to OH groups (NCO groups/OH groups) in the polyol and polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.1 to 3.0, still more preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0. It is preferable to adjust the equivalent ratio of NCO group/OH group to the above range because the re-peeling of the adhesive force can be suppressed.
< polyether Compound containing not less than 3 polyoxyalkylene chains in the molecule and containing no siloxane chain >
The adhesive composition of the present invention is characterized by containing a polyether compound containing not less than 3 polyoxyalkylene chains in a molecule and not containing a siloxane chain. The adhesive composition containing the polyether compound is preferably an embodiment because it can provide an adhesive sheet (adhesive layer) having excellent antistatic properties by interaction with an ionic compound, and further, the adhesive sheet is excellent in adhesion (adhesiveness) between a layer such as an interlayer filler provided on the surface of an adherend (for example, an optical member such as a polarizing film) after the adhesive sheet is peeled off from the adherend and the surface of the adherend after the adhesive sheet is peeled off. The "silicone chain" refers to a structure including a siloxane bond, and examples of the compound having a silicone chain include polydimethylsiloxane.
The polyether compound is a polyether compound having 3 or more polyoxyalkylene chains in the molecule, and preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. When the number of the polyoxyalkylene chain is 3 or more, the interaction with the ionic compound is enhanced, and the antistatic property is excellent, so that the polyoxyalkylene chain is preferable. The polyoxyalkylene chain is a polyoxyalkylene chain having 2 or more oxyalkylene units, and the polyoxyalkylene chain may be the same or different, and the number of the polyoxyalkylene chain is 3 or more.
The oxyalkylene unit is not particularly limited, and may be linear or branched, and examples thereof include: oxymethylene, oxyethylene, oxyalkylene, oxypropylene, oxybutylene, oxyethylene-oxypropylene block copolymers, oxyethylene-oxybutylene block copolymers, oxyethylene-oxypropylene random copolymers and the like, with oxyethylene or oxypropylene groups and the like being preferred.
The number of repeating units of the polyoxyalkylene is preferably 2 or more and 200 or less, and when the number of repeating units is more than 200, crystallization is caused and antistatic property is lowered, which is not preferable.
The end of the polyoxyalkylene chain may be a linear or branched alkyl group such as a hydrogen group, a methyl group or an ethyl group, an unsaturated fatty acid residue such as an oleic acid residue, a saturated fatty acid residue such as an isostearic acid residue, a carboxyl group, or the like, and more preferably the end of the polyoxyalkylene chain contains at least one selected from a linear or branched alkyl group, a saturated fatty acid residue, and an unsaturated fatty acid residue.
The polyoxyalkylene chain ends may be the same or different in the molecule. The presence of an alkyl group, an unsaturated fatty acid residue, and a saturated fatty acid residue as a low-polarity component (low-polarity group) is preferable because the ionic compound interacting with the polyoxyalkylene chain site is likely to segregate on the surface of the pressure-sensitive adhesive layer (the interface between the pressure-sensitive adhesive layer and the air, or the interface between the pressure-sensitive adhesive layer and the separator), and is excellent in antistatic properties, and the wettability of an interlayer filler or the like is improved, whereby the residual adhesive strength of the interlayer filler or the like is excellent. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an isononyl group, the saturated fatty acid residue is preferably a saturated fatty acid residue having 1 to 20 carbon atoms such as a butyric acid residue, a caproic acid residue, a lauric acid residue, a myristic acid residue, a palmitic acid residue, a stearic acid residue, and an isostearic acid residue, and the unsaturated fatty acid group is preferably an unsaturated fatty acid group having 1 to 20 carbon atoms such as a crotonic acid residue, a myristoleic acid residue, a palmitoleic acid residue, an oleic acid residue, a elaidic acid residue, and a cis.
The following chemical formulas 1 to 9 are chemical formulas exemplifying the above polyether compound, and the polyether compound in which chemical formula 1 is glycerol, chemical formula 2 is trimethylolpropane, chemical formula 3 is diglycerol, chemical formula 4 is pentaerythritol, chemical formula 5is methylglycoside, chemical formulas 6 and 7 are sorbitan fatty acid esters, chemical formula 8is sorbitan, and chemical formula 9 is castor oil is used.
In the following chemical formulas 1 to 9, R1 is a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutenyl group), and may be a homopolymer, a block copolymer, or a random copolymer. The number of repeating alkylene oxide units is preferably 2 to 200. When the number of repeating units is more than 200, crystallization is likely to occur, and antistatic property is lowered, and when it is less than 2, interaction with an ionic compound is lowered. This is not preferred because of the reduced antistatic properties. R1 may have the same or different structure in the molecule of the polyether compound.
R2 in the following chemical formulae 1 to 9 may be a linear or branched alkyl group such as a hydrogen group, a methyl group, an ethyl group, an unsaturated fatty acid residue such as an oleic acid residue, a saturated fatty acid residue such as an isostearic acid residue, a carboxyl group, or the like, and R2 preferably contains at least one selected from a linear or branched alkyl group, a saturated fatty acid residue, and an unsaturated fatty acid residue. R2 may have the same or different structure in the molecule of the polyether compound.
[ chemical formula 1]
Figure BDA0002111297040000131
[ chemical formula 2]
Figure BDA0002111297040000132
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
Figure BDA0002111297040000144
[ chemical formula 7]
[ chemical formula 8]
Figure BDA0002111297040000152
[ chemical formula 9]
Figure BDA0002111297040000153
Specific examples of the polyether compound include those having a polyoxyalkylene chain number of 3, such as GP250, GP400, GP600, GP1000, GP1500, GP3000, GP4000 (manufactured by Sanyo chemical Co., Ltd.), G-450, G-750, G-1200, TD-4S, GT-10IS, GT-20IS, GT-30IS, GM-8IS, GM-10IS, GM-15IS, GM-20IS, GM-30IS, GM-60IS, S-753, and 43TT-2500, as polyoxyethylene polyoxypropylene trimethylolpropane, 10TT-4500, polyoxyethylene polyoxypropylene glyceryl ether 50TG-32 (manufactured by Nichikoku K.K., supra), and compounds having 4 polyoxyalkylene chains include DGP-700 and DGP-950 as polyoxypropylene diglycerol ether, 5TP-300KB as polyoxyethylene polyoxypropylene pentaerythritol ether, RC-9050 as polyoxybutylene polyoxyethylene pentaerythritol ether, MG-10E, MG-20E as polyoxyethylene methyl glycoside, MG-2070 as polyoxybutylene polyoxyethylene polyoxypropylene methyl glycoside, OT-521, ST-5160, LT-221, PT-221, OT-206, OT-221, ST-206, LT-210, and PT-300 as polyoxyethylene sorbitan fatty acid ester, IST-221, MG-120TIS (manufactured by Nichikoku K.K.) as polyoxyethylene methyl glucose triisostearate, and compounds having 6 polyoxyalkylene chains include ST-6E, ST-30E, ST-30EC, ST-40E, ST-60E as polyoxyethylene sorbitol tetraoleate, SP-40E as polyoxyethylene sorbitol pentaoleate, polyoxyethylene sorbitol tetraisostearate ST-30IS, HS-1600D, HS-2000D as polyoxypropylene sorbitol, C-35 and HC-20M (manufactured by Nichikoku K.K.) as polyoxyethylene castor oil, and the like. These polyether compounds may be used alone, or may be used in combination of 2 or more.
The content of the polyether compound is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, even more preferably 0.04 to 10 parts by mass, particularly preferably 0.08 to 5 parts by mass, and most preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the adhesive polymer (which is a base polymer, for example, a (meth) acrylic polymer, a urethane polymer, or the like) constituting the adhesive composition. Within the above range, it is preferable because it is excellent in antistatic property and low-staining property.
< Ionic Compound >
The adhesive composition of the present invention contains an ionic compound. As the ionic compound, an alkali metal salt and/or an ionic liquid is preferably used. By containing the ionic compound, excellent antistatic property and peeling antistatic property can be provided.
The alkali metal salt has high ion dissociation property, so even a trace amount of addition can show excellent antistatic performance is preferred. Examples of the alkali metal salt include: from Li+、Na+、K+With a cation of (C) and including Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、C9H19COO-、CF3COO-、C3F7COO-、CH3SO3 -、CF3SO3 -、C4F9SO3 -、C2H5OSO3 -、C6H13OSO3 -、C8H17OSO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、(CF3SO2)(CF3CO)N-、(CH3)2PO4 -、(C2H5)2PO4 -、CH3(OC2H4)2OSO3 -、C6H4(CH3)SO3 -、(C2F5)3PF3 -、CH3CH(OH)COO-And (FSO)2)2N-The anion of (4) is a metal salt. More preferably, LiBr, LiI, LiBF are used4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(FSO2)2N、Li(CF3SO2)3Lithium salts such as C, etc., and more preferably LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C3F7SO2)2N、Li(C4F9SO2)2N、Li(FSO2)2N、Li(CF3SO2)3C. These alkali metal salts may be used alone, or may be used in combination of 2 or more.
The ionic liquid preferably includes an organic cationic component represented by the following formulae (a) to (E) and an anionic component. By using an ionic liquid having these cations, which has a melting point of 100 ℃ or lower, an ionic liquid having more excellent antistatic properties can be obtained.
[ chemical formula 10]
Figure BDA0002111297040000171
R in the above formula (A)aA hydrocarbon group having 4 to 20 carbon atoms, which may be a functional group obtained by substituting a part of the hydrocarbon group with a hetero atom, RbAnd RcThe functional groups may be the same or different and each represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom. Wherein, in the case where the nitrogen atom contains a double bond, R is absentc。
R in the above formula (B)dA hydrocarbon group having 2 to 20 carbon atoms, which may be a functional group obtained by substituting a part of the hydrocarbon group with a hetero atom, Re、RfAnd RgThe functional groups may be the same or different and each represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.
R in the above formula (C)hA hydrocarbon group having 2 to 20 carbon atoms, which may be a functional group obtained by substituting a part of the hydrocarbon group with a hetero atom, Ri、RjAnd RkThe functional groups may be the same or different and each represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.
Z in the above formula (D) represents a nitrogen, sulfur or phosphorus atom, Rl、Rm、RnAnd RoThe same or different hydrocarbyl groups having 1 to 20 carbon atoms may be substituted with a heteroatom in part of the hydrocarbyl group. Wherein, in the case where Z is a sulfur atom, R is absento。
R in the above formula (E)PThe hydrocarbon group having 1 to 18 carbon atoms may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.
Examples of the cation represented by the formula (a) include: pyridine compound
Figure BDA0002111297040000172
Cation, piperidineCation, pyrrolidine
Figure BDA0002111297040000174
Cation, cation having pyrroline skeleton, morpholine
Figure BDA0002111297040000181
Cations, and the like.
Specific examples thereof include: 1-ethylpyridines
Figure BDA0002111297040000182
Cationic, 1-butylpyridines
Figure BDA0002111297040000183
Cationic, 1-hexylpyridinesCationic, 1-butyl-3-methylpyridine
Figure BDA0002111297040000185
Cationic, 1-butyl-4-methylpyridine
Figure BDA0002111297040000186
Cationic, 1-hexyl-3-methylpyridine
Figure BDA0002111297040000187
Cationic, 1-butyl-3, 4-dimethylpyridine
Figure BDA0002111297040000188
Cationic, 1-dimethylpyrrolidineCationic, 1-ethyl-1-methylpyrrolidine
Figure BDA00021112970400001810
Cationic, 1-methyl-1-propylpyrrolidine
Figure BDA00021112970400001811
Cationic, 1-methyl-1-butylpyrrolidine
Figure BDA00021112970400001812
Cationic, 1-methyl-1-pentylpyrrolidines
Figure BDA00021112970400001813
Cationic, 1-methyl-1-hexylpyrrolidineCationic, 1-methyl-1-heptyl pyrrolidines
Figure BDA00021112970400001815
Cationic, 1-ethyl-1-propylpyrrolidine
Figure BDA00021112970400001816
Cationic, 1-ethyl-1-butylpyrrolidine
Figure BDA00021112970400001817
Cationic, 1-ethyl-1-pentylpyrrolidines
Figure BDA00021112970400001818
Cationic, 1-ethyl-1-hexylpyrrolidineCationic, 1-ethyl-1-heptyl pyrrolidinesCationic, 1-dipropylpyrrolidine
Figure BDA00021112970400001821
Cationic, 1-propyl-1-butylpyrrolidine
Figure BDA00021112970400001822
Cationic, 1-dibutylpyrrolidine
Figure BDA00021112970400001823
Cation, pyrrolidine
Figure BDA00021112970400001824
-2-keto cation, 1-propylpiperidine
Figure BDA00021112970400001825
Cationic, 1-pentylpiperidines
Figure BDA00021112970400001826
Cationic, 1-dimethylpiperidine
Figure BDA00021112970400001827
Cationic, 1-methyl-1-ethylpiperidine
Figure BDA00021112970400001828
Cationic, 1-methyl-1-propylpiperidinesCationic, 1-methyl-1-butylpiperidine
Figure BDA00021112970400001830
Cationic, 1-methyl-1-pentylpiperidines
Figure BDA00021112970400001831
Cationic, 1-methyl-1-hexylpiperidineCationic, 1-methyl-1-heptylpiperidinesCationic, 1-ethyl-1-propylpiperidines
Figure BDA00021112970400001834
Cationic, 1-ethyl-1-butylpiperidine
Figure BDA00021112970400001835
Cationic, 1-ethyl-1-pentylpiperidines
Figure BDA00021112970400001836
Cationic, 1-ethyl-1-hexylpiperidine
Figure BDA00021112970400001837
Cationic, 1-ethyl-1-heptylpiperidines
Figure BDA00021112970400001838
Cationic, 1-dipropylpiperidine
Figure BDA00021112970400001839
Cationic, 1-propyl-1-butylpiperidine
Figure BDA00021112970400001840
Cationic, 1-dibutylpiperidine
Figure BDA00021112970400001841
Cation, 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1, 2-dimethylindole cation, 1-ethylcarbazole cation, N-ethyl-N-methylmorpholine
Figure BDA00021112970400001842
Cations, and the like.
Examples of the cation represented by the formula (B) include: imidazole
Figure BDA00021112970400001843
Cationic, tetrahydropyrimidines
Figure BDA00021112970400001844
Cationic dihydropyrimidines
Figure BDA00021112970400001845
Cations, and the like.
Specific examples thereof include: 1, 3-dimethylimidazole
Figure BDA00021112970400001846
Cationic, 1, 3-diethylimidazoles
Figure BDA00021112970400001847
Cationic, 1-ethyl-3-methylimidazole
Figure BDA00021112970400001848
Cationic, 1-butyl-3-methylimidazole
Figure BDA00021112970400001849
Cationic, 1-hexyl-3-methylimidazole
Figure BDA00021112970400001850
Cationic, 1-octyl-3-methylimidazole
Figure BDA00021112970400001851
Cationic, 1-decyl-3-methylimidazoleCationic, 1-dodecyl-3-methylimidazole
Figure BDA00021112970400001853
Cationic, 1-tetradecyl-3-methylimidazole
Figure BDA00021112970400001854
Cationic, 1, 2-dimethyl-3-propylimidazoles
Figure BDA00021112970400001855
Cationic, 1-ethyl-2, 3-dimethylimidazole
Figure BDA00021112970400001856
Cationic, 1-butyl-2, 3-dimethylimidazole
Figure BDA00021112970400001857
Cationic, 1-hexyl-2, 3-dimethylimidazole
Figure BDA00021112970400001858
Cationic, 1- (2-methoxyethyl) -3-methylimidazole
Figure BDA00021112970400001859
Cationic, 1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidine
Figure BDA00021112970400001860
Cationic, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidine
Figure BDA00021112970400001861
Cationic, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidine
Figure BDA00021112970400001862
Cation(s)1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidine
Figure BDA00021112970400001863
Cationic, 1, 3-dimethyl-1, 4-dihydropyrimidines
Figure BDA00021112970400001864
Cationic, 1, 3-dimethyl-1, 6-dihydropyrimidines
Figure BDA00021112970400001865
Cationic, 1,2, 3-trimethyl-1, 4-dihydropyrimidines
Figure BDA00021112970400001866
Cationic, 1,2, 3-trimethyl-1, 6-dihydropyrimidines
Figure BDA0002111297040000191
Cationic, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidines
Figure BDA0002111297040000192
Cationic, 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidine
Figure BDA0002111297040000193
Cations, and the like.
Examples of the cation represented by the formula (C) include: pyrazoles
Figure BDA0002111297040000194
Cationic pyrazolines
Figure BDA0002111297040000195
Cations, and the like.
Specific examples thereof include: 1-methylpyrazole
Figure BDA0002111297040000196
Cationic, 3-methylpyrazoles
Figure BDA0002111297040000197
Cationic, 1-ethyl-2-methylpyrazoline
Figure BDA0002111297040000198
Cationic, 1-ethyl-2, 3, 5-trimethylpyrazoles
Figure BDA0002111297040000199
Cationic, 1-propyl-2, 3, 5-trimethylpyrazoles
Figure BDA00021112970400001910
Cationic, 1-butyl-2, 3, 5-trimethylpyrazoles
Figure BDA00021112970400001911
Cationic, 1-ethyl-2, 3, 5-trimethylpyrazoline
Figure BDA00021112970400001912
Cationic, 1-propyl-2, 3, 5-trimethylpyrazoline
Figure BDA00021112970400001913
Cationic, 1-butyl-2, 3, 5-trimethylpyrazoline
Figure BDA00021112970400001914
Cations, and the like.
Examples of the cation represented by the formula (D) include: tetraalkylammonium cations, trialkylsulfonium cations, tetraalkyl radicals
Figure BDA00021112970400001915
And cations obtained by substituting a part of the alkyl group with an alkenyl group, an alkoxy group, and an epoxy group.
As specific examples, for example: tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexyltrimethylammonium cationSulfonium cation, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, dimethyldecyl sulfonium cation, tetramethylCationic, tetraethyl radical
Figure BDA00021112970400001917
Cationic, tetrabutyl
Figure BDA00021112970400001918
Cationic, tetrahexyl
Figure BDA00021112970400001919
Cationic, tetraoctyl
Figure BDA00021112970400001920
Cation, triethyl methyl
Figure BDA00021112970400001921
Cationic, tributylethyl
Figure BDA00021112970400001922
Cationic, trimethyldecyl
Figure BDA00021112970400001923
Cation, diallyldimethylammonium cation, tributyl- (2-methoxyethyl)Cations, and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfinium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylammonium cation, and the like are preferably used
Figure BDA00021112970400001925
Cationic, tributylethyl
Figure BDA00021112970400001926
Cationic, trimethyldecylCation such as asymmetric tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkyl
Figure BDA00021112970400001928
A cation, an N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, a glycidyltrimethylammonium cation, a diallyldimethylammonium cation, an N, N-dimethyl-N-ethyl-N-propylammonium cation, an N, N-dimethyl-N-ethyl-N-butylammonium cation, an N, N-dimethyl-N-ethyl-N-pentylammonium cation, an N, N-dimethyl-N-ethyl-N-hexylammonium cation, an N, N-dimethyl-N-ethyl-N-heptylammonium cation, an N, N-dimethyl-N-ethyl-N-nonylammonium cation, an N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, an N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N-diethyl-N-propyl-N-butylammonium cation, N-dimethyl-N-propyl-N-pentylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-butyl-N-hexylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, n-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-diethylpropylphosphonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethylpropyl, N, N-dipropyl-N, N-dihexylammonium cation, N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation.
Examples of the cation represented by the formula (E) include a sulfonium cation and the like. R in the above formula (E)PSpecific examples of (3) include methyl and ethylAlkyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl, and the like.
On the other hand, the anionic component is not particularly limited as long as it is an anionic component that becomes an ionic liquid, and for example: cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、C4F9SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N-、C9H19COO-、(CH3)2PO4 -、(C2H5)2PO4 -、CH3OSO3 -、C2H5OSO3 -、C4H9OSO3 -、C6H13OSO3 -、C8H17OSO3 -、CH3(OC2H4)2OSO3 -、C6H4(CH3)SO3 -、(C2F5)3PF3 -、CH3CH(OH)COO-、(FSO2)2N-、B(CN)4 -、C(CN)3 -、N(CN)2 -P-toluenesulfonate anion, 2- (2-methoxyethyl) ethylsulfate anion, and the like.
These ionic liquids may be used alone, or 2 or more kinds may be mixed and used.
The content of the ionic compound is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, even more preferably 0.1 to 2 parts by mass, and particularly preferably 0.2 to 1 part by mass, based on 100 parts by mass of the adhesive polymer (which is a base polymer, for example, a (meth) acrylic polymer, a urethane polymer, or the like) constituting the adhesive composition. Within the above range, the pressure-sensitive adhesive sheet of the present invention is preferable because it easily has both antistatic properties and low staining properties.
< crosslinking agent >
In the pressure-sensitive adhesive sheet (surface protective film) of the present invention, the pressure-sensitive adhesive composition preferably contains a crosslinking agent. In the present invention, the adhesive layer can be formed using the adhesive composition. For example, when the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive containing the (meth) acrylic polymer, a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having more excellent heat resistance can be obtained by crosslinking the composition by appropriately adjusting the constituent unit and the constituent ratio of the (meth) acrylic polymer, the selection and addition ratio of the crosslinking agent, and the like.
As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine-based resin, an aziridine derivative, a metal chelate compound, and the like can be used, and in particular, an isocyanate compound is preferably used. These compounds may be used alone or in combination of 2 or more.
Examples of the isocyanate compound include: trimethylene diisocyanate, butylene diisocyanate, hexamethyleneAliphatic polyisocyanates such as diisocyanate (HDI) and dimer acid diisocyanate, alicyclic isocyanates such as cyclopentene diisocyanate, cyclohexene diisocyanate, isophorone diisocyanate (IPDI) and 1, 3-bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and Xylylene Diisocyanate (XDI), aromatic isocyanates such as allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonimine bond,
Figure BDA0002111297040000211
Modified polyisocyanates obtained by modifying the above isocyanate compounds with diazinetrione bonds or the like. For example, commercially available products include tradenames of Takenate 300S, Takenate500, Takenate 600, Takenate D165N, Takenate D178N (manufactured by Mitsui chemical Co., Ltd.), Sumidile T80, Sumidile L, Desmodur N3400 (manufactured by Mitsubishane corporation), MILLONATE MR, MILLONATE MT, CORONATE L, CORONATE HL, and CORONATE HX (manufactured by Tosoh Co., Ltd.). These isocyanate compounds may be used alone, or 2 or more kinds thereof may be mixed and used, or a 2-functional isocyanate compound and a 3-functional or more isocyanate compound may be used in combination. By using a crosslinking agent in combination, both adhesiveness and repulsion resistance (adhesiveness to a curved surface) can be achieved, and a psa sheet with more excellent adhesive properties can be obtained.
Examples of the epoxy compound include: n, N, N ', N' -tetraglycidyl o-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi gas chemical Co., Ltd.), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi gas chemical Co., Ltd.), and the like.
Examples of the melamine-based resin include hexamethylolmelamine. Examples of aziridine derivatives include: commercially available products such as HDU, TAZM and TAZO (manufactured by CROSS CORPORATION, Inc.).
Examples of the metal chelate compound include aluminum, iron, tin, titanium, and nickel as the metal component, and examples of the chelate component include acetylene, methyl acetoacetate, and ethyl lactate.
The content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, still more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 18 parts by mass, based on 100 parts by mass of the (meth) acrylic polymer. When the content is less than 0.01 part by mass, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the obtained adhesive layer becomes small, and sufficient heat resistance may not be obtained, and the content tends to cause paste residue. On the other hand, when the content is more than 30 parts by mass, the cohesive force of the polymer is large, the fluidity is lowered, the wetting with an adherend (for example, a polarizing film) becomes insufficient, and there is a tendency that the swelling is caused between the adherend and the adhesive layer (adhesive composition layer).
The adhesive composition may further contain a crosslinking catalyst for allowing any of the above crosslinking reactions to proceed more efficiently. As the crosslinking catalyst, for example: tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron, tris (hexane-2, 4-diketo) iron, tris (heptane-3, 5-diketo) iron, tris (5-methylhexane-2, 4-diketo) iron, tris (octane-2, 4-diketo) iron, tris (6-methylheptane-2, 4-diketo) iron, tris (2, 6-dimethylheptane-3, 5-diketo) iron, tris (nonane-2, 4-diketo) iron, tris (nonane-4, 6-diketo) iron, tris (2,2,6, 6-tetramethylheptane-3, 5-diketo) iron, tris (nonane-2, 4-diketo) iron, tris (nonane-4, 6-diketo) iron, tris (2,6, 6-tetramethylheptane-3, 5-diketo) iron, and, Tri (tridecane-6, 8-diketo) iron, tri (1-phenylbutane-1, 3-diketo) iron, tri (hexafluoroacetylacetonato) iron, tri (ethyl acetoacetate) iron, tri (n-propyl acetoacetate) iron, tri (isopropyl acetoacetate) iron, tri (n-butyl acetoacetate) iron, tri (sec-butyl acetoacetate) iron, tri (tert-butyl acetoacetate) iron, tri (methyl propionylacetate) iron, tri (ethyl propionylacetate) iron, tri (n-propyl propionylacetate) iron, tri (isopropyl propionylacetate) iron, tri (n-butyl propionylacetate) iron, tri (sec-butyl propionylacetate) iron, tri (tert-butyl propionylacetate) iron, tri (benzyl acetoacetate) iron, tri (dimethyl malonate) iron, tri (diethyl malonate) iron, trimethoxyiron, triethoxy iron, triisopropoxyberric, tri (propyloxy) iron, tri (tert-butyl acrylate) iron, tri (tert-butyl propionylacetate) iron, tri (benzyl acetoacetate) iron, tri (dimethyl malonate) iron, tri (diethyl malonate) iron, Iron-based catalysts such as ferric chloride. These crosslinking catalysts may be used in 1 kind, or 2 or more kinds may be used in combination.
The content of the crosslinking catalyst is not particularly limited, and is, for example, preferably about 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylic polymer. When the content is within the above range, the crosslinking reaction speed is high and the pot life of the pressure-sensitive adhesive composition is prolonged in the formation of the pressure-sensitive adhesive layer, which is a preferable embodiment.
In addition, a compound that causes keto-enol tautomerism may be contained in the above adhesive composition. For example, in an adhesive composition containing a crosslinking agent or an adhesive composition capable of being used in combination with a crosslinking agent, a method of containing a compound that causes the above keto-enol tautomerism can be preferably employed. This can suppress excessive increase in viscosity and gelation of the pressure-sensitive adhesive composition after blending of the crosslinking agent, and can achieve the effect of extending the pot life of the pressure-sensitive adhesive composition. In the case of using at least an isocyanate compound as the above-mentioned crosslinking agent, it is particularly interesting to contain a compound which causes keto-enol tautomerism. This technique is preferably applied to a case where the adhesive composition is in the form of an organic solvent solution or a solvent-free form, for example.
As the compound which gives the above keto-enol tautomerism, various β -dicarbonyl compounds can be used. Specific examples thereof include β -diketones such as acetylacetone, 2, 4-hexanedione, 3, 5-heptanedione, 2-methylhexane-3, 5-dione, 6-methylheptane-2, 4-dione, and 2, 6-dimethylheptane-3, 5-dione; acetoacetic acid esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, and tert-butyl acetoacetate; propionyl acetic acid esters such as propionyl ethyl acetate, propionyl isopropyl acetate, propionyl tert-butyl acetate, and the like; isobutyrylacetic acid esters such as ethyl isobutyrylacetate, isopropyl isobutyrylacetate, and tert-butyl isobutyrylacetate; malonic esters such as methyl malonate and ethyl malonate; and so on. Among these, acetylacetone and acetoacetates are preferable. The compound which causes keto-enol tautomerism may be used alone, or 2 or more compounds may be used in combination.
The content of the compound which causes keto-enol tautomerism is, 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 (meth) acrylic polymer. When the amount of the above compound is too small, it may be difficult to exhibit sufficient use effects. On the other hand, when the above compound is used in an amount exceeding the required limit, it may remain in the pressure-sensitive adhesive layer, and the cohesive force may be reduced.
The pressure-sensitive adhesive composition may contain other known additives, and for example, powders of lubricants, colorants, pigments, etc., plasticizers, tackifiers, low-molecular weight polymers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, softeners, antioxidants, heat stabilizers, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils, solvents, etc., may be added as appropriate depending on the application.
< pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet (surface protective film) >
The pressure-sensitive adhesive sheet of the present invention preferably has a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition on at least one side of the substrate film. The pressure-sensitive adhesive layer is obtained by crosslinking the pressure-sensitive adhesive composition, and is usually carried out after application of the pressure-sensitive adhesive composition, but a pressure-sensitive adhesive layer made of the crosslinked pressure-sensitive adhesive composition may be transferred to a substrate film or the like.
The method for forming the pressure-sensitive adhesive layer on the base film is not particularly limited, and for example, the pressure-sensitive adhesive composition (solution) is applied to the base film, and the polymerization solvent or the like is dried and removed to form the pressure-sensitive adhesive layer on the base film. Then, aging may be performed for the purpose of adjusting the movement of the components of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like. In the case of producing a pressure-sensitive adhesive sheet by applying the pressure-sensitive adhesive composition to a substrate film, 1 or more solvents other than the polymerization solvent may be newly added to the pressure-sensitive adhesive composition, so that the pressure-sensitive adhesive composition can be uniformly applied to the substrate film.
As a method for forming the pressure-sensitive adhesive layer in the production of the pressure-sensitive adhesive sheet of the present invention, a known method used for the production of pressure-sensitive adhesive tapes can be used. Specific examples thereof include: roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
The adhesive sheet of the present invention is generally produced so that the thickness of the adhesive layer is about 0.1 to 100 μm, preferably about 1 to 80 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, a proper balance between removability and adhesiveness can be easily obtained, and therefore, the pressure-sensitive adhesive layer is preferable.
The total thickness of the adhesive sheet of the present invention is preferably 8 to 300. mu.m, more preferably 10 to 200. mu.m, and most preferably 20 to 100. mu.m. When the content is within the above range, the adhesive properties (removability, adhesiveness, etc.), handling properties, and appearance properties are excellent, and a preferable embodiment is obtained. The total thickness is the total thickness of all layers including the base film, the adhesive layer, and other layers.
< separator >
In the adhesive sheet of the present invention, a separator is preferably attached to the surface of the adhesive layer opposite to the surface thereof in contact with the substrate film. The separator may be bonded to the surface of the pressure-sensitive adhesive layer as needed for the purpose of protecting the pressure-sensitive adhesive surface.
The material constituting the separator includes paper and a plastic film, and a plastic film is preferably used in view of excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm. When the content is within the above range, the adhesion workability to the pressure-sensitive adhesive layer and the peeling workability from the pressure-sensitive adhesive layer are excellent, and therefore, the preferred range is. If necessary, the separator may be subjected to release and antifouling treatment using a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, or antistatic treatment such as coating type, mixing type, vapor deposition type, or the like.
< optical Member >
The pressure-sensitive adhesive sheet is preferably adhered (protected) to the optical member of the present invention. The pressure-sensitive adhesive sheet is excellent in antistatic properties when peeled off after being adhered to the surface of an optical member such as a polarizing film, and in adhesion (adhesiveness) between the surface of the optical member from which the pressure-sensitive adhesive sheet has been peeled off and a layer such as an interlayer filler newly provided on the surface of the peeled optical member, and therefore, can be used for surface protection applications (surface protection films) in processing, transportation, shipment, and the like, and is useful for protecting the surface of the optical member.
< interlaminar Filler >
In an image display device such as a liquid crystal display, when any impact is applied from the outer surface, a front transparent plate (also referred to as a "window layer") such as an acrylic plate or a glass plate may be provided on the viewing side of an optical member such as a polarizing film from the viewpoint of preventing the impact from being transmitted to the optical member such as the polarizing film and being damaged. In an image display device including such a front transparent plate, when an air layer is present between an optical member such as a polarizing film and the front transparent plate, reflection loss may occur due to a refractive index difference in an interface with the air layer, and visibility may be deteriorated such that double images are observed. Therefore, in order to prevent an air layer from being present between the optical member such as the polarizing film and the front transparent plate, the two may be bonded to each other with a layer of an interlayer filler (a layer of an interlayer filler) interposed therebetween. Examples of the layer of the interlayer filler (pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet) include: a model "SVR 7000 series" manufactured by DEXERIALS, a liquid interlayer filler such as "WORLD ROCK HRJ-21" manufactured by synechia corporation, an optical transparent pressure sensitive adhesive tape (trade name "luciac series") manufactured by hitong electrical corporation, and the like. Among them, the pressure-sensitive adhesive sheet of the present invention, which is obtained by using an optical clear pressure-sensitive adhesive tape (trade name "luciac series") made by the above-mentioned japanese-east electrical corporation containing an acrylic polymer which is easy to handle because it is in a tape state, is excellent in adhesion (adhesiveness) when a layer of the interlayer filler is provided on the surface of an optical member after peeling off at a stage where it is unnecessary, even when the pressure-sensitive adhesive sheet is attached to the surface of the display panel (polarizing plate or the like), and is a preferable embodiment.
Examples
The present invention will be described below with reference to some examples, but the present invention is not limited to the specific examples. In the following description, "part(s)" and "%" are based on mass unless otherwise specified.
The characteristics in the following description are measured or evaluated as follows.
< measurement of weight average molecular weight (Mw) >
The weight average molecular weight (Mw) of the polymer used was measured by a GPC apparatus (HLC-8220GPC) manufactured by Tosoh corporation, and the measurement conditions were as follows.
Sample concentration: 0.2% by mass (THF solution)
Sample injection amount: 10 μ l
Eluent: THF (tetrahydrofuran)
Flow rate: 0.6ml/min
Measuring temperature: 40 deg.C
Column:
a sample column; TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)
A reference column; TSKgel SuperH-RC (1 root)
A detector: differential Refractometer (RI)
The weight average molecular weight is determined as a polystyrene equivalent.
< theoretical value of glass transition temperature (Tg) >
The glass transition temperature Tg (c) was determined by the following formula using the following literature values as the glass transition temperature Tgn (c) of the homopolymer of each monomer.
Formula (II): 1/(Tg +273) ═ Σ [ Wn/(Tgn +273) ] (in the formula, Tg (° c) represents the glass transition temperature of the copolymer, Wn (-) represents the mass fraction of each monomer, Tgn (° c) represents the glass transition temperature of a homopolymer of each monomer, and n represents the type of each monomer. Angle (c)
Literature values:
2-ethylhexyl acrylate (2 EHA): -70 deg.C
2-hydroxyethyl acrylate (HEA): -15 deg.C
4-hydroxybutyl acrylate (4 HBA): -32 deg.C
Acrylic Acid (AA): 106 deg.C
The above literature values refer to "synthesis and design of acrylic resin and development of new use" (issued by central office of business and development) and "Polymer Handbook" (John Wiley & Sons).
< production of acrylic Polymer (1) >
To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, 91 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), 0.02 part by mass of Acrylic Acid (AA), 0.2 part by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate were charged, and nitrogen gas was introduced while slowly stirring, so that the liquid temperature in the flask was maintained at about 65 ℃ and polymerization reaction was carried out for 6 hours, thereby preparing a solution (40 mass%) of the acrylic polymer (1). The acrylic polymer (1) had a weight average molecular weight (Mw) of 54 ten thousand and a glass transition temperature (Tg) of-67 ℃.
< production of acrylic Polymer (2) >
98.5 parts by mass of 2-ethylhexyl acrylate (2EHA), 1.5 parts by mass of 4-hydroxybutyl acrylate (4HBA), 0.006 part by mass of Acrylic Acid (AA), 0.2 part by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate were charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, and nitrogen gas was introduced while slowly stirring, and the liquid temperature in the flask was maintained at about 65 ℃ to conduct polymerization for 6 hours, thereby preparing a solution (40 mass%) of the acrylic polymer (2). The acrylic polymer (2) had a weight average molecular weight (Mw) of 48 ten thousand and a glass transition temperature (Tg) of-70 ℃.
< production of acrylic Polymer (3) >
96 parts by mass of 2-ethylhexyl acrylate (2EHA), 4 parts by mass of 2-hydroxyethyl acrylate (HEA), 0.2 part by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate were charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, and nitrogen gas was introduced while slowly stirring, and the liquid temperature in the flask was maintained at about 65 ℃ to conduct a polymerization reaction for 6 hours, thereby preparing a solution (40 mass%) of the acrylic polymer (3). The acrylic polymer (3) had a weight average molecular weight (Mw) of 48 ten thousand and a glass transition temperature (Tg) of-68 ℃.
< example 1>
[ preparation of acrylic adhesive solution ]
The acrylic polymer (1) solution (40 mass%) was diluted to 20 mass% with ethyl acetate, to 500 parts by mass of this solution (100 parts by mass of solid content) were added polyoxypropylene glycerol ether (SunnixGP3000, manufactured by Sanyo chemical industry Co., Ltd.) as a polyether compound 0.5 part by mass, lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo chemical industry Co., Ltd., LiTFSI) as an ionic compound 0.3 part by mass, isocyanurate compound of hexamethylene diisocyanate (manufactured by Tokyo chemical industry Co., Ltd., CORONATE: C/HX, 3-functional isocyanate compound) as a crosslinking agent 1.5 parts by mass (1.5 parts by mass of solid content), and dioctyltin dilaurate (1% ethyl acetate solution) as a crosslinking catalyst 3 parts by mass (0.03 part by mass of solid content), followed by mixing and stirring to prepare an acrylic adhesive solution.
[ production of antistatic treatment film ]
Polyester resin VIRONAL MD-1480 (25% aqueous solution, manufactured by Toyo Boseki Co., Ltd.) as a binder was added to a mixed solvent of water/ethanol (1/1) in an amount of 100 parts by mass in terms of solid content, of poly (3, 4-ethylenedioxythiophene) (PEDOT)/polystyrene sulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck Co., Ltd.) as a conductive polymer, and 10 parts by mass in terms of solid content, of hexamethylolmelamine as a crosslinking agent, and the mixture was stirred for about 20 minutes to be sufficiently mixed. An antistatic agent solution having NV (nonvolatile content) of about 0.4% was thus prepared.
The antistatic agent solution thus obtained was applied to a polyethylene terephthalate (PET) film (thickness: 38 μm) as a base film using a Meyer rod, and dried at 130 ℃ for 1 minute to remove the solvent and form an antistatic layer (thickness: 0.2 μm) to prepare an antistatic-treated film (base film with an antistatic layer).
[ production of adhesive sheet (surface protective film) ]
The acrylic pressure-sensitive adhesive solution was applied to the surface of the antistatic-treated film opposite to the surface having the antistatic layer (antistatic-treated surface), and heated at 130 ℃ for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 10 μm. Next, an adhesive sheet (surface protective film) was produced by bonding a silicone-treated surface of a polyethylene terephthalate (PET) film (separator, thickness 25 μm) having been subjected to a silicone treatment to a surface of the adhesive layer not in contact with the PET film as the base film (see fig. 1).
< examples 2 to 23 and comparative examples 1 to 3>
An adhesive sheet (surface protective film) was produced in the same manner as in example 1, except that the raw materials shown in table 3 were used in place of the adhesive polymer, polyether compound, and ionic compound used in example 1, and the compounding amounts shown in table 3 were used.
< example 24>
[ preparation of a urethane adhesive solution ]
A urethane adhesive solution was obtained by mixing 100 parts by mass of a polyol PREMINOL S3011 having 3 hydroxyl groups (manufactured by Asahi glass company, Mn: 10000) AS a polyol, 8.9 parts by mass of an isocyanate compound (CORONATE HX: C/HX, manufactured by Nippon polyurethane Co., Ltd.) AS a crosslinking agent, 0.04 part by mass of iron (III) acetylacetonate (manufactured by Tokyo chemical industry Co., Ltd.) AS a catalyst, 0.5 part by mass of ST-30E (manufactured by Nichio oil Co., Ltd.) AS a polyether compound, 0.45 part by mass of AS110 (manufactured by first Industrial pharmaceutical Co., Ltd.) AS an ionic compound, and 210 parts by mass of ethyl acetate AS a diluting solvent.
[ production of adhesive sheet (surface protective film) ]
The urethane adhesive solution was applied to the surface of the antistatic-treated film opposite to the antistatic-treated surface, and the film was heated at 130 ℃ for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, an adhesive sheet (surface protective film) was produced by bonding a silicone-treated surface of a polyethylene terephthalate (PET) film (separator, thickness 25 μm) having been subjected to a silicone treatment to a surface of the adhesive layer not in contact with the PET film as the base film (see fig. 1).
< examples 25 to 28>
A pressure-sensitive adhesive sheet (surface protective film) was produced in the same manner as in example 24, except that the raw materials and the amounts thereof to be blended shown in table 4 were used.
< example 29>
[ preparation of a urethane adhesive solution ]
A urethane adhesive solution was obtained by mixing 100 parts by mass of urethane prepolymer SH109(TOYOCHEM CO., LTD.), 3.8 parts by mass of an isocyanate compound (CORONATE L: C/L, manufactured by Nippon polyurethane Co., Ltd.), 0.04 part by mass of iron (III) acetylacetonate (manufactured by Tokyo chemical industry Co., Ltd.) AS a catalyst, 0.5 part by mass of ST-30E (manufactured by Nichikura oil Co., Ltd.) AS a polyether compound, 0.45 part by mass of AS110 (manufactured by first Industrial pharmaceutical Co., Ltd.) AS an ionic compound, and 210 parts by mass of ethyl acetate AS a diluent solvent.
[ production of adhesive sheet (surface protective film) ]
The urethane adhesive solution was applied to the surface of the antistatic-treated film opposite to the antistatic-treated surface, and the film was heated at 130 ℃ for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, an adhesive sheet (surface protective film) was produced by bonding a silicone-treated surface of a polyethylene terephthalate (PET) film (separator, thickness 25 μm) having been subjected to a silicone treatment to a surface of the adhesive layer not in contact with the PET film as the base film (see fig. 1).
< example 30>
[ preparation of a urethane adhesive solution ]
Mixing 85 parts by mass of polyol PREMINOL S3011 (manufactured by Asahi glass company, Mn: 10000) having 3 hydroxyl groups AS a polyol, 13 parts by mass of polyol Sunnix GP3000 (manufactured by Sanyo chemical Co., Ltd., Mn: 3000) having 3 hydroxyl groups, 2 parts by mass of polyol Sunnix GP1000 (manufactured by Sanyo chemical Co., Ltd., Mn: 1000) having 3 hydroxyl groups, 18 parts by mass of isocyanate compound (CORONATE HX: C/HX, manufactured by Nippon polyurethane Co., Ltd.) AS a crosslinking agent, 0.04 part by mass of iron (III) acetylacetonate AS a catalyst (manufactured by Tokyo chemical industry Co., Ltd.), 0.5 part by mass of ST-30E (manufactured by Nichio oil Co., Ltd.) AS a polyether compound, 0.45 part by mass of AS110 (manufactured by first Industrial pharmaceutical Co., Ltd.) AS an ionic compound, 210 parts by mass of ethyl acetate AS a diluting solvent, a urethane adhesive solution was obtained.
[ production of adhesive sheet (surface protective film) ]
The urethane adhesive solution was applied to the surface of the antistatic-treated film opposite to the antistatic-treated surface, and the film was heated at 130 ℃ for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, an adhesive sheet (surface protective film) was produced by bonding a silicone-treated surface of a polyethylene terephthalate (PET) film (separator, thickness 25 μm) having been subjected to a silicone treatment to a surface of the adhesive layer not in contact with the PET film as the base film (see fig. 1).
The contents of the above-described compounding, various measurements and evaluation results of the pressure-sensitive adhesive sheets of examples and comparative examples are shown in tables 1 to 5. The amounts in tables 3 and 4 represent the effective components. In examples 2 to 23 and comparative examples 1 to 3 except for example 1, the same amount as in example 1 was added to the crosslinking catalyst and the like whose amounts are not shown in tables 3 and 4. The thickness of the obtained pressure-sensitive adhesive layer was also prepared in the same manner as in example 1.
[ Table 1]
Figure BDA0002111297040000301
Figure BDA0002111297040000311
Hereinafter, the abbreviations in table 3 and table 4 will be described.
(Ionic Compound)
And (3) LiTFSI: lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo chemical Co., Ltd.), alkali metal salt
And (3) LiTFS: lithium trifluoromethanesulfonate (manufactured by Tokyo chemical industry Co., Ltd.) and alkali metal salt
The AS 110: 1-ethyl-3-methylimidazoleBis (fluoromethanesulfonyl) imide (manufactured by first Industrial pharmaceutical Co., Ltd.) ", Ionic liquid
The AS 210: 1-ethyl-3-methylimidazole
Figure BDA0002111297040000322
Bis (fluorosulfonyl) imide (manufactured by first Industrial pharmaceutical Co., Ltd.), Ionic liquid
And the CIL 312: 1-butyl-3-methylpyridine
Figure BDA0002111297040000323
Bis (trifluoromethanesulfonyl) imide (manufactured by Carlit corporation, Japan), and ionic liquid
CIL 313: 1-ethyl-3-methylpyridine
Figure BDA0002111297040000324
Trifluoromethanesulfonic acid (manufactured by Carlit, Japan) and ionic liquid
MTOATFSI: trioctylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Wako pure chemical industries, Ltd.), and ionic liquid
(crosslinking agent)
C/HX: isocyanurate of hexamethylene diisocyanate (product of Tosoh Cornate HX)
C/L: trimethylolpropane/tolylene diisocyanate (product of Tosoh Corp., trade name: CORONATE L)
C/HL: trimethylolpropane adduct of hexamethylene diisocyanate (product of Tosoh Corp., CORONATE HL)
[ Table 3]
Figure BDA0002111297040000331
[ Table 4]
Figure BDA0002111297040000341
< preparation of film with hardcoat >
To a urethane acrylate type ultraviolet curable resin solution (product name "UNICIC 17-806" manufactured by DIC K.K., solid content concentration 80%), 5 parts by mass of a photopolymerization initiator (product name "IRGACURE 906" manufactured by Ciba specialty Chemicals) and 0.03 part by mass of a leveling agent (product name "GRANDIC PC 4100" manufactured by DIC K.K.) were added to 100 parts by mass of the solid content in the solution. Then, butyl acetate was added to the solution so that the solid content concentration in the solution became 75%, and cycloheptanone was further added to the solution so that the solid content concentration in the solution became 50%. The hard coat layer-forming material for forming the hard coat layer is thus prepared.
Next, the hard coat layer-forming material was applied to a triacetyl cellulose film (manufactured by Fuji film Co., Ltd., product name "TD 80 UL", thickness 80 μm) so that the cured thickness became 7.5 μm, and a coating film was formed. The coating film was dried at 80 ℃ for 2 minutes. Then, the coating was irradiated with a cumulative light amount of 300mJ/cm by using a high-pressure mercury lamp2Thereby producing a film with a hard coat layer.
< measurement of peeling electrification Voltage >
The adhesive sheet 10 of each example was cut into a size of 70mm in width and 130mm in length, and after peeling the separator, the surface of the hard coat film (70 mm in width and 100mm in length) 12 bonded to the glass plate 11 was pressed with a hand pressure roller so that one end of the adhesive sheet 10 was exposed 30mm from the end of the hard coat film 12.
The sample was left to stand in an atmosphere of 23 ℃ X50% RH for 1 day and then mounted at a predetermined position on a sample fixing table 13 having a height of 20mm as shown in FIG. 2. The end of the adhesive sheet 10 exposed 30mm from the hard-coated film 12 was fixed to an automatic winder (not shown), and was peeled at a peeling angle of 150 ° and a peeling speed of 30 m/min. The surface potential of the adherend (hard-coated film 12) generated at this time was measured for "peel charged voltage" with a potentiometer 14 (model "statron DZ-4" manufactured by shishishido electrostatic co., ltd.) fixed at a position 30mm in height from the center of the hard-coated film 12. The measurement was carried out at 23 ℃ and 50% RH.
The peeling electrification voltage (kV, absolute value) is preferably 1kV or less, more preferably 0.8kV or less, and still more preferably 0.6kV or less. When the peeling electrification voltage is within the above range, damage to the panel due to static electricity is less likely to occur, and the like, which is a preferable mode.
< measurement of residual adhesive Strength >
After the separator of each adhesive sheet was peeled off, the surface of the hard coat film (width 70mm, length 100mm)12 was pressed by a hand pressure roller.
After the sample was left to stand in an atmosphere of 23 ℃ C.. times.50% RH for 1 day, the adhesive sheet was peeled off, and the acrylic adhesive tape (No. 31B, width 19mm, substrate thickness 25 μm) was pressure-bonded to the surface of the film 12 with the hard coat layer by a hand roller. The sample was left to stand in an atmosphere of 23 ℃ X50% RH for 30 minutes, and then the peel force (N/19mm) at a peel angle of 180 ℃ and a peel speed of 0.3m/min was measured to determine the residual adhesive force (N/19 mm).
The residual adhesive strength (N/19mm) is preferably 4.5N/19mm or more, more preferably 4.8N/19mm or more, still more preferably 5N/19mm or more, and particularly preferably 5.5N/19mm or more. When the residual adhesive force is within the above range, for example, after the adhesive sheet is adhered to the surface of the optical member (polarizing film or the like), and then peeled off, and then the interlayer filler or the like is newly provided on the surface of the peeled optical member, the adhesion (adhesiveness) between the surface of the optical member (polarizing film or the like) and the interlayer filler or the like is not reduced, and a problem such as peeling is not caused, which is a preferable mode.
< residual adhesion Rate >
The adhesive strength of No.31B on the film surface with the hard coat layer before the adhesive sheet was attached was measured and calculated by the following formula.
Residual adhesion rate (%) < 100 × [ (No. 31B adhesion after peeling of the adhesive sheet of each example)/(No. 31B adhesion before applying the adhesive sheet) ]
The residual adhesion rate (%) is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 90% or more. When the residual adhesion ratio is within the above range, for example, after the adhesive sheet is adhered to the surface of the optical member (polarizing film or the like), and then peeled off, and then the interlayer filler or the like is newly provided on the surface of the peeled optical member, the adhesion (adhesiveness) between the surface of the optical member (polarizing film or the like) and the interlayer filler or the like is not reduced, and a problem such as peeling is not caused, which is a preferable mode. It is assumed that the residual adhesion rate is high because the wettability is improved in relation to an interlayer filler or the like newly provided after the polyether compound is transferred to the surface of the optical member as an adherend, although the details are not clear, when the residual adhesion rate is more than 100%.
[ Table 5]
Figure BDA0002111297040000371
As can be seen from the evaluation results in table 5, in all the examples, a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) was obtained which was excellent in antistatic property when peeled from the surface of an adherend (in this case, a film with a hard coat layer), excellent in residual adhesive strength and residual adhesive ratio of an acrylic tape which was adhered to the surface of the adherend after peeling the pressure-sensitive adhesive sheet from the surface of the adherend, and excellent in adhesion (adhesiveness) between the acrylic pressure-sensitive adhesive tape and the surface of the adherend after peeling the pressure-sensitive adhesive sheet.
On the other hand, from the evaluation results of table 5, it was confirmed that in comparative example 1, when the pressure-sensitive adhesive solution (composition) was prepared, the polyether compound containing a siloxane chain was used, and therefore, the residual adhesive force and the residual adhesive ratio were low, and the adhesiveness (adhesiveness) was poor, and in comparative examples 2 and 3, the number of polyoxyalkylene chains was less than the desired range, and therefore, the interaction with the ionic compound was weak, and the antistatic property was poor.
Industrial applicability
The adhesive sheet disclosed herein is suitable as a surface protective film for protecting an optical member used as a component of a liquid crystal display panel, a Plasma Display Panel (PDP), an organic Electroluminescence (EL) display, a touch panel, or the like, during the production of the optical member, during transportation, or the like. In particular, the film is useful as a surface protective film (surface protective film for optical use) applied to optical members such as a polarizing film for a liquid crystal display panel, a wavelength plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light diffusion sheet, and a reflection sheet.

Claims (5)

1. An adhesive composition comprising:
an adhesive polymer,
A polyether compound containing 3 or more polyoxyalkylene chains in the molecule and containing no siloxane chain, and an ionic compound.
2. The adhesive composition according to claim 1, wherein the adhesive polymer is a (meth) acrylic polymer, and/or a urethane-based polymer.
3. The adhesive composition according to claim 1 or 2, wherein the polyoxyalkylene chain has at least one terminal selected from the group consisting of a linear or branched alkyl group, a saturated fatty acid residue, and an unsaturated fatty acid residue.
4. An adhesive sheet comprising a substrate film and, formed on at least one surface thereof, an adhesive layer comprising the adhesive composition according to any one of claims 1 to 3.
5. An optical member to which the adhesive sheet according to claim 4 is attached.
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