TW202000816A - Adhesive composition, adhesive sheet and optical member having excellent antistatic property and sealability - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition, an adhesive sheet with an adhesive layer formed by the adhesive composition, and an optical member adhered onto (protecting) the adhesive sheet. The adhesive composition is able to obtain the following adhesive sheet (adhesive layer): having excellent antistatic properties when the adhesive sheet is peeled off from the surface of an optical member (for example, a polarizing film or the like) to which an adhesive sheet used for surface protection is adhered, and excellent sealability (adhesion) between the optical member surface and a layer of an interlayer filler or the like when a new layer of the interlayer filler or the like is provided on the surface after peeling off the adhesive sheet. The adhesive composition of the present invention is characterized in that: comprising an adhesive polymer, a polyether compound containing three or more polyoxyalkylene chains in a molecule but not containing a silicone chain, and an ionic compound.

Description

Adhesive composition, adhesive sheet and optical member

The invention relates to an adhesive composition, an adhesive sheet and an optical member. In particular, the adhesive sheet obtained from the above-mentioned adhesive composition is suitable for application to plastic products that easily generate static electricity (for example, liquid crystal display panels, plasma display panels (PDP), organic electroluminescence (EL)) Display, etc.), among them, for the protection of optical members (for example, polarizing films, wavelength plates, retardation plates, optical compensation films, reflective sheets, brightness enhancement films, touch panel members used in liquid crystal displays, etc.), etc. Surface protective films used for surface purposes are particularly useful.

The adhesive sheet (surface protective film) usually has a configuration in which an adhesive layer is provided on a film-shaped substrate film. The adhesive sheet is bonded to the adherend (protected body) via the adhesive layer, and is used for the purpose of protecting the adherend from damage or contamination during processing and transportation. For example, a liquid crystal display panel is formed by bonding an optical member such as a polarizing film or a wave plate to a liquid crystal cell through an adhesive layer. In the manufacture of the liquid crystal display panel, after the polarizing film attached to the liquid crystal cell is temporarily manufactured into a roll form, it is rolled out from the roll and cut to a desired size corresponding to the shape of the liquid crystal cell for use. Here, the polarizing film may be rubbed with the conveying roller and the like during the processing of the polarizing film and during transportation, so in order to prevent this, it is taken on one side or both sides of the polarizing film (typically single side) Measures for protection by bonding the sheet. Moreover, the adhesive sheet is peeled off at a stage when it becomes unnecessary.

Generally, the adhesive sheet (surface protective film) or optical member is made of plastic material, so the electrical insulation is high, and static electricity is generated due to friction or peeling. Therefore, when the adhesive sheet is peeled off from an optical member such as a polarizing film, static electricity is easily generated. If a voltage is applied to the liquid crystal in a state where the static electricity remains, there is a loss of alignment of liquid crystal molecules, and there is a concern that the panel may be damaged. In addition, the existence of static electricity may also become the main reason for attracting dust or reducing workability. Due to the above, in order to impart antistatic properties to the adhesive layer itself constituting the adhesive sheet, the adhesive (adhesive composition) contains polyether-modified polysiloxane or ionicity that functions as an antistatic agent Compound (see Patent Document 1).

In addition, after peeling off the adhesive sheet (surface protection film) from the surface of the optical member, a layer having other functions may be provided on the surface of the optical member. For example, a layer such as an interlayer filler may be provided in order to connect the surface of an optical member such as a polarizing film or a layer having a touch panel function with a protective layer made of glass, plastic, etc. (see Patent Document 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-236266 [Patent Document 2] Japanese Patent Laid-Open No. 2016-113467

[Problems to be solved by the invention]

However, if an adhesive sheet (adhesive layer) formed of an adhesive containing polyether-modified polysiloxane is attached to an optical member such as a polarizing film, it will be peeled off when it becomes unnecessary The following problems: the polyether-modified polysiloxane component contained in the adhesive sheet (adhesive layer) is transferred to the surface of the optical member, and after the generation, a layer such as an interlayer filler provided on the surface of the optical member, and the above After the adhesive sheet is peeled off, the adhesion (adhesion) of the surface of the optical member decreases.

Therefore, diligent research was conducted in view of the above circumstances, and as a result, an object of the present invention is to provide an adhesive composition, an adhesive sheet having an adhesive layer formed of the adhesive composition, and attaching (protecting) the adhesive sheet Optical member, the above adhesive composition can obtain the following adhesive sheet (adhesive layer): peel off the adhesive sheet from the surface of the optical member (for example, polarizing film, etc.) attached with an adhesive sheet for surface protection It has excellent antistatic properties, and when a layer of an interlayer filler or the like is newly provided on the surface of the optical member after the above-mentioned adhesive sheet is peeled off, the adhesion (adhesion) between the surface of the optical member and the layer of the interlayer filler or the like is excellent. [Technical means to solve the problem]

That is, the adhesive composition of the present invention is characterized by containing an adhesive polymer, a polyether compound containing three or more polyoxyalkylene chains in a molecule but not containing a polysiloxane chain, and an ionic compound.

In the adhesive composition of the present invention, it is preferable that the adhesive polymer is a (meth)acrylic polymer and/or a urethane polymer.

In the adhesive composition of the present invention, it is preferable that the terminal of the polyoxyalkylene chain contains at least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues, and unsaturated fatty acid residues .

The adhesive sheet of the present invention preferably has an adhesive layer formed of the adhesive composition on at least one side of the base film.

The optical member of the present invention is preferably attached with the above-mentioned adhesive sheet. [Effect of invention]

In the present invention, an adhesive sheet having an adhesive layer formed of an adhesive composition containing an adhesive polymer, an ionic compound as an antistatic agent, and a specific polyether compound is attached to the surface of an optical member such as a polarizing film , It is excellent in antistatic property when peeled off when it becomes unnecessary, and the adhesion between the surface of the optical member after the above-mentioned adhesive sheet is peeled, and the interlayer filler and the like re-placed on the surface of the above-mentioned optical member (adhesiveness) )Excellent and useful.

Hereinafter, the embodiments of the present invention will be described in detail.

<The overall structure of the adhesive sheet (surface protective film)> The adhesive sheets disclosed herein are generally referred to as adhesive tapes, adhesive labels, adhesive films, etc., and are particularly suitable as optical components (for example, optical components used as components of liquid crystal display panels such as polarizing films and wave plates) ) A surface protective film that protects the surface of optical parts during processing or during transportation. The adhesive layer in the surface protection film is typically formed continuously, but it is not limited to this form. For example, it may be an adhesive layer formed in a regular or irregular pattern such as dots and stripes. In addition, the adhesive sheet (surface protective film) disclosed herein may be in the form of a roll or a sheet.

<Base film> The adhesive sheet (surface protective film) of the present invention preferably has a base film. In the technique disclosed herein, the resin material constituting the base film can be used without particular limitation, and it is preferable to use, for example, transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, flexibility, and dimensional stability Materials with excellent properties such as sex. In particular, since the base film has flexibility, the adhesive composition can be applied by a roll coater or the like, and it can be wound into a roll, which is useful.

As the base film, for example, polyester-based polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate can be used; Cellulose-based polymers such as acetyl cellulose and triethyl acetyl cellulose; polycarbonate-based polymers; acrylic-based polymers such as polymethyl methacrylate; cycloolefin-based polymers, etc. as the main resin component (of the resin components) The main component, typically a component that accounts for more than 50% by mass), a plastic film made of a resin material is preferably used as the base film. As another example of the above-mentioned resin material, styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer; polyethylene, polypropylene, cyclic or polyolefin having a reduced ene structure, ethylene-propylene Olefin-based polymers such as copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon 6, nylon 6,6, and aromatic polyamides as resin materials. As another example of the above-mentioned resin materials, amide imide-based polymers, lanthanide-based polymers, polyether lanthanide-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers can be cited , Vinylidene chloride-based polymer, vinyl butyral-based polymer, aryl ester-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, etc. It may also be a base film containing a blend of two or more of the above polymers.

As the substrate film, a plastic film containing a transparent thermoplastic resin material can be preferably used. Among the above-mentioned plastic films, the use of polyester film is a better form. Here, the polyester film means that polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, etc. have an ester bond as the basic The polymer material (polyester resin) of the main skeleton is set as the main resin component. The polyester film has excellent characteristics such as excellent optical characteristics and dimensional stability as a base film of an adhesive sheet (surface protective film). On the other hand, the polyester film itself has the property of being easily charged.

Various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.) may be blended in the resin material constituting the base film as needed. Known or conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of primers can also be performed. Such surface treatment can be, for example, a treatment for improving the adhesion between the base film and the adhesive layer (grabbing of the adhesive layer).

The adhesive sheet (surface protection film) of the present invention can also use a plastic film that has undergone antistatic treatment as the above-mentioned base film. By using the above-mentioned base film, the charging of the adhesive sheet itself during peeling can be suppressed, which is preferable. In addition, the base film is a plastic film, and by performing antistatic treatment on the plastic film, the charging of the adhesive sheet itself can be reduced, and a film with excellent antistatic ability to the adherend can be obtained. In addition, the method of imparting an antistatic function is not particularly limited, and a conventionally known method can be used. For example, coating an antistatic resin containing an antistatic agent and a resin component or containing a conductive polymer or a conductive substance The method of conductive resin; the method of evaporation or plating of conductive materials; and the method of mixing antistatic agents, etc.; the method of forming antistatic layers, etc.

The thickness of the base film is usually 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the above-mentioned base film is within the above-mentioned range, it is excellent in adhesion workability to the adherend and peeling workability from the adherend, which is preferable.

The adhesive sheet disclosed herein can be implemented in the form of an antistatic layer and other layers in addition to the base film and the adhesive layer. Examples of the other layers described above include an undercoat layer (adhesion layer) that improves the antistatic layer or adhesive layer's gripping property.

<Adhesive composition> The adhesive composition of the present invention can be used without particular limitation as long as it contains an adhesive polymer having adhesiveness, and an adhesive layer can be formed from the adhesive composition. As the above-mentioned adhesive composition, for example, acrylic adhesives, urethane adhesives, synthetic rubber adhesives, natural rubber adhesives, etc., among which the more preferable adhesive polymer is ( Methacrylic acid polymer and/or urethane polymer, more preferably using (containing) an acrylic adhesive containing (meth)acrylic polymer and/or containing urethane For the polymer-based urethane-based adhesive, it is particularly preferred to use an acrylic adhesive of the (meth)acrylic polymer used as the above-mentioned adhesive polymer.

<Acrylic Adhesive> When an acrylic adhesive is used for the adhesive layer, for the (meth)acrylic polymer as the adhesive polymer constituting the acrylic adhesive, as the raw material monomer constituting the polymer, As the main monomer, a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms is used. As the (meth)acrylic monomer, one kind or two or more kinds can be used. By using the above-mentioned (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is easy to control the peeling force (adhesive force) of the adherend (protected body) to be low and obtain light peeling Adhesive sheet (surface protective film) with excellent performance or re-peelability. Furthermore, in the present invention, (meth)acrylic polymer means acrylic polymer and/or methacrylic polymer, and (meth)acrylate means acrylate and/or 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, and (meth)acrylic acid. Butyl ester, second butyl (meth)acrylate, third butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (methyl ) Isodecyl acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc.

Among them, when the adhesive sheet of the present invention is used as a surface protective film, 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, iso-(meth) acrylate Decyl esters, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc., having an alkyl group having 4 to 14 carbon atoms ( Methacrylic acid monomers are preferred. In particular, by using a (meth)acrylic monomer having an alkyl group having 4 to 14 carbon atoms, it is easy to control the peeling force (adhesive force) to the adherend to be low, and the removability is excellent.

In particular, it is preferably 70% by mass of a (meth)acrylic monomer containing an alkyl group having 1 to 14 carbon atoms relative to 100% by mass of the total monomer components constituting the (meth)acrylic polymer. The above is more preferably 80% by mass or more, further preferably 85 to 99.9% by mass, and particularly preferably 90 to 99.5% by mass. When it is less than 70% by mass, the moderate wettability of the adhesive composition or the cohesive force of the adhesive layer becomes poor, which is not good.

In addition, 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, one kind or two or more kinds can be used. By using the above-mentioned hydroxyl group-containing (meth)acrylic monomer, it is easy to control the crosslinking of the adhesive composition, etc., and it is easy to control the improvement of wettability by flow and the reduction of the peeling force (adhesive force) during peeling balance.

Examples of the hydroxyl-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-hydroxylauryl (meth)acrylate, (4-hydroxymethyl acrylate) Cyclohexyl) methyl ester, N-methylol (meth) acrylamide, etc. In particular, by using a hydroxyl group-containing (meth)acrylic monomer having an alkyl group with a carbon number of 4 or more, light peeling during high-speed peeling becomes easy, which is preferable.

It is preferably 30% by mass or less, and more preferably 20% by mass or less, based on 100% by mass of the total monomer components constituting the (meth)acrylic polymer. Furthermore, it is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass. When it is within the above range, it is easy to control the balance between the wettability of the adhesive composition and the cohesive force of the obtained adhesive layer, which is preferable.

In addition, as other polymerizable monomer components, in order to easily obtain a balance of adhesion performance, the Tg can be adjusted to 0°C or lower (usually -100°C or higher), and used for adjustment within the range that does not impair the effects of the present invention (A Group) Acrylic polymer glass transition temperature, peelable polymerizable monomers, etc.

Other polymerizable than the above (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the above hydroxyl-containing (meth)acrylic monomer used as the (meth)acrylic polymer As the monomer, a carboxyl group-containing (meth)acrylic monomer can be used. By using the above-mentioned carboxyl group-containing (meth)acrylic monomer, it is possible to suppress the increase in the adhesive force of the adhesive sheet (adhesive layer) over time, and the removability, the adhesive force increase prevention property, and the workability are excellent, and, The cohesive force and shear force of the adhesive layer are also excellent, which is better.

Examples of the carboxyl group-containing (meth)acrylic monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate.

The carboxyl group-containing (meth)acrylic monomer is preferably 0 to 3% by mass, more preferably 0 to 2% by mass relative to 100% by mass of the total monomer components constituting the (meth)acrylic polymer. It is further preferably 0 to 1% by mass, and particularly preferably 0.001 to 0.5% by mass. When it is within the above range, it is easy to control the balance between the wettability of the adhesive composition and the cohesive force of the obtained adhesive layer, which is preferable.

In addition, when the above-mentioned hydroxyl group-containing (meth)acrylic monomer and carboxyl group-containing (meth)acrylic monomer are used in combination, the total amount of monomer components constituting the (meth)acrylic polymer is 100 The mass% preferably contains 0.005-0.1 mass% of the carboxyl group-containing (meth)acrylic monomer. By adjusting to the above range, an adhesive sheet (adhesive layer) excellent in re-peelability and prevention of increase in adhesion can be obtained, which is effective.

In addition, other polymerizable monomers can be used without particular limitation as long as the characteristics of the present invention are not impaired. For example, cohesiveness/heat resistance improving components such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, amide imine group-containing monomers, amine group-containing monomers, Components containing epoxy group-containing monomers, N-acryloyl morpholine, vinyl ether monomers, etc. that increase the peeling force (adhesion) or have functional groups that function as crosslinking groups. Among them, nitrogen-containing monomers such as cyano group-containing monomers, amide group-containing monomers, amide imine group-containing monomers, amine group-containing monomers, and N-propenyl morpholine are preferably used. By using a nitrogen-containing monomer, it is possible to ensure that moderate peeling force (adhesive force) such as bumping or peeling is not generated, and an adhesive sheet (surface protective film) with more excellent shearing force can be obtained, which is useful. One kind or two or more kinds of these polymerizable monomers can be used.

Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

Examples of the amidyl group-containing monomers include, for example, acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N ,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N , N-dimethylaminopropylpropylacrylamide, N,N-dimethylaminopropylmethacrylamide, diacetoneacrylamide, etc.

Examples of the above-mentioned iminium group-containing monomers include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and ikonamide.

Examples of the amine group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylamine (meth)acrylate. Propyl ester and so on.

Examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl laurate.

Examples of the aromatic vinyl monomers include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether.

Examples of the vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

In the present invention, the other polymerizable monomer is preferably 0 to 30% by mass, and more preferably 0 to 20% by mass relative to 100% by mass of the total monomer component constituting the (meth)acrylic polymer. In order to obtain the desired characteristics, the other polymerizable monomers described above can be appropriately adjusted.

In addition, the (meth)acrylic polymer may further contain an epoxy alkyl group-containing reactive monomer as a monomer component. By using the (meth)acrylic polymer containing the above-mentioned epoxyalkyl group-containing reactive monomer as the monomer component as the base polymer, the compatibility of the base polymer with the above-mentioned polyether compound is improved, It is possible to suitably suppress the leakage to the adherend, and obtain an adhesive composition that is resistant to contamination (low contamination).

The weight average molecular weight (Mw) of the (meth)acrylic polymer is preferably 100,000 to 2 million, more preferably 200,000 to 1 million, still more preferably 300,000 to 800,000, and particularly preferably 300,000 to 700 thousand. When the weight-average molecular weight is less than 100,000, there is a tendency for the paste to remain due to the reduced cohesive force of the adhesive layer. On the other hand, when the weight average molecular weight exceeds 2 million, the fluidity of the polymer decreases, and the wetting of the adherend (such as a polarizing film) becomes insufficient, resulting in the adherend and the adhesive sheet ( The surface protective film) tends to swell out between the adhesive layers. In addition, the weight average molecular weight is obtained by GPC (gel permeation chromatography) measurement.

In addition, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0°C or lower, more preferably -20°C or lower, even more preferably -40°C or lower, and particularly preferably -50°C or lower ( Usually above -100°C). When the glass transition temperature is higher than 0°C, there is a polymer that does not flow easily, for example, the wetting of the polarizing film as an optical member becomes insufficient, resulting in the adhesive between the polarizing film and the adhesive sheet (surface protective film) There is a tendency to bulge between layers. Among them, in particular, by setting the glass transition temperature to -60° C. or lower, an adhesive layer excellent in wettability and light peelability to an optical member (for example, a polarizing film) can be easily obtained. Furthermore, the glass transition temperature of the (meth)acrylic polymer can be adjusted within the above range by appropriately changing the monomer component or composition ratio used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and it can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., especially from the viewpoint of workability or the adherend ( In terms of characteristics such as low pollution of the protected body, solution polymerization is better. Moreover, the obtained polymer may be any copolymer among random copolymers, block copolymers, alternating copolymers, graft copolymers and the like.

<urethane adhesives> When a urethane-based adhesive is used in the above-mentioned adhesive layer, any appropriate urethane-based adhesive can be used. As such a urethane-based adhesive, preferably, an urethane-based polymer containing an adhesive polymer obtained by reacting a polyol and a polyfunctional isocyanate compound, or as an amino group A carbamate-based polymer of an adhesive polymer obtained by reacting a formate prepolymer with a polyfunctional isocyanate compound.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-based polyol, and the like. The polyol may be only one kind, or two or more kinds.

The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. Alcohol, 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, glycerin, trimethylolpropane , Pentaerythritol, hexanetriol, polypropylene glycol, etc. Examples of the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and 1,14-fourteen Alkanedioic 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-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, anhydrides of these, etc.

Examples of polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxybenzene. (Catechol, resorcinol, hydroquinone, etc.) etc. as the starting agent, polyether polyether obtained by the addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. alcohol. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

Examples of polycarbonate polyols include polycarbonate polyols obtained by subjecting the above-mentioned polyol component and phosgene to polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, and dipropyl carbonate Ester, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate and other carbonate diesters are obtained by transesterification condensation Polycarbonate polyol; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components; polycarbonate polyol obtained by subjecting the above various polycarbonate polyols to a carboxyl-containing compound by esterification reaction ; Polycarbonate polyol obtained by etherification reaction of the above-mentioned various polycarbonate polyols and hydroxyl-containing compounds; Polycarbonate polyol obtained by transesterification of the above-mentioned various polycarbonate polyols and ester compounds; Polycarbonate polyol obtained by subjecting the above various polycarbonate polyols and hydroxyl-containing compounds to transesterification; Polyester polycarbonate obtained by subjecting the above various polycarbonate polyols and dicarboxylic acid compounds to polycondensation reaction Polyol; copolymerized polyether-based polycarbonate polyol obtained by copolymerizing the above various polycarbonate polyols with alkylene oxide, etc.

Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with the aforementioned polyol components. Specifically, for example, castor oil-based polyol obtained by reacting castor oil fatty acid with polypropylene glycol can be cited.

The number average molecular weight (Mn) of the polyol is preferably 300 to 100,000, more preferably 400 to 75,000, still more preferably 450 to 50,000, and particularly preferably 500 to 30,000. By adjusting the number average molecular weight (Mn) of the polyol within the above-mentioned range, the wettability of the adhesive layer can be improved, so that it can be attached without entrapment of air bubbles.

Examples of the polyfunctional isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, cyclopentyl diisocyanate, Cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl) cyclohexane and other alicyclic isocyanates, 2,4-toluene diisocyanate, 4,4' -Aromatic isocyanates such as diphenylmethane diisocyanate, xylylene diisocyanate (XDI), via allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea Bond, carbodiimide bond, uretonimine bond, 㗁二𠯤trione bond, etc. modified polyisocyanate modified from the above isocyanate compound. For example, as a commercially available product, trade names include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, manufactured by Mitsui Chemicals Corporation), Sumidur T80, Sumidur L, Desmodur N3400 (above, Sumika Bayer Urethane Corporation). Manufacturing), MILLIONATE MR, MILLIONATE MT, CORONATE L, CORONATE HL, CORONATE HX (above, manufactured by Tosoh Corporation). These isocyanate compounds may be used alone or in combination of two or more kinds. A bifunctional isocyanate compound and a trifunctional 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 the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.1 to 3.0, further preferably 0.2 to 2.5, and particularly preferably 0.3 to 2.25, preferably 0.5 to 2.0. By adjusting the equivalent ratio of the NCO group/OH group to the above range, the re-peeling of the adhesive force can be suppressed, which is preferable.

<Polyether compounds containing more than 3 polyoxyalkylene chains in the molecule and no polysiloxane chains> The adhesive composition of the present invention is characterized by containing a polyether compound containing 3 or more polyoxyalkylene chains in its molecule and not containing polysiloxane chains. By containing the above polyether compound in the adhesive composition, an adhesive sheet (adhesive layer) excellent in antistatic property can be obtained by interacting with the ionic compound, and the adhesive sheet can be self-adhered (Optical members such as polarizing films) After peeling, the adhesion (adhesion) between the layer of the interlayer filler provided on the surface of the adherend and the surface of the adherend after peeling the above-mentioned adhesive sheet is excellent, so it is preferable Appearance. In addition, "polysiloxane chain" refers to a structure containing a siloxane bond. As the compound containing a polysiloxane chain, for example, polydimethylsiloxane can be cited.

The polyether compound contains 3 or more polyoxyalkylene chains in the molecule, preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. When the polyoxyalkylene chain is 3 or more, the interaction with the ionic compound is enhanced and the antistatic property is excellent, which is preferable. In addition, the said polyoxyalkylene chain means the one which contains 2 or more oxyalkylene units, the said polyoxyalkylene chain exists 3 or more, and each polyoxyalkylene chain may be the same or different.

In addition, the oxyalkylene unit is not particularly limited, and may be linear or branched, for example, oxymethylene, oxyethyl, oxyalkyl, oxypropyl, oxygen Butylidene oxide, ethylene oxide-propylene oxide block copolymer, ethylene oxide-butylene oxide block copolymer, ethylene oxide-propylene oxide random copolymer, etc., preferably oxyethylidene or oxypropylene.

The number of repeating units of the polyoxyalkylene group is preferably 2 or more and 200 or less. When the number of repeating units exceeds 200, crystallization is caused and the antistatic property is reduced, which is not good.

In addition, the ends of the polyoxyalkylene chain may be linear or branched alkyl groups such as hydrogen, methyl, ethyl, unsaturated fatty acid residues such as oleic acid residues, and saturated fatty acids such as isostearic acid residues. The residue, carboxyl group, etc., more preferably, the end of the polyoxyalkylene chain contains at least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues, and unsaturated fatty acid residues.

The ends of the above polyoxyalkylene chains may be the same or different in the molecule. Due to the presence of alkyl or unsaturated fatty acid residues and saturated fatty acid residues as low-polarity components (low-polarity groups), ionic compounds that interact with the above-mentioned polyoxyalkylene chain sites are likely to segregate to the surface of the adhesive layer ( (The interface between the adhesive layer and the air, or the interface between the adhesive layer and the separator), excellent antistatic properties, and further improve the wettability of the interlayer filler, etc., by which the residual adhesion of the interlayer filler, etc. is excellent, which is preferred . In addition, the alkyl group is preferably a methyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isononyl. Alkyl groups, as saturated fatty acid residues, preferably butyric acid residues, hexanoic acid residues, lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, isostearic acid residues Saturated fatty acid residues having 1 to 20 carbon atoms are preferred as unsaturated fatty acid groups, preferably crotonic acid residues, myristic oleic acid residues, palmitoleic acid residues, oleic acid residues, elaidic acid residues, Unsaturated fatty acid groups with 1 to 20 carbon atoms, such as cod oleic acid residues.

The following chemical formulae 1 to 9 are examples of the above polyether compounds. Chemical formula 1 is glycerin, chemical formula 2 is trimethylolpropane, chemical formula 3 is diglycerin, chemical formula 4 is pentaerythritol, and chemical formula 5 is methyl glucoside Formula, Chemical Formula 6 and Chemical Formula 7 are sorbitan fatty acid ester series, Chemical Formula 8 is sorbitan series, and Chemical Formula 9 is a castor oil-based polyether compound. Furthermore, R1 in the following chemical formulas 1 to 9 is a polyoxyalkylene group (for example, polyoxyethylene group, polyoxypropylene group, polyoxybutylene group), which may be a homopolymer or block copolymerization It can also be a random copolymer. In addition, the number of repeating units of the oxyalkylene unit is preferably 2 to 200. When the number of repeating units exceeds 200, crystallization is likely to occur, and the antistatic property is reduced. When it is less than 2, the interaction with the ionic compound is reduced. The antistatic property is reduced, which is not good. In addition, R1 may have the same structure in the molecule of the polyether compound, or may be different. R2 in the following chemical formulas 1 to 9 may be linear or branched alkyl groups such as hydrogen, methyl, ethyl and the like, unsaturated fatty acid residues such as oleic acid residues, and saturated fatty acid residues such as isostearic acid residues , Carboxyl group and the like, more preferably R2 includes at least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues, and unsaturated fatty acid residues. In addition, R2 may have the same structure in the molecule of the polyether compound, or may be different.

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As a specific example of the above polyether compound, a compound having three polyoxyalkylene chains includes GP250, GP400, GP600, GP1000, GP1500, GP3000, GP4000 (above, Sanyo Chemical Co., Ltd.) as polyoxypropylene glyceryl ether (Manufactured), G-450, G-750, G-1200 as polyoxyethylene glyceryl ether, TD-4S as polyoxyethylene trimethylolpropane distearate, as polyoxyethylene glycerol triisostearate GT-10IS, GT-20IS, GT-30IS of esters, GM-8IS, GM-10IS, GM-15IS, GM-20IS, GM-30IS, GM-60IS as polyoxyethylene glycerol isostearate S-753 as polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, 43TT-2500, 10TT-4500 as polyoxyethylene polyoxypropylene trimethylolpropane, polyoxyethylene polyoxypropylene glyceryl ether 50TG-32 (Above, manufactured by NOF Corporation), the compound having 4 polyoxyalkylene chains includes DGP-700, DGP-950 as polyoxypropylene diglyceryl ether, and polyoxyethylene polyoxypropylene pentaerythritol ether as polyoxyethylene 5TP-300KB, RC-9050 as polyoxybutylene polyoxyethylene pentaerythritol ether, MG-10E, MG-20E as polyoxyethylene methyl glucoside, polyoxyethylene polyoxypropylene methyl glucose as polyoxybutylene MG-2070 of glycoside, OT-521, ST-521, ST-5160, LT-221, PT-221, OT-206, OT-221, ST-206, polyoxyethylene sorbitan fatty acid ester LT-210, IST-221, MG-120TIS (above, manufactured by NOF Corporation) as polyoxyethylene methylglucose triisostearate, compounds with 6 polyoxyalkylene chains can be cited as ST-6E, ST-30E, ST-30EC, ST-40E, ST-60E of polyoxyethylene sorbitol tetraoleate, SP-40E as polyoxyethylene sorbitol pentaoleate, polyethylene oxide Sorbitol tetraisostearate ST-30IS, HS-1600D, HS-2000D as polyoxypropylene sorbitol, C-35, HC-20M (above, manufactured by NOF Corporation) as polyoxyethylene castor oil )Wait. These polyether compounds may be used alone or in combination of two or more.

With respect to 100 parts by mass of the adhesive polymer (which is a base polymer such as a (meth)acrylic polymer or a urethane polymer, etc.) constituting the above adhesive composition, the content of the above polyether compound is It is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, still 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. When it is within the above range, the antistatic property and the low pollution property are excellent, which is preferable.

<Ionic compound> The adhesive composition of the present invention is characterized by containing an ionic compound. As the ionic compound, it is preferable to use an alkali metal salt and/or an ionic liquid. By containing the above-mentioned ionic compound, excellent antistatic property or peeling antistatic property can be imparted.

The alkali metal salt has a high ion dissociation property, so it is preferable in that it can exhibit excellent antistatic ability even in a small amount of addition. Examples of the alkali metal salt, for example, may be preferably used include a Li ^+, Na ^+, K ⁺ of the cation, and including ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, _{^{PF 6 -, SCN -, ClO}} 4 -, NO 3 -, CH 3 COO -, C 9 H 19 COO -, CF 3 COO -, C 3 F 7 COO -, CH 3 SO 3 -, CF 3 SO 3 - ^{_{, C 4 F 9 SO 3 -}} , C 2 H 5 OSO 3 -, C 6 H 13 OSO 3 -, C 8 H 17 OSO 3 -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2 _{^{) 2 N -, (C 3}} F 7 SO 2) 2 N -, (C 4 F 9 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 - ^{_{, TaF 6 -, F (HF}} ) n -, (CN) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CH 3) 2 PO 4 -, (C 2 H 5) 2 PO _{^{4 -, CH 3 (OC 2}} H 4) 2 OSO 3 -, C 6 H 4 (CH 3) SO 3 -, (C 2 F 5) 3 PF 3 -, CH 3 CH (OH) COO - and (FSO ₂ ) A metal salt composed of ₂ N ^- anions. More preferably, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C and other lithium salts, preferably LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₃ F ₇ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C. These alkali metal salts may be used alone or in combination of two or more.

It is preferable that the ionic liquid contains an organic cation component and an anion component represented by the following formulas (A) to (E). By using the ionic liquid having the cation with a melting point of 100°C or less, one with more excellent antistatic ability can be obtained.

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In the above formula (A), R _a represents _a hydrocarbon group having 4 to 20 carbon atoms, and may also be a functional group obtained by replacing a part of the above hydrocarbon group with a hetero atom. R _b and R _{c are the} same or different, and represent hydrogen or carbon number 1 The hydrocarbon group of ~16 may also be a functional group obtained by replacing a part of the above hydrocarbon group with a hetero atom. However, when the nitrogen atom contains a double bond, there is no R _c .

The above-described formula (B), the R _d represents a hydrocarbon group having 2 to 20 carbon atoms, the hydrocarbon groups may also be part of the hetero atoms is substituted with the functional group is obtained, R _e, R _f are identical or different and R _g, represents hydrogen or The hydrocarbon group having 1 to 16 carbon atoms may also be a functional group obtained by replacing a part of the above hydrocarbon group with a hetero atom.

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

Z in the above formula (D) represents a nitrogen, sulfur or phosphorus atom, R _l , R _m , R _n and R _{o are the} same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, or a part of the above hydrocarbon group may be hetero atoms The functional group obtained by substitution. However, when Z is a sulfur atom, there is no R _o .

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

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

Specific examples include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4 -Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-B 1-methyl-1-pyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidine Onium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1 -Butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 ,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propyl Piperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperium Pyridinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl- 1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation , 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperium Pyridinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1,2-dimethylindole cation , 1-ethylcarbazole cation, N-ethyl-N-methylmorpholinium cation, etc.

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

Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl -3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-di Methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3 -Methylimidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidine Onium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetra Hydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl -1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidine Onium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, etc.

Examples of the cation represented by formula (C) include pyrazolium cations and pyrazolinium cations.

Specific examples include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolium cation, 1-ethyl-2,3, 5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1- Ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-tri Methylpyrazolium cation, etc.

Examples of the cation represented by the formula (D) include tetraalkylammonium cations, trialkylammonium cations, tetraalkylphosphonium cations, and a part of the above-mentioned alkyl groups are substituted with alkenyl groups or alkoxy groups, and then epoxy groups The cations obtained.

As specific examples, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethyl can be preferably used. Ammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl tri Methylammonium cation, trimethylammonium cation, triethylammonium cation, tributylammonium cation, trihexylammonium cation, diethylmethylammonium cation, dibutylethylammonium cation, dimethyldecylammonium cation Cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyl Decylphosphonium cation, diallyldimethylammonium cation, tributyl-(2-methoxyethyl)phosphonium cation, etc. Among them, it is preferable to use triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylammonium cation, dibutylethylammonium cation, dimethyldecane Asymmetric tetraalkylammonium cations such as tribasic ammonium cations, triethylmethylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations, trialkylammonium cations, tetraalkylphosphonium cations, or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, diallyldimethylammonium cation, N,N- Dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N -Amyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexyl ammonium cation, N,N-dimethyl-N-ethyl-N-heptyl ammonium cation, N,N-di Methyl-N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-N-butyl Ammonium cation, N,N-dimethyl-N-propyl-N-pentyl ammonium cation, N,N-dimethyl-N-propyl-N-hexyl ammonium cation, N,N-dimethyl- N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexyl ammonium cation, N,N-diethyl-N-butyl-N-heptyl ammonium cation , N,N-dimethyl-N-pentyl-N-hexyl ammonium cation, N,N-dimethyl-N,N-dihexyl ammonium cation, trimethylheptyl ammonium cation, N,N-di Ethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N- Heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N ,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-N-butyl -N-hexyl ammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N-methyl-N-pentyl ammonium cation, N,N-di Butyl-N-methyl-N-hexyl ammonium cation, trioctyl methyl ammonium cation, N-methyl-N-ethyl-N-propyl-N-pentyl ammonium cation.

Examples of the cation represented by the formula (E) include cations such as yam. In addition, specific examples of R _P in the above formula (E) include methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl , Tetradecyl, octadecyl, etc.

On the other hand, as an anion component, as long as it becomes an ionic liquid are satisfied, not particularly limited, and may be used e.g. ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 - _{^{, SCN -, ClO 4 -,}} NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, C 4 F 9 SO 3 -, (CF 3 SO 2) 2 N _{^{-, (C 2 F 5 SO}} 2) 2 N -, (C 3 F 7 SO 2) 2 N -, (C 4 F 9 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 _{^{-, SbF 6 -, NbF 6}} -, TaF 6 -, F (HF) n -, (CN) 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 _{^{F 7 COO -, (CF 3}} SO 2) (CF 3 CO) N -, C 9 H 19 COO -, (CH 3) 2 PO 4 -, (C 2 H 5) 2 PO 4 -, CH 3 OSO 3 _{^{-, C 2 H 5 OSO 3}} -, C 4 H 9 OSO 3 -, C 6 H 13 OSO 3 -, C 8 H 17 OSO 3 -, CH 3 (OC 2 H 4) 2 OSO 3 -, C 6 H ^{_{4 (CH 3) SO 3 -}} , (C 2 F 5) 3 PF 3 -, CH 3 CH (OH) COO -, (FSO 2) 2 N -, B (CN) 4 -, C (CN) 3 - , N (CN) ₂ ^-, p-toluenesulfonate anion, 2- (2-methoxyethyl) ethyl sulfate anion.

These plasma liquids can be used alone or in combination of two or more.

With respect to 100 parts by mass of the adhesive polymer (which is a base polymer, such as (meth)acrylic polymer, urethane polymer, etc.) constituting the above adhesive composition, the content of the above ionic compound is It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, still more preferably 0.1 to 2 parts by mass, and particularly preferably 0.2 to 1 part by mass. When it is within the above range, the adhesive sheet of the present invention is easy to achieve both antistatic properties and low contamination, which is preferable.

<Crosslinking agent> For the adhesive sheet (surface protective film) of the present invention, it is preferable that the above-mentioned adhesive composition contains a crosslinking agent. In addition, in the present invention, the above adhesive composition can be used to form an adhesive layer. For example, in the case where the adhesive composition is an acrylic adhesive containing the (meth)acrylic polymer, by appropriately adjusting the constitutional unit, composition ratio, crosslinking of the (meth)acrylic polymer The selection and addition ratio of the agent and crosslinking can obtain an adhesive sheet (adhesive layer) with more excellent heat resistance.

As the crosslinking agent used in the present invention, isocyanate compounds, epoxy compounds, melamine-based resins, aziridine derivatives, metal chelate compounds, etc. can be used, and in particular, the use of isocyanate compounds is preferred. In addition, these compounds may be used alone or in combination of two or more.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, cyclopentane diisocyanate, and cyclohexane. Alicyclic isocyanates such as diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, 4,4'-di Aromatic isocyanates such as phenylmethane diisocyanate and xylylene diisocyanate (XDI), through allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, A polyisocyanate modified product obtained by modifying the above-mentioned isocyanate compound with a carbodiimide bond, a uretonimine bond, and a diketone bond. For example, as a commercially available product, trade names include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, manufactured by Mitsui Chemicals Corporation), Sumidur T80, Sumidur L, Desmodur N3400 (above, Sumika Bayer Urethane Corporation). Manufacturing), MILLIONATE MR, MILLIONATE MT, CORONATE L, CORONATE HL, CORONATE HX (above, manufactured by Tosoh Corporation). These isocyanate compounds may be used alone or in combination of two or more kinds. A bifunctional isocyanate compound and a trifunctional or more isocyanate compound may be used in combination. By using a cross-linking agent in combination, both the adhesiveness and the rebound resistance (adhesion to the curved surface) can be taken into account, and an adhesive sheet with more excellent adhesive properties can be obtained.

Examples of the epoxy compound include N,N,N',N'-tetraglycidyl metaxylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-bis(N , N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Company), etc.

Examples of the melamine-based resin include hexamethylolmelamine and the like. Examples of the aziridine derivatives include commercially available products under the trade names of HDU, TAZM, and TAZO (above, manufactured by Muta Pharmaceutical Co., Ltd.) and the like.

Examples of the metal chelate compound include metal components such as aluminum, iron, tin, titanium, and nickel. Examples of the chelate component include acetylene, methyl acetoacetate, and ethyl lactate.

The content of the crosslinking agent used in the present invention is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and still more preferably 0.5 to 100 parts by mass of the (meth)acrylic polymer. 20 parts by mass, particularly preferably 1 to 18 parts by mass. In the case where the above content is less than 0.01 parts by mass, the cross-linking formation by the cross-linking agent may become insufficient, the cohesive force of the obtained adhesive layer may become small, and sufficient heat resistance may not be obtained, and there may be a paste The tendency of the agent residue. On the other hand, when the content exceeds 30 parts by mass, there is a large cohesive force of the polymer, the fluidity is reduced, and the wetting of the adherend (such as a polarizing film) becomes insufficient, resulting in the adherend and adhesion The agent layer (adhesive composition layer) tends to swell out.

The above adhesive composition may further contain a crosslinking catalyst for making any of the above crosslinking reactions more efficient. As the crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetone) iron, tris(hexane-2,4-dione) Iron, tri(heptane-2,4-diketo) iron, tri(heptane-3,5-diketo) iron, tri(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 -Diketone) iron, tri(nonane-2,4-dioneyl) iron, tri(nonane-4,6-diketoyl) iron, tri(2,2,6,6-tetramethyl Heptane-3,5-diketo) iron, tri(tridecane-6,8-diketo) iron, tri(1-phenylbutane-1,3-diketo) iron, tri( Hexafluoroacetoacetone) iron, tris(ethylacetate) iron, tris(acetate acetate n-propyl) iron, tris(acetate acetate) iron, tris(acetoacetate n-butyl) iron , Iron tris(second butyl acetate), iron tris(third butyl acetate) iron, iron tris(propyl acetate) iron, iron tris(ethyl acetate) iron, tris(propyl acetate) N-propyl ester) iron, tri(isopropyl propyl acetate) iron, tri(propyl propyl acetate n-butyl) iron, tri(propyl propyl acetate second butyl) iron, tri(propyl acetyl acetate third butyl acetate) ) Iron, tris(benzyl acetate) iron, tris(dimethyl malonate) iron, tris(diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy Iron-based catalysts such as base iron and ferric chloride. These crosslinking catalysts may be one kind, or two or more kinds may be used in combination.

The content of the cross-linking catalyst is not particularly limited. For example, it is preferably about 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 part by mass relative to 100 parts by mass of the (meth)acrylic polymer. When it is within the above range, the speed of the cross-linking reaction is faster when the adhesive layer is formed, and the pot life of the adhesive composition also becomes longer, which is a better aspect.

Furthermore, a compound that generates keto-enol tautomerism can be contained in the above adhesive composition. For example, in the adhesive composition containing a cross-linking agent or the adhesive composition used to formulate the cross-linking agent, it may be preferable to adopt a form containing the above-mentioned compound that generates the keto-enol tautomerism. Thereby, the effect of suppressing excessive viscosity increase or gelation of the adhesive composition after the preparation of the crosslinking agent can be achieved, and the pot life of the adhesive composition can be extended. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly meaningful to include a compound that generates keto-enol tautomerism. This technique can be preferably applied to the case where the above adhesive composition is in the form of an organic solvent solution or a solvent-free form.

As the above-mentioned compound that generates keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include: acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2, Β-diketones such as 4-dione, 2,6-dimethylheptane-3,5-dione; methyl acetoacetate, ethyl acetate, isopropyl acetoacetate, acetoacetate Acetyl acetates such as third butyl ester; ethyl acetate, ethyl acetate, isopropyl acetate, third butyl acetate and other acetyl acetates; ethyl butyl acetate , Ethyl isobutyrate, isopropyl isobutyl acetate, tertiary butyl isobutyl acetate and other isobutyl acetate; methyl malonate, ethyl malonate and other malonates, etc. . Among them, preferred compounds include acetone and acetoacetate. The ketone-enol tautomeric compound may be used alone or in combination of two or more.

The content of the keto-enol tautomerism-generating compound relative to 100 parts by mass of the (meth)acrylic polymer can be set to, for example, 0.1 to 20 parts by mass, and is usually suitably set to 0.5 to 15 parts by mass (for example 1 to 10 parts by mass). When the amount of the above compound is too small, there may be cases where it is difficult to exert a sufficient use effect. On the other hand, when the above-mentioned compound is used as much as necessary, it may remain in the adhesive layer and reduce the cohesive force.

Furthermore, the above-mentioned adhesive composition may also contain other well-known additives, for example, powders such as lubricants, colorants, and pigments, plasticizers, adhesion-imparting agents, low-molecular-weight polymers, and surfaces may be appropriately added according to the application. Lubricants, leveling agents, antioxidants, anti-corrosion agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, softeners, anti-aging agents, heat stabilizers, silane coupling agents, inorganic or organic fillers, metal powders, Particles, foils, solvents, etc.

<Adhesive layer and adhesive sheet (surface protective film)> The adhesive sheet of the present invention preferably has an adhesive layer formed of the adhesive composition on at least one side of the base film. Furthermore, the above-mentioned adhesive layer is obtained by cross-linking the above-mentioned adhesive composition, which is usually carried out after applying the adhesive composition, but it is also possible to transfer the adhesive layer containing the cross-linked adhesive composition Print to substrate film, etc.

In addition, the method of forming the adhesive layer on the base film is not particularly limited, for example, by applying the above adhesive composition (solution) to the base film, drying and removing the polymerization solvent, etc., the adhesive layer is formed on the base Manufactured on the material film. Then, for the purpose of adjusting the component movement of the adhesive layer or adjusting the cross-linking reaction, it can also be cured. In addition, when the adhesive composition is applied to the base film to prepare an adhesive sheet, one or more solvents other than the polymerization solvent can be added to the adhesive composition to achieve uniformity on the base film地涂。 Ground coating.

In addition, as a method of forming the adhesive layer when manufacturing the adhesive sheet of the present invention, a known method used in the manufacture of adhesive tapes can be used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating method, extrusion coating method using a die coater, etc. may be mentioned.

The adhesive sheet of the present invention is usually produced in such a manner that the thickness of the adhesive layer becomes 0.1 to 100 μm, preferably about 1 to 80 μm. When the thickness of the adhesive layer is within the above range, it is easy to obtain a moderate balance between re-peelability and adhesiveness, which is preferable.

In addition, the total thickness of the adhesive sheet of the present invention is preferably 8 to 300 μm, more preferably 10 to 200 μm, and most preferably 20 to 100 μm. When it is within the above-mentioned range, the adhesive characteristics (repeelability, adhesiveness, etc.), workability, and appearance characteristics are excellent, and it becomes a preferable aspect. Furthermore, the above-mentioned total thickness refers to the total thickness of all layers including the base film, the adhesive layer, and other layers.

＜isolation film＞ For the adhesive sheet of the present invention, it is preferable to attach a release film to the surface opposite to the surface of the adhesive layer in contact with the substrate film. For the above-mentioned isolation film, for the purpose of protecting the adhesive surface as needed, the isolation film can be attached to the surface of the adhesive layer.

As a material constituting the above-mentioned separator, there is a paper or a plastic film, and in terms of excellent surface smoothness, a plastic film can be preferably used. The film is not particularly limited as long as it can protect the adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, and polymethylpentene film. Polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm. When it is within the above-mentioned range, the adhesion workability to the adhesive layer and the peeling workability of the self-adhesive layer are excellent, which is preferable. For the above-mentioned separator, mold release and antifouling treatment using polysilicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silica powder, etc., or coating type can also be implemented , Anti-static treatment of mixing type, evaporation type, etc.

<Optical components> The optical member of the present invention is preferably attached (protected) to the aforementioned adhesive sheet. The antistatic property when the above-mentioned adhesive sheet is attached to the surface of an optical member such as a polarizing film and the like after peeling, and the interlayer filler, etc., on the surface of the optical member after peeling off the above-mentioned adhesive sheet and the surface of the optical member after being peeled off, etc. The layer has excellent adhesion (adhesion), so it can be used for surface protection applications (surface protection film) such as processing, transportation, and shipping, and is useful for protecting the surface of the optical member.

<Interlayer filler> In an image display device such as a liquid crystal display, when any impact is applied from the outer surface, in order to prevent the impact from being transmitted to an optical member such as a polarizing film and damaging it, it is sometimes closer to the optical member such as a polarizing film A transparent front plate such as an acrylic plate or a glass plate (also called a "window layer", etc.) is provided on the viewing side. In an image display device provided with such a front transparent plate, when an air layer exists between an optical member such as a polarizing film and the front transparent plate, there is a reflection loss due to a refractive index difference at the interface with the air layer, or observation When the image becomes double, the visibility becomes lower. Therefore, in order that there is no air layer between the optical member such as a polarizing film and the front transparent plate, the two may be bonded via a layer formed of an interlayer filler (interlayer filler layer). Examples of the above-mentioned interlayer filler layer (adhesive layer, adhesive sheet) include liquids such as the model "SVR7000 series" manufactured by DEXERIALS, and the brand name "WORLD ROCK HRJ-21" manufactured by Kyoritsu Chemical Industry Co., Ltd. Interlayer filler, or optical transparent adhesive tape (trade name "LUCIACS series") manufactured by Nitto Denko Corporation, etc. Among them, the transparent adhesive tape for optics (trade name "LUCIACS series") manufactured by Nitto Denko Co., Ltd., which contains acrylic polymers that are easy to handle because of the tape state, is used. If it is an adhesive sheet in the present invention, then When attached to the surface of the display panel (polarizing plate, etc.), etc., and when the layer of the interlayer filler is provided on the surface of the optical member after the peeling becomes unnecessary, the adhesion (adhesion) is also excellent, becoming Good looks. [Example]

Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in this specific example. In addition, as long as there is no special explanation, the "parts" and "%" in the following description are the quality standards.

In addition, each characteristic in the following description is measured or evaluated as follows.

<Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer used was measured using a GPC device (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows. Sample concentration: 0.2% by mass (THF (tetrahydrofuran, tetrahydrofuran) solution) Sample injection volume: 10μl Dissolution solution: THF Flow rate: 0.6 ml/min Measuring temperature: 40℃ Column: Sample column; TSKguardcolumn SuperHZ-H (1 piece) + TSKgel SuperHZM-H (2 pieces) Reference column; TSKgel SuperH-RC (1 piece) Detector: Differential Refractometer (RI) In addition, the weight average molecular weight is calculated in terms of polystyrene.

<Theoretical value of glass transition temperature (Tg)> The glass transition temperature Tg (°C) is obtained by the following formula using the following document value as the glass transition temperature Tgn (°C) of the homopolymer of each monomer.

Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)] [In the formula, Tg(℃) represents the glass transition temperature of the copolymer, Wn(-) represents the mass fraction of each monomer, and Tgn(℃) represents The glass transition temperature of the homopolymer of each monomer, n represents the type of each monomer] Literature value: 2-Ethylhexyl acrylate (2EHA): -70℃ 2-Hydroxyethyl acrylate (HEA): -15℃ 4-Hydroxybutyl acrylate (4HBA): -32℃ Acrylic acid (AA): 106℃

In addition, as the above literature value, refer to "Synthesis, Design and New Use of Acrylic Resin" (published by the Central Business Development Center Publishing Department) and "Polymer Handbook" (John Wiley & Sons).

<Preparation of acrylic polymer (1)> In a four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler, 91 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were added 0.02 parts by mass, 0.22 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate, while slowly stirring while introducing nitrogen gas, the temperature of the liquid in the flask was kept near 65°C A polymerization reaction was carried out for 6 hours to prepare an acrylic polymer (1) solution (40% by mass). The weight average molecular weight (Mw) of the acrylic polymer (1) was 540,000, and the glass transition temperature (Tg) was -67°C.

<Preparation of acrylic polymer (2)> 98.5 parts by mass of 2-ethylhexyl acrylate (2EHA), 1.5 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were added to a four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler 0.006 parts by mass, 0.22 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate, while slowly stirring while introducing nitrogen gas, the temperature of the liquid in the flask was kept near 65°C A polymerization reaction was carried out for 6 hours to prepare an acrylic polymer (2) solution (40% by mass). The weight average molecular weight (Mw) of the acrylic polymer (2) was 480,000, and the glass transition temperature (Tg) was -70°C.

<Preparation of acrylic polymer (3)> 96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler as a polymerization start 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate, nitrogen gas was introduced while slowly stirring, the liquid temperature in the flask was kept at around 65°C, and a polymerization reaction was carried out for 6 hours. An acrylic polymer (3) solution (40% by mass) was prepared. The weight average molecular weight (Mw) of the acrylic polymer (3) was 480,000, and the glass transition temperature (Tg) was -68°C.

<Example 1> [Preparation of acrylic adhesive solution] The above acrylic polymer (1) solution (40% by mass) was diluted with ethyl acetate to 20% by mass, and polyoxypropylene glycerin as a polyether compound was added to 500 parts by mass of this solution (100 parts by mass of solid content). Ether (Sannix GP3000, manufactured by Sanyo Chemical Industry Co., Ltd.) 0.5 parts by mass, bis(trifluoromethanesulfonyl)imide lithium as an ionic compound (manufactured by Tokyo Chemical Industry Co., Ltd., LiTFSI) 0.3 parts by mass, as a crosslinking agent Isocyanurate body of hexamethylene diisocyanate (manufactured by Tosoh Corporation, CORONATE HX: C/HX, trifunctional isocyanate compound) 1.5 parts by mass (solid content 1.5 parts by mass), as a crosslinking catalyst 3 parts by mass of dioctyltin laurate (1% by mass ethyl acetate solution) (0.03 parts by mass of solid content) were mixed and stirred to prepare an acrylic adhesive solution.

[Manufacture of antistatic treatment film] Polyvinyl resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder was used as a conductive polymer poly(3,4-ethylenedioxythiophene) based on 100 parts by mass of solid content ( PEDOT)/polystyrene sulfonic acid (PSS) (made by Baytron P, HC Starck) 100 parts by mass based on the solid content, and hexamethylolmelamine as a crosslinking agent was added in 10 parts by mass based on the solid content Into a mixed solvent of water/ethanol (1/1), stir for about 20 minutes and mix thoroughly. In this way, an antistatic agent solution of about 0.4% of NV (non-volatile content) was prepared. Using a Mayer bar, the obtained antistatic agent solution was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm) as a base film, and dried at 130° C. for 1 minute, by which The solvent is removed, an antistatic layer (thickness 0.2 μm) is formed, and an antistatic treatment film (base film with antistatic layer) is produced.

[Preparation of adhesive sheet (surface protective film)] Apply the acrylic adhesive solution to the surface of the antistatic treatment film opposite to the surface with the antistatic layer (antistatic treatment surface) and heat at 130°C for 1 minute to form an adhesive layer with a thickness of 10 μm . Then, a polyethylene terephthalate (PET) film (isolation film, thickness 25 μm) which was subjected to a polysiloxane treatment on one surface of the above adhesive layer not in contact with the PET film as the base film ) Of the polysilicon treated surface to make an adhesive sheet (surface protective film) (see Figure 1).

<Examples 2 to 23 and Comparative Examples 1 to 3> The raw materials described in Table 3 were used in place of the adhesive polymer, polyether compound, and ionic compound used in Example 1, except that the formulation amounts shown in Table 3 were used and the same method as in Example 1 was used. Production of adhesive sheet (surface protective film).

<Example 24> [Preparation of Carbamate Adhesive Solution] 100 parts by mass of polyol PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) as a polyol and 8.9 parts by mass of an isocyanate compound (CORONATE HX: C/HX, manufactured by Nippon Polyurethane Corporation) as a crosslinking agent , 0.04 parts by mass of acetoacetone iron (III) (produced by Tokyo Chemical Industry Co., Ltd.) as a catalyst, 0.5 parts by mass of ST-30E (manufactured by NOF Corporation) as a polyether compound, and AS110 (first (Industrial Pharmaceutical Company) 0.45 parts by mass and 210 parts by mass of ethyl acetate as a dilution solvent to obtain a carbamate-based adhesive solution.

[Preparation of adhesive sheet (surface protective film)] The above-mentioned carbamate-based adhesive solution was applied to the surface of the antistatic treatment film opposite to the antistatic treatment surface, and heated at 130°C for 1 minute to form an adhesive layer with a thickness of 10 μm. Then, a polyethylene terephthalate (PET) film (isolation film, thickness 25 μm) which was subjected to a polysiloxane treatment on one surface of the above adhesive layer not in contact with the PET film as the base film ) Of the polysilicon treated surface to make an adhesive sheet (surface protective film) (see Figure 1).

<Examples 25 to 28> Except for using the raw materials and blending amounts described in Table 4, in the same manner as in Example 24, an adhesive sheet (surface protective film) was produced.

<Example 29> [Preparation of Carbamate Adhesive Solution] 100 parts by mass of urethane prepolymer SH109 (manufactured by TOYOCHEM), 3.8 parts by mass of isocyanate compound (CORONATE L: C/L, manufactured by Japan Polyurethanes Co., Ltd.) as a crosslinking agent, and acetone as a catalyst Iron (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass, ST-30E (manufactured by NOF Corporation) as a polyether compound, 0.5 parts by mass, and AS110 (manufactured by Daiichi Pharmaceutical Co., Ltd.) as an ionic compound, 0.45 parts by mass 2. 210 parts by mass of ethyl acetate as a dilution solvent to obtain a carbamate-based adhesive solution.

[Preparation of adhesive sheet (surface protective film)] The above-mentioned carbamate-based adhesive solution was applied to the surface of the antistatic treatment film opposite to the antistatic treatment surface, and heated at 130°C for 1 minute to form an adhesive layer with a thickness of 10 μm. Then, a polyethylene terephthalate (PET) film (isolation film, thickness 25 μm) which was subjected to a polysiloxane treatment on one surface of the above adhesive layer not in contact with the PET film as the base film ) Of the polysilicon treated surface to make an adhesive sheet (surface protective film) (see Figure 1).

<Example 30> [Preparation of Carbamate Adhesive Solution] 85 parts by mass of polyol PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) and 13 parts by mass of polyol Sannix GP3000 (manufactured by Sanyo Chemicals Co., Ltd.) manufactured by Sanyo Chemical Co., Ltd. 2 parts by mass of polyol Sannix GP1000 (manufactured by Sanyo Chemicals Co., Ltd., Mn=1000) with 3 hydroxyl groups, 18 parts by mass of isocyanate compound (CORONATE HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, as a catalyst Acetyl iron (III) acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass, ST-30E (manufactured by NOF Corporation) as a polyether compound 0.5 part by mass, AS110 (manufactured by Daiichi Pharmaceutical Co., Ltd.) as an ionic compound ) 0.45 parts by mass and 210 parts by mass of ethyl acetate as a dilution solvent to obtain a carbamate-based adhesive solution.

[Preparation of adhesive sheet (surface protective film)] The above-mentioned carbamate-based adhesive solution was applied to the surface of the antistatic treatment film opposite to the antistatic treatment surface, and heated at 130°C for 1 minute to form an adhesive layer with a thickness of 10 μm. Then, a polyethylene terephthalate (PET) film (isolation film, thickness 25 μm) which was subjected to a polysiloxane treatment on one surface of the above adhesive layer not in contact with the PET film as the base film ) Of the polysilicon treated surface to make an adhesive sheet (surface protective film) (see Figure 1).

For the adhesive sheets of Examples and Comparative Examples, Table 1 to Table 5 show the results of the above-mentioned formulation and various measurements and evaluations. In addition, the formulation amount in Table 3 and Table 4 shows an active ingredient. In addition, in Examples 2 to 23 and Comparative Examples 1 to 3 other than Example 1, the same amounts as in Example 1 were prepared for the cross-linking catalysts, etc., whose formulation amounts are not described in Tables 3 and 4. In addition, the thickness of the obtained adhesive layer was also prepared in the same manner as in Example 1.

[Table 1]

[Table 2]

Hereinafter, the abbreviations in Table 3 and Table 4 will be described. (Ionic compound) LiTFSI: Lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), alkali metal salt LiTFS: lithium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), alkali metal salt AS110: 1-ethyl-3-methylimidazolium bis(fluoromethanesulfonyl)imide (manufactured by Daiichi Pharmaceutical Co., Ltd.), ionic liquid AS210: 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (manufactured by Daiichi Pharmaceutical Co., Ltd.), ionic liquid CIL312: 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide (manufactured by Japan Carlit), ionic liquid CIL313: 1-ethyl-3-methylpyridinium trifluoromethanesulfonic acid (manufactured by Japan Carlit), ionic liquid MTOATFSI: Methyltrioctylammonium bis(trifluoromethanesulfonyl)imide (made by Wako Pure Chemical Industries, Ltd.), ionic liquid (Crosslinking agent) C/HX: isocyanurate body of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: CORONATE HX) C/L: trimethylolpropane/toluene diisocyanate (manufactured by Tosoh Corporation, trade name: CORONATE L) C/HL: Trimethylolpropane adduct of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: CORONATE HL)

[table 3]

[Table 4]

<Preparation of film with hard coat layer> In a urethane acrylate ultraviolet curable resin solution (manufactured by DIC Corporation, trade name "UNIDIC 17-806", solid content concentration 80%), in this solution For every 100 parts by mass of solid content, add 5 parts by mass of photopolymerization initiator (manufactured by Ciba Chemicals, product name "IRGACURE906"), leveling agent (manufactured by DIC company, product name "GRANDIC PC4100") 0.03 Quality parts. Then, butyl acetate is added to the solution so that the solid content concentration in the solution becomes 75%, and cycloheptanone is added to the solution so that the solid content concentration in the solution becomes 50% . In this way, the hard coat layer forming material for forming the hard coat layer is prepared. Next, the above hard coat layer forming material was applied to triacetyl cellulose film (manufactured by Fujifilm Co., Ltd., product name "TD80UL", thickness 80 μm) so that the thickness after hardening became 7.5 μm to form a coating film . The above coating film was dried at 80°C for 2 minutes. Then, a high-pressure mercury lamp was used to irradiate the coating film with ultraviolet light with a cumulative light amount of 300 mJ/cm ² , thereby producing a film with a hard coat layer.

<Measurement of stripping voltage> The adhesive sheet 10 of each example was cut to a size of 70 mm in width and 130 mm in length, and after the separation film was peeled off, the film with a hard coating (70 mm in width and 100 mm in length) attached to the glass plate 11 was peeled off. The surface of 12 is crimped by a hand pressure roller in such a manner that the end on one side of the adhesive sheet 10 protrudes 30 mm from the end of the film 12 with a hard coating. After the sample was placed in an environment of 23° C.×50% RH for 1 day, as shown in FIG. 2, it was set at a predetermined position of the sample fixing table 13 with a height of 20 mm. The end of the adhesive sheet 10 extending 30 mm from the hard-coated film 12 was fixed to an automatic winder (not shown), and peeled at a peeling angle of 150° and a peeling speed of 30 m/min. Use the potentiometer 14 (manufactured by Shishido Electrostatic company, model "STATIRON DZ-4") fixed at a position with a height of 30 mm from the center of the film 12 with a hard coating to attach the adherend (with hard coating) Film 12) The "potential stripping voltage" of the potential measurement on the surface. The measurement was carried out in an environment of 23°C and 50% RH.

The peeling tape voltage (kV, absolute value) is preferably 1 kV or less, more preferably 0.8 kV or less, and still more preferably 0.6 kV or less. By making the peeling tape voltage within the above range, it is not easy to cause damage to the panel due to static electricity, etc., which is a preferable aspect.

<Measurement of residual adhesion> After peeling off the separation film of the adhesive sheet of each example, it was pressed against the surface of the above-mentioned hard-coated film (width 70 mm, length 100 mm) 12 by hand pressure roller. After the sample was left in an environment of 23° C.×50% RH for 1 day, the adhesive sheet was peeled off, and an acrylic tape (manufactured by Nitto Denko Co., Ltd., No. 31B, width 19 mm, substrate thickness 25 μm). After the sample was left in an environment of 23°C×50%RH for 30 minutes, the peeling force (N/19 mm) when peeling at a peeling angle of 180° and a peeling speed of 0.3 m/min was measured and used as the residual adhesive force ( N/19 mm).

The residual adhesive force (N/19 mm) is preferably 4.5 N/19 mm or more, more preferably 4.8N/19 mm or more, and further preferably 5 N/19 mm or more, and particularly preferably 5.5 N/19 mm or more. By setting the residual adhesive force to be in the above range, for example, after sticking an adhesive sheet on the surface of the optical member (polarizing film, etc.), and then peeling off the interlayer filler on the surface of the optical member, the optical member (polarized light) The adhesion (adhesion) between the surface of the film and the interlayer filler, etc. does not decrease, and does not cause defects such as peeling, which is a preferable aspect.

<Residual adhesion rate> The adhesion force of No. 31B to the surface of the film with a hard coat layer before bonding the adhesive sheet was measured and calculated by the following formula. Residual adhesion rate (%) = 100 × [(No. 31B adhesion force after peeling off the adhesive sheet in each case)/(No. 31B adhesion force before bonding the adhesion sheet)]

The above-mentioned 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. By setting the residual adhesion rate to be within the above range, for example, after sticking an adhesive sheet on the surface of the optical member (polarizing film, etc.), and then peeling off the surface of the optical member after the interlayer filler, etc., the optical member (polarized The adhesion (adhesion) between the surface of the film and the interlayer filler, etc. does not decrease, and does not cause defects such as peeling, which is a preferable aspect. In addition, in the case where the residual adhesion rate exceeds 100%, the details are not clear, but it is presumed that the polyether compound is transferred to the surface of the optical member as the adherend, and then, the relationship between the interlayer filler and the like that is reset In the middle, the wettability is improved, whereby the above-mentioned residual adhesion rate becomes higher.

[table 5]

According to the evaluation results in Table 5 above, in all the examples, the following adhesive sheets (adhesive layer) were obtained: antistatic properties when peeled from the surface of the adherend (here, the film with a hard coat layer) Excellent, the adhesive tape of the acrylic tape peeled from the surface of the above-mentioned adherend and adhered to the surface of the adherend is excellent in residual adhesive force and residual adhesion rate, and the acrylic tape and the surface of the adherend are peeled off after the above-mentioned adhesive sheet is peeled off Excellent adhesion (adhesion).

On the other hand, it can be confirmed from the evaluation results in Table 5 above that in Comparative Example 1, when preparing the adhesive solution (composition), a polyether compound containing a polysiloxane chain was used, so the residual adhesion or residual adhesion ratio was Low, poor adhesion (adhesion), in Comparative Examples 2 and 3, the number of polyoxyalkylene chains is less than the desired range, so the interaction with the ionic compound becomes weak and the antistatic property is poor .

[Industry availability] The adhesive sheet disclosed herein is suitable as a surface protective film used to protect the optical member during manufacturing, transportation, etc. The optical member is used as a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescent Use of components such as light-emitting (EL) displays and touch panels. In particular, it is useful as a surface protective film (optical surface protective film) applied to optical members such as polarizing films for liquid crystal display panels, wave plates, retardation plates, optical compensation films, brightness enhancement films, light diffusion sheets, reflective sheets, etc. .

1‧‧‧Antistatic layer 2‧‧‧ Base film 3‧‧‧Adhesive layer 4‧‧‧Isolation membrane 10‧‧‧adhesive sheet (surface protective film) 11‧‧‧Glass plate 12‧‧‧adhered body (film with hard coating) 13‧‧‧Sample fixing table 14‧‧‧potentiometer

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 a potential measuring unit.

Claims (5)

An adhesive composition characterized by containing: Adhesive polymer, Polyether compounds containing more than 3 polyoxyalkylene chains in the molecule and no polysiloxane chains, and Ionic compounds. The adhesive composition according to claim 1, wherein the adhesive polymer is a (meth)acrylic polymer and/or a urethane polymer. The adhesive composition according to claim 1 or 2, wherein the end of the polyoxyalkylene chain comprises a group selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues, and unsaturated fatty acid residues At least one of them. An adhesive sheet characterized by having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 3 on at least one side of a base film. An optical member characterized in that an adhesive sheet as claimed in claim 4 is attached.

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