TW201833599A - Adhesive composition, adhesive sheet, and optical member with excellent curling and adjusting performance - Google Patents

Abstract

According to the invention, the optical components such as the polarizing plate are not easy to slide (offset), warp, and peel. The curling and adjusting performances are excellent, and an adhesive composition capable of inhibiting the peeling voltage to be low are disclosed. In addition, the adhesive sheet formed from the adhesive composition, and the optical member adhered with the adhesive sheet are also disclosed. The adhesive composition is characterized by containing an adhesive polymer, a fluorine-containing oligomer having the average weight of molecular is 3500 or more, and an ionic compound are also disclosed.

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 applications such as liquid crystal display panels, plasma display panels (PDP), organic electroluminescence (EL) displays, etc. ), Among them, a surface used for the purpose of protecting the surface of an optical member (for example, a polarizing plate, a wavelength plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film) used in a liquid crystal display or the like A protective film is useful.

A surface protection film (also referred to as a surface protection sheet) generally has a configuration in which an adhesive layer is provided on a film-like base film (support). The protective film is adhered to the adherend (protected body) through the adhesive layer, and is used to protect the adherend from damage or stains during processing, transportation, and the like. For example, a panel of a liquid crystal display is formed by bonding optical members such as a polarizing plate and a wavelength plate to a liquid crystal cell via an adhesive layer. In the manufacture of the liquid crystal display panel, a polarizing plate attached to a liquid crystal cell is first manufactured into a roll form, and then unrolled from the roll, and cut into a desired size corresponding to the shape of the liquid crystal cell to be used. . Here, in order to prevent the polarizing plate from being damaged by friction with a transport roller or the like in an intermediate step, a countermeasure for bonding a surface protective film to one or both sides (typically, one side) of the polarizing plate is adopted. The surface protection film will be peeled off at a stage where the surface protection film is not needed.

Generally, since the surface protection film and the optical member are made of a plastic material, they have high electrical insulation properties and generate static electricity due to friction and peeling. Therefore, static electricity is easily generated even when the surface protection film is peeled off from an optical member such as a polarizing plate. When a voltage is directly applied to the liquid crystal in a state where the static electricity remains, there is a concern that the alignment of liquid crystal molecules may be lost or the panel may be damaged. In addition, the presence of static electricity may be a factor that attracts dust or reduces workability. Based on the above situation, an antistatic treatment is performed on the surface protection film, for example, by forming an antistatic layer or applying an antistatic coating as the surface layer (surface coating layer, back surface layer) of the surface protection film, thereby imparting antistatic properties. Electrostatic function (see Patent Documents 1 and 2).

Moreover, in order to provide antistatic property to the adhesive layer itself which comprises a surface protection film, the operation which made the adhesive contain an ionic compound, such as an alkali metal salt or an ionic liquid, which functions as an antistatic agent (refer patent document 3).

In addition, the surface protection film is required to have curl adjustment property, so that when it is adhered to the adherend (polarizing plate, etc.), it does not produce unwanted curl or Unexpected curl (Curly refers to a phenomenon of warping, for example, a phenomenon in which the entire flat plate is warped on any side, or a phenomenon in which the entire plate-shaped object is warped as a whole). When an unnecessary curl or an unexpected curl is generated, the operability is poor. For example, when an adherend such as a polarizing plate is adhered to a liquid crystal cell, defects such as bubble wrap may occur.

When curling occurs in a flat-shaped adherend, in the adhesive layer of the surface protection film adhered to the adherend, the force accompanying the curl acts in the shearing direction, and the adherend is caused by the force. Increasing slippage (offset) and the like with the adhesive layer are required to increase the shear force at the time of low-speed peeling.

In addition, during the processing and transportation of the adherend (protected body), in order to prevent the surface protection film from rising and peeling, it is required to have appropriate adhesive force and light peelability (repeelability) at low speed peeling. ).

Therefore, in order to achieve light peeling, various methods are performed on the adhesive composition used for a surface protection film. For example, there are reported examples in which the polymer used in the adhesive composition contains a component having a high glass transition temperature (Tg) or a reactive surfactant, and examples in which the adhesive composition is highly cross-linked. 4).

However, in the above method, even when light peeling is achieved, additives such as ionic compounds and surfactants are contained, and the additives bleed out at the interface between the adhesive layer and the adherend. It is easy to worry about sliding (offset). Prior Art Literature Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-223923 Patent Document 2: Japanese Patent Application Laid-Open No. 2008-255332 Patent Literature 3: Japanese Patent Application Laid-Open No. 9-165460 Patent Literature 4: Japanese Patent Application Laid-Open No. 2002-221906

Problems to be Solved by the Invention

Therefore, in the present invention, intensive research has been made in view of the above-mentioned circumstances, and as a result, an object of the present invention is to provide an optical member such as a polarizing plate that is less prone to slip (offset), warp, peel, and has excellent curl adjustability, In addition, an adhesive composition of an adhesive layer or an adhesive sheet capable of suppressing a peeling voltage to be low, an adhesive sheet formed of the adhesive composition, and an optical member to which the adhesive sheet is adhered. Means to solve the problem

That is, the adhesive composition of the present invention is characterized by containing an adhesive polymer, a fluorine-containing oligomer having a weight average molecular weight of 3500 or more, and an ionic compound.

The adhesive composition of the present invention preferably contains an oxygen-containing alkylene compound.

In the adhesive composition of the present invention, it is preferable that the adhesive polymer is selected from the group consisting of a (meth) acrylic polymer, a urethane polymer, and a polysiloxane polymer. At least one of the group.

In the adhesive sheet of the present invention, it is preferable that an adhesive layer formed of the adhesive composition is provided on at least one side of the base film, and the fluorine-containing oligomer is present inside and / or on the surface of the adhesive layer. Thing.

In the pressure-sensitive adhesive sheet of the present invention, a separator is preferably pasted on the surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the substrate film.

In the pressure-sensitive adhesive sheet of the present invention, the fluorine-containing oligomer is preferably present on the surface of the separator in contact with the pressure-sensitive adhesive layer.

The optical member of the present invention is preferably adhered to the above-mentioned adhesive sheet, or an adhesive sheet obtained by peeling off the separator from the adhesive sheet. Invention effect

In the present invention, by using an adhesive composition containing a specific fluorine-containing oligomer and an ionic compound, an adhesive sheet having an adhesive layer formed of the adhesive composition is bonded to an optical member such as a polarizing plate. Since it is possible to suppress the occurrence of slipping (offset), lifting, and peeling, it is excellent in curl adjustability, and it is useful to suppress peeling voltage to a low level.

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

< Overall Structure of Adhesive Sheet (Surface Protective Film)> The adhesive sheet disclosed herein is an object generally in the form of an adhesive tape, an adhesive label, an adhesive film, or the like, and is particularly suitable for use as an optical component (such as a polarizing plate A surface protective film that protects the surface of an optical component during processing or transportation during processing or transportation. The adhesive layer in the surface protection film is typically formed continuously. However, the adhesive layer is not limited to this configuration. For example, the adhesive layer may be an adhesive layer formed in a regular or random pattern such as a dot or a stripe. In addition, the surface protection film disclosed herein may be in a roll shape or in a paper shape (a leaf shape).

<Substrate film> The adhesive sheet (surface protection film) of this invention is characterized by having a substrate film. In the technology 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, dimensional stability, and the like. Resin material with excellent characteristics. In particular, by making the base film flexible, the adhesive composition can be applied by a roll coater or the like and can be wound into a roll shape, which is useful.

As the substrate film (substrate, support), for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate can be preferably used. Polyester polymers such as glycol esters; cellulose polymers such as diacetyl cellulose and triethyl cellulose; polycarbonate polymers; acrylic polymers such as polymethyl methacrylate; etc. A plastic film made of a resin material (a main component of the resin component, typically a component that accounts for 50% by mass or more) is a plastic film as the base film. As another example of the resin material, styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, Olefin polymers such as ethylene-propylene copolymers; vinyl chloride polymers; polyamide polymers such as nylon 6, nylon 6,6, and aromatic polyamines; and the like are examples of resin materials. As another example of the resin material, fluorene-based polymers, fluorene-based polymers, polyether fluorene-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, and vinyl groups can be mentioned. Alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, etc. It may also be a base film comprising a blend of two or more of the aforementioned polymers.

As the substrate film, a plastic film containing a transparent thermoplastic resin material can be preferably used. Among the above-mentioned plastic films, a case where a polyester film is used is a more preferable aspect. Here, the polyester film refers to a polymer having an ester bond, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, and the like. The polyester resin material (polyester resin) of the skeleton is a film whose main resin component is. The polyester film has characteristics that are preferred as a base film of a surface protection film, such as excellent optical characteristics and dimensional stability. On the other hand, the reduced sample has a property of being easily charged.

Various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, and the like) may be added to the resin material constituting the base film as necessary. For example, a known or conventional surface treatment such as a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, and application of a primer may be performed. Such a surface treatment may be, for example, a treatment for improving the adhesion between the substrate film and the adhesive layer (anchorability of the adhesive layer).

The adhesive sheet (surface protection film) of the present invention may use a plastic film subjected to antistatic treatment as the base film. The use of the above-mentioned base film is preferable because it is possible to suppress the electrification of the adhesive sheet itself at the time of peeling. In addition, the substrate film is a plastic film, and by performing an antistatic treatment on the plastic film, the electrification of the adhesive sheet itself can be reduced and a substrate film having excellent antistatic ability against an adherend can be obtained. In addition, there is no restriction | limiting in particular as a method of providing an antistatic function, A conventionally well-known method can be used, For example, the application of the antistatic resin containing an antistatic agent and a resin component, or a conductive polymer, A method of a conductive resin of a conductive material; a method of vapor-depositing or plating a conductive material; a method of kneading an antistatic agent; and the like.

The thickness of the substrate film is usually about 5 μm to about 200 μm, and preferably about 10 μm to about 100 μm. When the thickness of the base film is within the above range, it is preferable because it has excellent adhesion properties to the adherend and peelability from the adherend.

The adhesive sheet disclosed herein can also be implemented in a manner including other layers in addition to the base film and the adhesive layer. Examples of the other layers include an undercoat layer (anchor layer) and the like that improve the anchoring property of the antistatic layer or the adhesive layer.

<Adhesive composition> The adhesive composition of the present invention can be used without particular limitation as long as it is an adhesive composition containing an adhesive polymer having adhesive properties, and an adhesive layer can be formed from the adhesive composition. As the adhesive composition, for example, an acrylic adhesive, a urethane adhesive, a synthetic rubber adhesive, a natural rubber adhesive, a polysiloxane adhesive, or the like may be used. Among them, more The adhesive polymer is preferably at least one selected from the group consisting of a (meth) acrylic polymer, a urethane polymer, and a polysiloxane polymer, and is more preferably used (containing) It is selected from the group consisting of an acrylic adhesive containing a (meth) acrylic polymer, an urethane adhesive containing a urethane polymer, and a polysiloxane containing a polysiloxane polymer It is particularly preferable to use at least one of the group consisting of adhesives, and the acrylic adhesive is a (meth) acrylic polymer used as the adhesive polymer.

When an acrylic adhesive is used for the adhesive layer, as the (meth) acrylic polymer as the adhesive polymer constituting the acrylic adhesive, as a raw material monomer constituting the acrylic polymer, a polymer having A (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is used as a main monomer. As the (meth) acrylic monomer, one kind or two or more kinds can be used. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the peeling force (adhesive force) to the adherend (protected body) can be easily controlled to be low, and light weight can be obtained. Adhesive sheet (surface protection film) excellent in releasability and repeelability. In addition, (meth) acrylic polymer in this invention means an acrylic polymer and / or a methacrylic polymer, and (meth) acrylate means an acrylate and / or a methyl Acrylate.

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) N-butyl acrylate, sec-butyl (meth) acrylate, t-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, (meth) ) Isodecyl acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.

Among these, when the adhesive sheet of the present invention is used as a surface protection film, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (formyl) N-octyl acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate Esters, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms ( A meth) acrylic monomer is a suitable raw material monomer. 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 it is an adhesive with excellent re-peelability. sheet.

In particular, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably contained in an amount of 50% by mass or more based on 100% by mass of the total monomer components constituting the (meth) acrylic polymer. It is more preferably 80% by mass or more, still more preferably 85% by mass to 99.9% by mass, and most preferably 90% by mass to 99% by mass. If it is less than 50% by mass, the appropriate wettability of the adhesive composition or the cohesive force of the adhesive layer is deteriorated, which is not preferable.

Moreover, in the adhesive composition of this invention, it is preferable that the said (meth) acrylic-type polymer contains a hydroxyl-containing (meth) acrylic-type monomer as a raw material monomer. These hydroxyl-containing (meth) acrylic monomers can be used alone or in combination of two or more. By using the above-mentioned hydroxyl-containing (meth) acrylic monomer, it is easy to control the cross-linking of the adhesive composition and the like, and it is easy to control the balance between the improvement of the wettability by the flow and the reduction of the peeling force (adhesive force) during peeling. .

Examples of the hydroxy-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 4-hydroxylauryl (meth) acrylate Methyl cyclohexyl) methyl ester, N-hydroxymethyl (meth) acrylamide and the like. In particular, by using a hydroxyl-containing (meth) acrylic monomer having an alkyl group having 4 or more carbon atoms, light peeling at the time of high-speed peeling becomes easy, which is preferable.

With respect to 100% by mass of the total monomer components constituting the (meth) acrylic polymer, the hydroxy-containing (meth) acrylic monomer is preferably contained in an amount of 25% by mass or less, and more preferably 20% by mass or less. It is preferably 0.1% to 15% by mass, and most preferably 1% to 10% by mass. When it is in the said range, since it is easy to control the balance of the wettability of an adhesive composition and the cohesive force of the obtained adhesive layer, it is preferable.

In addition, as another polymerizable monomer component, for the reason that it is easy to achieve a balance in adhesive properties, it is possible to use a range for not adjusting the effect of the present invention for adjusting the glass transition temperature and peelability of the (meth) acrylic polymer. Polymerizable monomers such that the Tg is 0 ° C or lower (usually -100 ° C or higher).

As the (meth) acrylic polymer, other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the hydroxyl-containing (meth) acrylic monomer described above As the polymerizable monomer, a carboxyl group-containing (meth) acrylic monomer can be used. By using the carboxyl group-containing (meth) acrylic monomer, it is possible to suppress an increase in the adhesive force of the adhesive layer (adhesive sheet) over time, and it is excellent in re-peelability, increase in anti-adhesive force, and workability. In addition, both the cohesive force and the shear force of the adhesive layer are excellent, which is preferable.

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

With respect to 100 mass% of the total monomer components constituting the (meth) acrylic polymer, the carboxyl group-containing (meth) acrylic monomer is preferably 0 to 5 mass%, and more preferably 0 to 3 mass%. It is more preferably 0 to 2% by mass, and most preferably 0 to 1% by mass. When it is in the said range, since it is easy to control the balance of the wettability of an adhesive composition and the cohesive force of the obtained adhesive layer, it is preferable.

In addition, when the above-mentioned hydroxyl-containing (meth) acrylic monomer and carboxyl-containing (meth) acrylic monomer are used in combination, the total mass of the monomer components constituting the (meth) acrylic polymer is 100 mass. %, Preferably 0.005% to 0.1% by mass of the carboxyl group-containing (meth) acrylic monomer. By adjusting to the said range, it is effective to obtain the adhesive layer (adhesive sheet) which is more excellent in re-peelability and anti-adhesion-force improvement property.

In addition, as the (meth) acrylic polymer, the (meth) acrylic monomer having a C1-C14 alkyl group, a hydroxyl-containing (meth) acrylic monomer, and a carboxyl group are used. The polymerizable monomer other than the (meth) acrylic monomer can be used without particular limitation as long as it does not impair the characteristics of the present invention. Suitable components such as cyano-containing monomers, vinyl ester monomers, and aromatic vinyl monomers can be used as appropriate to improve cohesion and heat resistance; fluorenamine-containing monomers, fluorenimine-containing monomers, and amine-containing monomers A monomer, an epoxy-group-containing monomer, an N-acrylfluorenylmorpholine, a vinyl ether monomer, and the like, components that increase the peeling force (adhesive force) or have a functional group that functions as a crosslinking point. Among these, nitrogen-containing monomers such as a cyano-containing monomer, a fluorene-amine-containing monomer, a fluorene-imide-containing monomer, an amine-containing monomer, and N-acrylic fluorenylmorpholine are preferably used. The use of a nitrogen-containing monomer is useful because it can ensure that an appropriate peeling force (adhesive force) such as warping or peeling does not occur, and an adhesive sheet (surface protective film) having excellent shearing force can be obtained. These polymerizable monomers can be used alone or in combination of two or more.

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

Examples of the amidino group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl acrylamide, diacetone acrylamide, and the like.

Examples of the fluorenimine-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconicimide, and the like.

Examples of the amine-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-di (meth) acrylate Methyl aminopropyl esters and the like.

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

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

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

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

In the present invention, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms and the hydroxyl group-containing monomer are added to 100% by mass of the total monomer components constituting the (meth) acrylic polymer. The polymerizable monomer other than the (meth) acrylic monomer and the carboxyl group-containing (meth) acrylic monomer is preferably 0 to 50% by mass, and more preferably 0 to 20% by mass. In order to obtain desired characteristics, the other polymerizable monomers described above may be appropriately adjusted.

The (meth) acrylic polymer may further contain an alkylene oxide-containing reactive monomer as a monomer component.

The average number of moles of oxyalkylene units of the alkylene oxide-containing reactive monomer is preferably 1 to 40 from the viewpoint of compatibility with the oxyalkylene-containing compound. , More preferably 3 to 40, still more preferably 4 to 35, and particularly preferably 5 to 30. When the average number of added moles is 1 or more, there is a tendency that the effect of reducing contamination of the adherend (protected body) is efficiently obtained. Further, when the average number of added moles is more than 40, the interaction with the oxygen-containing alkylene compound is large, and the viscosity of the adhesive composition tends to increase, making it difficult to apply, which is not preferable. It should be noted that the end of the oxyalkylene chain may be a hydroxyl group itself, or may be substituted with another functional group or the like.

The above-mentioned alkylene oxide-containing reactive monomers may be used alone or in combination of two or more kinds. It is preferable that the content of the above-mentioned alkylene oxide-containing reactive monomers is the same as that of the (meth) acrylic polymer. The total body composition content is 0 to 20% by mass, and more preferably 0 to 10% by mass. When the content of the alkylene oxide-containing reactive monomer exceeds 20% by mass, the contamination of the adherend is deteriorated, which is not preferable.

Examples of the oxyalkylene unit of the above-mentioned alkylene oxide-containing reactive monomer include an alkylene unit having 1 to 6 carbon atoms, and examples thereof include oxymethylene, oxyethyl, and oxygen. Propylene, oxybutyl, etc. The hydrocarbon group of the oxyalkylene chain may be a straight chain or a branched chain.

Moreover, it is more preferable that the said epoxy alkylene group-containing reactive monomer is a reactive monomer which has an epoxy ethylene group. By using a (meth) acrylic polymer containing a reactive monomer having an epoxyethyl group as a base polymer, the phase of the base polymer with a fluorine-containing oligomer or an ionic compound or an oxyalkylene compound The capacitance is improved, and the bleeding to the adherend is suitably suppressed to obtain a low-contamination adhesive composition.

Examples of the alkylene oxide-containing reactive monomer include, for example, (meth) acrylic acid alkylene oxide adducts, and reactive substitutions such as acrylamido, methacryl, and allyl in the molecule. Based reactive surfactants and the like.

Specific examples of the (meth) acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol ( (Meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, lauryloxy polyethylene glycol ( (Meth) acrylate, stearyloxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octyloxy Polyethylene glycol-polypropylene glycol (meth) acrylate and the like.

Moreover, as a specific example of the said reactive surfactant, the anionic reactive surfactant which has a (meth) acryl fluorenyl group or an allyl group, a nonionic reactive surfactant, and a cationic type are mentioned, for example. Reactive surfactants, etc.

The aforementioned (meth) acrylic polymer preferably has a weight average molecular weight (Mw) of 100,000 to 5 million, more preferably 200,000 to 4 million, still more preferably 300,000 to 3 million, and most preferably 300,000. ~ 950,000. When the weight-average molecular weight is less than 100,000, the cohesive force of the adhesive layer tends to be small, and the paste tends to remain. On the other hand, when the weight-average molecular weight exceeds 5 million, the fluidity of the polymer decreases, and the wettability of the adherend (for example, a polarizing plate) becomes insufficient, and the adherence to the adherend and the adhesive sheet ( Surface protection film) tends to cause bulges between the adhesive layers. In addition, a weight average molecular weight means the weight average molecular weight measured by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C or lower, and more preferably -10 ° C or lower (usually -100 ° C or higher). When the glass transition temperature is higher than 0 ° C, the polymer is difficult to flow, and for example, the polarizing plate as an optical member has insufficient wetting, and it becomes an adhesive layer between the polarizing plate and the adhesive sheet (surface protection film). A tendency to cause a bulge. In particular, by adjusting the glass transition temperature to -61 ° C or lower, it is easy to obtain an adhesive layer having excellent wettability and light peelability to a polarizing plate. In addition, the glass transition temperature of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio used suitably.

The method of polymerizing the (meth) acrylic polymer is not particularly limited, and it can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. However, from the viewpoint of workability, especially for adherends ( In view of characteristics such as low pollution resistance of the protected object, solution polymerization is a more preferred method. The obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

In the case where a polyurethane-based adhesive is used in the adhesive layer, any appropriate urethane-based adhesive can be used. Examples of such a urethane-based adhesive include a urethane-based adhesive containing a urethane-based polymer, which is an adhesive polymer obtained by reacting a polyol and a polyisocyanate compound. Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the polyisocyanate compound include diphenylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

When a polysiloxane-type adhesive is used for the said adhesive layer, any suitable polysiloxane-type adhesive can be used. As such a polysiloxane adhesive, a polysiloxane adhesive obtained by blending or aggregating a polysiloxane polymer as an adhesive polymer can be preferably used.

Examples of the polysiloxane-based adhesive include addition reaction-curable polysiloxane-based adhesives and peroxide-curable polysiloxane-based adhesives. Among these polysiloxane-based adhesives, an addition reaction-curable polysiloxane-based adhesive is preferred because it does not use a peroxide (benzidine peroxide or the like) and does not generate decomposition products.

As the curing reaction of the addition reaction-curable polysiloxane-based adhesive, for example, when a polyalkyl polysiloxane-based adhesive is obtained, in general, polyalkyl hydrogen can be exemplified by using a platinum catalyst. Method for curing a siloxane composition.

< Fluorine-containing oligomer> The adhesive composition of the present invention is characterized by containing an adhesive polymer, a fluorine-containing oligomer having a weight average molecular weight of 3500 or more, and an ionic compound. By containing a fluorine-containing oligomer having a weight-average molecular weight of 3500 or more in the adhesive composition, when the obtained adhesive layer (adhesive sheet) is bonded to an optical member such as a polarizing plate, the fluorine-containing The light peeling effect of the low surface free energy of the fluorine site in the type oligomer. In addition, the fluorinated type oligomer functions as a tackifier resin, improves the adhesion, and can suppress the sliding (offset of the surface protection film). ), Lifting, peeling, etc. In other words, it is possible to achieve both light peelability (re-peelability) and adhesiveness, which is a preferred method. Moreover, it is preferable that the adhesive sheet of this invention has the adhesive layer which consists of the adhesive composition as described in any one of Claims 1-3 in at least one surface of a base film, and is provided in the said adhesive layer. The above-mentioned fluorine-containing oligomer is present on the inside and / or the surface. In addition, the "inside" of the said adhesive layer means, for example, when the said adhesive composition which mixes the said fluorine-containing oligomer is used to form an adhesive layer, it is contained in the said adhesive layer Case. The “surface” of the adhesive layer means, for example, a case where the fluorine-containing oligomer contained in the adhesive layer containing the fluorine-containing oligomer is present (exposed) on the surface of the adhesive layer, Alternatively, in a case where the surface of the separator adhered to protect the surface of the adhesive layer is previously coated (laminated) with the fluorine-containing oligomer and the separator is adhered to the adhesive layer, the fluorine-containing oligomer In the case of being transferred (transferred) from the surface of the separator to the surface of the adhesive layer.

The weight average molecular weight (Mw) of the fluorine-containing oligomer is 3500 or more, preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. When the fluorine-containing oligomer has a weight-average molecular weight of 3500 or more, it further functions as a tackifier resin, which improves the tackiness and can suppress slipping (offset), warping, and peeling of the surface protective film. Further, when the weight-average molecular weight is 20,000 or more, foaming at the time of blending of the adhesive (composition) can be suppressed, and the appearance after application of the adhesive is excellent, which is preferable. The upper limit of the weight average molecular weight (Mw) of the fluorine-containing oligomer is preferably 200,000 or less, and more preferably 100,000 or less. When it is 200,000 or less, a fluorine-containing oligomer is easy to segregate on a surface, and it is easy to exhibit a light peeling effect, and it is preferable.

Specific examples of the fluorine-containing oligomer include, for example, commercially available product names Megafac F-251, F-253, F-281, F-410, F-430, F-444, and F- 477, F-510, F-511, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-571, F-572 (the above are manufactured by DIC Corporation), Surflon S-611, S- 651, S-386 (above manufactured by AGC SEIMICHEMICAL), Ftergent 610FM, 710FL, 710FM, 710FS, 730FL, 730LM (made by NEOS), etc. These compounds may be used singly or in combination of two or more kinds.

With respect to 100 parts by mass of an adhesive polymer (which is a base polymer, such as a (meth) acrylic polymer, a urethane-based polymer, a polysiloxane-based polymer, etc.) constituting the adhesive composition, The content of the fluorine-containing oligomer is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 7.5 parts by mass, still more preferably 0.03 to 5.5 parts by mass, and most preferably 0.04 to 4.8 parts by mass. Serving. When it is in the said range, it is preferable after bonding the adhesive sheet of this invention to an optical member etc., since it can suppress sliding (offset), lifting, peeling, etc., and it is excellent in light peelability. In addition, in order to satisfy the pollution resistance, the content of the fluorine-containing oligomer is preferably 0.01 to 5.5 parts by mass based on 100 parts by mass of the adhesive polymer.

< Ionic Compound> The adhesive composition contains an ionic compound, and as the ionic compound, at least any one of an alkali metal salt, an ionic liquid, and a polysiloxane containing an ionic group is preferably used. By containing at least any one of these ionic compounds, excellent antistatic properties and peeling electrical properties can be imparted.

Since the said alkali metal salt has high ion dissociation property, it is preferable from the point which can exhibit the outstanding antistatic ability even with a small amount of addition. Examples of the alkali metal, it is suitable for use for example containing Li ^+, Na ^+, K ⁺ cations and containing ^{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) 2} N ^- anion composed of metal salts. 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 ) Lithium salts such as ₂ N, Li (CF ₃ SO ₂ ) ₃ C, and more 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.

As the ionic liquid, an ionic liquid containing an organic cation component and an anion component represented by the following formulae (A) to (E) is preferably used. Among ionic liquids having these cations, an ionic liquid having a better antistatic ability can be obtained by using an ionic liquid having a melting point of 100 ° C. or lower.

[Chemical Formula 1]

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

The above-described formula _(B), R _d represents a hydrocarbon group having a carbon number of 2 to 20, may be heteroatom substituted with a functional group as part of the hydrocarbon group, R _e, the same or different R _f and R _g, represents a hydrogen or carbon atoms The hydrocarbon group of 1 to 16 may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.

The above formula _(C), R _h represents a hydrocarbon group having a carbon number of 2 to 20, may be heteroatom substituted with a functional group as part of the hydrocarbon group, R _i, identical or different, R _j and R _k, represents a hydrogen or carbon atoms The hydrocarbon group of 1 to 16 may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.

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

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

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

Specific examples include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl- 4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1- Ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrole Alkylium 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, pyrrolidinium-2-one cation, 1-propane Piperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium Ion, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1 -Pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1 -Ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperium Pyridinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrrole A phosphonium cation, a 1-ethyl-2-phenylindole cation, a 1,2-dimethylindole cation, a 1-ethylcarbazole cation, an N-ethyl-N-methylmorpholinium cation, and the like.

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

Specific examples include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl-3 -Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecane Methyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3- Dimethylimidazolium 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-tetrahydro Pyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6- Tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl -1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, a 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation.

Examples of the cation represented by the formula (C) include a pyrazolium cation and a pyrazolium dihydrogen cation.

Specific examples include 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 -Trimethylpyrazolium cation and the like.

Examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylphosphonium cation, a tetraalkylphosphonium cation, and a part of the alkyl group is substituted with an alkenyl group, an alkoxy group, or a cyclic group. Cation after oxy and so on.

Specific examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cation, tributylethylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, epoxypropyltriam Methylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium Cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyl Decylsulfonium cation, diallyldimethylammonium cation, tributyl- (2-methoxyethyl) sulfonium cation, and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylphosphonium cation, dibutylethylphosphonium cation, and dimethyldecyl are preferably used. Asymmetric tetraalkylammonium cations such as hydrazone cations, triethylmethylsulfonium cations, tributylethylsulfonium cations, trimethyldecylsulfonium cations, trialkylsulfonium cations, tetraalkylsulfonium cations, or N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, epoxypropyltrimethylammonium cation, diallyldimethylammonium cation, N, N-diamine Methyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N- Amyl ammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl -N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium Cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl-N-propyl-N-hexylammonium cation, N, N-dimethyl-N -Propyl-N-heptyl Cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N -Pentyl-N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N- Propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diamine Ethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-formyl -N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N-hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N- Hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation.

Examples of the cation represented by the formula (E) include a sulfonium cation. Specific examples of R _P in the formula (E) include methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, and tridecyl. , Tetradecyl, octadecyl and the like.

On the other hand, as the anionic component concerned, as long as it satisfies an anionic component of the ionic liquid is 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 ionic liquids may be used alone or in combination of two or more.

Moreover, as said polysiloxane containing an ionic group, the polysiloxane represented by following formula (1) is preferable. [Chemical Formula 2] It should be noted that R ₁ to R ₄ in the formula (1) may be the same or different, and include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, In any of the ionic groups, one or more of R ₁ to R ₄ include an ionic group. n is an integer from 0 to 100.

In addition, as the ionic group contained in one or more of R ₁ to R ₄ , an ionic group having an ammonium cation group or a sulfonium cation group is preferable. Among them, one or more of R ₁ to R ₄ preferably include a cationic structure and an anionic component represented by the following formula (a) or (b), or preferably a zwitterionic structure represented by (c) or (d).

[Chemical Formula 3] R ₅ to R ₇ in the formula (a) may be the same or different, and represent any one of an alkyl group, an aryl group, and a fluorine-substituted alkyl group having 1 to 10 carbon atoms. m is an integer from 1 to 10.

[Chemical Formula 4] R ₈ to R ₁₀ in the formula (b) may be the same or different, and represent any of an alkyl group, an aryl group, and a fluorine-substituted alkyl group having 1 to 10 carbon atoms. m is an integer from 1 to 10.

On the other hand, the anionic component is not particularly limited, and for example, Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO _{3 are used. ^{-, 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 -, C 2 H 5 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 ^- and (FSO ₂ ) ₂ N ^- and the like.

[Chemical Formula 5] R ₁₁ and R ₁₂ in the formula (c) may be the same or different, and represent any of an alkyl group having 1 to 10 carbon atoms, an aryl group, and a fluorine-substituted alkyl group. R ₁₁ and R ₁₂ may form a ring. In this case, an alkylene group is shown. m is an integer from 1 to 10, and p is an integer from 1 to 6.

[Chemical Formula 6] R ₁₃ and R ₁₄ in the formula (d) may be the same or different, and represent any one of an alkyl group, an aryl group, and a fluorine-substituted alkyl group having 1 to 10 carbon atoms, and R ₁₃ and R ₁₄ may form a ring. In this case, an alkylene group is shown. m is an integer from 1 to 10, and p is an integer from 1 to 6.

Since such a polysiloxane containing an ionic group contains a polysiloxane chain, the low surface free energy of the polysiloxane chain allows the adhesive layer to be adhered to an adherend (for example, polarized light). (Plate) When stored in a high-temperature environment on the surface, the polysiloxane containing ionic groups described above does not penetrate into the adherend (from the surface of the adherend to the inside of the adherend) but stays there. On the surface of the adhesive layer, the peeling and charging characteristics are stable over time, the antistatic performance can be maintained for a long period of time, and it can be suitably used as an antistatic agent.

Specific examples of the polysiloxane containing an ionic group include, for example, commercially available products under the trade names X-40-2450 and X-40-2750 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.). These compounds may be used singly or in combination of two or more kinds.

With respect to 100 parts by weight of an adhesive polymer (which is a base polymer, for example, (methacrylic polymer, urethane-based polymer, polysiloxane-based polymer, etc.) constituting the adhesive composition, the above The content of the ionic compound is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 7.5 parts by mass, still more preferably 0.03 to 5.5 parts by mass, and most preferably 0.04 to 4.8 parts by mass. Within the range, the pressure-sensitive adhesive sheet of the present invention is easy to achieve both antistatic properties and suppression of slippage (offset), which is preferable.

< Oxylate-containing compound> The adhesive composition of the present invention preferably contains an oxyalkylene-containing compound, and among them, more preferably contains an organopolysiloxane having an oxyalkylene chain, and further preferably contains an oxyalkylene group. Organic polysiloxane in the main chain. It is presumed that by using the above-mentioned organopolysiloxane, the surface free energy on the surface of the adhesive is reduced, thereby achieving light peeling.

As the organic polysiloxane, a known organic polysiloxane having a polyoxyalkylene main chain can be suitably used, and an organic polysiloxane represented by the following formula (2) is preferable. [Chemical Formula 7] It should be noted that in the formula (2), R ₁ and / or R ₂ has an oxyalkylene chain having 1 to 6 carbon atoms, and the alkylene group in the oxyalkylene chain may be a straight chain or a branched chain. The end of the oxyalkylene chain may be an alkoxy group or a hydroxyl group. Either R ₁ or R ₂ may be a hydroxyl group, or may be an alkyl group or an alkoxy group, or may be a functional group in which a part of the alkyl group and the alkoxy group is substituted with a hetero atom. n is an integer from 1 to 300.

As the organic polysiloxane, an organic polysiloxane containing a site containing a siloxane (a site of a siloxane) as a main chain and an oxygen alkylene chain bonded to a terminal of the main chain is used. It is presumed that by using the above-mentioned organosiloxane having an oxyalkylene chain, the compatibility with (meth) acrylic polymers, fluorine-containing oligomers, ionic compounds, etc. is achieved, and light peeling is achieved Into.

Moreover, as said organic polysiloxane in this invention, the structure shown below can be used, for example. Specifically, R ₁ and / or R ₂ in the formula has an oxyalkylene chain containing a hydrocarbon group having 1 to 6 carbon atoms. Examples of the oxyalkylene chain include oxymethylene and oxyethylene. , Oxypropyl, oxybutyl and the like, of which oxyethyl and oxypropyl are preferred. Incidentally, R ₁ and R ₂ in each case have the alkylene oxide chain, it may be the same or different.

The hydrocarbon group of the oxyalkylene chain may be a straight chain or a branched chain.

The terminal of the oxyalkylene chain may be an alkoxy group or a hydroxyl group, and among these, an alkoxy group is more preferred. In the case where the separator is attached to the surface of the adhesive layer for the purpose of protecting the adhesive surface, the organic polysiloxane having a hydroxyl group at the end generates an interaction with the separator, and sometimes the surface of the adhesive layer Adhesion (peeling) force when the separator is peeled increases.

In addition, n is an integer of 1 to 300, preferably 10 to 200, and more preferably 20 to 150. When n is within the above range, a balance between compatibility with the base polymer is obtained, and this is a preferred embodiment. The molecule may have a reactive substituent such as a (meth) acrylfluorenyl group, an allyl group, or a hydroxyl group. These organic polysiloxanes can be used alone or in combination of two or more.

Specific examples of the organopolysiloxane having an oxyalkylene chain in the main chain include, for example, trade names X-22-4952, X-22-4272, and X-22-6266 as commercial products. , KF-6004, KF-889 (above manufactured by Shin-Etsu Chemical Industry Co., Ltd.), BY16-201, SF8427 (above manufactured by Toray Dow Corning), IM22 (made by Asahi Kasei WACKER), etc. These compounds may be used singly or in combination of two or more kinds.

In addition to the organosiloxane having an (oxygenated) oxyalkylene chain in the main chain described above, an organosiloxane having an (oxygenated) oxyalkylene chain in a side chain can also be used, and It is more preferable to use an organosiloxane having an oxyalkylene chain in a side chain than an organosiloxane having an oxyalkylene chain in a main chain. As said organopolysiloxane, a well-known organopolysiloxane which has a polyoxyalkylene side chain can be used suitably, It is preferable that it is an organopolysiloxane represented by following formula (3). [Chemical Formula 8] It should be noted that in the above formula (2), R ₁ is a monovalent organic group, R ₂ , R ₃ and R ₄ are alkylene groups, R ₅ is hydrogen or an organic group, and m and n are 0 to 1000. Integer. However, m and n are not 0 at the same time. a and b are integers of 0-100. However, a and b are not 0 at the same time.

Moreover, as said organic polysiloxane in this invention, the structure shown below can be used, for example. Specifically, R ₁ in the formula is a monovalent organic group exemplified by alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl and tolyl, or aralkyl groups such as benzyl and phenethyl. Each may have a substituent such as a hydroxyl group. As R ₂ , R ₃ and R _4, an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, or propyl can be used. Here, R ₃ and R ₄ are different alkylene groups, and R ₂ may be the same as R ₃ or R ₄ , or may be different from R ₃ or R ₄ . R ₅ may be a monovalent organic group exemplified by an alkyl group such as methyl, ethyl, and propyl, or a fluorenyl group such as ethenyl and propionyl, and each may have a substituent such as a hydroxyl group. These compounds may be used singly or in combination of two or more kinds. The molecule may have a reactive substituent such as a (meth) acrylfluorenyl group, an allyl group, or a hydroxyl group. Among the above-mentioned organosiloxanes having a polyoxyalkylene side chain, it is presumed that an organosiloxane having a polyoxyalkylene side chain having a hydroxyl end is easily compatible in compatibility and is therefore preferred.

Specific examples of the organosiloxane having an oxyalkylene chain in the above-mentioned side chain include, for example, trade names KF-351A, KF-352A, KF-353, KF-354L, and KF- 355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (the above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122 , FZ-2164, FZ-2203, FZ-7001, SH8400, SH8700, SF8410, SF8422 (the above are manufactured by Toray Dow Corning), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446 , TSF-4452, TSF-4460 (manufactured by Momentive Performance Materials), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (BYK-CHEMIE JAPAN). These compounds may be used singly or in combination of two or more kinds.

The organosiloxane used in the present invention preferably has an HLB (Hydrophile-Lipophile Balance) value of 1 to 16, and more preferably 3 to 14. When the HLB value deviates from the above range, the contamination property to the adherend is deteriorated, which is not preferable.

The above-mentioned adhesive composition may contain an oxygen-containing alkylene compound which does not include an organopolysiloxane. When the above-mentioned compound is contained in the adhesive, an adhesive having more excellent wettability to the adherend can be obtained.

Specific examples of the above-mentioned oxygen-containing alkylene compound which does not include an organopolysiloxane include polyoxyalkylene alkylamine, polyoxyalkylene diamine, and polyoxyalkylene fatty acid. Ester, polyoxyalkylene desorbide fatty acid ester, polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkylallyl ether, polyoxyalkylene Non-ionic surfactants such as alkylene phenyl allyl ether; polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl Anionic surfactants such as phenyl ether sulfate, polyoxyalkylene alkyl phenyl ether phosphate; and cationic surfactants with a polyoxyalkylene chain (polyoxyalkylene chain) or Amphoteric surfactants, polyether compounds (and derivatives thereof) having a polyoxyalkylene chain, acrylic compounds (and derivatives thereof) having a polyoxyalkylene chain, and the like. A polyoxyalkylene chain-containing monomer may be blended as the polyoxyalkylene chain-containing compound. The polyoxyalkylene chain-containing compound may be used alone, or two or more kinds may be used in combination.

Specific examples of the polyether-based compound (polyether component) having a polyoxyalkylene chain include a polypropylene glycol (PPG) -polyethylene glycol (PEG) block copolymer, and PPG-PEG- Block copolymers of PPG, block copolymers of PEG-PPG-PEG, and the like. Examples of the derivative of the polyether-based compound having a polyoxyalkylene chain include an oxypropylene-containing compound (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.) having an etherified terminal. , Oxygenated propylated compounds (such as terminal acetylated PPG, etc.) after the end is acetylated.

Moreover, as a specific example of the said acrylic compound which has a polyoxyalkylene chain, the (meth) acrylate polymer which has an oxyalkylene group is mentioned. As the oxyalkylene group, the number of moles of addition of the oxyalkylene unit is preferably 1 to 50, more preferably 2 to 30, and still more preferably 2 to 20. The terminal of the oxyalkylene chain may be a hydroxyl group itself or substituted with an alkyl group, a phenyl group, or the like.

The (meth) acrylate polymer having an oxyalkylene group is preferably a polymer containing (meth) acrylic acid alkylene oxide as a monomer unit (component), and as a specific example of the (meth) acrylic acid alkylene oxide Examples of the (meth) acrylate containing a glycol group include methoxydiethylene glycol (meth) acrylate and methoxytriethylene glycol (meth) acrylate Iso-methoxy polyethylene glycol (meth) acrylate type; ethoxy diethylene glycol (meth) acrylate, ethoxy triethylene glycol (meth) acrylate, etc. Alcohol (meth) acrylate type; Butoxy polyethylene glycol (meth) acrylate such as butoxydiethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate Type; phenoxy diethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, and other phenoxy polyethylene glycol (meth) acrylate type; 2-ethylhexyl Polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate type; methoxy polypropylene glycol (meth) acrylate type such as methoxydipropylene glycol (meth) acrylate .

In addition, as the monomer unit (component), other monomer units (components) other than the (meth) acrylic alkylene oxide group may be used. Specific examples of other monomer components include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and (meth) ) Tert-butyl acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (iso) (meth) acrylate Octyl ester, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, n-dodecyl (meth) acrylate Acrylates and / or methacrylates having an alkyl group having 1 to 14 carbon atoms such as n-tridecyl (meth) acrylate and n-tetradecyl (meth) acrylate.

In addition, as other monomer units (components) other than the (meth) acrylic acid alkylene oxide, a carboxyl group-containing (meth) acrylate, a phosphate group-containing (meth) acrylate, and a cyano group ( (Meth) acrylates, vinyl esters, aromatic vinyl compounds, (meth) acrylates containing anhydride groups, (meth) acrylates containing hydroxyl groups, (meth) acrylates containing amine groups, and amine groups (Meth) acrylates, epoxy-containing (meth) acrylates, N-acrylfluorenylmorpholine, vinyl ethers, and the like.

In a more preferred embodiment, the polyoxyalkylene chain-containing compound excluding the organopolysiloxane is a compound having a (poly) ethylene oxide chain in at least a part. By blending the compound containing the (poly) ethoxylate chain, the compatibility of the base polymer with the fluorine-containing oligomer or ionic compound is improved, and the oozing out of the adherend is suitably suppressed to obtain low pollution. Sexual adhesive composition. Among them, particularly when a block copolymer of PPG-PEG-PPG is used, a binder excellent in low pollution is obtained. The weight of the (poly) epoxyethyl chain-containing compound in the entire polyoxyalkylene chain-containing compound excluding the organopolysiloxane as described above. It is preferably 5 mass% to 90 mass%, more preferably 5 mass% to 85% by mass, still more preferably 5 mass% to 80 mass%, and most preferably 5 mass% to 75 mass%.

As the molecular weight of the polyoxyalkylene chain-containing compound excluding the organopolysiloxane, a compound having a number average molecular weight (Mn) of 50,000 or less is suitable, preferably 200 to 30,000, and more preferably 200 to 10,000, usually a compound having a number average molecular weight of 200 to 5000 is preferably used. When the Mn ratio is too large than 50,000, the compatibility with the acrylic polymer decreases, and the adhesive layer tends to whiten. When the Mn ratio is more than 200, contamination due to the polyoxyalkylene compound may easily occur. In addition, Mn here means the polystyrene conversion value obtained by GPC (gel permeation chromatography).

In addition, as specific examples of commercially available products of the polyoxyalkylene chain-containing compound that does not include the organopolysiloxane, for example, Adeka Pluronic 17R-4, Adeka Pluronic 25R-2 (all of which are from Adek (Made by ADEKA)); Latemul PD-420, Latemul PD-420, Latemul PD-450, Emulgen 120 (made by Kao Corporation); Aqualon HS-10, KH-10, Noigen EA-87, EA-137, EA- 157, EA-167, EA-177 (the above are manufactured by Daiichi Pharmaceutical Co., Ltd.), etc.

The content of the oxygen-containing alkylene compound is relative to the adhesive polymer (which is the base polymer, for example, a (meth) acrylic polymer, a urethane-based polymer, or the like) constituting the adhesive composition. 100 parts by mass, preferably 0.01 to 5.0 parts by mass, more preferably 0.02 to 2 parts by mass, still more preferably 0.03 to 1.6 parts by mass, and most preferably 0.1 part by mass Parts to 0.8 parts by mass. When it is in the said range, since the sliding (offset) and light peelability (re-peelability) of the adhesive sheet of this invention can be made compatible easily, it is preferable.

< Crosslinking agent> In the adhesive sheet (surface protection film) of this invention, it is preferable that the said adhesive composition contains a crosslinking agent. In the present invention, an adhesive layer can be formed using the above-mentioned adhesive composition. For example, when the adhesive composition is an acrylic adhesive containing the (meth) acrylic polymer, the constitutional unit, the composition ratio, and the crosslinking agent of the (meth) acrylic polymer are appropriately adjusted. The cross-linking can be achieved by selecting and adding ratios, etc., to obtain an adhesive sheet (adhesive layer) having more excellent heat resistance.

As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine-based resin, an aziridine derivative, a metal chelate compound, and the like can be used. In particular, the use of an isocyanate compound is a preferred embodiment. 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; and cyclopentyl diisocyanate. Alicyclic isocyanates such as isocyanate, cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane; 2,4-toluene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI) and other aromatic isocyanates; Urea bond, biuret bond, isocyanurate bond, uretdione A polyisocyanate modified product obtained by modifying the isocyanate compound, such as a bond, a urea bond, a carbodiimide bond, a uretonimine bond, or an oxadiazine trione bond. Examples of commercially available products include Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above manufactured by Takeda Pharmaceutical Industries, Inc.), Sumidule T80, Sumidule L, Desmodur N3400 (above, Sumika Bayeramine) Ethyl ester (manufactured by Sumika Bayer Urethane), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (the above are manufactured by Japan Polyurethane Industrial Co., Ltd.) and the like. These isocyanate compounds may be used singly or in combination of two or more kinds, and a bifunctional isocyanate compound and a trifunctional or more isocyanate compound may be used in combination. By using a cross-linking agent in combination, it is possible to achieve both adhesiveness and rebound resilience (adhesiveness to curved surfaces), and an adhesive sheet having more excellent adhesive reliability can be obtained.

When a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound are used in combination as the isocyanate compound, it is preferable to use [difunctional isocyanate compound] / [3 as the mixing ratio (mass ratio) of the two compounds. Isocyanate compound having a functional or higher content (mass ratio) of 0.1 / 99.9 to 50/50, more preferably 0.1 / 99.9 to 20/80, still more preferably 0.1 / 99.9 to 10/90, and still more preferably 0.1 / 99.9 to 5/95, most preferably 0.1 / 99.9 to 1/99. It is a preferable aspect to mix | blend by adjusting to the said range, and obtaining the adhesive layer excellent in adhesiveness and resilience.

Examples of the epoxy compound include N, N, N ', N'-tetraepoxypropylm-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

Examples of the melamine-based resin include hexamethylolmelamine. Examples of the aziridine derivative include, for example, commercially available products under the trade names HDU, TAZM, and TAZO (the above are manufactured by Kakuya Kogyo).

Examples of the metal chelate compound include aluminum, iron, tin, titanium, and nickel as the metal component, and examples of the chelate component include acetylene, acetamidine methyl acetate, and ethyl lactate.

The content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer. It is more preferably 0.5 to 10 parts by mass, and most preferably 1 to 6 parts by mass. When the content is less than 0.01 parts by mass, the cross-linking formation by the cross-linking agent becomes insufficient, and the cohesive force of the obtained adhesive layer tends to be small, and sufficient heat resistance may not be obtained, and This is the cause of the sticky residue. On the other hand, when the content exceeds 20 parts by mass, the cohesive force of the polymer is large, and the fluidity is reduced, which tends to insufficiently wet the adherend (for example, a polarizing plate), resulting in adhesion between the adherend and the adherend. Causes of bulging between the agent layers (adhesive composition layers). These crosslinking agents may be used alone or in combination of two or more.

The said adhesive composition may further contain the crosslinking catalyst for making the said arbitrary crosslinking reaction more efficient. As the cross-linking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate; tris (acetamidineacetone) iron (acetamidineacetonate iron (III)), Tris (hexane-2,4-dione) iron, tris (heptane-2,4-dione) iron, tris (heptane-3,5-dione) iron, tris (5-methyl Hexane-2,4-diketone) iron, tris (octane-2,4-diketone) iron, tris (6-methylheptane-2,4-diketone) iron, tris ( 2,6-dimethylheptane-3,5-diketone) iron, tris (nonane-2,4-diketone) iron, tris (nonane-4,6-diketone) iron, Tris (2,2,6,6-tetramethylheptane-3,5-dione) iron, tris (tridecane-6,8-dione) iron, tris (1-phenylbutane -1,3-diketone) iron, tris (hexafluoroacetoneacetone) iron, tris (ethylacetate) iron, tris (ethylacetate) propyl, tris (ethylacetate) isopropyl Ester) iron, tris (n-butylacetate) iron, tris (sec-butylacetate) iron, tris (tert-butylacetate) iron, tris (methylacetate) iron, tris (propyl)醯 Ethyl acetate) iron, tris (n-propyl propyl acetate) iron, tris (isopropyl propyl acetate) iron, tris (n-butyl propyl acetate) iron, tris (propyl propyl) Sec-butyl acetate) iron, tris (propionylacetate tert-butyl) iron, tris (benzylacetate) iron, tris (dimethylmalonate) iron, tris (diethylmalonate) iron , Trimethoxy iron, triethoxy iron, triisopropoxy iron, iron chloride and other iron catalysts. These crosslinking catalysts may be used singly or in combination of two or more kinds.

The content of the cross-linking catalyst is not particularly limited. For example, it is preferably about 0.0001 to about 1 part by mass, and more preferably 0.001 to 0.5 parts by mass based on 100 parts by mass of the (meth) acrylic polymer. When it is in the said range, the speed of a crosslinking reaction when forming an adhesive layer is fast, and the pot life of an adhesive composition becomes long, and it is a preferable aspect.

Moreover, the said adhesive composition may contain the compound which produces a keto-enol tautomerism. For example, in the adhesive composition containing a crosslinking agent or the adhesive composition which can mix | blend a crosslinking agent, the aspect containing the compound which produces the said keto-enol tautomerism is preferable. Accordingly, it is possible to suppress an excessive increase in viscosity and gelation of the adhesive composition after the crosslinking agent is blended, and to achieve an effect of extending the pot life of the adhesive composition. In the case where at least an isocyanate compound is used as the above-mentioned crosslinking agent, it is particularly interesting to include a compound that produces keto-enol tautomerism. For example, in the case where the above-mentioned adhesive composition is in the form of an organic solvent solution or a solvent-free form, this technique can be preferably applied.

As the keto-enol tautomerism-producing compound described above, various β-dicarbonyl compounds can be used. Specific examples include acetoacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane. Β-diketones such as alkane-2,4-dione, 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl ethyl acetate, isopropyl ethyl acetate Acetic acid acetates such as tert-butyl acetate, tert-butyl acetic acid acetate; propyl acetates such as ethyl propyl acetate, ethyl propyl acetate, isopropyl propyl acetate, tert-butyl propyl acetate, etc; Isobutylammonium acetates such as ethyl acetate, ethyl isobutylammonium acetate, isopropyl isobutylammonium acetate, tert-butyl isobutylammonium acetate; malonates such as methyl malonate and ethyl malonate ;Wait. Among them, preferred compounds include acetoacetone and acetoacetate. The keto-enol tautomerism-generating compound may be used alone, or two or more kinds may be used in combination.

The content of the keto-enol tautomerization compound may be set to, for example, 0.1 to 20 parts by mass, and usually 0.5 to 15 parts by mass based on 100 parts by mass of the (meth) acrylic polymer. Parts (for example, 1 to 10 parts by mass) are suitable. When the amount of the above compound is too small, it may be difficult to exhibit a sufficient use effect. On the other hand, when the above-mentioned compound is used in a large amount more than necessary, it may remain in the adhesive layer to reduce the cohesive force.

In addition, the above-mentioned adhesive composition may contain other known additives, for example, powders such as lubricants, colorants, and pigments, plasticizers, tackifiers, low-molecular-weight polymers, and surface lubrication may be appropriately added according to the application to be used. Agents, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils, etc.

< Adhesive Layer and Adhesive Sheet (Surface Protective Film)> The adhesive sheet of the present invention is an adhesive sheet obtained by forming the above-mentioned adhesive layer on at least one side of a base film. In this case, the crosslinking of the adhesive composition is usually performed during the adhesion. After the adhesive composition is applied, the adhesive layer containing the crosslinked adhesive composition may be transferred onto a substrate film or the like.

The method for forming the adhesive layer on the base film is not particularly limited. For example, it can be produced by applying the above-mentioned adhesive composition (solution) to the base film, drying and removing the polymerization solvent, etc. An adhesive layer is formed on the film. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the adhesive layer or adjusting the crosslinking reaction. In addition, when an adhesive composition is coated on a base film to prepare an adhesive sheet, one or more solvents other than a polymerization solvent may be added to the above-mentioned adhesive composition to enable uniform application on the base film. .

In addition, as a method for forming an adhesive layer when producing the adhesive sheet of the present invention, a known method used in the production of an adhesive tape is used. Specifically, for example, a roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, an air knife coating method, an extrusion coating method using a mouth pattern coater, and the like can be cited.

The pressure-sensitive adhesive sheet of the present invention is usually produced so that the thickness of the pressure-sensitive adhesive layer is about 3 μm to about 100 μm, and preferably about 5 μm to about 50 μm. When the thickness of an adhesive layer exists in the said range, it is easy to obtain suitable balance of re-peelability and adhesiveness, and it is preferable.

The adhesive sheet of the present invention preferably has a total thickness of 8 μm to 300 μm, more preferably 10 μm to 200 μm, and most preferably 20 μm to 100 μm. When it is in the said range, it is a preferable aspect which is excellent in adhesive characteristics (removability, adhesiveness, etc.), workability, and an external appearance characteristic. In addition, the said total thickness means the total thickness of all layers including a base film, an adhesive layer, and other layers.

<Separator> In the pressure-sensitive adhesive sheet of the present invention, it is preferable that the separator is adhered to the surface of the adhesive layer opposite to the surface in contact with the substrate film. For the above-mentioned separator, the separator may be adhered to the surface of the adhesive layer for the purpose of protecting the adhesive surface as needed.

As a material constituting the separator, there are paper and a plastic film, but a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the adhesive layer, and examples thereof include polyethylene films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene. Film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film Wait.

The thickness of the separator is usually about 5 μm to about 200 μm, and preferably about 10 μm to about 100 μm. When it is in the said range, it is preferable since it is excellent in the adhesiveness property with respect to an adhesive bond layer, and peeling workability from an adhesive bond layer. If necessary, the separator may be subjected to a mold release and antifouling treatment using a polysiloxane, a fluorine-containing type, a long-chain alkyl group, or a fatty acid ammonium-based mold release agent or silica powder, or coating. Type, kneading type, evaporation type and other antistatic treatment.

In the pressure-sensitive adhesive sheet of the present invention, the fluorine-containing oligomer is preferably present (coated and laminated) on the surface of the separator that is in contact with the pressure-sensitive adhesive layer (see FIG. 1). When the fluorine-containing oligomer is present on the surface of the separator in contact with the adhesive layer, when the separator is adhered to the adhesive layer, the fluorine-containing oligomer is separated from the separator. After the surface of the piece is transferred (transferred) to the surface of the adhesive layer, and the adhesive layer is adhered to the adherend (such as a polarizing plate), the light peeling effect caused by the low surface free energy of the fluorine site can be achieved, and It functions as a tackifier resin, improves the adhesiveness, and can suppress the sliding (offset), warping, and peeling of the surface protective film (combination of re-peelability and adhesiveness), which is a more preferable method.

< Optical member> The optical member of the present invention is preferably adhered (protected) by the adhesive sheet or when the separator is adhered, preferably by an adhesive sheet from which the separator is peeled. The adhesive sheet is excellent in curl adjustability and light peelability, and therefore can be used for surface protection applications (surface protection films) during processing, transportation, and shipping. Therefore, the adhesive sheet is useful for protecting the surface of the optical member (polarizing plate, etc.). Adhesive sheet. Examples

Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to the range shown by the specific examples. It should be noted that “parts” and “%” in the following description are quality standards unless otherwise specified. In addition, the blending amount (addition amount) in the table is shown.

In addition, each characteristic in the following description was each measured or evaluated by the following method.

<Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer and the like used was measured using a GPC device (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are shown below. Sample concentration: 0.2% by mass (tetrahydrofuran (THF) solution) Injection volume: 10 μl Eluent: THF Flow rate: 0.6 ml / min Measurement temperature: 40 ° C Chromatography column: Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2) Reference column: TSKgel SuperH-RC (1) Detector: Differential refractometer (RI) It should be noted that the weight-average molecular weight is calculated in terms of polystyrene. In addition, when measuring the number average molecular weight (Mn), it measured similarly to the weight average molecular weight (Mw).

<Foaming of the adhesive composition (solution)> The adhesive composition (solution) of each example was mixed and stirred, and then foaming of the adhesive composition (solution) was visually observed. In addition, regarding evaluation, the case where foaming was not recognized was described as "○", the case where foaming was slightly confirmed was described as "△", and the case where foaming was clearly confirmed was described as "X".

<Shearing force> The surface protection film was cut into a size of 10 mm in width and 100 mm in length, the separator was peeled off, and then the TAC polarizing plate was bonded so that the adhesive area of the adhesive layer of the adhesive sheet was 1 cm ² ( (SEG1423DU polarizer manufactured by Nitto Denko Corporation, width: 25mm, length: 100mm), stretched in the shearing direction at 23 ° C at a tensile speed of 0.06mm / min, and the maximum load at this time (N / cm ² ) As a shear force.

In the surface protection film of the present invention, the shear force at 23 ° C. × 50% RH of the adhesive layer used in the surface protection film to the polarizing plate is preferably 5 N / cm ² or more, and more preferably 5 N / cm ² ~ 50N / cm ^2, more preferably ^{7N / cm 2 ~ 40N / cm} 2. By adjusting the shearing force to 5 N / cm ² or more, it is possible to suppress slipping (offset), lifting, peeling, and the like after sticking to the adherend, and it is excellent in curl adjustability.

< Measurement of peeling electrification voltage> The adhesive sheet 1 of each example was cut into a width of 70 mm and a length of 130 mm, the release liner (spacer) was peeled off, and then one end of the adhesive sheet 1 was removed from the polarizing plate by a manual roller. The end portion of 20 protrudes by 30 mm and is crimped to the surface of a polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length: 100 mm) bonded to the glass plate 10. This sample was left in an environment of 23 ° C. × 50% RH for one day, and then, as shown in FIG. 2, it was set at a predetermined position of the sample fixing table 30 having a height of 20 mm. The end of the adhesive sheet (surface protection film) 1 protruding 30 mm from the polarizing plate 20 was fixed to an automatic winder (not shown) so that the peeling angle was 150 ^° and the peeling speed was 30 m / min. . For the potential at the surface of the adherend (polarizing plate 20) generated at this time, a potentiometer 40 (manufactured by SHISHIDO Electrostatic Corporation, model "STATIRON DZ-4") fixed at a position 30 mm in height from the center of the polarizing plate 20 was used. ) The "peeling charging voltage" was measured. The measurement was performed under the environment of 23 ° C and 50% RH.

In addition, as peeling charging voltage (kV) (absolute value) in this invention, 1.0 or less is preferable, 0.5 or less is more preferable, and 0.3 or less is more preferable. When it is in the said range, it is a preferable aspect because it is excellent in antistatic property and peeling electric property, and it is excellent in workability | operativity.

< Presence or absence of pollution (pollution resistance)> The adhesive sheet of each example was cut into a size of 50 mm in width and 80 mm in length, the separator was peeled off, and then a pressure roller was used to pressure-contact the TAC polarizing plate (Nitto Denko Corporation) Production, SEG1423DU polarizer, width: 70mm, length: 100mm), and evaluation samples were produced. The above evaluation sample was left in an environment at 70 ° C. for 120 hours, and then the adhesive sheet was peeled from the adherend by hand, and the traces of bubbles on the surface of the adherend at this time were visually observed. In addition, regarding evaluation, the case where a bubble trace is not observed is described as "(circle)", and the case where a bubble trace is observed is described as "x".

< Measurement of low-speed peeling force> A surface protection film cut into a width of 25 mm and a length of 100 mm was left to stand in an environment of 23 ° C. × 50% RH for 24 hours, and was laminated to a pressure of 0.25 MPa and a speed of 0.3 m / min. A TAC polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length: 100 mm) was used to prepare an evaluation sample. After the above lamination, it was left to stand in an environment of 23 ° C. × 50% RH for 30 minutes, and then the low-speed peeling at the time of peeling at a peeling speed of 0.3 m / min (low-speed peeling) and a peeling angle of 180 ^° was measured using a universal tensile tester. Force (N / 25mm). The measurement was performed in an environment of 23 ° C. × 50% RH.

For the surface protection film of the present invention, the 180 ^° peeling adhesion force of the adhesive layer used in the surface protection film to a polarizing plate at 23 ° C. × 50% RH (stretching speed 0.3 m / min: low-speed peeling force is preferred) ) Is 0.15 N / 25 mm or less, more preferably 0.01 N / 25 mm to 0.15 N / 25 mm, and still more preferably 0.02 N / 25 mm to 0.14 N / 25 mm. By adjusting the above-mentioned peeling adhesive force (stretching speed 0.3m / min) to 0.15N / 25mm or less, when a surface protective film is not required, the peeling operation becomes easier (re-peelability), and the adhesion of the adherend can be prevented. Damage and the like are preferred.

< Preparation of acrylic polymer (1)> A four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser was charged with 96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 2-hydroxyethyl acrylate. (HEA) 4 parts by mass, 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate as polymerization initiators, nitrogen was introduced while slowly stirring, and the temperature of the liquid in the flask was maintained A polymerization reaction was performed at about 65 ° C. for 6 hours, thereby preparing an acrylic polymer (1) solution (40% by mass). The weight average molecular weight (Mw) of the acrylic polymer (1) was 540,000.

<Preparation of acrylic polymer (2)> A four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser was charged with 91 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4-hydroxybutyl acrylate. (4HBA) 9 parts by mass, 0.02 parts by mass of acrylic acid (AA), 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate as polymerization initiators, and nitrogen was introduced while slowly stirring The temperature of the liquid in the flask was maintained at about 65 ° C., and a polymerization reaction was performed 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 540,000.

< Preparation of acrylic polymer (3)> A four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser was charged with 98.5 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4-hydroxybutyl acrylate. (4HBA) 1.5 parts by mass, 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate as polymerization initiators, nitrogen was introduced while slowly stirring, and the temperature of the liquid in the flask was maintained A polymerization reaction was performed at about 65 ° C. for 6 hours, thereby preparing an acrylic polymer (3) solution (40% by mass). The weight average molecular weight (Mw) of the acrylic polymer (3) was 550,000.

<Example 1> [Preparation of acrylic adhesive solution] The above-mentioned acrylic polymer (1) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100% by mass of solid content) 0.5 parts by mass of a solution obtained by diluting a fluorine-containing oligomer (Megafac F-562, manufactured by DIC Corporation) to 10% with ethyl acetate (solid content: 0.05 parts by mass), 5 parts by mass of a solution obtained by diluting LiTFSI as an ionic compound to 10% (solid content of 0.5 parts by mass), a cross-linking agent, and a hexamethylene diisocyanate isocyanate compound as a trifunctional isocyanate compound Form (manufactured by Tosoh Corporation, Coronate HX) 3 parts by mass (3 parts by mass of solid content), 3 parts by mass of dibutyltin dilaurate (1% by mass ethyl acetate solution) (0.03 part by mass of solid content) Parts), and mixed and stirred to prepare an acrylic adhesive solution.

[Production of antistatic treatment film] An antistatic agent (manufactured by SOLVEX Corporation, MICRO SOLVER RMd-142, containing tin oxide and polyester resin as a main component) was used by using a mixed solvent containing 30 parts by mass of water and 70 parts by mass of methanol. 10 A part by mass was diluted to prepare an antistatic solution. The obtained antistatic agent solution was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm) using a Meyer bar, and dried at 130 ° C. for 1 minute to remove the solvent to form an antistatic agent. An electrostatic layer (thickness: 0.2 μm), thereby producing an antistatic film.

[Preparation of Adhesive Sheet (Surface Protection Film)] The acrylic adhesive solution was applied to the surface of the antistatic treated film opposite to the antistatic treated surface, and heated at 130 ° C for 2 minutes to form a 15 μm thick adhesive.剂 层。 The agent layer. Next, a polysiloxane treated surface of a polyethylene terephthalate film (thickness: 25 μm) treated with a polysiloxane on one side was bonded to the surface of the adhesive layer to produce an adhesive sheet.

< Examples 2 to 12> An adhesive sheet was produced by the same method as in Example 1 based on the raw materials and compounding amounts described in Table 1.

< Example 13> [Preparation of urethane-based adhesive solution] As a polyol, 85 parts by mass of PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three hydroxyl groups, was used as 13 parts by mass of SANNIX GP3000 (manufactured by Sanyo Kasei Co., Ltd., Mn = 3000) with 3 hydroxyl groups, 2 parts by mass of SANNIX GP1000 (manufactured by Sanyo Kasei Co., Ltd., Mn = 1000), and 3 parts by mass as crosslinks 18 parts by mass of an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.), 0.04 parts by mass of acetoacetone iron (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst, and a fluorine-containing oligomer Megafac F-562 (manufactured by DIC Corporation) 0.2 parts by mass, 1 part by mass of 1-ethyl-3-methylimidazolium tris (fluoromethanesulfonium) imine salt (EMITFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) as an ionic compound And 210 parts by mass of ethyl acetate as a diluting solvent was mixed to obtain a polyurethane-based adhesive solution. Then, in the same manner as in Example 1, an adhesive sheet was prepared in which the heating conditions and the like or the thickness of the obtained adhesive layer was adjusted.

< Example 14> [Preparation of polysiloxane adhesive solution] As a polysiloxane adhesive, 100 parts by mass of "X-40-3229" (solid content of 60% by mass, (Shin-Etsu Chemical Industry Co., Ltd.), 0.5 parts by mass of "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a platinum catalyst, 0.2 parts by mass of fluorine-containing oligomer Megafac F-562 (manufactured by DIC Corporation) 1 part by mass of 1-ethyl-3-methylimidazolium tris (fluoromethanesulfonium) imine salt (EMITFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent, and 100 parts by mass of toluene as a solvent were mixed to obtain polysilicon. Oxane adhesive solution. Then, in the same manner as in Example 1, an adhesive sheet was prepared in which the heating conditions and the like or the thickness of the obtained adhesive layer was adjusted.

< Comparative Examples 1 to 3> An adhesive sheet was produced in the same manner as in Example 1 based on the raw materials and compounding amounts described in Table 1.

For the adhesive sheets of Examples and Comparative Examples, Table 1 and Table 2 show the contents of the above blending, and the results of various measurements and evaluations. In addition, the compounding quantity in Table 1 shows an active ingredient. The abbreviations in Table 1 are described below.

[Fluoro-type oligomer] F-562: Fluoro-type oligomer, weight average molecular weight 27900, manufactured by DIC Corporation, trade name: Megafac F-562 F-558: Fluoro-type oligomer, weight average molecular weight 11900 Manufactured by DIC Corporation, trade name: Megafac F-558 F-569: Fluoro-type oligomer, weight average molecular weight 6920, DIC Corporation, Trade name: Megafac F-569 222F: Fluoro-type oligomer, weight average Molecular weight 2940, manufactured by NEOS, trade name: Ftergent 222F

[Oxyalkylene-containing alkylene compound] PD-420: Oxyalkylene-containing compound (HLB value: 12.6) excluding organic polysiloxane, manufactured by Kao Corporation, trade name: Latemul PD-420 KF-353: oxygen-containing Polyalkylsiloxane with extended alkyl chain, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353

[Ionic compound] LiTFSI: lithium bis (trifluoromethanesulfonium) imide, manufactured by Tokyo Chemical Industry Co. Bu ₃ MePTFSI: tributylmethylfluorene bis (trifluoromethanesulfonium) imine salt, manufactured by Tokyo Chemical Industry Co., Ltd. X -40-2450: Polysiloxane containing ionic groups, manufactured by Shin-Etsu Chemical Co., Ltd. BMPTFSI: 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imine salt, manufactured by Wako Pure Chemical Industries, Ltd. MTOATFSI: methyltrioctylammonium bis (trifluoromethanesulfonium) imine salt, manufactured by Tokyo Chemical Industry Co., Ltd.EMITFSI: 1-ethyl-3-methylimidazolium tri (fluoromethanesulfonium) imine salt, Tokyo Manufactured by chemical industry co., Ltd.

Table 1

Table 2

From Table 2, it was confirmed that in all the examples, the shear force and the peeling charging voltage were excellent. In addition, when 100 parts by mass of the polymer was used, the amount of the fluorine-containing oligomer was adjusted to 5.5 parts by mass or less, which is excellent in pollution resistance, and it was confirmed that the pollution resistance (low pollution) It is also excellent. Moreover, in the Example which used the fluorine-containing oligomer whose weight average molecular weight is 20000 or more, it was confirmed that the foaming of an adhesive composition (solution) can be suppressed.

On the other hand, it was confirmed from Table 2 that, in Comparative Example 1, since the ionic compound was not compounded, the peeling charging voltage was different. In Comparative Example 2, the fluorine-containing oligomer was not compounded, so the shear force was poor. . In Comparative Example 3, since a fluorine-containing oligomer having a weight-average molecular weight of less than 3500 was used, a difference in shear force was confirmed. In Comparative Example 3, since a fluorinated oligomer 222F having a weight average molecular weight of less than 20,000 was used, foaming of the adhesive composition (solution) was confirmed.

INDUSTRIAL APPLICABILITY The adhesive sheet disclosed herein is suitable for use in manufacturing, transporting, and the like of an optical member used as a constituent element such as a liquid crystal display panel, a plasma display panel (PDP), and an organic electroluminescence (EL) display. A surface protective film for protecting the optical member. In particular, it is used as a surface protection film for optical components such as polarizing plates (polarizing films) for liquid crystal display panels, wavelength plates, retardation plates, optical compensation films, brightness enhancement films, light diffusion sheets, and reflection sheets (optical surface protection) Film) useful.

1‧‧‧adhesive sheet

10‧‧‧ glass plate

11‧‧‧ divider

12‧‧‧ Fluorine-type oligomer coating film

13‧‧‧Adhesive layer

14‧‧‧ substrate film

20‧‧‧ polarizing plate

30‧‧‧ sample fixing table

40‧‧‧ Potentiometer

FIG. 1 is a schematic cross-sectional view showing one configuration example of an adhesive sheet (surface protection film) of the present invention. FIG. 2 is an explanatory diagram showing a method for measuring a peeling voltage.

Claims (7)

An adhesive composition comprising an adhesive polymer, a fluorine-containing oligomer having a weight average molecular weight of 3500 or more, and an ionic compound. The adhesive composition according to claim 1, which contains an oxygen-containing alkylene compound. The adhesive composition according to claim 1 or 2, wherein the adhesive polymer is selected from the group consisting of a (meth) acrylic polymer, a polyurethane polymer, and a polysiloxane polymer. At least one of the group. An adhesive sheet characterized by having an adhesive layer formed of the adhesive composition according to any one of claims 1 to 3 on at least one side of a base film, and being inside and / or the surface of the aforementioned adhesive layer The aforementioned fluorine-containing oligomers exist. As in the adhesive sheet of claim 4, a separator is adhered on the side of the adhesive layer opposite to the side in contact with the substrate film. The adhesive sheet according to claim 5, wherein the fluorine-containing oligomer exists on the surface of the separator in contact with the adhesive layer. An optical member characterized in that an adhesive sheet as claimed in claim 4 or an adhesive sheet after the aforementioned separator has been peeled off from the adhesive sheet as claimed in claim 5 or 6.