Adhesive sheets and optical components

Abstract

This invention relates to adhesive sheets and optical components. The invention provides an adhesive sheet (surface protective film) with excellent adhesion, re-peelability, pick-up, and workability, capable of preventing adhesive strength increase over time, and possessing excellent whitening resistance and other properties. An adhesive sheet has an adhesive layer formed of an adhesive composition on one side of a supporting film, the supporting film having a cover coating on the side opposite to the side having the adhesive layer. The cover coating is characterized in that it contains a wax as a lubricant and a polyester resin as an adhesive, and the adhesive strength ratio (A / B) of the back adhesion force (A) at a peel speed of 0.3 m / min after being bonded to the surface of the cover coating at 23°C for 30 minutes is 3 or more, compared to the adhesion force (B) at a peel speed of 30 m / min after the adhesive side of the adhesive layer is bonded to a TAC surface at 50°C for 1 week.

Description

[0001] This application is a divisional application of Chinese patent application No. 201410366695.5, filed on July 29, 2014. Technical Field

[0002] This invention relates to adhesive sheets and optical components.

[0003] The adhesive sheet of the present invention is useful as a surface protection film for use in protecting the surfaces of optical components such as polarizers, wavelength plates, phase difference plates, optical compensation films, reflective sheets, and brightness enhancement films used in liquid crystal displays and the like. Background Technology

[0004] In recent years, when transporting or mounting optical and electronic components onto printed circuit boards, the components are transferred by packaging them in prescribed sheets or attaching adhesive tape. Surface protective films are particularly widely used in the fields of optical and electronic components.

[0005] Surface protective films are generally attached to the object being protected by applying an adhesive to the side of a support film, and are used to prevent scratches or stains that occur during the processing or transportation of the protected object (Patent Document 1). For example, the panel of a liquid crystal display is formed by attaching optical components such as polarizing plates and wavelength plates to a liquid crystal cell using an adhesive. Surface protective films are attached to these optical components using an adhesive to prevent scratches or stains that occur during the processing or transportation of the protected object.

[0006] Furthermore, the surface protective film is peeled off when it is not needed. However, with the increasing size and thinning of liquid crystal display panels, damage to the polarizing plate or liquid crystal cell is easily caused during the peeling process. Therefore, it is required that the peeling be light when the peeling is high speed.

[0007] Furthermore, when visually inspecting a surface protective film after it has been adhered to an object (such as a polarizing plate), it is required to be resistant to scratches. This is because scratches on the surface protective film make it difficult to determine whether the scratch is on the adhered object or on the surface protective film itself.

[0008] One method to reduce the likelihood of scratches on the back side of a protective film is to apply a hard surface layer (coating) to the aforementioned back side. The coating is typically formed by applying a coating material to the back side of a substrate and then drying and curing it. Furthermore, the coating's moderate lubricity allows for enhanced scratch resistance.

[0009] As an additive (lubricant) used to impart lubricity to the coating, polysiloxane lubricants or fluorinated lubricants are typically used.

[0010] However, when using a topcoat coating such as a polysiloxane lubricant, exposure to high temperature and high humidity conditions results in a whitening phenomenon, which reduces visibility during visual inspection.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent Application Publication No. 9-165460 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] Therefore, the object of the present invention is to provide an adhesive sheet (surface protective film) with excellent adhesion or re-peelability, pick-up and workability, which can prevent the adhesive force from increasing over time and has excellent whitening resistance, in order to solve the problems of existing adhesive sheets.

[0016] means for solving problems

[0017] That is, the adhesive sheet of the present invention has an adhesive layer formed of an adhesive composition on one side of a supporting film, and the supporting film has a cover coating on the side opposite to the side having the adhesive layer. The cover coating is characterized in that the cover coating contains a wax as a lubricant and a polyester resin as an adhesive, and the ratio (A / B) of the back adhesion force (A) after being bonded at 23°C for 30 minutes and peeled at a speed of 0.3 m / min to the adhesion force (B) after the adhesive side of the adhesive layer is bonded on a TAC surface at 50°C for 1 week and peeled at a speed of 30 m / min is 3 or more.

[0018] In the adhesive sheet of the present invention, the adhesive force (B) is preferably 1.5 N / 25 mm or less.

[0019] In the adhesive sheet of the present invention, the adhesive composition preferably contains a (meth)acrylic polymer having hydroxyl and carboxyl groups.

[0020] In the adhesive sheet of the present invention, it is preferable that the amount of carboxyl-containing (meth)acrylic monomers is less than 2% by weight relative to the total amount of monomer components constituting the (meth)acrylic polymer.

[0021] In the adhesive sheet of the present invention, preferably, 15% by weight or less of hydroxyl-containing (meth)acrylic monomers are contained relative to the total amount of monomer components constituting the (meth)acrylic polymer.

[0022] In the adhesive sheet of the present invention, preferably, 50% by weight or more of (meth)acrylic monomers having an alkyl group having 1 to 14 carbon atoms are contained relative to the total amount of monomer components constituting the (meth)acrylic polymer.

[0023] In the adhesive sheet of the present invention, the adhesive composition preferably contains a crosslinking agent.

[0024] In the adhesive sheet of the present invention, the adhesive composition preferably contains an organopolysiloxane having an oxyalkylene chain.

[0025] In the adhesive sheet of the present invention, the adhesive composition preferably contains an ionic compound.

[0026] In the adhesive sheet of the present invention, the wax is preferably an ester of higher fatty acids and higher alcohols.

[0027] In the adhesive sheet of the present invention, the topcoat coating preferably contains an antistatic component.

[0028] The optical component of the present invention is preferably protected by the aforementioned adhesive sheet. Attached Figure Description

[0029] Figure 1 This is an explanatory diagram illustrating the method for measuring back adhesion (A).

[0030] Figure 2 This is an explanatory diagram illustrating a method for peeling off an adhesive sheet according to one embodiment.

[0031] Figure 3 This is a schematic diagram of the potential measuring section used for measuring electrostatic voltage in the embodiments, etc.

[0032] Figure Labels

[0033] 1. Adhesive sheet (surface protective film)

[0034] 1A Topcoat Coating Surface

[0035] 2 polarizing plates

[0036] 3. Acrylic resin boards

[0037] 4. Fixed platform

[0038] 5 Potentiometer

[0039] 12 Supporting film

[0040] 14 Topcoat

[0041] 20 Adhesive layers

[0042] 20A Adhesive Surface

[0043] 50 Planar polarizing plate

[0044] 60 Single-sided adhesive tape

[0045] 62 Adhesive layer (bonding surface)

[0046] 64 Substrate

[0047] 130 Double-sided adhesive tape

[0048] 132 stainless steel sheet

[0049] 160 Single-sided adhesive tape

[0050] 162 Acrylic adhesives (adhesive layer)

[0051] 162A Adhesive Surface

[0052] 164 Polyester film (supporting film) Detailed Implementation

[0053] The embodiments of the present invention will now be described in detail.

[0054] <Adhesive Composition>

[0055] The adhesive sheet of the present invention has an adhesive layer formed of an adhesive composition on one side of a supporting film, and the supporting film has a topcoat coating on the side opposite to the side having the adhesive layer. As for the adhesive composition, any composition with adhesive properties can be used without particular limitation, such as acrylic, synthetic rubber, natural rubber, polysiloxane, or any other adhesive. Furthermore, from the viewpoint of ease of adjusting adhesive properties, using an acrylic adhesive is more preferred.

[0056] In the adhesive sheet of the present invention, the adhesive composition preferably contains a (meth)acrylic polymer. Reasons for using an acrylic adhesive (adhesive composition) containing the aforementioned (meth)acrylic polymer as the adhesive sheet include: ease of adjusting adhesive properties, transparency, heat resistance, etc.

[0057] <(meth)acrylic acid polymers>

[0058] As for the (meth)acrylic polymer, there are no particular limitations as long as it is an adhesive (meth)acrylic polymer. It is preferred to use (meth)acrylic monomers with alkyl groups having 1 to 14 carbon atoms as the main component of the monomer composition, and more preferably (meth)acrylic monomers with alkyl groups having 6 to 14 carbon atoms. As the (meth)acrylic monomer, one or more of them can be used as the main component.

[0059] In particular, relative to the total amount of monomer components constituting the (meth)acrylic polymer, it is preferable to contain 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, and most preferably 90 to 97% by weight of (meth)acrylic monomers having alkyl groups having 1 to 14 carbon atoms. When the content is less than 50% by weight, the appropriate wetting and cohesiveness of the adhesive composition deteriorates, and therefore it is not preferred. Furthermore, in this invention, (meth)acrylic polymers refer to acrylic polymers and / or methacrylic polymers, and (meth)acrylic esters refer to acrylates and / or methacrylates.

[0060] Specific examples of (meth)acrylate monomers having alkyl groups having 1 to 14 carbon atoms include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, n-tridecyl methacrylate, n-tetradecyl methacrylate, etc.

[0061] When the adhesive sheet of the present invention is used as a surface protective film, preferred (meth)acrylate monomers include alkyl groups having 6 to 14 carbon atoms, such as (meth)acrylate hexyl acrylate, (meth)acrylate 2-ethylhexyl acrylate, (meth)acrylate n-octyl acrylate, (meth)acrylate isooctyl acrylate, (meth)acrylate n-nonyl acrylate, (meth)acrylate isononyl acrylate, (meth)acrylate n-decyl acrylate, (meth)acrylate n-trigedecyl acrylate, (meth)acrylate n-tetradecyl acrylate, and (meth)acrylate n-tetradecyl acrylate. By using (meth)acrylates having alkyl groups having 6 to 14 carbon atoms, it is easy to control the adhesion to the adhered objects to a low level, resulting in excellent re-peelability.

[0062] The adhesive composition used in this invention preferably contains a (meth)acrylic polymer having hydroxyl and carboxyl groups. By using the (meth)acrylic polymer having hydroxyl and carboxyl groups, the crosslinking of the hydroxyl groups can be easily controlled, and the carboxyl groups can prevent the adhesive strength from increasing over time, which is a preferred approach.

[0063] Relative to the total amount of monomer components constituting the (meth)acrylic polymer, it is preferable to contain 15% by weight or less, more preferably 1 to 13% by weight, further preferably 2 to 11% by weight, and most preferably 3.5 to 10% by weight of hydroxyl-containing (meth)acrylic monomers. Within this range, it is easier to control the balance between the wettability and cohesiveness of the adhesive composition, and therefore preferred. In particular, by using the hydroxyl-containing (meth)acrylic monomers, it is easier to control crosslinking of the adhesive composition, and thus easier to control the balance between the improvement in wettability caused by flow and the decrease in adhesive strength during peeling. Furthermore, unlike carboxyl groups or sulfonate groups that generally function as crosslinking sites, hydroxyl groups have a moderate interaction with ionic compounds that act as antistatic agents or organopolysiloxanes having oxyalkylene chains, and therefore are also preferred in terms of antistatic properties. In particular, it is preferable to contain 11 to 15% by weight in order to improve creep properties.

[0064] Examples of hydroxyl-containing (meth)acrylic acid monomers include: 2-hydroxyethyl (meth)acrylic acid, 2-hydroxypropyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, 6-hydroxyhexyl (meth)acrylic acid, 8-hydroxyoctyl (meth)acrylic acid, 10-hydroxydecyl (meth)acrylic acid, 12-hydroxylaurate (meth)acrylic acid, methyl (4-hydroxymethylcyclohexyl)acrylate, N-hydroxymethyl (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. In particular, using hydroxyl-containing (meth)acrylic acid monomers with 4 or more carbon atoms in the alkyl group facilitates easy and gentle peeling during high-speed peeling, and is therefore preferred.

[0065] Furthermore, relative to the total amount of monomer components constituting the (meth)acrylic polymer, it is preferable to contain 2% by weight or less, more preferably 0.005% to 2% by weight, even more preferably 0.006% to 1.9% by weight, and most preferably 0.01% to 1.0% by weight of carboxyl-containing (meth)acrylic monomers. When it exceeds 2% by weight, it cannot suppress the increase in adhesive strength over time, and the re-peelability, anti-adhesion strength increase, and workability deteriorate, therefore it is not preferred. Additionally, when a large number of acidic functional groups such as carboxyl groups with strong polarity are present, in the case of using an ionic compound as an antistatic agent, the interaction between the acidic functional groups such as carboxyl groups and the ionic compound may hinder ion conduction, thereby reducing conductivity and failing to obtain sufficient antistatic properties, therefore it is not preferred.

[0066] Examples of (meth)acrylic acid monomers having a carboxyl group include: (meth)acrylic acid, (meth)acrylic acid carboxyethyl ester, (meth)acrylic acid carboxypentyl ester, itaconic acid, maleic acid, fumaric acid, etc.

[0067] In addition, as other polymerizable monomer components, for the purpose of easily achieving a balance of adhesive properties, polymerizable monomers such as those used to adjust the glass transition temperature or peelability of (meth)acrylic polymers can be used to make the Tg below 0°C (typically above -100°C) without impairing the effects of the present invention.

[0068] Other polymerizable monomers used in the (meth)acrylic polymers, besides the carboxyl-containing (meth)acrylic monomers, hydroxyl-containing (meth)acrylic monomers, and alkyl (meth)acrylic monomers having 1 to 14 carbon atoms, may be used without particular restriction, provided that they do not impair the characteristics of the present invention. For example, components that improve cohesiveness and heat resistance, such as cyano monomers, vinyl ester monomers, and aromatic vinyl monomers, and components that improve adhesiveness or have functional groups that act as crosslinking sites, such as amide monomers, imide monomers, amino monomers, epoxy monomers, N-acryloylmorpholine, and vinyl ether monomers, may be appropriately used. These polymerizable monomers may be used alone or in mixtures of two or more.

[0069] Examples of cyano-containing monomers include acrylonitrile and methacrylonitrile.

[0070] Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl laurate.

[0071] Examples of aromatic vinyl monomers include styrene, chlorostyrene, and chloromethylstyrene. -Methylstyrene, other substituted styrene, etc.

[0072] Examples of monomers containing amide groups include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, and diacetoneacrylamide.

[0073] Examples of monomers containing an imide group include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconitumide.

[0074] Examples of amino-containing monomers include aminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, and N,N-dimethylaminopropyl methacrylate.

[0075] Examples of epoxy-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether.

[0076] Examples of vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

[0077] In this invention, the polymerizable monomers other than carboxyl-containing (meth)acrylic acid monomers, hydroxyl-containing (meth)acrylic acid monomers, and alkyl (meth)acrylic acid monomers having 1 to 14 carbon atoms are preferably 0 to 40% by weight, more preferably 0 to 30% by weight, in the total monomer composition (all monomer components) constituting the (meth)acrylic acid polymer. By using the other polymerizable monomers within the aforementioned range, good interaction with ionic compounds that can be used as antistatic agents and good re-peelability can be appropriately adjusted.

[0078] In the adhesive composition of the present invention, the (meth)acrylic polymer may further contain a reactive monomer containing an alkylene oxide group as a monomer component.

[0079] The average molar number of oxyalkylene units added to the reactive monomer containing the alkylene oxide group is preferably 1 to 40, more preferably 3 to 40, further preferably 4 to 35, and particularly preferably 5 to 30, from the viewpoint of compatibility with ionic compounds. When the average molar number of addition is 1 or more, it tends to effectively reduce contamination of the protected material. However, when the average molar number of addition is greater than 40, the interaction with ionic compounds is large, which tends to increase the viscosity of the adhesive composition and make it difficult to coat, and is therefore not preferred. In addition, the end of the oxyalkylene chain can be a hydroxyl group as is, or it can be replaced by other functional groups, etc.

[0080] The reactive monomer containing alkylene oxide groups can be used alone or in combination of two or more. The overall content of the monomer component in the (meth)acrylic polymer is preferably 20% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, even more preferably 4% by weight or less, particularly preferably 3% by weight or less, and still preferably 1% by weight or less. When the content of the reactive monomer containing alkylene oxide groups exceeds 10% by weight, the interaction with ionic compounds increases, hindering ion conduction and decreasing antistatic properties, therefore it is not preferred.

[0081] The oxoalkylene unit, which is a reactive monomer containing an alkylene oxide group in this invention, can be an alkylene unit having 1 to 6 carbon atoms, such as oxomethylene, oxoethylene, oxopropylene, oxobutylene, etc. The hydrocarbon group of the oxoalkylene chain can be straight-chain or branched.

[0082] Furthermore, it is even more preferable that the reactive monomer containing alkylene oxide groups is a reactive monomer having ethylene oxide groups. By using a (meth)acrylic acid polymer having a reactive monomer having ethylene oxide groups as the base polymer, the compatibility of the base polymer with ionic compounds is improved, and exudation into the adherend can be appropriately suppressed, resulting in a low-fouling adhesive composition.

[0083] Examples of reactive monomers containing alkylene oxide groups in this invention include, for example, (meth)acrylate alkylene oxide adducts and reactive surfactants having reactive substituents such as acryloyl, methacryloyl, and allyl groups in their molecules.

[0084] Specific examples of the alkylene oxide adducts of (meth)acrylates include, for example: polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, octoxy polyethylene glycol (meth)acrylate, lauroxy polyethylene glycol (meth)acrylate, stearoxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, octoxy polyethylene glycol-polypropylene glycol (meth)acrylate, etc.

[0085] In addition, specific examples of the reactive surfactants mentioned above include anionic reactive surfactants having (meth)acryloyl or allyl groups, nonionic reactive surfactants, cationic reactive surfactants, etc.

[0086] The weight-average molecular weight of the (meth)acrylic acid polymer is 100,000 to 5,000,000, preferably 200,000 to 4,000,000, and more preferably 300,000 to 3,000,000. When the weight-average molecular weight is less than 100,000, there is a tendency for paste residue to form due to the reduced cohesiveness of the adhesive composition. On the other hand, when the weight-average molecular weight exceeds 5,000,000, the polymer's fluidity decreases, resulting in insufficient wetting of the polarizing plate and a tendency for bubbling to occur between the polarizing plate and the adhesive composition layer of the adhesive sheet. Furthermore, the weight-average molecular weight refers to the weight-average molecular weight determined by GPC (gel permeation chromatography).

[0087] Furthermore, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably below 0°C, more preferably below -10°C (generally above -100°C). When the glass transition temperature is above 0°C, the polymer is difficult to flow and tends to produce bubbles between the polarizing plate and the adhesive composition layer of the adhesive sheet, for example, due to insufficient wetting of the polarizing plate. In particular, by adjusting the glass transition temperature to below -61°C, an adhesive composition with excellent wetting of the polarizing plate and light peelability is easily obtained. In addition, the glass transition temperature of the (meth)acrylic polymer can be adjusted to the aforementioned range by appropriately changing the monomer composition or composition ratio used.

[0088] The polymerization method for the (meth)acrylic acid polymers used in this invention is not particularly limited, and polymerization can be carried out by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. In particular, from the viewpoint of workability and low pollution to the protected material, solution polymerization is a more preferred method. In addition, the obtained polymer can be any of the following: random copolymer, block copolymer, alternating copolymer, graft copolymer, etc.

[0089] <Ionic compounds>

[0090] In the adhesive sheet of the present invention, the adhesive composition preferably contains an ionic compound, such as alkali metal salts and / or ionic liquids. The presence of these ionic compounds imparts excellent antistatic properties.

[0091] The alkali metal salt exhibits high ionic dissociation, thus it is preferred from the perspective of demonstrating excellent antistatic properties even in trace amounts. As the alkali metal salt, it is preferable to use, for example, a salt containing Li. + Na + K + cations and containing Cl - ,Br - I - AlCl4 - Al2Cl7 - BF4 - PF6 - SCN - ClO4 - NO3 - CH3COO - C9H 19 COO - CF3COO - C3H7COO - CH3SO3 - CF3SO3- C4F9SO3 - C2H5OSO3 - C6H 13 OSO3 - C8H 17 OSO3 - (CF3SO2)2N - (C2F5SO2)2N - (C3F7SO2)2N - (C4F9SO2)2N - (CF3SO2)3C - AsF6 - SbF6 - NbF6 - TaF6 - F(HF) n - (CN)2N - (CF3SO2)(CF3CO)N - (CH3)2PO4 - (C2H5)2PO4 - CH3(OC2H4)2OSO3 - C6H4(CH3)SO3 - (C2F5)3PF3 - CH3CH(OH)COO - and (FSO2)2N - The metal salts are composed of anions. More preferably, lithium salts such as LiBr, LiI, LiBF4, LiPF6, LiSCN, LiClO4, LiCF3SO3, Li(CF3SO2)2N, Li(C2F5SO2)2N, Li(FSO2)2N, and Li(CF3SO2)3C are used, and even more preferably, LiCF3SO3, Li(CF3SO2)2N, Li(C2F5SO2)2N, Li(C3F7SO2)2N, Li(C4F9SO2)2N, Li(FSO2)2N, and Li(CF3SO2)3C are used. These alkali metal salts can be used alone or in mixtures of two or more.

[0092] Furthermore, by using the ionic liquid as an antistatic agent, an adhesive layer with high antistatic effect can be obtained without compromising adhesive properties. The detailed reasons for obtaining excellent antistatic properties by using ionic liquids are not yet clear, but are believed to be as follows: ionic liquids have a low melting point (below 100°C) compared to ordinary ionic compounds, therefore their molecules move easily, resulting in excellent antistatic capabilities. Especially when attempting to antistatically transfer the ionic liquid to the adhered object, a very small amount is transferred onto the adhered object, thereby achieving excellent anti-peeling static properties. In particular, ionic liquids with a melting point below room temperature (25°C) can transfer to the adhered object more effectively, resulting in excellent antistatic properties.

[0093] Furthermore, ionic liquids are liquid below 100°C, making them easier to add to, disperse, or dissolve in adhesives compared to solid salts. Additionally, ionic liquids have no vapor pressure (non-volatile), thus their antistatic properties do not disappear over time. Ionic liquids are molten salts (ionic compounds) with a melting point below 100°C and a liquid state.

[0094] As the ionic liquid, it is preferable to use an ionic liquid composed of an organic cation and anion components represented by the following general formulas (A) to (E). Using an ionic liquid containing these cations, superior antistatic properties can be obtained.

[0095]

[0096] R in equation (A) a R represents a hydrocarbon group with 4 to 20 carbon atoms, which can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom. b and R c Whether the groups are the same or different, they represent hydrocarbon groups with 1 to 16 hydrogen or carbon atoms, and can be functional groups in which a portion of the hydrocarbon group is replaced by a heteroatom. In the case where the nitrogen atom contains a double bond, R is absent. c .

[0097] R in equation (B) d R represents a hydrocarbon group with 2 to 20 carbon atoms, which can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom. e R f and R g The same or different, representing a hydrocarbon group with 1 to 16 hydrogen or carbon atoms, can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom.

[0098] R in equation (C) h R represents a hydrocarbon group with 2 to 20 carbon atoms, which can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom. i Rj and R k The same or different, representing a hydrocarbon group with 1 to 16 hydrogen or carbon atoms, can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom.

[0099] In formula (D), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and R... l R m R n and R o Whether the groups are the same or different, they represent hydrocarbon groups with 1 to 20 carbon atoms. A group can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom. In the case where Z is a sulfur atom, R is absent. o .

[0100] R in equation (E) P A hydrocarbon group representing 1 to 18 carbon atoms can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom.

[0101] Examples of cations represented by formula (A) include pyridine. Cations, piperidine cationic, pyrrolidine Cations, cations with a pyrrololine skeleton, cations with a pyrrole skeleton, morpholine Cations, etc.

[0102] As a specific example, one could include: 1-ethylpyridine Cationic, 1-Butylpyridine Cationic, 1-hexylpyridine Cationic, 1-Butyl-3-methylpyridine Cationic, 1-Butyl-4-methylpyridine Cationic, 1-hexyl-3-methylpyridine Cationic, 1-Butyl-3,4-dimethylpyridine Cationic, 1,1-dimethylpyrrolidine Cationic, 1-ethyl-1-methylpyrrolidine Cationic, 1-methyl-1-propylpyrrolidine Cationic, 1-methyl-1-butylpyrrolidine Cationic, 1-methyl-1-pentylpyrrolidine Cationic, 1-methyl-1-hexylpyrrolidine Cationic, 1-methyl-1-heptylpyrrolidine Cationic, 1-ethyl-1-propylpyrrolidine Cationic, 1-ethyl-1-butylpyrrolidine Cationic, 1-ethyl-1-pentylpyrrolidine Cationic, 1-ethyl-1-hexylpyrrolidine Cationic, 1-ethyl-1-heptylpyrrolidine Cationic, 1,1-dipropylpyrrolidine Cationic, 1-propyl-1-butylpyrrolidine Cationic, 1,1-dibutylpyrrolidine cationic, pyrrolidine -2-keto cation, 1-propylpiperidine Cation, 1-pentylpiperidine Cation, 1,1-dimethylpiperidine Cation, 1-Methyl-1-ethylpiperidine Cationic, 1-methyl-1-propylpiperidine Cationic, 1-methyl-1-butylpiperidine Cationic, 1-methyl-1-pentylpiperidine Cationic, 1-methyl-1-hexylpiperidine Cation, 1-Methyl-1-heptylpiperidine Cationic, 1-ethyl-1-propylpiperidine Cationic, 1-ethyl-1-butylpiperidine Cationic, 1-ethyl-1-pentylpiperidine Cationic, 1-ethyl-1-hexylpiperidine Cationic, 1-ethyl-1-heptylpiperidine Cation, 1,1-dipropylpiperidine Cation, 1-propyl-1-butylpiperidine Cationic, 1,1-dibutylpiperidine Cations, 2-methyl-1-pyrrolidone cations, 1-ethyl-2-phenylindole cations, 1,2-dimethylindole cations, 1-ethylcarbazole cations, N-ethyl-N-methylmorpholine cation.

[0103] Examples of cations represented by formula (B) include imidazole. Cations, Tetrahydropyrimidine Cations, dihydropyrimidines Cations, etc.

[0104] As a specific example, one could include: 1,3-dimethylimidazole Cationic, 1,3-diethylimidazole Cationic, 1-ethyl-3-methylimidazolium Cationic, 1-Butyl-3-methylimidazolium Cationic, 1-hexyl-3-methylimidazolium Cationic, 1-octyl-3-methylimidazolium Cationic, 1-decyl-3-methylimidazolium Cationic, 1-dodecyl-3-methylimidazolium Cationic, 1-tetradecyl-3-methylimidazole Cationic, 1,2-dimethyl-3-propylimidazolium Cationic, 1-ethyl-2,3-dimethylimidazole Cationic, 1-Butyl-2,3-dimethylimidazole Cationic, 1-hexyl-2,3-dimethylimidazole Cationic, 1-(2-methoxyethyl)-3-methylimidazole Cationic, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidine Cationic, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidine Cationic, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidine Cationic, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidine Cationic, 1,3-dimethyl-1,4-dihydropyrimidine Cationic, 1,3-dimethyl-1,6-dihydropyrimidine Cationic, 1,2,3-trimethyl-1,4-dihydropyrimidine Cationic, 1,2,3-trimethyl-1,6-dihydropyrimidine Cationic, 1,2,3,4-tetramethyl-1,4-dihydropyrimidine Cationic, 1,2,3,4-tetramethyl-1,6-dihydropyrimidine Cations, etc.

[0105] Examples of cations represented by formula (C) include: pyrazole. Cationic, pyrazoline Cations, etc.

[0106] As a specific example, one could include: 1-methylpyrazole cationic, 3-methylpyrazole Cationic, 1-ethyl-2-methylpyrazole Cationic, 1-ethyl-2,3,5-trimethylpyrazole Cationic, 1-propyl-2,3,5-trimethylpyrazole Cationic, 1-butyl-2,3,5-trimethylpyrazole Cationic, 1-ethyl-2,3,5-trimethylpyrazoline Cationic, 1-propyl-2,3,5-trimethylpyrazoline Cationic, 1-Butyl-2,3,5-Trimethylpyrazoline Cations, etc.

[0107] Examples of cations represented by formula (D) include: tetraalkylammonium cations, trialkylsulfonium cations, and tetraalkyl... The cations include cations in which a portion of the alkyl group is replaced by an alkenyl group, an alkoxy group, or an epoxy group.

[0108] Specific examples include: tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethyl... cationic, tetraethyl cationic, tetrabutyl Cation, Tetrahexyl Cation, Tetraoctyl cationic, triethylmethyl cationic, tributylethyl Cation, Trimethyldecyl Cationic, diallyl dimethylammonium cationic, tributyl(2-methoxyethyl) Cations, etc. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, and triethylmethyl... cationic, tributylethyl Cation, Trimethyldecyl Asymmetric tetraalkylammonium cations, trialkylsulfonium cations, tetraalkyl... Cations, or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cations, glycidyltrimethylammonium cations, diallyldimethylammonium cations, N,N-dimethyl-N-ethyl-N-propylammonium cations, N,N-dimethyl-N-ethyl-N-butylammonium cations, N,N-dimethyl-N-ethyl-N-pentylammonium cations, N,N-dimethyl-N-ethyl-N-hexylammonium cations, N,N-dimethyl-N-ethyl-N-heptylammonium cations 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-heptylammonium cation, N,N-Dimethyl-N-butyl-N-hexylammonium cation, N,N-Diethyl-N-butyl-N-heptylammonium cation Ammonium 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-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-N-butyl-N-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.

[0109] Examples of cations represented by formula (E) include sulfonium cations. Additionally, R in formula (E) can also be represented by... P Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl, etc.

[0110] On the other hand, as an anionic component, there are no particular restrictions as long as it meets the requirements for becoming an ionic liquid; for example, Cl can be used. - ,Br - I - AlCl4 - Al2Cl7 - BF4 - PF6 -ClO4 - NO3 - CH3COO - CF3COO - CH3SO3 - CF3SO3 - C4F9SO3 - (CF3SO2)2N - (C2F5SO2)2N - (C3F7SO2)2N - (C4F9SO2)2N - (CF3SO2)3C - AsF6 - SbF6 - NbF6 - TaF6 - F(HF) n - (CN)2N - C4F9SO3 - (C2F5SO2)2N - C3F7COO - (CF3SO2)(CF3CO)N - C9H 19 COO - (CH3)2PO4 - (C2H5)2PO4 - C2H5OSO3 - C6H 13 OSO3 - C8H 17 OSO3 - CH3(OC2H4)2OSO3 - C6H 14 (CH3)SO3 - (C2F5)3PF3 - CH3CH(OH)COO - and (FSO2)2N - wait.

[0111] Alternatively, anions represented by the following formula (F) can also be used as an anionic component.

[0112]

[0113] Furthermore, as an anionic component, it is particularly preferable to use an anionic component containing fluorine atoms from the viewpoint of obtaining a low-melting-point ionic liquid.

[0114] As a specific example of the ionic liquid used in this invention, it can be appropriately selected from the aforementioned combination of cationic and anionic components, for example: 1-butylpyridine. Tetrafluoroborate, 1-Butylpyridine Hexafluorophosphate, 1-Butyl-3-methylpyridine Tetrafluoroborate, 1-Butyl-3-methylpyridine Trifluoromethanesulfonate, 1-butyl-3-methylpyridine Bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridine Bis(pentafluoroethanesulfonyl)imide, 1-hexylpyridine Tetrafluoroborate, 1,1-dimethylpyrrolidone Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-methyl-1-butylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidine Bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpyrrolidine Bis(trifluoromethanesulfonyl)imine, 1-propylpiperidine Bis(trifluoromethanesulfonyl)imide, 1-pentylpiperidine Bis(trifluoromethanesulfonyl)imine, 1,1-dimethylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-ethylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-propylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-butylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-pentylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-hexylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-methyl-1-heptylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-ethyl-1-propylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-ethyl-1-butylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-ethyl-1-pentylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-ethyl-1-hexylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-ethyl-1-heptylpiperidine Bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpiperidine Bis(trifluoromethanesulfonyl)imine, 1-propyl-1-butylpiperidine Bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpiperidine bis(trifluoromethanesulfonyl)imide, 1,1-dimethylpyrrolidine bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidine bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidine bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpyrrolidine bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidine bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpyrrolidine Bis(pentafluoroethanesulfonyl)imine, 1-propylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-pentylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1,1-dimethylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-ethylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-propylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-butylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-pentylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-hexylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-methyl-1-heptylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-ethyl-1-propylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-ethyl-1-butylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-ethyl-1-pentylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-ethyl-1-hexylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-ethyl-1-heptylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1,1-dipropylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1-propyl-1-butylpiperidine Bis(pentafluoroethanesulfonyl)imine, 1,1-dibutylpiperidine Bis(pentafluoroethanesulfonyl)imine, 2-methyl-1-pyrrolline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium Tetrafluoroborate, 1-ethyl-3-methylimidazolium Acetate, 1-ethyl-3-methylimidazolium Trifluoroacetate, 1-ethyl-3-methylimidazolium Heptafluorobutyrate, 1-ethyl-3-methylimidazolium Trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium Perfluorobutyrate, 1-ethyl-3-methylimidazole dicyandiamide salt, 1-ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium Tris(trifluoromethanesulfonyl)methyl compound, 1-butyl-3-methylimidazolium Tetrafluoroborate, 1-Butyl-3-methylimidazolium Hexafluorophosphate, 1-Butyl-3-methylimidazolium Trifluoroacetate, 1-butyl-3-methylimidazolium Heptafluorobutyrate, 1-Butyl-3-methylimidazolium Trifluoromethanesulfonate, 1-Butyl-3-methylimidazolium Perfluorobutyrate, 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium Chloride, 1-hexyl-3-methylimidazolium Tetrafluoroborate, 1-hexyl-3-methylimidazolium Hexafluorophosphate, 1-hexyl-3-methylimidazolium Trifluoromethanesulfonate, 1-octyl-3-methylimidazolium Tetrafluoroborate, 1-octyl-3-methylimidazolium Hexafluorophosphate, 1-hexyl-2,3-dimethylimidazole Tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methylpyrazole Tetrafluoroborate, 2-methylpyrazole Tetrafluoroborate, 1-ethyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazole Bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazole Bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazole Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazole Bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoline Bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoline Bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoline Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl)trifluoroacetamide, tetrapentyltrifluoromethanesulfonate ammonium, tetrapentylammonium bis(trifluoromethanesulfonyl)imide, tetrahexyltrifluoromethanesulfonate ammonium, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, tetraheptyltrifluoromethanesulfonate ammonium, tetraheptylammonium bis(trifluoromethanesulfonyl)imide, diallyl dimethyltetrafluoroborate ammonium, diallyl dimethyltrifluoromethanesulfonate ammonium, diallyl dimethylammonium bis(trifluoromethanesulfonyl)imide, diallyl dimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2- Ammonium tetrafluoroborate (methoxyethyl), N,N-diethyl-N-methyl-N-(2-methoxyethyl)trifluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl)imide, glycidyltrimethyltrifluoromethanesulfonate, glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammonium bis(pentafluoroethanesulfonyl)imide, tetraoctyl Trifluoromethanesulfonate, tetraoctyl bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl)imide, N N,N-Dimethyl-N-propyl-N-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N-propyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N,N-di ... -Dihexylammonium bis(trifluoromethanesulfonyl)imide, Trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, Triethylpropylammonium bis(trifluoromethanesulfonyl)imide, Triethylpentylammonium bis(trifluoromethanesulfonyl)imide, Triethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl- N-Ethylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, 1-Butylpyridine (Trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridine (Trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (Trifluoromethanesulfonyl)trifluoroacetamide, N-ethyl-N-methylmorpholine Thiocyanate, 4-ethyl-4-methylmorpholine Methyl carbonate salts, etc.

[0115] The ionic liquid can be a commercially available product or synthesized as follows. There are no particular restrictions on the method of synthesizing the ionic liquid, as long as the target ionic liquid can be obtained. Generally, the halide method, hydroxide method, ester method, complexation method, and neutralization method described in the literature "Ionic Liquids - The Frontier and Future of Development" (published by CMC Co., Ltd.) can be used.

[0116] The following sections discuss the halide method, hydroxide method, ester method, complexation method, and neutralization method, using nitrogen-containing compounds. Taking salt as an example, its synthesis method will be explained. For other sulfur-containing... Salt, phosphorus Salts and other ionic liquids can also be obtained using the same method.

[0117] The halide method is carried out through the reactions shown in equations (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction equation (1), using chlorine, bromine, or iodine as halogens). The obtained halide is then reacted with an anionic structure (A) of the target ionic liquid. - The target ionic liquid (R4NA) is obtained by reacting the acid (HA) or salt (MA, where M is a cation that forms a salt with the target anion, such as ammonium, lithium, sodium, or potassium) with the target anion.

[0118]

[0119] The hydroxide method is carried out through the reactions shown in (4) to (8). First, the halide (R4NX) is electrolyzed by ion exchange membrane method (reaction (4)), by OH-type ion exchange resin method (reaction (5)), or by reaction with silver oxide (Ag2O) (reaction (6)) to obtain hydroxide (R4NOH) (using chlorine, bromine, or iodine as halogens). The obtained hydroxide is then reacted with the reactions shown in (7) to (8) in the same way as the aforementioned halogenation method to obtain the target ionic liquid (R4NA).

[0120]

[0121] The ester method is carried out through the reactions shown in (9) to (11). First, a tertiary amine (R3N) is reacted with an ester to obtain an esterified product (reaction formula (9), using esters of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid, or esters of organic acids such as methanesulfonic acid, methylphosphonic acid, and formic acid as esters). The obtained esterified product is then reacted with the reactions shown in (10) to (11) in the same manner as the aforementioned halogenation method to obtain the target ionic liquid (R4NA). Alternatively, the ionic liquid can be obtained directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, etc., as esters.

[0122]

[0123] The complexation method is carried out through the reactions shown in (12) to (15). First, quaternary ammonium halides (R4NX), quaternary ammonium hydroxides (R4NOH), quaternary ammonium carbonates (R4NOCO2CH3), etc., are reacted with hydrogen fluoride (HF) or ammonium fluoride (NH4F) to obtain fluorinated quaternary ammonium salts (reaction formulas (12) to (14)). By subjecting the obtained fluorinated quaternary ammonium salts to complexation reactions with fluorides such as BF3, AlF3, PF5, AsF5, SbF5, NbF5, and TaF5, ionic liquids can be obtained (reaction formula (15)).

[0124]

[0125]

[0126] The neutralization method is carried out by the reaction shown in (16). It can be obtained by reacting the tertiary amine with organic acids such as HBF4, HPF6, CH3COOH, CF3COOH, CF3SO3H, (CF3SO2)2NH, (CF3SO2)3CH, and (C2F5SO2)2NH.

[0127]

[0128]

[0129] In the aforementioned formulas (1) to (16), R represents a hydrocarbon group with 1 to 20 carbon atoms, which can be a functional group in which a portion of the hydrocarbon group is replaced by a heteroatom.

[0130] In addition, the aforementioned ionic liquids can be used alone or in combination of two or more.

[0131] Furthermore, relative to 100 parts by weight of the aforementioned (meth)acrylic acid polymer, the content of the aforementioned ionic compound is preferably 1 part by weight or less, more preferably 0.001 to 0.9 parts by weight, even more preferably 0.005 to 0.8 parts by weight, and most preferably 0.01 to 0.5 parts by weight. Within the aforementioned ranges, it is easy to balance antistatic properties and low pollution, therefore these are preferred.

[0132] <Organopolysiloxanes with oxyalkylene chains>

[0133] In the adhesive sheet of the present invention, the adhesive composition preferably contains an organopolysiloxane having an oxyalkylene chain, and more preferably an organopolysiloxane having an oxyalkylene backbone. It is presumed that by using the organopolysiloxane, the surface free energy of the adhesive surface is reduced, thus achieving easy peeling.

[0134] The organopolysiloxane may appropriately use known organopolysiloxanes having a polyoxyalkylene backbone, preferably substances represented by the following formula.

[0135]

[0136] (In the formula, R1 and / or R2 have an oxoalkylene chain with 1 to 6 carbon atoms, wherein the alkylene chain can be straight or branched, and the terminal of the oxoalkylene chain can be an alkoxy or a hydroxyl group. Additionally, either R1 or R2 can be a hydroxyl group, or an alkyl or alkoxy group, or a functional group in which a portion of the alkyl or alkoxy group is substituted with a heteroatom. n is an integer from 1 to 300.)

[0137] The aforementioned organopolysiloxane uses an organopolysiloxane with a siloxane-containing portion (siloxane portion) as the main chain and an oxyalkylene chain attached to the end of the main chain. It is speculated that by using the organosiloxane with the oxyalkylene chain, a balance of compatibility with (meth)acrylic polymers and ionic compounds is achieved, thus enabling light exfoliation.

[0138] Furthermore, the aforementioned organopolysiloxane in this invention can use, for example, the following configuration. Specifically, R1 and / or R2 in the formula have an oxoalkylene chain containing a hydrocarbon group having 1 to 6 carbon atoms. Examples of such oxoalkylene chains include oxomethylene, oxoethylene, oxopropylene, and oxobutylene, among which oxoethylene or oxopropylene is preferred. Additionally, if both R1 and R2 have oxoalkylene chains, they can be the same or different.

[0139]

[0140] In addition, the hydrocarbon group of the aforementioned oxyalkylene chain can be either straight-chain or branched.

[0141] Furthermore, the terminus of the aforementioned alkylene chain can be alkoxy or hydroxyl, with alkoxy being more preferred. When a spacer is attached to the surface of the adhesive layer for the purpose of protecting the adhesive surface, organopolysiloxanes with hydroxyl-terminated ends sometimes interact with the spacer, resulting in an increase in adhesive (peel) force when the spacer is peeled off from the surface of the adhesive layer.

[0142] Furthermore, n is an integer from 1 to 300, preferably from 10 to 200, and more preferably from 20 to 150. Achieving a balance of compatibility with the base polymer when n is within the aforementioned range is preferred. Additionally, the molecule may contain reactive substituents such as (meth)acryloyl, allyl, and hydroxyl groups. The aforementioned organopolysiloxanes can be used alone or in combination of two or more.

[0143] Specific examples of the aforementioned organopolysiloxanes with oxyalkylene chains include, for instance, commercially available products under the trade names X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (all manufactured by Toray D. Corning Co., Ltd.), and IM22 (manufactured by Asahi Kasei Wakeman Co., Ltd.). These compounds can be used alone or in combination of two or more.

[0144] In addition to organosiloxanes with (bonded) oxyalkylene chains in their main chain, organosiloxanes with (bonded) oxyalkylene chains in their side chains can also be used. Compared with organosiloxanes with oxyalkylene chains in their main chain, using organosiloxanes with oxyalkylene chains in their side chains is a more preferred approach. The aforementioned organopolysiloxanes can appropriately use known organopolysiloxanes with polyoxyalkylene side chains, preferably substances represented by the following formula.

[0145]

[0146] (In the formula, R1 is a monovalent organic group, R2, R3 and R4 are alkylene groups, R5 is hydrogen or an organic group, m and n are integers from 0 to 1000, where m and n are not both 0, and a and b are integers from 0 to 100, where a and b are not both 0.)

[0147] Furthermore, the aforementioned organopolysiloxanes of the present invention can use, for example, the following configuration. Specifically, R1 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 of which may have substituents such as hydroxyl. R2, R3, and R4 can be alkylene groups with 1 to 8 carbon atoms such as methylene, ethylene, and propylene. Here, R3 and R4 are different alkylene groups, and R2 may be the same as or different from R3 or R4. In order to increase the concentration of ionic compounds that can be dissolved in the polyoxyalkylene side chain, it is preferable that either R3 or R4 is ethylene or propylene. R5 can be a monovalent organic group exemplified by alkyl groups such as methyl, ethyl, and propyl, or acyl groups such as acetyl and propionyl, each of which may have substituents such as hydroxyl. These compounds can be used alone or in combination. In addition, the molecule may have reactive substituents such as (meth)acryloyl, allyl, and hydroxyl. It is speculated that organosiloxanes having the above-mentioned polyoxyalkylene side chains, especially those having polyoxyalkylene side chains with hydroxyl terminals, are more likely to achieve a compatibility balance and are therefore preferred.

[0148]

[0149] Specific examples of the aforementioned polysiloxanes include: commercially available products under the trade names KF-351A, KF-352A, KF-353, KF-354L, 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 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SF8428, FZ-2162, SH3749, FZ-77, and L-7001. FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ-7001, SH8400, SH8700, SF8410, SF8422 (all manufactured by Toray D. Corning), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (manufactured by Momentive Advanced Materials), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (Bikkemi) (Manufactured by Japan Co., Ltd.) etc. These compounds can be used alone or in combination of two or more.

[0150] The organosiloxane used in this invention preferably has an HLB (hydrophilic-lipophilic balance) value of 1 to 16, more preferably 3 to 14. HLB values ​​outside the aforementioned range deteriorate the contamination of the adhered material and are therefore undesirable.

[0151] Furthermore, relative to 100 parts by weight of the aforementioned (meth)acrylic polymer, the content of the aforementioned organopolysiloxane is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, even more preferably 0.05 to 1 part by weight, and most preferably 0.05 to 0.5 parts by weight. Within the aforementioned range, it is easy to balance antistatic properties and light peelability (re-peelability), therefore it is preferred.

[0152] Crosslinking agent

[0153] In the adhesive sheet of the present invention, the adhesive composition preferably contains a crosslinking agent. Furthermore, in the present invention, the adhesive composition is used to form an adhesive layer. By appropriately adjusting the constituent units, composition ratio, selection of the crosslinking agent, and addition ratio of the (meth)acrylic polymer for crosslinking, an adhesive sheet (adhesive layer) with superior heat resistance can be obtained.

[0154] As the crosslinking agent used in this invention, isocyanate compounds, epoxy compounds, melamine resins, aziridine derivatives, and metal chelates can be used, with isocyanate compounds being the preferred option. Furthermore, these compounds can be used alone or in combination of two or more.

[0155] Examples of isocyanate compounds include: aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer diisocyanate; alicyclic isocyanates such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate (IPDI); aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl dimethylene diisocyanate (XDI); and polyisocyanate modified by modifying the aforementioned isocyanate compounds through urea-formate bonds, biuret bonds, isocyanurate bonds, urea-dione bonds, urea bonds, carbodiimide bonds, urea-dione imide bonds, and oxadiazine trione bonds. For example, commercially available products include the trade names of Decondens 300S, Decondens 500, Decondensed D165N , タケネーD178N (the above is manufactured by Takeda Pharmaceutical Co., Ltd.), スミジュールT80, スミジュールL, Micron バイエルウレタン Co., Ltd.), Micron MR, Micron MRートMT, コロネートL, コロネートHL, コロネートHX (the above are manufactured by Japan Polyurethane Industry Co., Ltd.), etc. These isocyanate compounds can be used alone, in combination of two or more, or in combination of difunctional and trifunctional or higher isocyanate compounds. By combining crosslinking agents, both adhesion and resilience (adhesion to curved surfaces) can be achieved, resulting in adhesive sheets with superior adhesive reliability.

[0156] Furthermore, when a difunctional isocyanate compound is used in combination with a trifunctional or higher isocyanate compound as the isocyanate compound, it is preferable to use a weight ratio (of the two compounds) of [difunctional isocyanate compound] / [trifunctional or higher isocyanate compound] of 0.1 / 99.9 to 50 / 50, more preferably 0.1 / 99.9 to 20 / 80, even more preferably 0.1 / 99.9 to 10 / 90, more preferably 0.1 / 99.9 to 5 / 95, and most preferably 0.1 / 99.9 to 1 / 99. By adjusting the ratio to the range described above, an adhesive composition with excellent adhesion and resilience can be obtained, which is a preferred method.

[0157] Examples of epoxy compounds include: N,N,N',N'-tetraglycidylm-phenylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.

[0158] Examples of melamine resins include hexamethylolmelamine. Examples of aziridine derivatives include commercially available products under the trade names HDU, TAZM, and TAZO (all manufactured by Mutual Pharmaceutical Co., Ltd.).

[0159] As metal chelates, metal components can include aluminum, iron, tin, titanium, nickel, etc., while chelating components can include acetylene, methyl acetoacetate, ethyl lactate, etc.

[0160] The crosslinking agent used in this invention preferably contains 0.01 to 10 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic polymer, more preferably 0.1 to 8 parts by weight, even more preferably 0.5 to 5 parts by weight, and most preferably 1.0 to 2.5 parts by weight. When the content is less than 0.01 parts by weight, the crosslinking formation using the crosslinking agent may be insufficient, resulting in weak cohesion of the adhesive composition, inadequate heat resistance, and a tendency to cause paste residue. On the other hand, when the content exceeds 10 parts by weight, the cohesion of the adhesive composition is strong, the fluidity decreases, and the wetting of the polarizing plate is insufficient, tending to cause bubbling between the polarizing plate and the adhesive layer (adhesive composition layer). In addition, a high crosslinking agent dosage tends to decrease the peel electrostatic properties. Furthermore, these crosslinking agents can be used alone or in combination of two or more.

[0161] The aforementioned adhesive composition may further contain a crosslinking catalyst in order to make any of the above-mentioned crosslinking reactions more effective. As the crosslinking catalyst, tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tri(acetylacetonate), tri(hexane-2,4-diketone), tri(heptane-2,4-diketone), tri(heptane-3,5-diketone), tri(5-methylhexane-2,4-diketone), tri(octane-2,4-diketone), tri(6-methylheptane-2,4-diketone), tri(2,6-dimethylheptane-3,5-diketone), tri(nonane-2,4-diketone), tri(nonane-4,6-diketone), tri(2,2,6,6-tetramethylheptane-3,5-diketone), tri(tetrane-6,8-diketone), and tri... Iron catalysts include (1-phenylbutane-1,3-diketone)ferric, tri(hexafluoroacetylacetone)ferric, tri(ethyl acetoacetate)ferric, tri(n-propyl acetoacetate)ferric, tri(isopropyl acetoacetate)ferric, tri(n-butyl acetoacetate)ferric, tri(sec-butyl acetoacetate)ferric, tri(tert-butyl acetoacetate)ferric, tri(methyl propionyl acetate)ferric, tri(ethyl propionyl acetate)ferric, tri(n-propyl propionyl acetate)ferric, tri(isopropyl propionyl acetate)ferric, tri(n-butyl propionyl acetate)ferric, tri(sec-butyl propionyl acetate)ferric, tri(tert-butyl propionyl acetate)ferric, tri(benzyl acetoacetate)ferric, tri(dimethyl malonate)ferric, tri(diethyl malonate)ferric, trimethoxyferric, triethoxyferric, triisopropoxyferric, and ferric chloride. These crosslinking catalysts can be used individually or in combination of two or more.

[0162] There is no particular limitation on the content (amount) of the crosslinking catalyst. For example, it is preferably about 0.0001 to about 1 part by weight, more preferably about 0.001 to about 0.5 parts by weight, relative to 100 parts by weight of the (meth)acrylic polymer. Within the aforementioned range, the crosslinking reaction is faster when the adhesive layer is formed, and the pot life of the adhesive composition is also longer, which is a preferred approach.

[0163] The adhesive composition of the present invention may contain polyoxyalkylene chain compounds that do not contain organopolysiloxanes. By including the above-mentioned compounds in the adhesive composition, an adhesive composition with better wetting properties on the adherends can be obtained.

[0164] Specific examples of the aforementioned compounds containing polyoxyalkylene chains that do not contain organopolysiloxanes include, for example, nonionic surfactants such as polyoxyalkylene alkylamines, polyoxyalkylene diamines, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, and polyoxyalkylene alkylphenyl allyl ethers; anionic surfactants such as polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ether sulfates, and polyoxyalkylene alkylphenyl ether phosphates; and cationic or amphoteric surfactants having polyoxyalkylene chains (polyalkylene oxide chains), polyether compounds having polyoxyalkylene chains (and their derivatives), and acrylic compounds having polyoxyalkylene chains (and their derivatives). Additionally, monomers containing polyoxyalkylene chains can be incorporated into acrylic polymers to create polyoxyalkylene chain-containing compounds. The polyoxyalkylene chain-containing compound can be used alone or in combination of two or more.

[0165] Specific examples of the aforementioned polyether compounds having polyoxyalkylene chains include: polypropylene glycol (PPG)-polyethylene glycol (PEG) block copolymers, PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, etc. Derivatives of the aforementioned polyether compounds having polyoxyalkylene chains include terminally etherified oxypropylene compounds (PPG monoalkyl ethers, PEG-PPG monoalkyl ethers, etc.) and terminally acetylated oxypropylene compounds (terminally acetylated PPG, etc.).

[0166] Furthermore, as a specific example of the aforementioned acrylic compounds having polyoxyalkylene chains, (meth)acrylate polymers having oxyalkylene groups can be cited. From the viewpoint of coordination of ionic compounds, the molar number of oxyalkylene units added is preferably 1 to 50, more preferably 2 to 30, and even more preferably 2 to 20. Additionally, the terminus of the aforementioned oxyalkylene chain can be a hydroxyl group as is, or it can be substituted with an alkyl group, phenyl group, or the like.

[0167] The aforementioned (meth)acrylate polymers containing alkylene oxides are preferably polymers containing (meth)acrylate alkylene oxides as monomer units (components). Specific examples of the aforementioned (meth)acrylate alkylene oxides include: (meth)acrylates containing ethylene glycol groups, such as methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and other methoxy polyethylene glycol (meth)acrylate types; and ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, and other ethoxy... Polyethylene glycol (meth) acrylate type, butoxydiethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, etc., butoxy polyethylene glycol (meth) acrylate type, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, etc., phenoxy polyethylene glycol (meth) acrylate type, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate type, methoxydipropylene glycol (meth) acrylate, etc., methoxydipropylene glycol (meth) acrylate type, etc.

[0168] In addition, other monomer units (components) besides the aforementioned (meth)acrylate alkylene oxides can be used as the aforementioned monomer units (components). Specific examples of other monomer components include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, n-tridecyl methacrylate, n-tetradecyl methacrylate, and other acrylates and / or methacrylates having alkyl groups having 1 to 14 carbon atoms.

[0169] In addition, other monomer units (components) besides the aforementioned (meth)acrylate alkylene oxides may also be appropriately used, such as carboxyl (meth)acrylates, phosphate (meth)acrylates, cyano (meth)acrylates, vinyl esters, aromatic vinyl compounds, anhydride (meth)acrylates, hydroxyl (meth)acrylates, amide (meth)acrylates, amino (meth)acrylates, epoxy (meth)acrylates, N-acryloylmorpholine, vinyl ethers, etc.

[0170] As a more preferred embodiment, the aforementioned polyoxyalkylene chain-containing compound that does not contain organopolysiloxane is a compound having (poly)ethylidene oxide chains in at least a portion. By incorporating the aforementioned (poly)ethylidene oxide chain-containing compound, the compatibility between the base polymer and the antistatic component is improved, and exudation into the adherend is appropriately suppressed, resulting in a low-fouling adhesive composition. In particular, when using PPG-PEG-PPG block copolymers, an adhesive composition with excellent low-fouling properties can be obtained. As the aforementioned polyethylidene oxide chain-containing compound, it is preferable that the weight of the (poly)ethylidene oxide chain accounts for 5 to 90% by weight of the total weight of the aforementioned polyoxyalkylene chain-containing compound that does not contain organopolysiloxane, more preferably 5 to 85% by weight, even more preferably 5 to 80% by weight, and most preferably 5 to 75% by weight.

[0171] For the aforementioned polyoxyalkylene chain compounds that do not contain organopolysiloxanes, a number average molecular weight (Mn) of 50,000 or less is suitable, preferably 200 to 30,000, more preferably 200 to 10,000, and generally preferably 200 to 5,000. When Mn is too high (below 50,000), compatibility with acrylic polymers decreases, and the adhesive layer tends to whiten. When Mn is too low (below 200), contamination caused by the aforementioned polyoxyalkylene compounds may easily occur. Furthermore, here, Mn refers to the value converted from polystyrene obtained by GPC (gel permeation chromatography).

[0172] In addition, as specific examples of commercially available products containing polyoxyalkylene chain compounds that do not contain organopolysiloxanes, examples include: Adegapur Ronic 17R-4, Adegapur Ronic 25R-2 (all of which are manufactured by ADEKA Corporation), Emalgen 120 (manufactured by Kao Corporation), etc.

[0173] The amount of the polyoxyalkylene chain compound that does not contain organopolysiloxane, relative to 100 parts by weight of the acrylic polymer, can be set to, for example, 0.005 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and most preferably 0.1 to 1 part by weight. If the amount is too small, the effect of preventing the antistatic component from seeping out is reduced; if it is too large, contamination caused by the aforementioned polyoxyalkylene compound may easily occur.

[0174] Furthermore, the aforementioned adhesive composition may contain acrylic oligomers. The weight-average molecular weight of the acrylic oligomers is preferably 1000 or more and less than 30000, more preferably 1500 or more and less than 20000, and even more preferably 2000 or more and less than 10000. The acrylic oligomers are (meth)acrylic polymers containing (meth)acrylic monomers having an alicyclic structure represented by the following general formula (1) as monomer units. When used as the acrylic adhesive composition for re-peeling in this embodiment, it acts as a tackifying resin, improving adhesiveness and effectively suppressing the lifting of the adhesive sheet.

[0175] CH2=C(R) 1 COOR 2 (1)

[0176] In equation (1), R 1 R is a hydrogen atom or a methyl group. 2 [Alicyclic hydrocarbon group with an alicyclic structure]

[0177] As the alicyclic hydrocarbon group R in general formula (1) 2 Examples of alicyclic hydrocarbon groups include cyclohexyl, isobornyl, and tetrahydrodicyclopentadienyl. Examples of (meth)acrylates containing such alicyclic hydrocarbon groups include cyclohexyl methacrylate (containing cyclohexyl), isobornyl methacrylate (containing isobornyl), and tetrahydrodicyclopentadienyl methacrylate (containing tetrahydrodicyclopentadienyl), which are esters of (meth)acrylate and alicyclic alcohols. By using acrylic oligomers with acrylic monomers having such large-volume structures as monomer units, adhesive properties can be improved.

[0178] Furthermore, in this embodiment, the alicyclic hydrocarbon groups constituting the aforementioned acrylic oligomer preferably have a bridged ring structure. A bridged ring structure refers to an alicyclic structure with three or more rings. By giving the acrylic oligomer a larger structure such as a bridged ring structure, the adhesiveness of the acrylic adhesive composition for re-peeling (acrylic adhesive sheet for re-peeling) can be further improved.

[0179] As the aforementioned alicyclic hydrocarbon group R with a bridged ring structure 2Examples of suitable monomers include tetrahydrodicyclopentadienyl (represented by formula (3a), dihydrodicyclopentadienyl (represented by formula (3b), adamantyl (represented by formula (3c), tetrahydrotricyclopentadienyl (represented by formula (3d), and dihydrotricyclopentadienyl (represented by formula (3e)). Furthermore, when UV polymerization is used in the synthesis of acrylic oligomers or the preparation of adhesive compositions, from the viewpoint of minimizing polymerization inhibition, monomers containing alicyclic structures with three or more rings having a bridged ring structure, particularly those with saturated structures such as tetrahydrodicyclopentadienyl (represented by formula (3a), adamantyl (represented by formula (3c), and tetrahydrotricyclopentadienyl (represented by formula (3d)), are preferred as monomers constituting acrylic oligomers.

[0180]

[0181] Furthermore, examples of (meth)acrylate monomers containing alicyclic structures with three or more rings having a bridged ring structure include: tetrahydrodicyclopentadienyl methacrylate, tetrahydrodicyclopentadienyl acrylate, tetrahydrodicyclopentadienyloxyethyl methacrylate, tetrahydrodicyclopentadienyloxyethyl methacrylate, tetrahydrotricyclopentadienyl methacrylate, tetrahydrotricyclopentadienyl methacrylate, 1-adamantyl methacrylate, 1-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, and 2-ethyl-2-adamantyl methacrylate. These (meth)acrylate monomers can be used alone or in combination of two or more.

[0182] The acrylic oligomers in this embodiment can be homopolymers of (meth)acrylic acid monomers with an alicyclic structure, or copolymers of (meth)acrylic acid monomers with an alicyclic structure and other (meth)acrylic acid ester monomers or copolymerizable monomers.

[0183] Examples of the aforementioned (meth)acrylate monomers can be listed as follows:

[0184] Alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, etc.

[0185] Aryl esters of (meth)acrylate, such as phenyl (meth)acrylate and benzyl (meth)acrylate;

[0186] (Meth)acrylates obtained from alcohol derivatives of terpenoid compounds; etc.

[0187] These (meth)acrylates can be used alone or in combination of two or more.

[0188] In addition, the acrylic oligomers can be obtained by copolymerizing other monomeric components (copolymerizable monomers) that are copolymerizable with (meth)acrylate, in addition to the (meth)acrylate component unit.

[0189] Other monomers capable of copolymerizing with (meth)acrylates can be listed as follows:

[0190] Monomers containing carboxyl groups, such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc.

[0191] Alkoxyalkyl ester monomers of (meth)acrylate, such as (meth)acrylate methoxyethyl ester, (meth)acrylate ethoxyethyl ester, (meth)acrylate propoxyethyl ester, (meth)acrylate butoxyethyl ester, (meth)acrylate ethoxypropyl ester, etc.

[0192] Salts, such as alkali metal salts of methacrylate;

[0193] Di(meth)acrylate monomers of (poly)alkylene glycols, such as di(meth)acrylate of ethylene glycol, di(meth)acrylate of diethylene glycol, di(meth)acrylate of triethylene glycol, di(meth)acrylate of polyethylene glycol, di(meth)acrylate of propylene glycol, di(meth)acrylate of dipropylene glycol, di(meth)acrylate of tripropylene glycol, etc.

[0194] Poly(meth)acrylate monomers, such as trimethylolpropane tri(meth)acrylate, etc.;

[0195] Vinyl esters, such as vinyl acetate and vinyl propionate;

[0196] Halogenated vinyl compounds, such as vinylidene chloride and 2-chloroethyl (meth)acrylate;

[0197] contain Polymerizable compounds with an oxolinyl group, such as 2-vinyl-2- Azoline, 2-vinyl-5-methyl-2- Azoline, 2-isopropenyl-2- azoline, etc.;

[0198] Polymerizable compounds containing aziridinium groups, such as (meth)acryloylaziridinium, 2-aziridinium ethyl methacrylate, etc.

[0199] Vinyl monomers containing epoxy groups, such as allyl glycidyl ether, glycidyl (meth)acrylate, ethyl glycidyl ether (meth)acrylate, etc.

[0200] Vinyl monomers containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and adducts of lactones and 2-hydroxyethyl (meth)acrylate;

[0201] Macromolecular monomers of polyalkylene glycols, such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polybutane glycol, copolymers of polyethylene glycol and polypropylene glycol, and copolymers of polybutane glycol and polyethylene glycol, have unsaturated groups such as (meth)acryloyl, styrene, and vinyl groups attached to their ends.

[0202] Fluorinated vinyl monomers, such as fluorinated substituted alkyl (meth)acrylates, etc.

[0203] Monomers containing anhydride groups, such as maleic anhydride and itaconic anhydride;

[0204] Aromatic vinyl monomers, such as styrene, methylstyrene, vinyltoluene, etc.;

[0205] Reactive halogenated vinyl monomers, such as 2-chloroethyl vinyl ether and vinyl monochloroacetate;

[0206] Vinyl monomers containing amide groups, such as (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethylpropane (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-acryloylmorpholine, etc.;

[0207] Succinimide monomers, such as N-(meth)acryloyloxymethylene succinimide, N-[6-(meth)acryloyloxyhexamethylene]succinimide, N-[8-(meth)acryloyloxyoctamethylene]succinimide, etc.;

[0208] Maleimide monomers, such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, etc.

[0209] Itaconimid monomers, such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, etc.

[0210] Nitrogen-containing heterocyclic monomers, such as N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazolium, N-vinylpyrrole, N-vinylimidazole, N-vinyl azole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinylpyrazole, N-vinylisocyanate azoles, N-vinylthiazoles, N-vinylisothiazoles, N-vinylpyridazines, etc.;

[0211] N-vinylcarboxylic acid amides;

[0212] Lactam monomers, such as N-vinylcaprolactam;

[0213] Cyano-containing monomers, such as (meth)acrylonitrile;

[0214] Aminoalkyl ester monomers of (meth)acrylate, such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, etc.

[0215] Monomers containing imide groups, such as cyclohexylmaleimide and isopropylmaleimide;

[0216] Monomers containing isocyanate groups, such as ethyl 2-isocyanate of (meth)acrylate;

[0217] Vinyl monomers containing organosilicon, such as vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane, etc.

[0218] Hydroxyl monomers, such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate, hydroxyoctyl methacrylate, hydroxydecyl methacrylate, hydroxylauryl methacrylate, methyl methacrylate (4-hydroxymethylcyclohexyl) and hydroxyalkyl methacrylates, etc.

[0219] Acrylate monomers containing heterocycles, halogen atoms, silicon atoms, etc., such as tetrahydrofurfuryl (meth)acrylate, fluorine-containing (meth)acrylates, polysiloxane (meth)acrylates, etc.

[0220] Olefin monomers, such as isoprene, butadiene, and isobutene;

[0221] Vinyl ether monomers, such as methyl vinyl ether and ethyl vinyl ether;

[0222] Olefins or dienes, such as ethylene, butadiene, isoprene, isobutene, etc.

[0223] Vinyl ethers, such as vinyl alkyl ethers, etc.

[0224] vinyl chloride;

[0225] And macromonomers of vinyl groups that have free radical polymerizable ends at the monomers obtained by polymerizing vinyl groups; etc.

[0226] These monomers can be copolymerized with the above-mentioned (meth)acrylates, either alone or in combination.

[0227] Examples of the aforementioned acrylic oligomers include: copolymers of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA); copolymers of cyclohexyl methacrylate (CHMA) and isoborneol methacrylate (IBXMA); copolymers of methyl methacrylate (MMA) and isoborneol methacrylate (IBXMA); copolymers of cyclohexyl methacrylate (CHMA) and acrylamide (ACMO); copolymers of cyclohexyl methacrylate (CHMA) and diethylacrylamide (DEAA); copolymers of 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA); copolymers of tetrahydrodicyclopentadienyl methacrylate (DCPMA) and isoborneol methacrylate (IBXMA); and tetrahydrodicyclopentadienyl methacrylate (DCPMA). Copolymers of methyl methacrylate (MMA), copolymers of tetrahydrodicyclopentadienyl methacrylate (DCPMA) and N-vinyl-2-pyrrolidone (NVP), copolymers of tetrahydrodicyclopentadienyl methacrylate (DCPMA) and hydroxyethyl methacrylate (HEAA), copolymers of tetrahydrodicyclopentadienyl methacrylate (DCPMA) and acrylic acid (AA), tetrahydrodicyclopentadienyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), tetrahydrodicyclopentadienyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), and homopolymers of methyl methacrylate (MMA), etc.

[0228] Furthermore, functional groups that are reactive with epoxy or isocyanate groups can be introduced into the acrylic oligomers. Examples of such functional groups include hydroxyl, carboxyl, amino, amide, and mercapto groups, and monomers having such functional groups can be used (copolymerized) when manufacturing acrylic oligomers.

[0229] When the acrylic oligomer is configured as a copolymer of a (meth)acrylic acid monomer with an alicyclic structure and other (meth)acrylic acid ester monomers or copolymerizable monomers, the proportion of the (meth)acrylic acid monomer with an alicyclic structure in the total monomers constituting the acrylic oligomer is 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and even more preferably 30% by weight or more (generally less than 100% by weight, preferably less than 90% by weight). If it contains 5% by weight or more of the (meth)acrylic acid monomer with an alicyclic structure, the adhesiveness can be improved without reducing the transparency.

[0230] The weight-average molecular weight of the acrylic oligomer is 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, and more preferably 2,000 or more and less than 10,000. When the weight-average molecular weight is 30,000 or more, the adhesiveness decreases. Furthermore, when the weight-average molecular weight is less than 1,000, it is a low molecular weight, thus causing a decrease in the adhesive strength of the adhesive sheet.

[0231] The amount of the acrylic oligomer used is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the (meth)acrylic acid polymer, more preferably 0.1 to 7 parts by weight, even more preferably 0.2 to 5 parts by weight, and most preferably 0.3 to 2 parts by weight. Using the amount within the aforementioned range improves the adhesion to the substrate and easily suppresses lifting, which is a preferred method.

[0232] In addition, the adhesive composition used in the adhesive sheet of the present invention may contain other known additives, such as powders of colorants, pigments, etc., surfactants, plasticizers, tackifiers, low molecular weight polymers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, granules, foils, etc., depending on the intended use.

[0233] <Adhesive Layer / Adhesive Sheet>

[0234] The adhesive sheet of the present invention has the adhesive layer formed on the support film. In this case, the cross-linking of the adhesive composition is generally carried out after the adhesive composition is coated, but the adhesive layer composed of the cross-linked adhesive composition can also be transferred onto the support film or the like.

[0235] Furthermore, there are no particular limitations on the method for forming the adhesive layer on the support film. For example, it can be produced by coating the aforementioned adhesive composition onto the support film and drying off the polymerization solvent to form the adhesive layer on the support film. Then, curing can be performed for purposes such as adjusting the migration of components in the adhesive layer or adjusting the crosslinking reaction. In addition, when producing an adhesive sheet by coating the adhesive composition (solution) onto the support film, one or more solvents other than the polymerization solvent can be added to the aforementioned adhesive composition to enable uniform coating onto the support film.

[0236] Furthermore, as a method for forming the adhesive layer when manufacturing the adhesive sheet of the present invention, known methods used in the manufacture of adhesive tapes can be used. Specifically, examples include: roller coating, gravure coating, reverse coating, roller brush coating, spray coating, air knife coating, extrusion coating using a die coater, etc.

[0237] The adhesive sheet of the present invention typically has an adhesive layer thickness of about 3 to about 100 mm. m, preferably about 5 to about 50 The adhesive sheet is manufactured in the manner described in m. When the thickness of the adhesive layer is within the aforementioned range, it is easy to obtain a moderate balance between re-peelability and adhesiveness, which is therefore preferred. The adhesive sheet is formed by coating the aforementioned adhesive layer on one side of a plastic film such as polyester film or a support film made of various porous materials such as paper or non-woven fabric, and forming it into an adhesive sheet in the form of a sheet or strip.

[0238] <Supporting Thin Film>

[0239] The adhesive sheet of the present invention has an adhesive layer formed of an adhesive composition on one side of a supporting film, and the supporting film has a cover coating on the side opposite to the side having the adhesive layer. The supporting film is preferably a plastic film. Furthermore, when the adhesive sheet is used as a surface protection film, the supporting film is preferably a plastic film that has undergone antistatic treatment. By performing antistatic treatment on the supporting film, static electricity in the surface protection film itself can be suppressed during peeling, which is therefore preferable. In addition, having an adhesive layer obtained by crosslinking an adhesive composition that achieves the effects described above (using an antistatic agent, etc.), antistatic properties can be achieved on the untreated protected object during peeling, resulting in a surface protection film that reduces contamination of the protected object. Therefore, antistatic surface protection films are very useful in the fields of optical and electronic components, where static electricity and contamination are particularly serious problems. Furthermore, since the supporting film is a plastic film, by performing antistatic treatment on the plastic film, the static electricity in the surface protection film itself can be reduced, and a surface protection film with excellent antistatic properties for the protected object can be obtained.

[0240] The supporting film (substrate) is preferably a plastic film that is heat-resistant, solvent-resistant, and flexible. Because the supporting film is flexible, the adhesive composition can be coated using a roller coater or similar machine, and it can be wound into a roll.

[0241] As for the aforementioned plastic films, there are no particular restrictions on any material that can be formed into sheets or films. Examples include: polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer, and other polyolefin films; polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, and other polyester films; polyacrylate films; polystyrene films; nylon 6, nylon 66, some aromatic polyamides, and other polyamide films; polyvinyl chloride films; polyvinylidene chloride films; and polycarbonate films.

[0242] The thickness of the supporting film is typically about 5 to about 200 mm. m, preferably about 10 to about 100 m. When the thickness of the support film is within the specified range, it provides excellent adhesion to and peeling performance from the substrate, and is therefore preferred.

[0243] The supporting film can be subjected to various treatments as needed, such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, and antistatic treatments, including coating type, kneading type, and vapor deposition type.

[0244] There are no particular limitations to the aforementioned antistatic treatment. Generally, methods such as providing an antistatic layer on at least one side of the supporting film (substrate) or kneading a kneaded antistatic agent into a plastic film can be used. Examples of methods for providing an antistatic layer on at least one side of the supporting film include coating with an antistatic resin or conductive polymer containing an antistatic agent and resin components, coating with a conductive resin containing a conductive substance, or vapor deposition or plating of a conductive substance.

[0245] Antistatic agents contained in antistatic resins can include quaternary ammonium salts and pyridine. Salts, cationic antistatic agents with cationic functional groups such as primary, secondary, and tertiary amino groups, anionic antistatic agents with anionic functional groups such as sulfonate or sulfate salts, phosphonates, and phosphate salts, amphoteric antistatic agents such as alkyl betaine and its derivatives, imidazoline and its derivatives, and alanine and its derivatives, nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives, as well as ionically conductive polymers obtained by polymerizing or copolymerizing monomers having the above-mentioned cationic, anionic, and amphoteric ion-conductive groups. These compounds can be used alone or in combination.

[0246] Examples of cationic antistatic agents include: alkyl trimethylammonium salts, ammonium trimethylammonium methyl sulfates, alkyl benzyl methylammonium salts, acyl choline chloride, poly(meth)acrylate copolymers with quaternary ammonium groups such as dimethylaminoethyl methacrylate, styrene copolymers with quaternary ammonium groups such as polyvinyl benzyltrimethylammonium chloride, and diallylamine copolymers with quaternary ammonium groups such as polydiallyl dimethylammonium chloride. These compounds can be used alone or in combination.

[0247] Examples of anionic antistatic agents include: alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, alkyl phosphates, and styrene copolymers containing sulfonic acid groups. These compounds can be used alone or in combination of two or more.

[0248] Examples of amphoteric antistatic agents include: alkyl betaine and alkyl imidazole. Betaine and carbobetaine graft copolymers. These compounds can be used alone or in combination of two or more.

[0249] Examples of nonionic antistatic agents include: fatty acid alkanolamides, bis(2-hydroxyethyl)alkylamines, polyoxyethylene alkylamines, fatty acid glycerides, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol, polyoxyethylene diamine, copolymers containing polyethers, polyesters, and polyamides, and methoxy polyethylene glycol (meth)acrylates. These compounds can be used alone or in combination of two or more.

[0250] Examples of conductive polymers include polyaniline, polypyrrole, and polythiophene. These compounds can be used alone or in combination of two or more.

[0251] Examples of conductive materials mentioned above include: tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, copper iodide, and their alloys or mixtures.

[0252] As a resin component used in antistatic and conductive resins, general-purpose resins such as polyester, acrylic resins, polyvinyl resins, polyurethane, melamine resins, and epoxy resins can be used. Alternatively, polymer-type antistatic agents may not contain resin components. Furthermore, antistatic resin components may contain hydroxymethylated or hydroxyalkylated compounds such as melamine, urea, glyoxal, and acrylamide, as well as epoxy compounds and isocyanate compounds as crosslinking agents.

[0253] As a method for forming an antistatic layer, for example, the above-mentioned antistatic resin, conductive polymer, or conductive resin can be diluted with a solvent such as an organic solvent or water, and the coating liquid can be applied to a plastic film and dried.

[0254] Examples of organic solvents used to form the aforementioned antistatic layer include: methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, isopropanol, etc. These solvents can be used alone or in mixtures of two or more.

[0255] For the coating method in the formation of the aforementioned antistatic layer, well-known coating methods can be appropriately used, specifically including roller coating, gravure coating, reverse coating, roller brush coating, spraying, air knife coating, impregnation and curtain coating.

[0256] The thickness of the aforementioned antistatic resin layer, conductive polymer, and conductive resin is typically about 0.001 to about 5 mm. m, preferably about 0.03 to about 1 m. Within the aforementioned range, the possibility of impairing the heat resistance, solvent resistance, and flexibility of the plastic film is small, and therefore preferred.

[0257] Methods for vapor deposition or plating of the aforementioned conductive materials include, for example, vacuum vapor deposition, sputtering, ion plating, chemical vapor deposition, spray thermal decomposition, electroplating, etc.

[0258] The thickness of the aforementioned conductive material layer is typically 0.002 to 1 mm. m, preferably 0.005~0.5 m. Within the aforementioned range, the possibility of impairing the heat resistance, solvent resistance, and flexibility of the plastic film is small, and therefore preferred.

[0259] Furthermore, the aforementioned antistatic agent can be appropriately used as a kneading-type antistatic agent. The amount of the kneading-type antistatic agent, relative to the total weight of the plastic film, is preferably 0.05 to 10% by weight or less. Within this range, the possibility of impairing the heat resistance, solvent resistance, and flexibility of the plastic film is low, and therefore preferred. As for the kneading method, there are no particular limitations as long as it can uniformly mix the aforementioned antistatic agent into the resin used in the plastic film; for example, heated rollers, Banbury mixers, pressure kneaders, twin-screw extruders, etc., can be used.

[0260] <Topcoat Coating>

[0261] The adhesive sheet of the present invention has an adhesive layer formed of an adhesive composition on one side of a supporting film, and the supporting film has a topcoat coating on the side opposite to the side having the adhesive layer. The topcoat coating is characterized in that it contains a wax as a lubricant and a polyester resin as an adhesive. The adhesive sheet (surface protective film) exhibits improved scratch resistance by having the topcoat coating, which is a preferred embodiment.

[0262] <Adhesive>

[0263] The aforementioned topcoat contains a polyester resin as a binder and a wax as a lubricant. The polyester resin is preferably a resin material containing polyester as a main component (typically more than 50% by weight, preferably 75% by weight or more, for example, 90% by weight or more). The polyester typically preferably has a structure formed by the condensation of one or more compounds (polycarboxylic acid components) selected from polycarboxylic acids (typically dicarboxylic acids) and their derivatives (anhydrides, esters, acyl halides, etc. of the polycarboxylic acid) having two or more carboxyl groups in one molecule, and one or more compounds (polyol components) selected from polyols (typically diols) having two or more hydroxyl groups in one molecule.

[0264] Examples of compounds that can be used as components of the aforementioned polycarboxylic acids include: oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, and ( Malic acid, meso tartaric acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, ethynyldicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, pentenic acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyladipic acid, tetramethyladipic acid, methyleneadipic acid, adipadienoic acid, galactopyric acid, pimelic acid, octanoic acid, perfluorooctanoic acid, 3,3,6,6-tetramethyloctanoic acid, azelaic acid, sebacic acid, perfluorosediaic acid, tridecanoic acid, Aliphatic dicarboxylic acids such as tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid; alicyclic dicarboxylic acids such as cycloalkyl dicarboxylic acids (e.g., 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4-(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid (nadic acid, haimidic acid d), adamantanedicarboxylic acid, and spiroheptanedicarboxylic acid; and phthalic acid, isophthalic acid, dithioisophthalic acid, methylisophthalic acid, and dimethylisophthalic acid. Dicarboxylic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, chloro terephthalic acid, bromoterephthalic acid, naphthalene dicarboxylic acid, oxofluorene dicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, biphenylene dicarboxylic acid, dimethylbiphenylene dicarboxylic acid, 4,4”-p-phenylene dicarboxylic acid, 4,4”-p-tetraphenyl dicarboxylic acid, bibenzyl dicarboxylic acid, azophthalic acid, high-phthalic acid, phenylene diacetic acid, phenylene dipropionic acid, naphthalene dicarboxylic acid, naphthalene Aromatic dicarboxylic acids such as dipropionic acid, biphenyl diacetic acid, 3,3'-[4,4'-(methylene di-p-biphenylene)dipropionic acid], 4,4'-bibenzyl diacetic acid, 3,3'-(4,4'-bibenzyl)dipropionic acid, and oxydi-p-phenylene diacetic acid; anhydrides of any of the above polycarboxylic acids; esters (e.g., alkyl esters, which can be monoesters, diesters, etc.) of any of the above polycarboxylic acids; acyl halides (e.g., dicarboxylic acid acyl chlorides) corresponding to any of the above polycarboxylic acids; etc.

[0265] Preferred examples of compounds that can be used as components of the aforementioned polycarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and their anhydrides; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, nadic acid, and 1,4-cyclohexanedicarboxylic acid and their anhydrides; and lower alkyl esters of the aforementioned dicarboxylic acids (e.g., esters with monohydric alcohols having 1 to 3 carbon atoms).

[0266] On the other hand, examples of compounds that can be used as components of the aforementioned polyols include: ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, benzenediol, hydrogenated bisphenol A, bisphenol A, and other diols. Other examples include alkylene oxide adducts of these compounds (e.g., ethylene oxide adducts, propylene oxide adducts, etc.).

[0267] In a preferred embodiment, the aforementioned polyester resin comprises a water-dispersible polyester (typically comprising this water-dispersible polyester as a main component). The water-dispersible polyester can be, for example, a polyester whose water dispersibility has been improved by introducing hydrophilic functional groups (e.g., one or more hydrophilic functional groups such as sulfonic acid metal salt groups, carboxyl groups, ether groups, phosphate groups, etc.) into the polymer. As a method for introducing hydrophilic functional groups into the polymer, known methods such as copolymerizing compounds having hydrophilic functional groups, or modifying polyesters or their precursors (e.g., polycarboxylic acid components, polyol components, their oligomers, etc.) to generate hydrophilic functional groups can be appropriately employed. As a preferred example of a water-dispersible polyester, a polyester (copolyester) obtained by copolymerizing compounds having hydrophilic functional groups can be cited.

[0268] In the disclosed technology, the polyester resin used as an adhesive for the topcoat can be a saturated polyester or an unsaturated polyester as the main component. In a preferred embodiment of the disclosed technology, the main component of the polyester resin is a saturated polyester. It is preferable to use a polyester resin with a water-dispersible saturated polyester (e.g., a saturated copolyester) as the main component. Such a polyester resin (which can be a polyester resin prepared in the form of an aqueous dispersion) can be synthesized by known methods or can be readily obtained commercially available products.

[0269] Regarding the molecular weight of the aforementioned polyester resin, the weight-average molecular weight (Mw) converted from standard polystyrene determined by gel permeation chromatography (GPC) can be, for example, approximately 5 × 10⁻⁶. 3 ~ Approximately 1.5 × 10 5 (Preferred size: approximately 1×10) 4 ~ Approximately 6×10 4 In addition, the glass transition temperature (Tg) of the above-mentioned polyester resin can be, for example, 0°C to 120°C (preferably 10°C to 80°C).

[0270] The aforementioned topcoat coating may also contain resins other than polyester resin (e.g., one or more resins selected from acrylic resins, acrylic-urethane resins, acrylic-styrene resins, acrylic-polysiloxane resins, polysiloxane resins, polysilazane resins, polyurethane resins, fluorinated resins, and polyolefin resins) as an adhesive, to the extent that it does not significantly impair the performance of the adhesive sheet (surface protective film) disclosed herein. A preferred embodiment of the disclosed technology is a topcoat coating in which the adhesive substantially contains only polyester resin. For example, a topcoat coating in which the polyester resin constitutes 98 to 100% by weight is preferred. The proportion of the adhesive in the overall topcoat coating can be set, for example, to 50 to 95% by weight, and typically 60 to 90% by weight is appropriate.

[0271] Lubricant

[0272] The overcoat coating in the disclosed technology is characterized by containing a wax as a lubricant, preferably an ester comprising a higher fatty acid and a higher alcohol (hereinafter also referred to as "wax ester"). Here, "higher fatty acid" refers to a carboxylic acid (typically a monocarboxylic acid) with 8 or more carbon atoms (typically 10 or more, preferably 10 or more and 40 or less). "Higher alcohol" refers to an alcohol (typically a monohydric alcohol or a dihydric alcohol, preferably a monohydric alcohol) with 6 or more carbon atoms (typically 10 or more, preferably 10 or more and 40 or less). The overcoat coating comprising such a wax ester and the aforementioned binder (polyester resin) is less prone to whitening even under high temperature and high humidity conditions. Therefore, an adhesive sheet (surface protective film) having a support film (substrate) with the aforementioned overcoat coating can become an adhesive sheet (surface protective film) with higher appearance quality.

[0273] When implementing the technology disclosed herein, the reasons for achieving superior whitening resistance (e.g., the property of not easily whitening even under high temperature and high humidity conditions) through the above-described coating are not explicit, but as a possibility, the following reasons are considered. That is, it is presumed that conventionally used polysiloxane lubricants function by permeating the surface of the coating to impart lubricity to the surface. However, the degree of permeation of these polysiloxane lubricants can easily vary depending on storage conditions (temperature, humidity, time, etc.). Therefore, for example, when the amount of polysiloxane lubricant used is set to achieve adequate lubricity for a relatively long period (e.g., about 3 months) after the adhesive sheet (surface protective film) is manufactured, for example, under normal storage conditions (e.g., 25°C, 50%RH), if the adhesive sheet is stored under high temperature and high humidity conditions (e.g., 60°C, 95%RH) for 2 weeks, excessive permeation of the lubricant occurs. Such excessive permeation of the polysiloxane lubricant causes the coating (and consequently the adhesive sheet) to whiten.

[0274] The technology disclosed herein employs a specific combination of a wax ester as a lubricant and a polyester resin as a binder for a topcoat. Based on this combination of lubricant and binder, the degree to which the wax ester seeps out of the topcoat is less affected by storage conditions. It is believed that this improves the whitening resistance of the adhesive sheet (surface protective film).

[0275] As the wax esters mentioned above, one or more compounds represented by the following general formula (2) may be preferred.

[0276] X-COO-Y (2)

[0277] Here, X and Y in formula (2) above can each be independently selected from hydrocarbon groups with 10 to 40 carbon atoms (more preferably 10 to 35, even more preferably 14 to 35, for example 20 to 32). If the number of carbon atoms is too small, there may be a tendency to insufficiently impart lubricity to the coating. The hydrocarbon group can be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Saturated hydrocarbon groups are generally preferred. In addition, the hydrocarbon group can be a structure containing an aromatic ring or a structure without the aromatic ring (aliphatic hydrocarbon group). In addition, it can be a hydrocarbon group containing an aliphatic ring (alicyclic hydrocarbon group) or a chain-like hydrocarbon group (meaning including straight chain and branched chain).

[0278] As a preferred wax ester in the technology disclosed herein, examples can be exemplified by compounds in which X and Y in formula (2) above are each independently a chain alkyl group (more preferably a straight-chain alkyl group) having 10 to 40 carbon atoms. Specific examples of such compounds include bee wax ester (CH3(CH2)). 24 COO(CH2) 29 CH3), Myristyl palmitate (CH3(CH2))14 COO(CH2) 29 CH3), cetyl palmitate (CH3(CH2)) 14 COO(CH2) 15 CH3), stearate (CH3(CH2)) 16 COO(CH2) 17 CH3), etc.

[0279] The melting point of the aforementioned wax ester is preferably 50°C or higher (more preferably 60°C or higher, even more preferably 70°C or higher, for example 75°C or higher). Using this wax ester, higher resistance to whitening can be achieved. Furthermore, the melting point of the aforementioned wax ester is preferably 100°C or lower. The wax ester imparts high lubricity, thus allowing the formation of a topcoat coating with higher scratch resistance. A melting point of 100°C or lower is preferred from the viewpoint that an aqueous dispersion of the wax ester can be easily prepared. For example, beeswax ester can be preferably used.

[0280] As a raw material for the aforementioned topcoat coating, a natural wax containing such a wax ester can be used. Preferably, the natural wax used is one in which the content of the wax ester (or the total content of two or more wax esters) exceeds 50% by weight (preferably 65% ​​by weight or more, for example, 75% by weight or more) based on non-volatile components (NV). Examples include carnauba wax (generally containing 60% by weight or more, preferably 70% by weight or more, typically 80% by weight or more), palm wax, and other plant-based waxes; beeswax, cetacean, and other animal-based waxes; and other natural waxes. The melting point of the natural wax used is generally preferably 50°C or higher (more preferably 60°C or higher, even more preferably 70°C or higher, for example, 75°C or higher). Furthermore, as a raw material for the aforementioned topcoat coating, a chemically synthesized wax can be used, or a wax obtained by purifying the natural wax to increase the purity of the wax ester can be used. These raw materials can be used alone or in appropriate combinations.

[0281] The proportion of lubricant in the overall topcoat can be set at 5-50% by weight, with 10-40% by weight being generally appropriate. Too little lubricant tends to decrease scratch resistance, while too much lubricant may not adequately improve resistance to whitening.

[0282] In the technology disclosed herein, the topcoat may be implemented in a manner that, without significantly impairing its application effect, contains other lubricants besides the aforementioned wax esters. Examples of such other lubricants include various waxes other than wax esters, such as petroleum wax (paraffin wax, etc.), mineral wax (lignite wax, etc.), higher fatty acids (wax acids, etc.), and neutral fats (tripalmitoyl glycerol, etc.). Alternatively, in addition to the aforementioned wax esters, general polysiloxane lubricants, fluorinated lubricants, etc., may be supplementarily contained. The technology disclosed herein is preferably implemented in a manner that substantially does not contain the aforementioned polysiloxane lubricants, fluorinated lubricants, etc. (for example, their total content is less than 0.01% by weight of the total topcoat, or less than the detection limit). However, the inclusion of polysiloxane compounds used for purposes different from lubricants (for example, as defoamers for coating materials used to form the topcoat, as described later) is not excluded, provided that the application effect of the technology disclosed herein is not significantly impaired.

[0283] The topcoat in the technology disclosed herein may contain additives such as antistatic agents, crosslinking agents, antioxidants, colorants (pigments, dyes, etc.), flow modifiers (thixotropic agents, thickeners, etc.), film-forming aids, surfactants (defoamers, dispersants, etc.), and preservatives, as needed.

[0284] <Antistatic components of the topcoat>

[0285] In the adhesive sheet of the present invention, the topcoat coating preferably contains an antistatic component. The antistatic component is a component that can prevent or suppress static electricity in the adhesive sheet (surface protective film). When the topcoat coating contains an antistatic component, such as organic or inorganic conductive substances, various antistatic agents, etc., can be used as this antistatic component. Alternatively, the antistatic component used in the aforementioned antistatic layer can also be used.

[0286] Examples of organic conductive substances include: quaternary ammonium salts and pyridine. Cationic antistatic agents include salts; cationic antistatic agents with cationic functional groups such as primary, secondary, and tertiary amino groups; anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; zwitterionic antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives; ionicly conductive polymers obtained by polymerizing or copolymerizing monomers with the above-mentioned cationic, anionic, and zwitterionic ionic conductive groups (e.g., quaternary ammonium salts); and conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethylene imine, and allylamine polymers. Such antistatic agents can be used alone or in combination of two or more.

[0287] Examples of such inorganic conductive materials include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, copper iodide, ITO (indium oxide / tin oxide), and ATO (antimony oxide / tin oxide). Such inorganic conductive materials can be used alone or in combination of two or more.

[0288] Examples of the antistatic agent include cationic antistatic agents, anionic antistatic agents, amphoteric antistatic agents, nonionic antistatic agents, and ionically conductive polymers obtained by polymerizing or copolymerizing monomers having the above-mentioned cationic, anionic, or amphoteric ion-conductive groups.

[0289] In a preferred embodiment, the antistatic component used in the aforementioned topcoat contains an organic conductive material. Various conductive polymers are preferably used as the organic conductive material. This configuration facilitates a balance between good antistatic properties and high scratch resistance. Examples of conductive polymers include polythiophene, polyaniline, polypyrrole, polyethylene imine, and allylamine polymers. Such conductive polymers can be used alone or in combination of two or more. Furthermore, other antistatic components (inorganic conductive materials, antistatic agents, etc.) can be used in combination. The amount of conductive polymer used relative to 100 parts by weight of the binder contained in the topcoat can be set to, for example, 10 to 200 parts by weight, and typically 25 to 150 parts by weight (e.g., 40 to 120 parts by weight) is appropriate. If the amount of conductive polymer used is too small, the antistatic effect may be reduced. If the amount of conductive polymer used is too large, there is a tendency for insufficient compatibility of the conductive polymer in the topcoat, which may lead to a decrease in the appearance quality or solvent resistance of the topcoat.

[0290] In the disclosed technology, examples of preferred conductive polymers include polythiophene and polyaniline. As for polythiophene, a polystyrene-based weight-average molecular weight (hereinafter sometimes referred to as "Mw") of 4 × 10⁻⁶ is preferred. 5 The following polythiophene, more preferably 3×10 5 Below. For polyaniline, Mw is preferably 5 × 10⁻⁶. 5 The following polyaniline, preferably 3×10 5 Below. Additionally, the Mw of these conductive polymers is typically preferred to be 1×10⁻⁶. 3 The above is preferred, 5×10 3 That's all. Furthermore, the aforementioned polythiophene refers to polymers of unsubstituted or substituted thiophene. As a preferred example of a substituted thiophene polymer in the art disclosed herein, poly(3,4-ethylenedioxythiophene) can be cited.

[0291] As a method for forming a topcoat, when a coating material for forming a topcoat is applied to a supporting film (substrate) and then dried or cured, the conductive polymer used in the preparation of this coating material is preferably a substance in which the conductive polymer is dissolved or dispersed in water (a conductive polymer aqueous solution). This conductive polymer aqueous solution can be prepared, for example, by dissolving or dispersing a conductive polymer having hydrophilic functional groups (which can be synthesized by copolymerizing monomers having intramolecular hydrophilic functional groups) in water. Examples of such hydrophilic functional groups include sulfonyl, amino, amide, imino, hydroxyl, mercapto, hydrazine, carboxyl, quaternary ammonium, sulfate ester (-O-SO3H), and phosphate ester (e.g., -O-PO(OH)2). These hydrophilic functional groups can form salts. Commercially available polythiophene aqueous solutions include the "Denatron" series manufactured by Nagasek Tech Co., Ltd. In addition, as a commercially available product of polyaniline sulfonic acid aqueous solution, an example is the product manufactured by Mitsubishi Rayon Co., Ltd. under the trade name "aqua-PASS".

[0292] In a preferred embodiment of the disclosed technology, an aqueous solution of polythiophene is used in the preparation of the coating material. Preferably, an aqueous solution of polythiophene containing polystyrene sulfonate (PSS) is used (this can be in the form of polythiophene with PSS added as a dopant). The aqueous solution can be an aqueous solution containing polythiophene and PSS in a weight ratio of polythiophene:PSS of 1:1 to 1:10. The total content of polythiophene and PSS in the aqueous solution can, for example, be about 1 to 5% by weight. A commercially available example of such an aqueous solution of polythiophene is the product manufactured by HC Stark under the trade name "Baytron". Furthermore, when using an aqueous solution of polythiophene containing PSS as described above, the total amount of polythiophene and PSS can be set to 5 to 200 parts by weight (typically 10 to 100 parts by weight, for example 25 to 70 parts by weight) relative to 100 parts by weight of the binder.

[0293] The cover coating disclosed herein may, as needed, simultaneously contain a conductive polymer and one or more other antistatic components (organic conductive substances other than conductive polymers, inorganic conductive substances, antistatic agents, etc.). In a preferred embodiment, the cover coating substantially does not contain any antistatic components other than conductive polymers. That is, the technology disclosed herein can preferably be implemented in a manner in which the antistatic components contained in the cover coating substantially consist only of conductive polymers.

[0294] Crosslinking agent

[0295] In a preferred embodiment of the disclosed technology, the topcoat preferably contains a crosslinking agent. As the crosslinking agent, melamine-based, isocyanate-based, epoxy-based, or similar crosslinking agents commonly used in the crosslinking of resins can be appropriately selected. By using the aforementioned crosslinking agent, at least one of the following effects can be achieved: improved scratch resistance, improved solvent resistance, improved print adhesion, and reduced coefficient of friction (i.e., improved lubricity). In a preferred embodiment, the aforementioned crosslinking agent contains a melamine-based crosslinking agent. The topcoat can be a coating in which the crosslinking agent substantially only contains melamine-based crosslinking agents (melamine resins) (i.e., substantially does not contain crosslinking agents other than melamine-based crosslinking agents).

[0296] <Form of Topcoat>

[0297] The aforementioned topcoat coating can preferably be formed by a method comprising applying the aforementioned resin component to a support film (substrate) and dispersing or dissolving additives as needed in a suitable solvent to obtain a liquid composition (coating material for topcoat coating formation). For example, it is preferable to apply the aforementioned coating material to the first side of the support film (substrate), dry it, and then perform a curing treatment (heat treatment, ultraviolet treatment, etc.) as needed. The NV (non-volatile component) of the aforementioned coating material can be set to, for example, 5% by weight or less (typically 0.05% to 5% by weight), and it is generally appropriate to set it to 1% by weight or less (typically 0.10% to 1% by weight). When forming a topcoat coating with a small thickness, it is preferable to set the NV of the aforementioned coating material to, for example, 0.05% to 0.50% by weight (for example, 0.10% to 0.30% by weight). By using a coating material with such a low NV, a more uniform topcoat coating can be formed.

[0298] As the solvent constituting the coating material for forming the above-mentioned topcoat, a solvent capable of stably dissolving or dispersing the topcoat forming components is preferred. The solvent may be an organic solvent, water, or a mixture thereof. As the organic solvent, one or more may be selected from, for example, esters such as ethyl acetate, ketones such as methyl ethyl ketone, acetone, and cyclohexanone, cyclic ethers such as tetrahydrofuran (THF) and dioxane, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, and cyclohexanol, and glycol ethers such as alkylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether and ethylene glycol monoethyl ether), and glycol ethers such as diallyl glycol monoalkyl ethers. In a preferred embodiment, the solvent of the coating material is water or a mixture of solvents with water as the main component (e.g., a mixture of water and ethanol).

[0299] <Properties of the Topcoat>

[0300] The thickness of the overcoat coating in the disclosed technology is typically 3 nm to 500 nm (preferably 3 nm to 100 nm, for example 3 nm to 60 nm). When the thickness of the overcoat coating is too large, the transparency (light transmittance) of the adhesive sheet (surface protective film) tends to decrease. On the other hand, when the thickness of the overcoat coating is too small, it is difficult to form the overcoat coating uniformly (for example, the thickness deviation of the overcoat coating increases depending on the location), and therefore the appearance of the adhesive sheet may easily become uneven.

[0301] In a preferred embodiment of the disclosed technology, the thickness of the overcoat is 3 nm or more and less than 30 nm (e.g., 3 nm or more and less than 10 nm). An adhesive sheet (surface protective film) having the overcoat can become an adhesive sheet (surface protective film) with superior appearance quality. Based on such a superior appearance quality, the appearance inspection of the product (adhesive) can be performed more accurately through this film. The smaller thickness of the overcoat is preferred from the viewpoint of minimizing the impact on the characteristics (optical properties, dimensional stability, etc.) of the supporting film (substrate).

[0302] The thickness of the aforementioned overcoat coating can be determined by observing the cross-section of the overcoat coating using a transmission electron microscope (TEM). For example, for a target sample (which may be an indicator film with the overcoat coating, an adhesive sheet having the support film, etc.), after heavy metal staining to make the overcoat coating clear, resin embedding is performed, and the cross-section of the sample is observed by TEM using an ultrathin section method. The result obtained can preferably be used as the thickness of the overcoat coating in the art disclosed herein. As the TEM, a TEM manufactured by Hitachi, such as model "H-7650", can be used. In the embodiments described later, the cross-sectional image obtained under the conditions of an accelerating voltage of 100 kV and a magnification of 60,000x is binarized, and the thickness of the overcoat coating (the average thickness within the field of view) is determined by dividing the cross-sectional area of ​​the overcoat coating by the sample length within the field of view. Furthermore, if the overcoat coating can be observed clearly even without heavy metal staining, the heavy metal staining treatment can be omitted. Alternatively, a standard curve can be constructed and calculated based on the correlation between the thickness known by TEM and the detection results of various thickness measuring devices (e.g., surface roughness gauges, interferometric thickness gauges, infrared spectrometers, various X-ray diffraction devices, etc.), thereby determining the thickness of the topcoat.

[0303] In a preferred embodiment of the adhesive sheet (surface protective film) disclosed herein, the measured surface resistivity of the surface of the topcoat is 10⁻⁶. 12 The following (typically 10) 6 ~10 12 The adhesive sheet exhibiting the aforementioned surface resistivity is suitable for use as an adhesive sheet in the processing or transportation of static-sensitive articles, such as liquid crystal cells or semiconductor devices. More preferably, the surface resistivity is 10⁻⁶. 11 The following (typically 5×10) 6 ~10 11 For example, 10 7 ~10 10 The adhesive sheet. The above surface resistivity value can be calculated using a commercially available insulation resistance measuring device, from the surface resistance value measured at 23°C and 50%RH.

[0304] The coefficient of friction of the topcoat is preferably 0.4 or less. With such a low coefficient of friction, when a load (a load that causes scratching) is applied to the topcoat, the load can be avoided along the surface of the topcoat, reducing the friction caused by the load. This reduces the likelihood of agglomerated damage (a damage mode in which the topcoat breaks down internally) or interfacial damage (a damage mode in which the topcoat peels off from the back of the supporting film). Therefore, scratching on the adhesive sheet (surface protective film) can be better prevented. There is no particular limitation on the lower limit of the coefficient of friction; considering the balance with other properties (appearance quality, printability, etc.), it is generally appropriate to set the coefficient of friction to 0.1 or more (typically 0.1 or more and 0.4 or less), and preferably 0.15 or more (typically 0.15 or more and 0.4 or less). The coefficient of friction can be, for example, a value obtained by rubbing the surface of the topcoat with a vertical load of 40 mN under a measurement environment of 23°C and 50% RH. The amount of the aforementioned wax ester (lubricant) used can be set in a manner that achieves the preferred coefficient of friction described above. To adjust the coefficient of friction, it is also effective to increase the crosslinking density of the topcoat coating, for example, by adding a crosslinking agent or adjusting the film-forming conditions.

[0305] The adhesive sheet (surface protective film) disclosed herein preferably has a back side (the surface of the overcoat) that is easily printable with oil-based inks (e.g., using an oil-based marker). During processing or transport of the adhered object (e.g., an optical component) while the adhesive sheet is attached, it is suitable to display the identification number of the adhered object being protected on the adhesive sheet. Therefore, an adhesive sheet that is not only aesthetically pleasing but also has excellent printability is preferred. For example, it is preferable to have high printability with oil-based inks that are alcohol-based solvents and contain pigments. Furthermore, it is preferable that the printed ink is not easily removed by rubbing or transfer (i.e., excellent print adhesion). The adhesive sheet disclosed herein also preferably has solvent resistance to the extent that the appearance does not change significantly when the print is corrected or removed, even when the print is wiped with alcohol (e.g., ethanol). The degree of solvent resistance can be assessed, for example, by solvent resistance evaluation described later.

[0306] The topcoat in the disclosed technology contains wax (wax ester) as a lubricant, so sufficient lubricity (e.g., the preferred coefficient of friction described above) can be achieved even without further surface stripping treatment of the topcoat (e.g., applying a known stripping agent such as a polysiloxane stripper or a long-chain alkyl stripper and then drying it). This method of not further stripping the surface of the topcoat is preferred from the viewpoint of preventing whitening caused by the stripping agent (e.g., whitening due to storage under heated and humidified conditions). Furthermore, it is also advantageous from the viewpoint of solvent resistance.

[0307] The adhesive sheet (surface protective film) disclosed herein can be implemented by including other layers besides the support film, adhesive layer, and topcoat coating. Examples of these "other layers" include the space between the first side (back side) of the support film and the topcoat coating, and the space between the second side (front side) of the support film and the adhesive layer. The layer disposed between the back side of the support film and the topcoat coating can, for example, be a layer containing an antistatic component (the aforementioned antistatic layer). The layer disposed between the front side of the support film and the adhesive layer can, for example, be a primer coating (anchoring layer) that improves the anchoring of the adhesive layer to the second side, an antistatic layer, etc. The adhesive sheet (surface protective film) can be composed of an antistatic layer disposed on the front side of the support film, an anchoring layer disposed on the antistatic layer, and an adhesive layer disposed thereon.

[0308] The total thickness of the adhesive sheet (surface protective film) of the present invention is preferably 1 to 150 mm. m, more preferably 3 to 120 m, optimal value 5-100 m. Within the aforementioned range, excellent adhesion, workability, and appearance characteristics make it a preferred method. Furthermore, the aforementioned total thickness refers to the sum of the thicknesses of all layers, including the support film, adhesive layer, topcoat, and antistatic layer.

[0309] <spacer>

[0310] In the adhesive sheet (surface protective film) of the present invention, a spacer may be attached to the surface of the adhesive layer as needed for the purpose of protecting the adhesive surface.

[0311] Materials constituting the aforementioned spacer include paper and plastic film; from the viewpoint of excellent surface smoothness, plastic film is preferred. There are no particular limitations on the film, as long as it can protect the aforementioned adhesive layer; examples include: polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene-vinyl acetate copolymer film.

[0312] The thickness of the aforementioned spacers is typically about 5 to about 200 mm. m, preferably about 10 to about 100 m. Within the aforementioned range, the adhesion to and peeling from the adhesive layer are excellent, and therefore preferred. The spacer can be subjected to release and anti-fouling treatments using release agents such as polysiloxanes, fluorinated, long-chain alkyl, or fatty acid amides, silica powder, etc., or antistatic treatments such as coating, kneading, or vapor deposition, as needed.

[0313] The adhesive sheet of the present invention has an adhesive layer formed of an adhesive composition on one side of a supporting film, and the supporting film has a topcoat coating on the side opposite to the side having the adhesive layer. The ratio (A / B) of the back adhesion force (A) at a peel speed of 0.3 m / min after being bonded at 23°C for 30 minutes on the surface of the topcoat coating to the adhesion force (B) at a peel speed of 30 m / min after the adhesive side of the adhesive layer is bonded to a TAC surface at 50°C for 1 week is 3 or more, preferably 3.5 or more, more preferably 4 or more. Within this range, excellent pick-up performance is preferred.

[0314] The back adhesion force (A) of the adhesive sheet of the present invention (including the case where it is used as a surface protective film) is preferably 4.5 N / 24 mm or more, more preferably 5.0 N / 24 mm or more, and even more preferably 5.5 N / 24 mm or more. When the adhesion force is less than 4.5 N / 24 mm, sufficient adhesion force is not obtained, the pick-up performance deteriorates, and the peelability of the protective film is reduced, so it is not preferred.

[0315] In the adhesive sheet of the present invention (including cases used as surface protective films), the adhesive layer used in the adhesive sheet is effective against the polarizer at 23°C × 50%RH, at a peel angle of 150°. When peeling is performed at a peeling speed of 30 m / min (high-speed peeling), the potential (peeling electrostatic voltage: kV, absolute value) on the surface of the polarizing plate is preferably 1.0 kV or less, more preferably 0.8 kV or less, and even more preferably 0.5 kV or less. A peeling electrostatic voltage exceeding 1.5 kV may cause damage, for example, to the liquid crystal driver, and is therefore not preferred.

[0316] The optical components of the present invention are preferably protected by the aforementioned adhesive sheet. The aforementioned adhesive sheet prevents the adhesive force from increasing over time, has low adhesive force at high-speed peeling (e.g., 30 m / min), and exhibits excellent re-peeling and workability. Therefore, it can be used for surface protection applications (surface protective films) during processing, transportation, and shipping, and is thus useful for protecting the surface of the optical components (such as polarizers). Furthermore, when the adhesive layer constituting the adhesive sheet contains antistatic components, it is particularly useful for plastic products that are prone to static electricity. Therefore, it is very useful for antistatic applications in the fields of optical and electronic components where static electricity is a particularly serious problem.

[0317] Example

[0318] Hereinafter, embodiments embodying the structure and effects of the present invention will be described, but the present invention is not limited to these examples. Furthermore, the evaluation items in the embodiments, etc., were measured as follows.

[0319] [evaluate]

[0320] The (meth)acrylic polymers (polymers), adhesive layers (adhesive compositions), and adhesive sheets obtained in the examples and comparative examples were evaluated using the measurement or evaluation methods described below. Furthermore, as evaluation results, the physical properties of the polymers are shown in Table 1, the formulation and evaluation of the adhesive compositions are shown in Table 2, and the composition and evaluation results of the adhesive sheets (surface protective films) are shown in Table 3.

[0321] Determination of weight-average molecular weight (Mw)

[0322] Weight-average molecular weight (Mw) was determined using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. The determination conditions are as follows.

[0323] Sample concentration: 0.2% by weight (THF solution)

[0324] Sample injection volume: 10 l

[0325] Elution buffer: THF

[0326] Flow rate: 0.6 ml / min

[0327] Measurement temperature: 40℃

[0328] column:

[0329] Sample columns: TSK Super HZ-H guard column (1 column) + TSK Super HZM-H gel column (2 columns)

[0330] Reference column: TSK Super H-RC gel column (1 column)

[0331] Detector: Differential refractometer (RI)

[0332] In addition, the weight-average molecular weight is calculated from the polystyrene conversion value.

[0333] Glass transition temperature

[0334] Regarding the glass transition temperature Tg (°C), the following literature values ​​are used as the glass transition temperature Tgn (°C) of the homopolymer of each monomer, and are calculated by the following formula.

[0335] Formula: 1 / (Tg+273)= [Wn / (Tgn+273)]

[0336] [In the formula, Tg (°C) represents the glass transition temperature of the copolymer, Wn (-) represents the weight fraction of each monomer, Tgn (°C) represents the glass transition temperature of the homopolymer of each monomer, and n represents the type of each monomer].

[0337] Document value:

[0338] 2-Ethylhexyl acrylate (2EHA): -70℃

[0339] 4-Hydroxybutyl acrylate (4HBA): -32℃

[0340] Acrylic acid (AA): 106℃

[0341] Tetrahydrodicyclopentadienyl methacrylate (DCPMA): 175℃

[0342] Methyl methacrylate (MMA): 105℃

[0343] Additionally, as a reference, see "Synthesis of Acrylic Resins". "Design and New Applications" (Synthesis, Design and New Applications of Acrylic Resins) (Published by the Central Business Development Center Publishing Department) and "Polymer Handbook" (John Wiley & Sons).

[0344] <Determination of Glass Transition Temperature (Tg)>

[0345] The glass transition temperature (Tg) (°C) was determined using a dynamic viscoelasticity measuring apparatus (manufactured by Rheometrics, ARES) and by the following method.

[0346] Sheets of (meth)acrylic polymers (thickness: 20) m) Layered to a thickness of approximately 2mm, the resulting object is punched out. 7.9 mm, cylindrical particles were prepared as samples for glass transition temperature determination.

[0347] Fix the sample used in the above determination to On the clamp of the 7.9mm parallel plate, the temperature dependence of the loss elastic modulus G” was measured using the above-mentioned dynamic viscoelasticity measuring device, and the temperature at which the obtained G” curve reaches its maximum was taken as the glass transition temperature (°C).

[0348] The measurement conditions are as follows.

[0349] Measurement: Shear Mode

[0350] Temperature range: -70℃~150℃

[0351] Heating rate: 5℃ / minute

[0352] Frequency: 1Hz

[0353] <Thickness Measurement of Topcoat>

[0354] For each example of the adhesive section, after heavy metal staining, it was embedded in resin. Cross-sectional images were obtained using an ultrathin sectioning method with a Hitachi TEM "H-7650" at an accelerating voltage of 100 kV and a magnification of 60,000x. After binarization of the cross-sectional image, the thickness of the coating (average thickness within the field of view) was determined by dividing the cross-sectional area of ​​the coating by the sample length within the field of view.

[0355] <Evaluation of resistance to whitening>

[0356] The experiment was conducted by a gloved test subject using a 38mm thick... The back side (surface of the topcoat) of each example adhesive sheet was vigorously rubbed once with a polyethylene terephthalate film of m. The transparency of the rubbed part (rubbed area) was observed with the naked eye compared to the surrounding area (unrubbed area). When the difference in transparency between the unrubbed area and the rubbed area could be visually confirmed, it was judged as whitening. When whitening became significant, a clearer contrast was observed between the transparent rubbed area and its surrounding area (whitened unrubbed area).

[0357] The above visual observations were conducted in a dark room (reflection method, transmission method) and a bright room, as shown below.

[0358] (a) Observation by reflection in a darkroom: In a darkroom where external light is blocked, a 100W fluorescent lamp (manufactured by Mitsubishi Electric Corporation, trade name "Rupikaline") is placed 100cm from the back of the adhesive sheet (the surface of the overcoating) of each example, and the back of the sample is observed with the naked eye while changing the viewpoint.

[0359] (b) Observation by transmission method in darkroom: In the darkroom described above, the fluorescent lamp is placed 10 cm from the front of the adhesive sheet (the surface opposite to the side where the cover coating is applied), and the back of the sample is observed with the naked eye while changing the viewpoint.

[0360] (c) Observation in a bright room: On a sunny day, observe the back of the sample with the naked eye from the window where direct sunlight does not reach, in a room with a window that allows external light to enter (a bright room).

[0361] The observations under these three conditions are expressed on the following five levels.

[0362] 0: No whitening was observed under any observation conditions (both the rubbed and unrubbed areas were transparent).

[0363] 1: Slight whitening was observed during observations using the reflection method in a dark room.

[0364] 2: Slight whitening was observed during observations using transmission methods in a darkroom.

[0365] 3: Slight whitening was observed during observation in a brightly lit room.

[0366] 4: Obvious whitening was observed during observation in a brightly lit room.

[0367] The whitening resistance of the bonded sheets was evaluated as described above, both initially (after fabrication and storage at 50°C and 15%RH for 3 days) and after heating and humidification (after fabrication and storage at 50°C and 15%RH for 3 days, followed by storage at 60°C and 95%RH for 2 weeks). Furthermore, in the evaluation after heating and humidification, scores of 2 or below (0-2) in the aforementioned five evaluation levels were considered good.

[0368] <Soluble Resistance Evaluation>

[0369] In the aforementioned darkroom, the back of each example adhesive sheet (i.e., the surface of the overcoating) was wiped five times with a waste cloth soaked in ethanol, and the appearance of the back was observed with the naked eye. As a result, when no difference in appearance was found between the part wiped with ethanol and other parts (when no change in appearance was observed due to ethanol wiping), the solvent resistance was rated as "good"; when wiping marks were found, the solvent resistance was rated as "poor".

[0370] <Determination of stripping electrostatic voltage>

[0371] Cut the adhesive sheet 1 to a size of 70mm in width and 130mm in length. After peeling off the spacer, use a manual roller to press it onto the surface (TAC side) of the polarizing plate 2 (TAC polarizing plate manufactured by Nitto Denko Co., Ltd., SEG1423DU, width: 70mm, length: 100mm) that has been pre-de-electrified and pasted onto the acrylic resin plate 3 (thickness: 2mm, width: 70mm, length: 100mm), so that each end protrudes 30mm.

[0372] After being placed in an environment of 23℃×50%RH for 1 day, if... Figure 3 The sample is positioned as shown. The single end, protruding 30mm, is secured to the automatic winding machine at a peel angle of 150°. The peeling was performed at a peeling speed of 30 m / min. The surface potential (peeling electrostatic voltage: absolute value, kV) of the polarizing plate 2 was measured using a potentiometer 5 (manufactured by Kasuga Electric Co., Ltd., KSD-0103) fixed to the center of the polarizing plate 2. The measurement was conducted at 23°C and 50% RH.

[0373] The adhesive layer used in the adhesive sheet has a peel angle of 150° at 23°C × 50%RH for the polarizing plate. The potential (peeling electrostatic voltage: kV, absolute value) generated on the surface of the polarizing plate during peeling at a peeling speed of 30 m / min is preferably 1.0 kV or less, more preferably 0.8 kV or less, and even more preferably 0.5 kV or less. A peeling electrostatic voltage exceeding 1.0 kV may cause damage to, for example, liquid crystal drivers, and is therefore not preferred.

[0374] <Back Adhesion Strength (A) Measurement>

[0375] like Figure 1As shown, the adhesive sheet 1 in each example is cut to a size of 70 mm wide and 100 mm long. The adhesive side (the side where the adhesive layer 20 is applied) 20A of the adhesive sheet 1 is fixed to the SUS304 stainless steel plate 132 using double-sided adhesive tape 130. A single-sided adhesive tape (manufactured by Nichiban Corporation, trade name "Cerotep (registered trademark)", 24 mm wide) 160 with acrylic adhesive 162 on a polyester film (support film) 164 is cut to a length of 100 mm. The adhesive side 162A of the adhesive tape 160 is pressed onto the back side of the adhesive sheet 1 (i.e., the surface of the overcoating 14) 1A under a pressure of 0.25 MPa and a speed of 0.3 m / min. The resulting object is placed at 23°C and 50% RH for 30 minutes. Then, using a universal tensile testing machine, the adhesive tape 160 was peeled from the back side 1A of the adhesive sheet 1 at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees, and the adhesive force (A) [N / 24 mm] was measured.

[0376] Furthermore, the back adhesion force (A) is preferably 4.5 N / 24 mm or more, more preferably 5.0 N / 24 mm or more, and even more preferably 5.5 N / 24 mm or more. When the adhesion force is less than 4.5 N / 24 mm, sufficient adhesion force cannot be obtained, the pick-up performance deteriorates, and the peelability of the protective film decreases, so it is not preferred.

[0377] <Adhesion force of polarizing plate: initial>

[0378] After placing the TAC polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70mm, length: 100mm) in an environment of 23°C × 50%RH for 24 hours, an adhesive sheet (adhesive surface of the adhesive layer) cut to a width of 25mm and a length of 100mm was laminated onto the above-mentioned polarizing plate (TAC surface) at a pressure of 0.25MPa and a speed of 0.3m / min to prepare an evaluation sample.

[0379] After lamination, the product was placed at 23℃ and 50%RH for 30 minutes, and then tested using a universal tensile testing machine at a peel speed of 30 m / min (high-speed peel) and a peel angle of 180°. The initial adhesion force (N / 25mm) to the polarizing plate when the adhesive sheet is peeled off under the specified conditions was measured. The measurement was conducted at 23℃ × 50%RH.

[0380] <Adhesion strength of polarizing plate (B): Over time>

[0381] After placing the TAC polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70mm, length: 100mm) in an environment of 23°C × 50%RH for 24 hours, an adhesive sheet (adhesive surface of the adhesive layer) cut to a width of 25mm and a length of 100mm was laminated onto the above-mentioned polarizing plate (TAC surface) at a pressure of 0.25MPa and a speed of 0.3m / min to prepare an evaluation sample.

[0382] After lamination, the product was placed at 50°C for one week, and then tested using a universal tensile testing machine at a peel speed of 30 m / min (high-speed peel) and a peel angle of 180°. The adhesion force (B) to the polarizing plate when the adhesive sheet is peeled off under the specified conditions (over time) (N / 25mm). The measurement was conducted at 23℃ × 50%RH.

[0383] Furthermore, regarding the adhesion force of the polarizing plate, both the initial adhesion force and the over time adhesion force (B) are preferably 1.5 N / 25 mm or less, more preferably 0.05 to 1.5 N / 25 mm, and even more preferably 0.1 to 1.4 N / 25 mm. When the polarizing plate adhesion force (B) exceeds 1.5 N / 25 mm, the protective film is difficult to peel off from the adhered object, resulting in poor peeling performance when the protective film is not needed. In addition, the peeling process can damage the adhered object, which is not preferred. Furthermore, when the increase in the polarizing plate adhesion force (B) (over time) is large relative to the initial adhesion force, the adhesion force increase over time is poor, which is also not preferred.

[0384] <Evaluation of Adhesion Ratio (A / B)>

[0385] The adhesive force ratio (A / B) of the adhesive force (A) to the adhesive force (B) is 3 or more, preferably 3.5 or more, and more preferably 4 or more. Within this range, the pick-up performance is excellent, which is a preferred method.

[0386] <Pick-up>

[0387] like Figure 2 As shown, the adhesive sheet of each example is cut into a size of 50 mm in width and 100 mm in length. The adhesive surface (the side with the adhesive layer 20) 20A of the adhesive sheet 1 is pressed onto the planar polarizing plate (TAC polarizing plate, SEG1425DU manufactured by Nitto Denko Corporation) 50 with a pressure of 0.25 MPa and a speed of 0.3 m / min.

[0388] Single-sided adhesive tape 60 (manufactured by Nichiban Co., Ltd., trade name "Cerotep (registered trademark)", width 24mm) was cut into 50mm lengths. The adhesive layer (adhesive surface) 62 of the adhesive tape 60 was pressed by hand onto the center of the 50mm wide back side of the adhesive sheet 1 (i.e., the surface of the overcoating 14), causing the end to protrude 30mm. The resulting object was placed at 23°C and 50%RH for 10 seconds. Then, the single-sided adhesive tape 60 was peeled off by hand, and the peeling condition (pickup quality) of the adhesive sheet 1 was evaluated.

[0389] The evaluation criteria are as follows: cases where the adhesive sheet can be peeled off are rated as ○, and cases where it cannot be peeled off or where adhesive sheet remains are rated as ×.

[0390] Preparation of (meth)acrylic acid polymer A

[0391] A four-necked flask equipped with a stirring blade, thermometer, nitrogen inlet pipe, and condenser was filled with 100 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 4-hydroxybutyl acrylate (4HBA), 0.01 parts by weight of acrylic acid (AA), 0.2 parts by weight of 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) as a polymerization initiator, and 157 parts by weight of ethyl acetate. Nitrogen gas was introduced while stirring slowly, and the liquid temperature in the flask was maintained at approximately 65°C for 6 hours to prepare a (meth)acrylic acid polymer solution (40% by weight). The acrylic acid polymer had a weight-average molecular weight of 540,000 and a glass transition temperature (Tg) of -68°C.

[0392] Other (meth)acrylic acid polymers A were prepared using the same method as described above, according to the proportions in Table 1. The physical properties of the resulting polymers are also shown in Table 1.

[0393] <Preparation of acrylic oligomers>

[0394] 100 parts by weight of toluene, 60 parts by weight of tetrahydrodicyclopentadienyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 40 parts by weight of methyl methacrylate (MMA), and 3.5 parts by weight of methyl mercaptoacetate as a chain transfer agent were added to a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet pipe, condenser, and dropping funnel. Then, after stirring at 70°C under a nitrogen atmosphere for 1 hour, 0.2 parts by weight of 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile) as a polymerization initiator was added, and the reaction was carried out at 70°C for 2 hours, followed by a reaction at 80°C for 4 hours, and then a reaction at 90°C for 1 hour to obtain an acrylic oligomer. The weight-average molecular weight of the acrylic oligomer was 4000, and the glass transition temperature (Tg) was 144°C.

[0395] <Preparation of Topcoat E>

[0396] Prepare a dispersion containing 25% polyester resin (Toyobo Co., Ltd. product, trade name "Binarol MD-1480" (aqueous dispersion of saturated copolyester resin)) as binder A.

[0397] In addition, prepare an aqueous dispersion of carnauba wax as lubricant B. Also, prepare an aqueous solution containing 0.5% poly(3,4-ethylenedioxythiophene) (PEDOT) and 0.8% polystyrene sulfonate (number average molecular weight 150,000) (PSS) as conductive polymers (HC Stark Corporation, trade name "Baytron P").

[0398] In addition, 100 parts by weight of the above-mentioned binder dispersion (based on solids), 30 parts by weight of the above-mentioned lubricant dispersion (based on solids), 50 parts by weight of the above-mentioned conductive polymer aqueous solution (based on solids), and a melamine crosslinking agent (based on solids) were added to a mixed solvent of water and ethanol, and the mixture was stirred for about 20 minutes to mix thoroughly. Thus, a coating material with approximately 0.15% by weight of NV was prepared.

[0399] Next, a support film with a thickness of 38 mm was prepared, which had undergone corona treatment on one side (the first side). A transparent polyethylene terephthalate (PET) film S, with a width of 30 cm and a length of 40 cm, was prepared. The coating material was applied to the corona-treated surface of the PET film using a doctor blade coater, and then dried at 130°C for 2 minutes. This produced a support film (support film with a cover coating) having a transparent overcoat E with a thickness of 10 nm on the first side of the PET film.

[0400] In addition, when the thickness of the topcoat E is set to 50 nm, it is prepared by adjusting NV to about 0.3% by weight, and other conditions are the same as those for the 10 nm transparent topcoat E described above.

[0401] <Preparation of Topcoat F>

[0402] Prepare a solution in a water-alcohol solvent containing, by weight (NV basis) an antistatic agent (manufactured by Konishi Co., Ltd., trade name "Bondip-P Main Agent") consisting of a cationic polymer as binder C and an epoxy resin (manufactured by Konishi Co., Ltd., trade name "Bondip-P Hardener") as a curing agent, consisting of an antistatic agent (manufactured by Konishi Co., Ltd., trade name "Bondip-P Hardener") consisting of a cationic polymer as binder C and an epoxy resin ...

[0403] The solution was applied to a support film with a thickness of 38 mm that had undergone corona treatment on one side (the first side). A transparent polyethylene terephthalate (PET) film with a diameter of m, a width of 30 cm, and a length of 40 cm was corona-treated and dried to form a film with a density of 0.06 g / m (NV). 2 The topcoat coating.

[0404] Then, a coating of 0.02 g / m² based on NV standards is applied to the surface of the above-mentioned topcoat. 2 A long-chain alkyl urethane stripping agent (a product of Yifangsha Oil & Fat Industry Co., Ltd., trade name "Pierreil 1010") as lubricant D is dried, thereby preparing a cover coating F that imparts lubricity. As a result, a support film (support film with cover coating) having a transparent cover coating F with a thickness of 80 nm on the first side of a PET film is produced.

[0405] <Example 1>

[0406] [Preparation of Adhesive Solution]

[0407] The above-mentioned (meth)acrylic polymer A solution (40% by weight) was diluted to 20% by ethyl acetate. To 500 parts by weight of this solution (100 parts by weight of solids), 2 parts by weight of a solution obtained by diluting an organopolysiloxane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) to 10% by ethyl acetate (0.2 parts by weight of solids), 5 parts by weight of a solution obtained by diluting an alkali metal salt, lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2:LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) as an antistatic agent, to 1% by ethyl acetate (0.05 parts by weight of solids), 1 part by weight of isocyanurate form of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronato HX) as a crosslinking agent (1 part by weight of solids), and 2 parts by weight of dibutyltin dilaurate (1% by weight ethyl acetate solution) as a crosslinking catalyst (0.02 parts by weight of solids) were mixed and stirred to prepare adhesive composition A (acrylic adhesive solution).

[0408] [Making the Adhesive Sheet]

[0409] The acrylic adhesive solution described above is applied to the side of the support film (support film with cover coating E) having the cover coating E opposite to the cover coating E, and heated at 130°C for 2 minutes to form a thickness of 15 mm. An adhesive layer of m. Then, a polyethylene terephthalate film (25 mm thick) is laminated onto the surface of the adhesive layer A as a spacer with one side treated with polysiloxane. An adhesive sheet was fabricated by treating the polysiloxane surface of the m) material.

[0410] <Examples 2-6, 10-11, and Comparative Examples 1-3>

[0411] Based on the proportions in the table, adhesive sheets were prepared in the same manner as in Example 1. Furthermore, the proportions in Table 1 indicate the solid components. Additionally, for additives not listed in the table, the same proportions as in Example 1 were used. The same applies to additives not specifically described in Examples 7-9.

[0412] <Example 7>

[0413] One part by weight of acrylic oligomer was also added. Otherwise, based on the proportions in Tables 1 and 2, adhesive sheets were prepared in the same manner as in Example 1.

[0414] <Example 8>

[0415] Using 0.5 parts by weight of tri(acetylacetonate)ferric (1% ethyl acetate solution) (0.005 parts by weight of solids) instead of dibutyltin dilaurate as the crosslinking catalyst, adhesive sheets were prepared in the same manner as in Example 1, based on the proportions in Tables 1 and 2.

[0416] <Example 9>

[0417] One part by weight of acrylic oligomer was added and 0.5 parts by weight of tri(acetylacetonate)ferric (1% ethyl acetate solution) (0.005 parts by weight of solids) was used instead of dibutyltin dilaurate as the crosslinking catalyst. Otherwise, adhesive sheets were prepared in the same manner as in Example 1, based on the proportions in Tables 1 and 2.

[0418] Table 1

[0419]

[0420] Table 2

[0421]

[0422] The following explains the abbreviation symbols in Tables 1 and 2.

[0423] 2EHA: 2-Ethylhexyl acrylate

[0424] 4HBA: 4-Hydroxybutyl acrylate

[0425] AA: Acrylic acid (containing carboxyl (meth)acrylic acid monomers)

[0426] COOH monomers: carboxyl (meth) acrylic acid monomers

[0427] C / HX: Isocyanate compound, hexamethylene diisocyanate in the isocyanurate form (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate HX).

[0428] KF353: Organopolysiloxane (HLB value: 10, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KF-353)

[0429] LiTFSI: Alkali metal salt, lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2, (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0430] BMPTFSI: 1-Butyl-3-methylpyridine Bis(trifluoromethanesulfonyl)imide, ionic liquid (antistatic agent)

[0431] BMPPF: 1-Butyl-4-methylpyridine Hexafluorophosphate, ionic liquid (antistatic agent)

[0432] Table 3

[0433]

[0434] Note: The parts marked with (-) in Table 3 are those for which antistatic properties were not evaluated because no ionic compound was used as an antistatic agent.

[0435] The results in Table 3 above confirm that, in all embodiments, by incorporating a desired amount of acrylic acid (AA) as a carboxyl (meth)acrylic acid monomer, excellent adhesion, re-peelability, anti-adhesion rise, pick-up properties, and workability associated with these characteristics are also observed. Furthermore, examples incorporating an ionic compound as an antistatic agent also demonstrate excellent antistatic properties.

[0436] In contrast, in Comparative Example 1, the topcoat coating did not use the desired raw materials, resulting in poor resistance to whitening and solvents. In addition, the adhesive strength on the back (A) was lower than that on the polarizing plate (B), and the pick-up performance was also poor.

[0437] In addition, in Comparative Example 2, acrylic acid (AA) was not used in the preparation of the adhesive composition. Therefore, it was found that the adhesion (B) to the polarizing plate was high, but the resistance to adhesion increase was poor. Furthermore, the adhesion ratio (A / B) was outside the expected range, resulting in poor pick-up and poor workability.

[0438] Furthermore, in Comparative Example 3, a large amount of acrylic acid was incorporated during the preparation of the adhesive composition. Therefore, the initial adhesion force to the polarizing plate and the adhesion force to the polarizing plate (B) showed very high values. This resulted in poor adhesion strength, an adhesion force ratio (A / B) outside the expected range, poor pick-up performance, and poor workability. Additionally, although an antistatic agent was incorporated in Comparative Example 3, the large amount of acrylic acid resulted in poor antistatic properties.

Claims

1. An adhesive sheet having an adhesive layer formed of an adhesive composition on one side of a supporting film, the supporting film having a cover coating on a side opposite to the side having the adhesive layer, characterized in that, The topcoat contains wax as a lubricant and polyester resin as a binder. The adhesive composition contains a (meth)acrylic polymer and a crosslinking agent. Relative to the total amount of monomer components constituting the (meth)acrylic polymer, it contains 0.006% to 1.0% by weight of carboxyl-containing (meth)acrylic monomers. The crosslinking agent comprises 1.0 to 2.5 parts by weight, but excluding 1.0 part by weight, relative to 100 parts by weight of the (meth)acrylic polymer. The ratio (A / B) of the back adhesion force (A) of the single-sided adhesive tape (product name "Cerotep") manufactured by Mikibang Co., Ltd., after being applied to the surface of the topcoat at 23°C for 30 minutes at a peel speed of 0.3 m / min, to the adhesion force (B) of the adhesive layer on the TAC surface after being applied to the adhesive side at 50°C for 1 week at a peel speed of 30 m / min, is 3 or more. The back adhesion force (A) is 5.5 N / 24 mm or higher. The adhesive force (B) is less than 1.5 N / 25 mm.

2. The adhesive sheet as described in claim 1, characterized in that, The (meth)acrylic polymer is a (meth)acrylic polymer having hydroxyl and carboxyl groups.

3. The adhesive sheet as described in claim 1, characterized in that, The polymer contains less than 15% by weight of hydroxyl-containing (meth)acrylic monomers relative to the total amount of monomer components constituting the (meth)acrylic polymer.

4. The adhesive sheet as described in claim 1, characterized in that, The (meth)acrylic polymer contains 50% by weight or more of (meth)acrylic monomers having alkyl groups having 1 to 14 carbon atoms, relative to the total amount of monomer components constituting the (meth)acrylic polymer.

5. The adhesive sheet as described in claim 1, characterized in that, The adhesive composition contains an organopolysiloxane having an oxyalkylene chain.

6. The adhesive sheet as described in claim 1, characterized in that, The adhesive composition contains an ionic compound.

7. The adhesive sheet as described in claim 1, characterized in that, The wax is an ester of higher fatty acids and higher alcohols.

8. The adhesive sheet according to any one of claims 1 to 7, characterized in that, The coating contains antistatic components.

9. An optical component protected by an adhesive sheet according to any one of claims 1 to 8.

Images