WO2013058186A1 - 再剥離用水分散型アクリル系粘着剤組成物、及び粘着シート - Google Patents
再剥離用水分散型アクリル系粘着剤組成物、及び粘着シート Download PDFInfo
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- WO2013058186A1 WO2013058186A1 PCT/JP2012/076448 JP2012076448W WO2013058186A1 WO 2013058186 A1 WO2013058186 A1 WO 2013058186A1 JP 2012076448 W JP2012076448 W JP 2012076448W WO 2013058186 A1 WO2013058186 A1 WO 2013058186A1
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- 0 C1C2C1CCC*2 Chemical compound C1C2C1CCC*2 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a water-dispersed acrylic pressure-sensitive adhesive composition that can form a re-peelable pressure-sensitive adhesive layer. Specifically, re-peeling that can form an adhesive layer that is excellent in antistatic properties and removability, has low contamination to the adherend, and prevents the increase in peel strength (adhesive strength) over time.
- the present invention relates to a water-dispersed acrylic pressure-sensitive adhesive composition. Moreover, it is related with the adhesive sheet which provided the adhesive layer which consists of the said adhesive composition.
- optical members optical materials
- optical films such as polarizing plates, retardation plates, and antireflection plates
- a surface protective film is used by being attached to the surface of an optical member (see Patent Documents 1 and 2).
- a removable pressure-sensitive adhesive sheet in which a removable pressure-sensitive adhesive layer is provided on the surface of a plastic film substrate is generally used.
- Patent Documents 1 and 2 Conventionally, solvent-type acrylic pressure-sensitive adhesives have been used as pressure-sensitive adhesives for these surface protective film applications (see Patent Documents 1 and 2), but these solvent-type acrylic pressure-sensitive adhesives contain organic solvents. Therefore, from the viewpoint of work environment at the time of coating, conversion to a water-dispersed acrylic pressure-sensitive adhesive has been attempted (see Patent Documents 3 to 5).
- the surface protective film and the optical member are made of a plastic material, they have high electrical insulation and generate static electricity during friction and peeling. Therefore, static electricity is generated when the surface protective film is peeled off from the optical member such as a polarizing plate.
- the optical member such as a polarizing plate.
- adhesive residue (so-called “glue residue”) remains on the surface of the adherend (optical member, etc.) when the adhesive sheet is peeled off.
- Contamination of the adherend surface due to transfer of components contained in the adhesive layer to the adherend surface causes problems such as an adverse effect on the optical characteristics of the optical member. For this reason, the low adhesiveness with respect to a to-be-adhered body is strongly calculated
- the object of the present invention is to prevent the adherend from being charged at the time of peeling (antistatic property), excellent in re-peeling property, excellent in preventing peeling force (adhesive force) from increasing, and low contamination to the adherend.
- Water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling applications that can form a pressure-sensitive adhesive layer that has excellent properties, especially whitening contamination prevention (whitening contamination prevention) that occurs on an adherend in a high-humidity environment
- it is providing the adhesive sheet which has an adhesive layer by the said adhesive composition.
- the present inventors have a specific acrylic emulsion polymer obtained from a raw material monomer having a specific composition, a water-insoluble cross-linking agent, and an ionic compound as constituents, and are antistatic. It has been found that a water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling capable of forming a pressure-sensitive adhesive layer excellent in repellency, re-peelability, peel strength (adhesive strength), and low contamination is obtained. Was completed.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention comprises, as a raw material monomer, 70 to 99.5% by weight of (meth) acrylic acid alkyl ester (i) and a carboxyl group-containing unsaturated monomer (ii )
- An acrylic emulsion polymer composed of 0.5 to 10% by weight, a water-insoluble crosslinking agent, and an ionic compound.
- the ionic compound of the present invention is preferably an ionic liquid and / or an alkali metal salt.
- the ionic liquid contains at least one cation selected from the group consisting of cations represented by the following formulas (A) to (E): Is preferred.
- R a in Formula (A) represents a hydrocarbon group having 4 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom
- R b and R c May be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- R d in Formula (B) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom, and R e , R f And R g may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- [R h in Formula (C) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a heteroatom
- R i , R j , And R k may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- [Z in Formula (D) represents a nitrogen, sulfur, or phosphorus atom, and R 1 , R m , R n , and R o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.
- a functional group in which a part of the hydrocarbon group is substituted with a hetero atom may be used.
- Z is a sulfur atom
- [R P in the formula (E) represents a hydrocarbon group having 1 to 18 carbon atoms, a part of the hydrocarbon group may be substituted by a functional group with a heteroatom. ]
- the cation of the ionic liquid has an imidazolium-containing salt type, a pyridinium salt-containing type, a morpholinium-containing salt type, a pyrrolidinium salt-containing type, or a piperidinium salt-containing type. It is preferably at least one selected from the group consisting of an ammonium-containing salt type, a phosphonium-containing salt type, and a sulfonium-containing salt type.
- the ionic liquid contains at least one cation selected from the group consisting of cations represented by the following formulas (a) to (d): Is preferred.
- R 1 in Formula (a) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms
- R 2 represents hydrogen or a hydrocarbon group having 1 to 7 carbon atoms.
- R 3 in Formula (b) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms
- R 4 represents hydrogen or a hydrocarbon group having 1 to 7 carbon atoms.
- [R 5 in Formula (c) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms
- R 6 represents hydrogen or a hydrocarbon group having 1 to 7 carbon atoms
- [R 7 in Formula (d) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms
- R 8 represents hydrogen or a hydrocarbon group having 1 to 7 carbon atoms.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention preferably contains 4.9 parts by weight or less of the ionic liquid with respect to 100 parts by weight of the acrylic emulsion polymer (solid content).
- the alkali metal salt preferably has a fluorine-containing anion.
- the alkali metal salt is preferably a lithium salt.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention preferably contains 3 parts by weight or less of the alkali metal salt with respect to 100 parts by weight of the solid content of the acrylic emulsion polymer.
- the acrylic emulsion polymer is preferably a polymer obtained by polymerization using a reactive emulsifier containing a radical polymerizable functional group in the molecule. .
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention is the number of moles of functional groups capable of reacting with the carboxyl group of the water-insoluble crosslinking agent with respect to 1 mol of the carboxyl group of the carboxyl group-containing unsaturated monomer (ii). Is preferably 0.2 to 1.3 mol.
- the pressure-sensitive adhesive sheet of the present invention preferably has a pressure-sensitive adhesive layer formed from the re-peeling water-dispersed acrylic pressure-sensitive adhesive composition on at least one side of the substrate.
- the pressure-sensitive adhesive sheet of the present invention is preferably a surface protective film for optical members.
- the optical member of the present invention preferably has the adhesive sheet attached thereto.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention is a water-dispersed acrylic pressure-sensitive adhesive composition used for re-peeling applications, a specific acrylic emulsion polymer, a water-insoluble crosslinking agent, and since it contains an ionic compound, the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) formed of the pressure-sensitive adhesive composition has excellent antistatic properties, adhesiveness and removability. In particular, it is excellent in the ability to prevent the peel force (adhesive force) from increasing with time. In addition, it is excellent in low contamination, particularly whitening contamination prevention when stored in a high humidity environment. For this reason, the water-dispersed acrylic pressure-sensitive adhesive composition of the present invention is particularly useful as a surface protection application for optical films.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention contains 70 to 99.5 wt. Of (meth) acrylic acid alkyl ester (i) as a raw material monomer. %, And an acrylic emulsion polymer composed of 0.5 to 10% by weight of a carboxyl group-containing unsaturated monomer (ii), a water-insoluble crosslinking agent, and an ionic compound as essential components.
- “water-dispersed” means that it can be dispersed in an aqueous medium, that is, a pressure-sensitive adhesive composition that can be dispersed in an aqueous medium.
- the aqueous medium is a medium (dispersion medium) containing water as an essential component, and may be a mixture of water and a water-soluble organic solvent in addition to water alone.
- the pressure-sensitive adhesive composition of the present invention may be a dispersion using the aqueous medium or the like.
- the acrylic emulsion-based polymer has, as raw material monomers, 70 to 99.5% by weight of (meth) acrylic acid alkyl ester (i) and 0.5 to 10% by weight of carboxyl group-containing unsaturated monomer (ii). It is a composed polymer.
- the acrylic emulsion polymer can be used alone or in combination of two or more.
- “(meth) acryl” means “acryl” and / or “methacryl”.
- the (meth) acrylic acid alkyl ester (i) is used as a main monomer component, and mainly plays a role of developing basic characteristics as a pressure-sensitive adhesive (or pressure-sensitive adhesive layer) such as adhesiveness and peelability.
- acrylic acid alkyl esters tend to give flexibility to the polymer forming the pressure-sensitive adhesive layer, and exhibit the effect of developing adhesiveness and adhesiveness to the pressure-sensitive adhesive layer.
- the (meth) acrylic acid alkyl ester (i) is not particularly limited, but is linear, branched or cyclic having 2 to 16 carbon atoms (more preferably 2 to 10, more preferably 4 to 8).
- (meth) acrylic acid alkyl esters having the following alkyl groups are not particularly limited, but is linear, branched or cyclic having 2 to 16 carbon atoms (more preferably 2 to 10, more preferably 4 to 8).
- an acrylic acid alkyl ester having an alkyl group having 2 to 14 carbon atoms is preferable, such as n-butyl acrylate, isobutyl acrylate, acrylic acid s.
- n-butyl acrylate isobutyl acrylate
- acrylic acid s -Having a linear or branched alkyl group such as butyl, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate
- acrylic acid alkyl esters Of these, 2-ethylhexyl acrylate is preferable.
- alkyl methacrylate for example, alkyl methacrylate having an alkyl group having 2 to 16 carbon atoms (more preferably 2 to 10) is preferable, and ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid, Methacrylic acid alkyl ester having a linear or branched alkyl group such as n-butyl acid, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, isobornyl methacrylate And an alicyclic methacrylic acid alkyl ester.
- the (meth) acrylic acid alkyl ester (i) can be appropriately selected according to the intended adhesiveness and the like, and can be used alone or in combination of two or more.
- the content of the (meth) acrylic acid alkyl ester (i) is 70 to 99.5% by weight in the total amount of raw material monomers constituting the acrylic emulsion polymer of the present invention (total raw material monomers) (100% by weight). And is preferably 85 to 98% by weight, more preferably 87 to 96% by weight.
- the content of 70% by weight or more is preferable because the adhesiveness and removability of the pressure-sensitive adhesive layer are improved.
- the content exceeds 99.5% by weight the appearance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition may deteriorate due to a decrease in the content of the carboxyl group-containing unsaturated monomer (ii). is there.
- the total amount (total amount) of all the (meth) acrylic-acid alkylesters (i) should just satisfy the said range. .
- the carboxyl group-containing unsaturated monomer (ii) can exhibit a function of forming a protective layer on the surface of the emulsion particles made of the acrylic emulsion polymer of the present invention and preventing shearing of the particles. This effect is further improved by neutralizing the carboxyl group with a base.
- the stability of the particles against shear fracture is more generally referred to as mechanical stability.
- by combining one or more of the water-insoluble crosslinking agents of the present invention that react with carboxyl groups it can also act as a crosslinking point in the pressure-sensitive adhesive layer forming stage by water removal.
- the adhesiveness (anchoring property) with a base material can also be improved through a water-insoluble crosslinking agent.
- carboxyl group-containing unsaturated monomer (ii) examples include (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxyethyl acrylate, carboxypentyl acrylate, and the like. Is mentioned.
- the carboxyl group-containing unsaturated monomer (ii) includes acid anhydride group-containing unsaturated monomers such as maleic anhydride and itaconic anhydride.
- acrylic acid is preferable because the relative concentration on the particle surface is high and it is easy to form a denser protective layer.
- the content of the carboxyl group-containing unsaturated monomer (ii) is 0.5 to 10% by weight in the total amount of raw material monomers (total raw material monomer) (100% by weight) constituting the acrylic emulsion polymer of the present invention. It is preferably 1 to 5% by weight, more preferably 2 to 4% by weight.
- the carboxyl group-containing unsaturated monomer (ii) for example, acrylic acid
- the carboxyl group-containing unsaturated monomer (ii) is generally water-soluble, so that it is polymerized in water and thickened (increased viscosity). May cause.
- an ionic compound such as an ionic liquid or an alkali metal salt
- the content of 0.5% by weight or more is preferable because the mechanical stability of the emulsion particles is improved.
- the adhesiveness (throwing property) of an adhesive layer and a base material improves and adhesive residue can be suppressed, it is preferable.
- a raw material monomer constituting the acrylic emulsion polymer of the present invention for the purpose of imparting a specific function, other than the essential components [(meth) acrylic acid alkyl ester (i), carboxyl group-containing unsaturated monomer (ii)]
- Other monomer components may be used in combination.
- a monomer component for example, methyl methacrylate, vinyl acetate, diethyl acrylamide or the like can be used for the purpose of reducing appearance defects.
- these monomers are used, the stability of the emulsion particles is increased, gels (aggregates) can be reduced, and the affinity with the hydrophobic water-insoluble cross-linking agent is increased.
- an epoxy group-containing monomer such as glycidyl (meth) acrylate is used, or a polyfunctional monomer such as trimethylolpropane tri (meth) acrylate or divinylbenzene. Can also be used.
- the said compounding quantity (use amount) is content in the total amount (total raw material monomer) (100 weight%) of the raw material monomer which comprises the acrylic emulsion type polymer of this invention.
- a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate is preferably used in a smaller amount (used amount) from the viewpoint of further reducing whitening contamination.
- the blending amount of the hydroxyl group-containing unsaturated monomer is 1% by weight. Is preferably less than, more preferably less than 0.1% by weight, even more preferably substantially free (eg, less than 0.05% by weight).
- a crosslinking point such as crosslinking between a hydroxyl group and an isocyanate group or crosslinking between metal bridges, about 0.01 to 10% by weight may be added (used).
- the acrylic emulsion polymer of the present invention can be obtained by emulsion polymerization of the above raw material monomer (monomer mixture) with an emulsifier and a polymerization initiator.
- a reactive emulsifier having a radical polymerizable functional group introduced into the molecule may be used. preferable. These emulsifiers are used alone or in combination of two or more.
- the reactive emulsifier containing a radical polymerizable functional group (hereinafter referred to as “reactive emulsifier”) is an emulsifier containing at least one radical polymerizable functional group in a molecule (in one molecule).
- the reactive emulsifier is not particularly limited, and various reactive emulsifiers having a radical polymerizable functional group such as vinyl group, propenyl group, isopropenyl group, vinyl ether group (vinyloxy group), and allyl ether group (allyloxy group). 1 type or 2 or more types can be selected and used.
- Use of the reactive emulsifier is preferable because the emulsifier is incorporated into the polymer and contamination from the emulsifier is reduced.
- the reactive emulsifier examples include nonionic anionic emulsifiers such as sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl sulfosuccinate (nonionic).
- a reactive emulsifier having a form in which a radical polymerizable functional group (radical reactive group) such as propenyl group or allyl ether group is introduced into an anionic emulsifier having a hydrophilic hydrophilic group) (or corresponding to the above form) Can be mentioned.
- a reactive emulsifier having a form in which a radical polymerizable functional group is introduced into an anionic emulsifier is referred to as an “anionic reactive emulsifier”.
- a reactive emulsifier having a form in which a radical polymerizable functional group is introduced into a nonionic anionic emulsifier is referred to as a “nonionic anionic reactive emulsifier”.
- an anionic reactive emulsifier in particular, a nonionic anionic reactive emulsifier
- the emulsifier is incorporated into the polymer, so that low contamination can be improved.
- the water-insoluble crosslinking agent of the present invention is a polyfunctional epoxy-based crosslinking agent having an epoxy group
- the reactivity of the crosslinking agent can be improved by its catalytic action.
- an anionic reactive emulsifier is not used, the crosslinking reaction is not completed by aging, and there may be a problem that the peeling force (adhesive strength) of the pressure-sensitive adhesive layer changes with time.
- the anionic reactive emulsifier is incorporated in the polymer, it is used as a quaternary ammonium compound (see, for example, JP-A-2007-31585), which is generally used as a catalyst for an epoxy-based crosslinking agent. Since it does not precipitate on the surface of the adherend and cannot cause whitening contamination, it is preferable.
- Examples of such reactive emulsifiers include the trade name “ADEKA rear soap SE-10N” (manufactured by ADEKA Corporation), the trade name “AQUALON HS-10” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the trade name “AQUALON HS”.
- Commercial products such as “-05” (Daiichi Kogyo Seiyaku Co., Ltd.) and trade name “AQUALON HS-1025” (Daiichi Kogyo Seiyaku Co., Ltd.) can also be used.
- an emulsifier having an SO 4 2- ion concentration of 100 ⁇ g / g or less it is desirable to use an ammonium salt emulsifier.
- an appropriate method such as an ion exchange resin method, a membrane separation method, or a precipitation filtration method for impurities using alcohol can be used.
- the compounding amount (use amount) of the reactive emulsifier is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of raw material monomers (total raw material monomers) constituting the acrylic emulsion polymer of the present invention, The amount is more preferably 0.5 to 6 parts by weight, still more preferably 1 to 4.5 parts by weight.
- a blending amount of 0.1 part by weight or more is preferable because stable emulsification can be maintained.
- the blending amount is 10 parts by weight or less, the cohesive force of the pressure-sensitive adhesive (pressure-sensitive adhesive layer) is improved, contamination to the adherend can be suppressed, and contamination by the emulsifier can be suppressed, which is preferable.
- the polymerization initiator used in the emulsion polymerization of the acrylic emulsion polymer of the present invention is not particularly limited.
- the blending amount (use amount) of the polymerization initiator can be appropriately determined according to the type of the initiator and the raw material monomer, and is not particularly limited. However, the amount of the raw material monomer constituting the acrylic emulsion polymer of the present invention is not limited. The amount is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, based on 100 parts by weight of the total amount (total raw material monomers).
- Emulsion polymerization of the acrylic emulsion polymer of the present invention can be performed by emulsifying the monomer component in water and then emulsion polymerization in a conventional manner. Thereby, the aqueous dispersion (polymer emulsion) which contains the said acrylic emulsion type polymer as a base polymer can be prepared.
- the emulsion polymerization method is not particularly limited, and for example, a known emulsion polymerization method such as a batch charging method (batch polymerization method), a monomer dropping method, or a monomer emulsion dropping method can be employed. In the monomer dropping method and the monomer emulsion dropping method, continuous dropping or divided dropping is appropriately selected. These methods can be appropriately combined. Reaction conditions and the like are selected as appropriate, but the polymerization temperature is preferably about 40 to 95 ° C., for example, and the polymerization time is preferably about 30 minutes to 24 hours.
- the solvent-insoluble content of the acrylic emulsion polymer of the present invention is 70% from the viewpoint of low contamination and proper peeling force (adhesive strength). (% By weight) or more, preferably 75% by weight or more, and more preferably 80% by weight or more. If the solvent-insoluble content is less than 70% by weight, the acrylic emulsion polymer contains a large amount of low molecular weight, and therefore the low molecular weight component in the pressure-sensitive adhesive layer cannot be sufficiently reduced only by the effect of crosslinking. In some cases, adherend contamination derived from the above occurs, or the peel strength (adhesive strength) becomes too high.
- the solvent-insoluble content can be controlled by the polymerization initiator, reaction temperature, type of emulsifier and raw material monomer, and the like. Although the upper limit of the said solvent insoluble content is not specifically limited, For example, it is 99 weight%.
- the solvent-insoluble content of the acrylic emulsion polymer is a value calculated by the following “method for measuring the solvent-insoluble content”.
- Acrylic emulsion polymer About 0.1 g was sampled, wrapped in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Corporation) with an average pore size of 0.2 ⁇ m, and then bound with a string. The weight at the time is measured, and this weight is defined as the weight before immersion. The weight before immersion is the total weight of the acrylic emulsion polymer (collected above), the tetrafluoroethylene sheet, and the kite string. Further, the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is defined as the wrapping weight.
- sample acrylic emulsion polymer wrapped with a tetrafluoroethylene sheet and bound with a kite string
- sample is placed in a 50 ml container filled with ethyl acetate and left at 23 ° C. for 7 days.
- sample (after ethyl acetate treatment) is taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, the weight is measured, and the weight is immersed. After weight. And a solvent insoluble content is computed from a following formula.
- the weight average molecular weight (Mw) of the solvent-soluble component (sometimes referred to as “sol component”) of the acrylic emulsion polymer of the present invention is preferably 40,000 to 200,000, more preferably 50,000 to 150,000, More preferably, it is 60,000 to 100,000.
- Mw weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer is 40,000 or more, the wettability of the pressure-sensitive adhesive composition to the adherend is improved, and the adhesion to the adherend is improved.
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer is 200,000 or less, the residual amount of the pressure-sensitive adhesive composition on the adherend is reduced, and the low contamination property to the adherend is improved. To do.
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer is determined by air-drying the treated solution (ethyl acetate solution) after the ethyl acetate treatment obtained in the measurement of the solvent-insoluble component of the acrylic emulsion polymer at room temperature.
- the sample (solvent-soluble content of the acrylic emulsion polymer) obtained by the measurement can be obtained by measurement by GPC (gel permeation chromatography). Specific methods for measuring include the following methods.
- the GPC measurement is performed using a GPC apparatus “HLC-8220GPC” manufactured by Tosoh Corporation, and the molecular weight is obtained by a polystyrene conversion value.
- the measurement conditions are as follows. Sample concentration: 0.2% by weight (THF solution) Sample injection volume: 10 ⁇ l Eluent: THF Flow rate: 0.6 ml / min Measurement temperature: 40 ° C column: Sample column; 1 TSKguardcolumn SuperHZ-H + 2 TSKgel SuperHZM-H Reference column; 1 TSKgel SuperH-RC Detector: Differential refractometer
- the water-insoluble crosslinking agent of the present invention is a water-insoluble compound having 2 or more (for example, 2 to 6) functional groups capable of reacting with a carboxyl group in the molecule (in one molecule). .
- the number of functional groups capable of reacting with a carboxyl group in one molecule is preferably 3 to 5.
- the pressure-sensitive adhesive composition crosslinks densely (that is, the cross-linked structure of the polymer forming the pressure-sensitive adhesive layer becomes dense). For this reason, it becomes possible to prevent the wetting and spreading of the pressure-sensitive adhesive layer after forming the pressure-sensitive adhesive layer.
- the functional group (carboxyl group) in the pressure-sensitive adhesive layer segregates on the surface of the adherend, and the peeling force (adhesive strength) between the pressure-sensitive adhesive layer and the adherend. Can be prevented from rising over time.
- the number of functional groups capable of reacting with a carboxyl group in one molecule exceeds 6 and is too large, a gelled product may be formed.
- the functional group capable of reacting with a carboxyl group in the water-insoluble crosslinking agent of the present invention is not particularly limited, and examples thereof include an epoxy group, an isocyanate group, and a carbodiimide group.
- an epoxy group is preferable from the viewpoint of reactivity.
- Unreacted carboxyl groups in the pressure-sensitive adhesive layer have a peeling force (adhesive strength) with the adherend over time. From the viewpoint that it can be prevented from rising, a glycidylamino group is preferred.
- an epoxy-based crosslinking agent having an epoxy group is preferable, and among them, a crosslinking agent having a glycidylamino group (glycidylamino-based crosslinking agent) is preferable.
- a crosslinking agent having a glycidylamino group is preferable.
- the water-insoluble crosslinking agent of the present invention is an epoxy crosslinking agent (particularly a glycidylamino crosslinking agent)
- the number of epoxy groups (particularly glycidylamino group) in one molecule is 2 or more (for example, 2 to 6), and 3 to 5 are preferable.
- the water-insoluble crosslinking agent of the present invention is a water-insoluble compound.
- Water-insoluble means that the solubility in 100 parts by weight of water at 25 ° C. (the weight of the compound (crosslinker) soluble in 100 parts by weight of water) is 5 parts by weight or less, preferably 3 The amount is not more than parts by weight, more preferably not more than 2 parts by weight.
- the remaining cross-linking agent dissolves in water and is easily transferred to an adherend, and thus easily causes whitening contamination.
- the water-insoluble cross-linking agent has a higher contribution to the cross-linking reaction (reaction with a carboxyl group) than the water-soluble cross-linking agent, and has a high effect of preventing the peeling force (adhesive force) from increasing with time.
- the cross-linking reaction proceeds promptly by aging, and the peeling force (adhesive strength) from the adherend is increased by the unreacted carboxyl group in the pressure-sensitive adhesive layer. It is possible to prevent an increase over time.
- peeling itself may become difficult and is unpreferable.
- the solubility of the crosslinking agent in water can be measured, for example, as follows.
- water-insoluble crosslinking agent of the present invention 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (for example, trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) Etc.] [Solubility of 2 parts by weight or less with respect to 100 parts by weight of water at 25 ° C.] 1,3-bis (N, N-diglycidylaminomethyl) benzene (for example, Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD- X "etc.) [glycidylamino-based cross-linking agent such as solubility in 100 parts by weight of water at 25 ° C.
- Tris (2,3-epoxypropyl) isocyclicate for example, trade name“ Nissan Chemical Co., Ltd., trade name “ Other epoxy-based crosslinking agents such as “TEPIC-G” and the like] [solubility of 2 parts by weight or less with respect to 100 parts by weight of water at 25 ° C.] and the like.
- the blending amount of the water-insoluble crosslinking agent of the present invention is that of the carboxyl group-containing unsaturated monomer (ii) used as a raw material monomer of the acrylic emulsion polymer of the present invention. It is preferable that the amount of the functional group capable of reacting with the carboxyl group of the water-insoluble crosslinking agent of the present invention is 0.2 to 1.3 mol per mol of the carboxyl group.
- the ratio of “the total number of moles of functional groups capable of reacting with carboxyl groups” [functional group capable of reacting with carboxyl groups / carboxyl groups] is preferably 0.2 to 1.3, 0.3 Is more preferably 0.3 to 1.1, still more preferably 0.3 to 1.1, particularly preferably 0.3 to 1.0, and most preferably 0.4 to 1.0.
- the [epoxy group / carboxyl group] (molar ratio) is preferably 0.2 to 1.3, 0.3 Is more preferably 0.3 to 1.1, still more preferably 0.3 to 1.1, particularly preferably 0.3 to 1.0, and most preferably 0.4 to 1.0.
- the water-insoluble crosslinking agent of the present invention is a glycidylamino crosslinking agent, it is preferable that [glycidylamino group / carboxyl group] (molar ratio) satisfy the above range.
- the water-insoluble cross-linking agent having a functional group equivalent to a carboxyl group of 110 (g / eq) is added (blended) to the pressure-sensitive adhesive composition
- the water-insoluble cross-linking agent is added.
- the number of moles of the functional group that can react with the carboxyl group possessed by can be calculated as follows, for example.
- the re-peeling water-dispersible acrylic pressure-sensitive adhesive composition of the present invention contains an ionic compound as an essential component.
- the obtained pressure-sensitive adhesive layer pressure-sensitive adhesive sheet
- an adherend protected body
- Antistatic properties can be imparted.
- the ionic compound can be expected to have a compatibility with the acrylic emulsion polymer and a balanced interaction.
- the ionic compound it is preferable to use an ionic liquid or an alkali metal salt, which may be used alone or in combination.
- the ionic liquid in the present invention refers to a molten salt (ionic compound) that exhibits a liquid state at 25 ° C., and is not particularly limited. However, for the reason that excellent antistatic ability is obtained, the following formulas (A) to (E) are used. What consists of the organic cation component represented and the anion component is used preferably.
- R a in the formula (A) represents a hydrocarbon group having 4 to 20 carbon atoms, a part of the hydrocarbon group may be substituted with a hetero atom, and R b and R c are the same or Differently, it represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be substituted with a hetero atom. However, when the nitrogen atom contains a double bond, there is no R c .
- R d in the formula (B) represents a hydrocarbon group having 2 to 20 carbon atoms, a part of the hydrocarbon group may be substituted with a hetero atom
- R e , R f , and R g Are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be substituted with a hetero atom.
- R h in the formula (C) represents a hydrocarbon group having 2 to 20 carbon atoms, a part of the hydrocarbon group may be substituted with a hetero atom
- R i , R j , and R k Are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be substituted with a hetero atom.
- Z in the formula (D) represents a nitrogen, sulfur, or phosphorus atom
- R 1 , R m , R n , and R o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. A part of the hydrocarbon group may be substituted with a hetero atom. However, when Z is a sulfur atom, there is no Ro .
- R P in the formula (E) represents a hydrocarbon group having 1 to 18 carbon atoms, a part of the hydrocarbon group may be substituted by a functional group with a heteroatom.
- Examples of the cation represented by the formula (A) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and a morpholinium cation.
- Specific examples include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl.
- Examples of the cation represented by the formula (B) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
- Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-helium Xyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazole Rium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3 -Dimethylimidazolium cation, 1- (2-H Roxyeth
- Examples of the cation represented by the formula (C) include a pyrazolium cation and a pyrazolinium cation.
- Specific examples include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1 -Propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation and the like.
- Examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the alkyl group is substituted with an alkenyl group, an alkoxyl group, or an epoxy group. And so on.
- Specific examples include, for example, 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, dibutyl Ethyl
- asymmetric such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, etc.
- Examples of the cation represented by the formula (E) include a sulfonium cation. Further, the formula Specific examples of R P in (E) is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, An octadecyl group etc. are mentioned.
- the cation of the ionic liquid has an imidazolium-containing salt type, a pyridinium salt-containing type, a morpholinium-containing salt type, a pyrrolidinium salt-containing type, or a piperidinium salt-containing type. It is preferably at least one selected from the group consisting of an ammonium-containing salt type, a phosphonium-containing salt type, and a sulfonium-containing salt type.
- These ionic liquids correspond to those containing the cations of the above formulas (A), (B) and (D).
- the ionic liquid preferably contains at least one cation selected from the group consisting of cations represented by the following formulas (a) to (d). . These cations are included in the formulas (A) and (B).
- R 1 in the formula (a) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 carbon atom, and R 2 represents hydrogen or a carbon group having 1 to 7 carbon atoms.
- the hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms.
- R 3 in the formula (b) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 carbon atom, and R 4 represents hydrogen or a carbon group having 1 to 7 carbon atoms.
- the hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms.
- R 5 in the formula (c) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 carbon atom, and R 6 represents hydrogen or a carbon group having 1 to 7 carbon atoms.
- the hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms.
- R 7 in the formula (d) represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 carbon atom, and R 8 is hydrogen or 1 to 7 carbon atoms.
- the hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms.
- the anion component is not particularly limited as long as it satisfies that it becomes an ionic liquid.
- ionic liquid used in the present invention are appropriately selected from a combination of the cation component and the anion component.
- the ionic liquid used in the present invention are appropriately selected from a combination of the cation component and the anion component.
- the ionic liquid as described above may be a commercially available one, but can also be synthesized as follows.
- the method of synthesizing the ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but in general, it is referred to the document “Ionic liquids—the forefront and future of development” [issued by CMC Publishing Co., Ltd.].
- a halide method, a hydroxide method, an acid ester method, a complex formation method, a neutralization method, and the like are used.
- the halide method is a method carried out by reactions as shown in the following formulas (1) to (3). First, a tertiary amine and an alkyl halide are reacted to obtain a halide (reaction formula (1), and chlorine, bromine, and iodine are used as the halogen).
- the resulting halide is an acid (HA) or salt having the anion structure (A ⁇ ) of the target ionic liquid (MA ⁇ BR> AM forms a salt with the target anion such as ammonium, lithium, sodium, potassium, etc.
- the target ionic liquid (R 4 NA) is obtained by reacting with a cation).
- the hydroxide method is a method carried out by reactions as shown in (4) to (8).
- the obtained hydroxide is subjected to the reactions of the reaction formulas (7) to (8) in the same manner as in the halogenation method to obtain the target ionic liquid (R 4 NA).
- the acid ester method is a method carried out by reactions as shown in (9) to (11). First, a tertiary amine (R 3 N) is reacted with an acid ester to obtain an acid ester product (Reaction Formula (9)).
- an acid ester inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid are used. And esters of organic acids such as esters, methanesulfonic acid, methylphosphonic acid, formic acid, etc.).
- the target ionic liquid (R 4 NA) can be obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as in the halogenation method. Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as the acid ester, an ionic liquid can be obtained directly.
- the complex formation method is a method performed by the reactions shown in (12) to (15).
- a quaternary ammonium halide R 4 NX
- a quaternary ammonium hydroxide R 4 NOH
- a quaternary ammonium carbonate ester R 4 NOCO 2 CH 3
- HF hydrogen fluoride
- NH 4 F Reaction with ammonium fluoride
- An ionic liquid can be obtained by a complex formation reaction of the obtained quaternary ammonium fluoride salt with a fluoride such as BF 3 , AlF 3 , PF 5 , ASF 5 , SbF 5 , NbF 5 , TaF 5 (reaction formula) (15)).
- a fluoride such as BF 3 , AlF 3 , PF 5 , ASF 5 , SbF 5 , NbF 5 , TaF 5 (reaction formula) (15)).
- the neutralization method is a method performed by a reaction as shown in (16).
- Tertiary amine and HBF 4 , HPF 6 , CH 3 COOH, CF 3 COOH, CF 3 SO 3 H, (CF 3 SO 2 ) 2 NH, (CF 3 SO 2 ) 3 CH, (C 2 F 5 SO 2 ) 2 It can be obtained by reacting with an organic acid such as NH.
- R in the formulas (1) to (16) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom.
- the blending amount of the ionic liquid varies depending on the compatibility of the polymer to be used and the ionic liquid, and therefore cannot be generally defined, but is 100 parts by weight (solid content) of the base polymer (acrylic emulsion polymer). 4.9 parts by weight or less, preferably 0.001 to 4.9 parts by weight, more preferably 0.001 to 3 parts by weight or less, still more preferably 0.01 to 2 parts by weight, Most preferred is ⁇ 1 part by weight. If the amount is less than 0.001 part by weight, sufficient antistatic properties cannot be obtained, and if it exceeds 4.9 parts by weight, the contamination of the adherend tends to increase.
- the alkali metal salt of the present invention is not particularly limited, and examples thereof include metal salts composed of lithium, sodium, and potassium. Specifically, for example, cations composed of Li + , Na + , K + , Cl ⁇ , Br ⁇ , I ⁇ , BF 4 ⁇ , PF 6 ⁇ , SCN ⁇ , ClO 4 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , C 4 F 9 SO 3 ⁇ , CH 3 COO ⁇ , C 3 F 7 COO ⁇ , (CF 3 SO 2 ) (CF 3 CO) N ⁇ , (FSO 2 ) 2 N ⁇ , (C 4 F 9 SO 2 ) 2 N ⁇ , (CH 3 O) 2 PO 2 ⁇ , (C 2 H 5 O) 2 PO 2 ⁇ , (CN)
- a lithium salt such as 3 C.
- Lithium salt has a particularly high dissociation property among alkali metal salts, so that it is possible to obtain a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) excellent in antistatic properties, and particularly on the surface of optical members and the like that require antistatic properties. It can be used as a protective film.
- These alkali metal salts may be used alone or in combination of two or more.
- the compounding quantity of the alkali metal salt used for this invention it is preferable to mix
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention contains the acrylic emulsion-based polymer of the present invention, a water-insoluble crosslinking agent, and an ionic compound as essential components. Furthermore, you may contain other various additives as needed.
- the pressure-sensitive adhesive composition of the present invention includes a so-called non-reactive component other than a reactive (polymerizable) component that is incorporated into a polymer that forms a pressure-sensitive adhesive layer by reacting (polymerizing) with a raw material monomer of an acrylic emulsion polymer. It is preferable that a reactive (non-polymerizable) component (however, excluding components such as water that volatilizes by drying and does not remain in the pressure-sensitive adhesive layer) is not substantially contained. If non-reactive components remain in the pressure-sensitive adhesive layer, these components may be transferred to the adherend and cause whitening contamination. “Substantially free” means that it is not actively added unless it is inevitably mixed. Specifically, the pressure-sensitive adhesive composition (nonvolatile content) of these non-reactive components is used. ) Is preferably less than 1% by weight, more preferably less than 0.1% by weight, still more preferably less than 0.005% by weight.
- non-reactive component examples include a component that bleeds to the surface of the pressure-sensitive adhesive layer such as a phosphoric ester compound used in JP-A-2006-45412 and imparts releasability.
- Non-reactive emulsifiers such as sodium lauryl sulfate and ammonium lauryl sulfate are also included.
- the pressure-sensitive adhesive composition of the present invention may contain various additives other than those described above as long as they do not affect the contamination property.
- the various additives include pigments, fillers, leveling agents, dispersants, plasticizers, stabilizers, antioxidants, UV absorbers, UV stabilizers, antifoaming agents, anti-aging agents, and antiseptics. It is done.
- the pressure-sensitive adhesive composition of the present invention can be prepared by blending the acrylic emulsion polymer, a water-insoluble crosslinking agent, and an ionic compound. You may mix other various additives as needed.
- the mixing method may be a known and common emulsion mixing method, and is not particularly limited. For example, stirring using a stirrer is preferable.
- the stirring conditions are not particularly limited, but for example, the temperature is preferably 10 to 50 ° C, more preferably 20 to 35 ° C.
- the stirring time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
- the stirring speed is preferably 10 to 3000 rpm, more preferably 30 to 1000 rpm.
- the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) of the present invention is formed from the removable water-dispersed acrylic pressure-sensitive adhesive composition.
- the formation method of an adhesive layer is not specifically limited, The formation method of a well-known and usual adhesive layer can be used.
- the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition on a substrate or a release film (release liner) and then drying. In the case where the pressure-sensitive adhesive layer is formed on a release (release) film, the pressure-sensitive adhesive layer is bonded to a substrate and transferred.
- the solvent-insoluble content (gel fraction) of the pressure-sensitive adhesive layer (after crosslinking) in the pressure-sensitive adhesive sheet of the present invention is preferably 90% (% by weight) or more, more preferably 95% by weight or more.
- crosslinking) can be measured by the method similar to the measuring method of the solvent insoluble matter of the above-mentioned acrylic emulsion type polymer. Specifically, it can be measured by a method in which “acrylic emulsion polymer” is read as “pressure-sensitive adhesive layer (after crosslinking)” in the above-mentioned “method for measuring solvent insolubles”.
- the drying temperature is usually about 80 to 170 ° C., preferably 80 to 160 ° C., and the drying time is about 0.5 to 30 minutes, preferably 1 to 10 minutes. Further, the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) is produced by curing (aging) at room temperature to about 50 ° C. for 1 day to 1 week.
- Various methods are used for the application step of the pressure-sensitive adhesive composition. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the coating amount is controlled so that the formed pressure-sensitive adhesive layer has a predetermined thickness (thickness after drying).
- the thickness of the pressure-sensitive adhesive layer is usually about 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m.
- the constituent material of the release film examples include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
- porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- a plastic film is preferably used from the viewpoint of excellent surface smoothness.
- the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
- examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the release film is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- release film if necessary, mold release and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type, kneading type, vapor deposition
- An antistatic treatment such as a mold can also be performed.
- release (release) treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment
- the releasability from the pressure-sensitive adhesive layer can be further enhanced.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use.
- the said peeling film can be used as a separator of an adhesive optical film as it is, and can simplify in a process surface.
- a pressure-sensitive adhesive sheet By providing the above-mentioned pressure-sensitive adhesive layer (pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) on at least one surface of a base material (also referred to as “support” or “supporting base material”), a pressure-sensitive adhesive sheet ( An adhesive sheet with a substrate; an adhesive sheet having the adhesive layer on at least one side of the substrate can be obtained.
- the pressure-sensitive adhesive layer itself can be used as a substrate-less pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet with the substrate may be referred to as “the pressure-sensitive adhesive sheet of the present invention”.
- the pressure-sensitive adhesive sheet of the present invention (the pressure-sensitive adhesive sheet with the base material) is prepared by, for example, applying the pressure-sensitive adhesive composition of the present invention to the surface on at least one side of the base material and drying it as necessary. It is obtained by forming an adhesive layer on at least one side (direct copying method). Crosslinking is performed by dehydrating in the drying step, heating the pressure-sensitive adhesive sheet after drying, or the like. Moreover, after providing an adhesive layer once on a peeling film, an adhesive sheet can also be obtained by transferring an adhesive layer on a base material (transfer method).
- the pressure-sensitive adhesive layer is preferably provided by a so-called direct copying method in which the pressure-sensitive adhesive composition is directly applied to the substrate surface.
- the base material of the pressure-sensitive adhesive sheet of the present invention is preferably a plastic base material (for example, a plastic film or a plastic sheet) from the viewpoint of obtaining a highly transparent pressure-sensitive adhesive sheet.
- a plastic base material for example, Polyolefin (polyolefin resin), such as a polypropylene and polyethylene, Polyester (polyester resin), such as a polyethylene terephthalate (PET), A polycarbonate, polyamide, a polyimide, an acryl, a polystyrene Transparent resins such as acetate, polyethersulfone, and triacetyl cellulose are used. These resins may be used alone or in combination of two or more.
- the base material is preferably a polyester film or a polyolefin film, and more preferably a PET film, a polypropylene film or a polyethylene film.
- the polypropylene is not particularly limited, and examples thereof include homotypes that are homopolymers, random types that are ⁇ -olefin random copolymers, and block types that are ⁇ -olefin block copolymers.
- polyethylene include low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (L-LDPE). These may be used singly or in combination of two or more.
- the thickness of the substrate is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 30 to 100 ⁇ m.
- the surface of the substrate on the side where the pressure-sensitive adhesive layer is provided may be subjected to acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, etc. for the purpose of improving the adhesion with the pressure-sensitive adhesive layer. It is preferable that an easy adhesion treatment is performed. Moreover, you may provide an intermediate
- the pressure-sensitive adhesive sheet of the present invention can be a wound body, and can be wound into a roll while the pressure-sensitive adhesive layer is protected with a release film (separator).
- the back side of the adhesive sheet (the side opposite to the side where the adhesive layer is provided) is released from silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc. Treatment and / or antifouling treatment may be performed, and a back treatment layer (such as a release treatment layer or an antifouling treatment layer) may be provided.
- the pressure-sensitive adhesive sheet of the present invention the form of pressure-sensitive adhesive layer / base material / back treatment layer is particularly preferable.
- the pressure-sensitive adhesive sheet of the present invention is more preferably subjected to antistatic treatment.
- a general antistatic treatment method can be used and is not particularly limited. For example, a method of providing an antistatic layer on the back surface of the substrate (the surface opposite to the adhesive layer). Alternatively, a method of kneading a kneading type antistatic agent into the substrate can be used.
- an antistatic agent or an antistatic resin containing an antistatic agent and a resin component As a method of providing an antistatic layer, an antistatic agent or an antistatic resin containing an antistatic agent and a resin component, a method of applying a conductive resin composition or a conductive polymer containing a conductive substance and a resin component And a method of depositing or plating a conductive substance.
- the antistatic agent examples include cationic antistatic agents having a cationic functional group such as a quaternary ammonium salt and a pyridinium salt (for example, a primary amino group, a secondary amino group, and a tertiary amino group); Anionic antistatic agents having anionic functional groups such as salts, sulfates, phosphonates, phosphates; zwitterionic antistatics such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanine and their derivatives Agents; nonionic antistatic agents such as amino alcohol and derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof; and further, the cationic antistatic agent, anionic antistatic agent, and zwitterionic antistatic agent Obtained by polymerizing or copolymerizing monomers having ion conductive groups Ionic conductive polymers that can be cited.
- a cationic functional group such as a quaternary ammonium
- the cationic antistatic agent includes a quaternary ammonium group such as alkyltrimethylammonium salt, acyloylamidopropyltrimethylammonium methosulfate, alkylbenzylmethylammonium salt, acylcholine chloride, and polydimethylaminoethyl methacrylate.
- a quaternary ammonium group such as alkyltrimethylammonium salt, acyloylamidopropyltrimethylammonium methosulfate, alkylbenzylmethylammonium salt, acylcholine chloride, and polydimethylaminoethyl methacrylate.
- examples thereof include (meth) acrylate copolymers having, styrene copolymers having quaternary ammonium groups such as polyvinylbenzyltrimethylammonium chloride, and diallylamine copolymers having quaternary ammonium groups such as polydiallyldi
- anionic antistatic agent examples include alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, alkyl phosphate ester salt, and sulfonic acid group-containing styrene copolymer.
- zwitterionic antistatic agent examples include alkyl betaines, alkyl imidazolium betaines, carbobetaine graft copolymers, and the like.
- Nonionic antistatic agents include fatty acid alkylolamide, di- (2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid Examples thereof include esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycols, polyoxyethylene diamines, copolymers composed of polyethers, polyesters and polyamides, and methoxypolyethylene glycol (meth) acrylates.
- Examples of the conductive polymer include polyaniline, polypyrrole, and polythiophene.
- Examples of the conductive material include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, iodine. Examples thereof include copper chloride and alloys or mixtures thereof.
- the resin component general-purpose resins such as polyester, acrylic, polyvinyl, urethane, melamine, and epoxy are used.
- the antistatic agent is a polymer antistatic agent
- the antistatic resin may not contain the resin component.
- the antistatic resin may contain a methylolated or alkylolized melamine-based, urea-based, glyoxal-based, acrylamide-based compound, epoxy-based compound, or isocyanate-based compound as a crosslinking agent.
- the antistatic resin, conductive polymer, and conductive resin composition are diluted with a solvent or dispersion medium such as an organic solvent or water, and this coating liquid is used as a base material.
- a solvent or dispersion medium such as an organic solvent or water
- coating and drying is mentioned.
- the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, and isopropanol. These can be used alone or in combination.
- known coating methods are used, and specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, impregnation and curtain coating methods.
- the thickness of the antistatic layer (antistatic resin layer, conductive polymer layer, conductive resin composition layer) formed by the application is preferably 0.001 to 5 ⁇ m, more preferably 0.005 to 1 ⁇ m. is there.
- Examples of the method for depositing or plating the conductive material include vacuum deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, chemical plating, and electroplating.
- the thickness of the antistatic layer (conductive material layer) formed by vapor deposition or plating is preferably 20 to 10,000 mm (0.002 to 1 ⁇ m), more preferably 50 to 5000 mm (0.005 to 0.5 ⁇ m). is there.
- the antistatic agent is appropriately used.
- the amount of the kneading-type antistatic agent is preferably 20% by weight or less, more preferably 0.05 to 10% by weight, based on the total weight (100% by weight) of the substrate.
- the kneading method is not particularly limited as long as the kneading-type antistatic agent is a method that can be uniformly mixed with, for example, a resin used for a plastic substrate. Generally, a heating roll, a Banbury mixer, a pressure kneader is used. And a method using a twin-screw kneader.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling of the present invention is excellent in antistatic property, adhesiveness, and re-peelability (easy releasability), and can form a re-peelable pressure-sensitive adhesive layer. It is a composition and is used for forming a pressure-sensitive adhesive layer used for re-peeling (for re-peeling). That is, the adhesive sheet having the adhesive layer is re-peeled [for example, masking tape for building curing, masking tape for automobile coating, masking tape for electronic parts (lead frame, printed circuit board, etc.), masking tape for sandblast, etc.
- Masking tape surface protection film for aluminum sash, surface protection film for optical plastic, surface protection film for optical glass, surface protection film for automobile protection, surface protection film for metal plate, back grind tape, Pelicle fixing tape, dicing tape, lead frame fixing tape, cleaning tape, dust removal tape, carrier tape, cover tape, and other semiconductor / electronic component manufacturing process adhesive tape, electronic equipment and electronic component packaging tape In transit Sealing tapes, bundling tapes, preferably used in the label such], and the like.
- the pressure-sensitive adhesive layer formed from the water-dispersed acrylic pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive sheet of the present invention do not cause contamination such as whitening contamination on the adherend when used on the adherend. Excellent in low pollution.
- the pressure-sensitive adhesive sheet of the present invention requires a particularly excellent low contamination property, such as a polarizing plate, a phase difference plate, and an antireflection plate constituting a panel such as a liquid crystal display, organic electroluminescence (organic EL), and field emission display.
- It is preferably used as a surface protection application (surface protection film for optical members, etc.) of optical members (optical plastic, optical glass, optical film, etc.) such as plates, wave plates, optical compensation films, and brightness enhancement films.
- the application is not limited to this.
- Surface protection and damage prevention in the manufacture of microfabricated parts such as semiconductors, circuits, various printed boards, various masks, and lead frames, or removal of foreign substances, masking, etc. Can also be used.
- Example 1-1> (Preparation of acrylic emulsion polymer)
- 2EHA 2-ethylhexyl acrylate
- AA acrylic acid
- AQUALON HS-1025 a reactive nonionic anionic emulsifier
- Cross-linking agent [Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD-C”, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, epoxy equivalent: 110, number of functional groups: 4] 2.0 weight 1 part by weight of an ionic liquid having a cation of pyridinium type [manufactured by Nippon Carlit Co., Ltd., trade name “CIL-313”, N-butyl-3-methylpyridinium trifluoromethanesulfonate, active ingredient 100% by weight] The mixture was stirred and mixed under stirring conditions of 23 ° C., 300 rpm, and 10 minutes to prepare a water-dispersed acrylic pressure-sensitive adhesive composition for re-peeling.
- the re-peeling water-dispersed acrylic pressure-sensitive adhesive composition is applied to an applicator manufactured by Tester Sangyo Co., Ltd. on a corona-treated surface of a PET film (trade name “E7415”, manufactured by Toyobo Co., Ltd., thickness: 38 ⁇ m). And then dried so as to have a thickness of 15 ⁇ m after drying, followed by drying in a hot air circulating oven at 120 ° C. for 2 minutes, and then aging at room temperature for 1 week. A pressure-sensitive adhesive sheet was obtained.
- Examples 1-2 to 1-11 Comparative Examples 1-1 to 1-6>
- a redispersible water-dispersed acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1-1 by changing the types and blending amounts of the crosslinking agent and the ionic liquid.
- the additive which is not described in a table
- a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1-1 using the water-dispersible acrylic pressure-sensitive adhesive composition for repeeling.
- it is preferable that it is 1.3 kV or less as peeling voltage (absolute value) of the adhesive sheet of this invention, More preferably, it is 1.0 kV or less.
- peeling voltage absolute value
- the stripping voltage exceeds 1.3 kV, dust is easily adsorbed when the adhesive sheet is stripped, which is not preferable.
- peeling force adheresive strength when peeled at a peeling speed of 10 m / min and peeling angle of 180 ° with a universal tensile testing machine (N / 25 mm) ) And measured as “initial peel force”. The measurement was performed in an environment of 23 ° C. ⁇ 50% RH.
- the initial peel force of the pressure-sensitive adhesive sheet of the present invention is preferably 0.1 to 1.3 N / 25 mm, more preferably 0.2 to 1.2 N / 25 mm. It is preferable to set the peeling force to 1.3 N / 25 mm or less because the adhesive sheet can be easily peeled off in the manufacturing process of the polarizing plate and the liquid crystal display device, and the productivity and handleability are improved. Moreover, it is preferable by setting it as 0.1 N / 25mm or more because the float and peeling of an adhesive sheet are suppressed at a manufacturing process, and the protective function as an adhesive sheet for surface protection can fully be exhibited.
- the peel force (adhesive force) increase prevention property is excellent. Can be judged.
- the difference between the peel strength with time and the initial peel force [(peel peel strength) ⁇ (initial peel force)] of the pressure-sensitive adhesive sheet of the present invention is preferably less than 0.5 N / 25 mm, more preferably 0.0 to 0. .2 N / 25 mm. When the difference is 0.5 N / 25 mm or more, the peel strength (adhesive strength) increase prevention property is inferior, and the removability of the pressure sensitive adhesive sheet may deteriorate.
- the polarizing plate to which the pressure-sensitive adhesive sheet was bonded was allowed to stand at 80 ° C. for 4 hours with the pressure-sensitive adhesive sheet being bonded, and then the pressure-sensitive adhesive sheet was peeled off. Thereafter, the polarizing plate from which the pressure-sensitive adhesive sheet was peeled was allowed to stand for 12 hours in a humidified environment (23 ° C., 90% RH), and the surface of the polarizing plate was visually observed, and low contamination was evaluated according to the following criteria.
- a humidified environment 23 ° C., 90% RH
- Example 2-1> Preparation of acrylic emulsion polymer
- 2EHA 2-ethylhexyl acrylate
- AA acrylic acid
- AQUALON HS-1025 a reactive nonionic anionic emulsifier
- an epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd., trade name, which is a water-insoluble crosslinking agent, per 100 parts by weight of the acrylic emulsion polymer (solid content) “TETRAD-C”, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, epoxy equivalent: 110, functional group number: 4] 2.0 parts by weight, lithium trifluoromethanesulfonate [50% by weight aqueous solution] 2 parts by weight was stirred and mixed using a stirrer under stirring conditions of 23 ° C., 300 rpm, and 10 minutes to prepare a water-dispersed acrylic pressure-sensitive adhesive composition for re-peeling.
- the water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling is applied to a corona-treated surface of a PET film (manufactured by Toyobo Co., Ltd., trade name “E7415”, thickness: 38 ⁇ m) by Tester Sangyo Co., Ltd. Using an applicator, apply (coating) so that the thickness after drying is 15 ⁇ m, then dry in a hot air circulating oven at 120 ° C. for 2 minutes, and then age at room temperature for 1 week (aging). Thus, an adhesive sheet was obtained.
- Examples 2-2 to 2-5 Comparative Examples 2-1 to 2-6>
- a monomer emulsion was prepared in the same manner as in Example 2-1, except that the type and amount of the raw material monomer were changed.
- the additive which is not described in a table
- a water-dispersed acrylic pressure-sensitive adhesive composition for re-peeling and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 2-1.
- it is preferable that it is 1.3 kV or less as peeling voltage (absolute value) of the adhesive sheet of this invention, More preferably, it is 1.0 kV or less.
- peeling voltage absolute value
- the stripping voltage exceeds 1.3 kV, dust is easily adsorbed when the adhesive sheet is stripped, which is not preferable.
- peeling force adheresive strength
- peeling angle 180 ° with a universal tensile tester (N / 25 mm)
- the measurement was performed in an environment of 23 ° C. ⁇ 50% RH.
- the initial peel force of the pressure-sensitive adhesive sheet of the present invention is preferably 0.1 to 1.3 N / 25 mm, more preferably 0.2 to 1.2 N / 25 mm. It is preferable to set the peeling force to 1.4 N / 25 mm or less because the pressure-sensitive adhesive sheet can be easily peeled in the manufacturing process of the polarizing plate and the liquid crystal display device, and the productivity and handling properties are improved. Moreover, it is preferable by setting it as 0.1 N / 25mm or more because the float and peeling of an adhesive sheet are suppressed at a manufacturing process, and the protective function as an adhesive sheet for surface protection can fully be exhibited.
- the peel force (adhesive force) increase prevention property is excellent. Can be judged.
- the difference between the peel strength with time and the initial peel force [(peel peel strength) ⁇ (initial peel force)] of the pressure-sensitive adhesive sheet of the present invention is preferably less than 0.5 N / 25 mm, more preferably 0.0 to 0. .2 N / 25 mm. When the difference is 0.5 N / 25 mm or more, the peel strength (adhesive strength) increase prevention property is inferior, and the removability of the pressure sensitive adhesive sheet may deteriorate.
- the polarizing plate to which the pressure-sensitive adhesive sheet was bonded was allowed to stand at 80 ° C. for 4 hours with the pressure-sensitive adhesive sheet being bonded, and then the pressure-sensitive adhesive sheet was peeled off. Thereafter, the polarizing plate from which the pressure-sensitive adhesive sheet was peeled was allowed to stand for 12 hours in a humidified environment (23 ° C., 90% RH), and the surface of the polarizing plate was visually observed, and low contamination was evaluated according to the following criteria.
- a humidified environment 23 ° C., 90% RH
- TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD-C” (1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, epoxy equivalent: 110, functional group number: 4) (insoluble) Crosslinker)
- TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD-X” (1,3-bis (N, N-diglycidylaminomethyl) benzene, epoxy equivalent: 100, functional group number: 4)
- EX-512 manufactured by Nagase ChemteX Corporation, trade name “Denacol EX-512” (Polyglycerol Polyglycidyl Ether, epoxy equivalent: 168, number of functional groups: about 4)
- LiCF 3 SO 3 lithium trifluoromethanesulfonate (50 wt% aqueous solution), fluorine-containing alkali metal salt (antistatic agent
- Comparative Example 2-1 since an alkali metal salt as an antistatic agent was not blended, it was confirmed that the stripping voltage was very high and antistatic properties could not be obtained.
- Comparative Example 2-2 an antistatic agent was not blended, a water-insoluble crosslinking agent was not blended, and a water-soluble crosslinking agent was blended instead. As a result, the contamination was inferior.
- Comparative Example 2-3 since no antistatic agent was blended, not only the antistatic property was poor, but also the appearance of the pressure-sensitive adhesive layer was poor, and the peeling force itself could not be measured.
- Comparative Example 2-4 since an antistatic agent that is not an alkali metal salt was used, the antistatic property was not obtained, and the contamination was inferior.
- Comparative Example 2-5 since the blending ratio of the (meth) acrylic acid alkyl ester was high and the blending ratio of the acrylic acid which is a carboxyl group-containing unsaturated monomer was low, the initial peel force was high, and the peel strength with time was also high. It became very high, resulting in poor peel strength (adhesive strength) prevention and poor contamination. Moreover, although the antistatic agent was contained, the charging property was also bad. In Comparative Example 2-6, since the blending ratio of acrylic acid, which is a carboxyl group-containing unsaturated monomer, is high, aggregates were produced when adjusting the acrylic emulsion polymer, so that an adhesive sheet could be produced. There wasn't.
Abstract
Description
[式(A)中のRaは、炭素数4から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、RbおよびRcは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。但し、窒素原子が2重結合を含む場合、Rcはない。]
[式(B)中のRdは、炭素数2から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、Re、Rf、およびRgは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。]
[式(C)中のRhは、炭素数2から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、Ri、Rj、およびRkは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。]
[式(D)中のZは、窒素、硫黄、またはリン原子を表し、Rl、Rm、Rn、およびRoは、同一または異なって、炭素数1から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。但しZが硫黄原子の場合、Roはない。]
[式(E)中のRPは、炭素数1から18の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。]
[式(a)中のR1は、水素または炭素数1から3の炭化水素基を表し、R2は、水素または炭素数1から7の炭化水素基を表す。]
[式(b)中のR3は、水素または炭素数1から3の炭化水素基を表し、R4は、水素または炭素数1から7の炭化水素基を表す。]
[式(c)中のR5は、水素または炭素数1から3の炭化水素基を表し、R6は、水素または炭素数1から7の炭化水素基を表す。]
[式(d)中のR7は、水素または炭素数1から3の炭化水素基を表し、R8は、水素または炭素数1から7の炭化水素基を表す。]
前記アクリルエマルション系重合体は、原料モノマーとして、(メタ)アクリル酸アルキルエステル(i)を70~99.5重量%、及びカルボキシル基含有不飽和モノマー(ii)を0.5~10重量%から構成される重合体である。前記アクリルエマルション系重合体は、単独で又は2種以上組み合わせて使用することができる。なお、本発明では、「(メタ)アクリル」とは「アクリル」及び/又は「メタクリル」のことをいう。
前記ラジカル重合性官能基を含む反応性乳化剤(以下、「反応性乳化剤」と称する)は、分子中(1分子中)に少なくとも1つのラジカル重合性官能基を含む乳化剤である。前記反応性乳化剤としては、特に限定されず、ビニル基、プロペニル基、イソプロペニル基、ビニルエーテル基(ビニルオキシ基)、アリルエーテル基(アリルオキシ基)等のラジカル重合性官能基を有する種々の反応性乳化剤から、1種又は2種以上を選択して使用できる。前記反応性乳化剤を用いることにより、乳化剤が重合体中にとりこまれ、乳化剤由来の汚染が低減するため好ましい。
アクリルエマルション系重合体:約0.1gを採取し、平均孔径0.2μmの多孔質テトラフルオロエチレンシート(商品名「NTF1122」、日東電工株式会社製)に包んだ後、凧糸で縛り、その際の重量を測定し、該重量を浸漬前重量とする。なお、該浸漬前重量は、アクリルエマルション系重合体(上記で採取したもの)と、テトラフルオロエチレンシートと、凧糸の総重量である。また、テトラフルオロエチレンシートと凧糸の合計重量も測定しておき、該重量を包袋重量とする。
次に、上記のアクリルエマルション系重合体をテトラフルオロエチレンシートで包み凧糸で縛ったもの(「サンプル」と称する)を、酢酸エチルで満たした50ml容器に入れ、23℃にて7日間静置する。その後、容器からサンプル(酢酸エチル処理後)を取り出して、アルミニウム製カップに移し、130℃で2時間、乾燥機中で乾燥して酢酸エチルを除去した後、重量を測定し、該重量を浸漬後重量とする。そして、下記の式から溶剤不溶分を算出する。
溶剤不溶分(重量%)=(a-b)/(c-b)×100 (1)(式(1)において、aは浸漬後重量であり、bは包袋重量であり、cは浸漬前重量である。)
GPC測定は、東ソー株式会社製GPC装置「HLC-8220GPC」を用いて行い、ポリスチレン換算値にて分子量を求める。測定条件は下記の通りである。
サンプル濃度:0.2重量%(THF溶液)
サンプル注入量:10μl
溶離液:THF
流速:0.6ml/min
測定温度:40℃
カラム:
サンプルカラム;TSKguardcolumn SuperHZ-H 1本+TSKgel SuperHZM-H 2本
リファレンスカラム;TSKgel SuperH-RC 1本検出器:示差屈折計
本発明の非水溶性架橋剤は、非水溶性の化合物であり、分子中(1分子中)にカルボキシル基と反応しうる官能基を2個以上(例えば、2~6個)有する化合物である。1分子中のカルボキシル基と反応しうる官能基の個数は3~5個が好ましい。1分子中のカルボキシル基と反応しうる官能基の個数が多くなるほど、粘着剤組成物が密に架橋する(即ち、粘着剤層を形成するポリマーの架橋構造が密になる)。このため、粘着剤層形成後の粘着剤層のぬれ広がりを防ぐことが可能となる。また、粘着剤層を形成するポリマーが拘束されるため、粘着剤層中の官能基(カルボキシル基)が被着体面に偏析して、粘着剤層と被着体との剥離力(粘着力)が経時で上昇することを防ぐことが可能となる。一方、1分子中のカルボキシル基と反応しうる官能基の個数が6個を超えて多すぎる場合には、ゲル化物が生じる場合がある。
同重量の水(25℃)と架橋剤を、攪拌機を用いて回転数300rpm、10分の条件で混合し、遠心分離により水相と油相に分ける。次いで、水相を採取し120℃で1時間乾燥して、乾燥減量から水相中の不揮発分(水100重量部に対する不揮発成分の重量部)を求める。
力)上昇を効果的に防止できるため好ましい。また、1.3以下とすることにより、粘着剤層中の未反応の非水溶性架橋剤を低減し、非水溶性架橋剤による外観不良を抑制して、外観特性を向上させることができるため好ましい。
非水溶性架橋剤の有するカルボキシル基と反応しうる官能基のモル数=[非水溶性架橋剤の配合量(配合量)]/[官能基当量]=4/110
例えば、非水溶性架橋剤として、エポキシ当量が110(g/eq)のエポキシ系架橋剤を4g添加(配合)する場合、エポキシ系架橋剤の有するエポキシ基のモル数は、例えば、以下のように算出できる。
エポキシ系架橋剤の有するエポキシ基のモル数=[エポキシ系架橋剤の配合量(配合量)]/[エポキシ当量]=4/110
本発明におけるイオン液体とは、25℃で液状を呈する溶融塩(イオン性化合物)をいい、特に限定されないが、優れた帯電防止能が得られる理由から、下記式(A)~(E)で表される有機カチオン成分と、アニオン成分からなるものが好ましく用いられる。
-メトキシエチル)アンモニウムトリフルオロメタンスルホネート、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-Nメチル-N-(2-メトキシエチル)アンモニウムビス(ペンタフルオロエタンスルホニル)イミド、グリシジルトリメチルアンモニウムトリフルオロメタンスルホネート、グリシジルトリメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、グリシジルトリメチルアンモニウムビス(ペンタフルオロエタンスルホニル)イミド、テトラオクチルホスホニウムトリフルオロメタンスルホネート、テトラオクチルホスホニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ノニルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ペンチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリメチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-エチルアンモニウムビス(トリフルオロメダンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-ブチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリオクチルメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N-メチル-N-エチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、1-ブチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-ブチル-3-メチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-エチル-3-メチルイミダゾリウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、N-エチル-N-メチルモルフォリニウムチオシアネート、4-エチル-4-メチルモルフォリニウムメチルカーボネートなどがあげられる。
本発明のアルカリ金属塩としては、特に制限されないが、例えば、リチウム、ナトリウム、カリウムからなる金属塩があげられ、具体的には、たとえば、Li+、Na+、K+よりなるカチオンと、Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-、C4F9SO3 -、CH3COO-、C3F7COO-、(CF3SO2)(CF3CO)N-、(FSO2)2N-、(C4F9SO2)2N-、(CH3O)2PO2 -、(C2H5O)2PO2 -、(CN)2N-、CH3OSO3 -、C2H5OSO3 -、n-C8H17OSO3 -よりなるアニオンから構成される金属塩が好適に用いられる。なかでも特に、塩を構成するアニオンとして、フッ素を含有するものを用いることが好ましい。また、LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3Cなどのリチウム塩を用いることも、好ましい態様である。リチウム塩は、アルカリ金属塩の中でも、特に高い解離性を示すため、帯電防止性に優れた粘着剤層(粘着シート)を得ることができ、特に帯電防止性が要求される光学部材等の表面保護フィルムとして、使用することができる。なお、これらのアルカリ金属塩は、単独で使用してもよく、また2種以上を混合して使用してもよい。
本発明の再剥離用水分散型アクリル系粘着剤組成物は、上述の通り、本発明のアクリルエマルション系重合体、非水溶性架橋剤、及び、イオン性化合物を必須の成分として含有する。さらに、必要に応じて、その他の各種添加剤を含有してよい。
本発明の粘着剤層(粘着シート)は、前記再剥離性水分散型アクリル系粘着剤組成物により形成される。粘着剤層の形成方法は特に限定されず、公知慣用の粘着剤層の形成方法を用いることができる。粘着剤層の形成は、基材又は剥離フィルム(剥離ライナー)上に、前記粘着剤組成物を塗布した後、乾燥することより形成することができる。なお、粘着剤層を剥離(離型)フィルムに形成した場合には、前記粘着剤層を、基材に貼り合せて転写する。
(アクリルエマルション系重合体の調製)
容器に、水90重量部、及び、表1に示すように、アクリル酸2-エチルヘキシル(2EHA)96重量部、アクリル酸(AA)4重量部、反応性ノニオンアニオン系乳化剤(第一工業製薬(株)製、商品名「アクアロンHS-1025」)3重量部を配合した後、ホモミキサーにより攪拌混合し、モノマーエマルションを調製した。
前記アクリルエマルション系重合体の水分散液に、アクリルエマルション系重合体(固形分)100重量部(前記水分散液238重量部、42重量%)に対して、非水溶性架橋剤であるエポキシ系架橋剤[三菱ガス化学(株)製、商品名「TETRAD-C」、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4]2.0重量部、カチオンがピリジニウム型のイオン液体[日本カーリット(株)製、商品名「CIL-313」、N-ブチル-3-メチルピリジニウムトリフルオロメタンスルホネート、有効成分100重量%]1重量部を、攪拌機を用いて、23℃、300rpm、10分の攪拌条件で攪拌混合し、再剥離用水分散型アクリル系粘着剤組成物を調製した。
さらに、前記再剥離用水分散型アクリル系粘着剤組成物を、PETフィルム(東洋紡(株)製、商品名「E7415」、厚さ:38μm)のコロナ処理面上に、テスター産業(株)製アプリケーターを用いて、乾燥後の厚さが15μmとなるように塗布(コーティング)し、その後、熱風循環式オーブンで、120℃で2分間乾燥させ、さらにその後、室温で1週間養生(エージング)して、粘着シートを得た。
表1及び2に示すように、架橋剤およびイオン液体等の種類、配合量等を変更し、実施例1-1と同様にして再剥離用水分散型アクリル系粘着剤組成物を調製した。なお、表中に記載のない添加剤については、実施例1-1と同様の配合量で調製した。また、前記再剥離用水分散型アクリル系粘着剤組成物を用い、実施例1-1と同様にして、粘着シートを得た。
実施例および比較例で得られた水分散型アクリル系粘着剤組成物および粘着シートについて、下記の測定方法又は評価方法により評価を行った。なお、評価結果については、表1に示した。
作製した粘着シートを幅70mm、長さ130mmのサイズにカットし、セパレータを剥離した後、あらかじめ除電しておいたアクリル板(三菱レイヨン社製、アクリライト、厚み:1mm、幅:70mm、長さ:100mm)に貼り合わせた偏光板(日東電工(株)製、商品名「SEG1425DU」表面に、片方の端部が30mmはみ出すようにハンドローラーにて圧着した。続いて、23℃×24±2%RHの環境下に一日放置した後、図1に示すように所定の位置にサンプルをセットする。30mmはみ出した片方の端部を自動巻取り機に固定し、剥離角度150°、剥離速度10m/minとなるように剥離した。このときに発生する偏光板表面の電位を所定の位置に固定してある電位測定機(春日電機社製、KSD-0103)にて測定した。サンプルと電位測定機との距離はアクリル板表面測定時100mmとした。なお、測定は23℃×24±2%RHの環境下で行った。
作製した粘着シートを幅25mm、長さ100mmのサイズにカットし、セパレータを剥離した後、貼り合わせ機(テスター産業(株)製、小型貼り合わせ機)を用いて、偏光板(日東電工社製、SEG1425DU、幅:70mm、長さ:100mm)に0.25MPa、0.3m/minの条件でラミネートし、評価サンプルを作製した。
ラミネート後、23℃×50%RHの環境下に30分間放置した後、万能引張試験機にて剥離速度10m/min、剥離角度180°で剥離したときの剥離力(粘着力)(N/25mm)を測定し、「初期剥離力」とした。測定は23℃×50%RHの環境下で行った。
また、前記の粘着シートと、偏光板との貼り合わせサンプルを、40℃の環境下に、1週間保存した後、23℃50%RHの環境下に2時間放置した後、剥離速度10m/minにて180°剥離試験を行い、粘着シートの偏光板に対する剥離力(粘着力)(N/25mm)を測定し、「経時剥離力」とした。
実施例および比較例で得られた粘着シート(サンプルサイズ:25mm幅×100mm長さ)を、貼り合わせ機(テスター産業(株)製、小型貼り合せ機)を用いて、0.25MPa、0.3m/minの条件で、偏光板(日東電工(株)製、商品名「SEG1425DU」、サイズ:70mm幅×120mm長さ)上に貼り合わせた。
低汚染性良好(○):粘着シートを貼付した部分と貼付していない部分で変化が見られなかった。
低汚染性不良(×):粘着シートを貼付した部分に白化が見られた。
2EHA:アクリル酸2-エチルヘキシル
AA:アクリル酸
HS-1025:第一工業製薬(株)製、商品名「アクアロンHS-1025」(反応性ノニオンアニオン系乳化剤)
T/C:三菱ガス化学(株)製、商品名「TETRAD-C」(1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4)(非水溶性架橋剤)
EX-512:ナガセケムテックス(株)製、商品名「デナコール EX-512」(Polyglycerol Polyglycidyl Ether、エポキシ当量:168、官能基数:約4)水溶性架橋剤)
CIL-313:日本カーリット(株)製、N-ブチル-3-メチルピリジニウムトリフルオロメタンサルフェート(水溶性)
EtMePy-EF11:三菱マテリアル(株)製、N-エチル-3-メチルピリジニウムトリフルオロメタンスルホネート(水溶性)
EtMePy-EF31:三菱マテリアル(株)製、N-エチル-3-メチルピリジニウムパーフルオロプロパンスルホネート(水溶性)
EtMePy-EF41:三菱マテリアル(株)製、N-エチル-3-メチルピリジニウムパーフルオロブタンスルホネート(水溶性)
IL-110:第一工業製薬(株)製、1-エチル-3-メチルイミダゾリウムビス(フルオロスルホニル)イミド(非水溶性)
IL-120:第一工業製薬(株)製、1-メチル-1-プロピルピロリジニウムビス(フルオロスルホニル)イミド(非水溶性)
IL-130:第一工業製薬(株)製、1-メチル-1-プロピルピペリジニウムビス(フルオロスルホニル)イミド(非水溶性)
IL-210:第一工業製薬(株)製、1-エチル-3-メチルイミダゾリウムビス(トリフルオロメチルスルホニル)イミド(非水溶性)
IL-230:第一工業製薬(株)製、1-メチル-1-プロピルピペリジニウムビス(トリフルオロメチルスルホニル)イミド(非水溶性)
(アクリルエマルション系重合体の調製)
容器に、水90重量部、及び、表3に示すように、アクリル酸2-エチルヘキシル(2EHA)96重量部、アクリル酸(AA)4重量部、反応性ノニオンアニオン系乳化剤(第一工業製薬(株)製、商品名「アクアロンHS-1025」)3重量部を配合した後、ホモミキサーにより攪拌混合し、モノマーエマルションを調製した。
前記アクリルエマルション系重合体の水分散液に、アクリルエマルション系重合体(固形分)100重量部に対して、非水溶性架橋剤であるエポキシ系架橋剤[三菱ガス化学(株)製、商品名「TETRAD-C」、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4]2.0重量部、トリフルオロメタンスルホン酸リチウム[50重量%水溶液]2重量部を、攪拌機を用いて、23℃、300rpm、10分の攪拌条件で攪拌混合し、再剥離用水分散型アクリル系粘着剤組成物を調製した。
さらに、前記再剥離用水分散型アクリル系粘着剤組成物を、PETフィルム(東洋紡績(株)製、商品名「E7415」、厚さ:38μm)のコロナ処理面上に、テスター産業(株)製アプリケーターを用いて、乾燥後の厚さが15μmとなるように塗布(コーティング)し、その後、熱風循環式オーブンで、120℃で2分間乾燥させ、さらにその後、室温で1週間養生(エージング)して、粘着シートを得た。
表3に示すように、原料モノマーの種類、配合量等を変更し、実施例2-1と同様にして、モノマーエマルションを調製した。なお、表中に記載のない添加剤については、実施例2-1と同様の配合量で調製した。また、前記モノマーエマルションを用い、実施例2-1と同様にして、再剥離用水分散型アクリル系粘着剤組成物および粘着シートを得た。
実施例および比較例で得られた水分散型アクリル系粘着剤組成物および粘着シートについて、下記の測定方法又は評価方法により評価を行った。なお、評価結果については、表3に示した。
作製した粘着シートを幅70mm、長さ130mmのサイズにカットし、セパレータを剥離した後、あらかじめ除電しておいたアクリル板(三菱レイヨン社製、アクリライト、厚み:1mm、幅:70mm、長さ:100mm)に貼り合わせた偏光板(日東電工(株)製、商品名「SEG1425DU」表面に、片方の端部が30mmはみ出すようにハンドローラーにて圧着した。続いて、23℃×24±2%RHの環境下に一日放置した後、図1に示すように所定の位置にサンプルをセットする。30mmはみ出した片方の端部を自動巻取り機に固定し、剥離角度150°、剥離速度10m/minとなるように剥離した。このときに発生する偏光板表面の電位を所定の位置に固定してある電位測定機(春日電機社製、KSD-0103)にて測定した。サンプルと電位測定機との距離はアクリル板表面測定時100mmとした。なお、測定は23℃×24±2%RHの環境下で行った。
作製した粘着シートを幅25mm、長さ100mmのサイズにカットし、セパレータを剥離した後、貼り合わせ機(テスター産業(株)製、小型貼り合わせ機)を用いて、偏光板(日東電工社製、SEG1425DU、幅:70mm、長さ:100mm)に0.25MPa、0.3m/minの条件でラミネートし、評価サンプルを作製した。
ラミネート後、23℃×50%RHの環境下に30分間放置した後、万能引張試験機にて剥離速度30m/min、剥離角度180°で剥離したときの剥離力(粘着力)(N/25mm)を測定し、「初期剥離力」とした。測定は23℃×50%RHの環境下で行った。
また、前記の粘着シートと、偏光板との貼り合わせサンプルを、40℃の環境下に、1週間保存した後、23℃50%RHの環境下に2時間放置した後、剥離速度30m/minにて180°剥離試験を行い、粘着シートの偏光板に対する剥離力(粘着力)(N/25mm)を測定し、「経時剥離力」とした。
実施例および比較例で得られた粘着シート(サンプルサイズ:25mm幅×100mm長さ)を、貼り合わせ機(テスター産業(株)製、小型貼り合せ機)を用いて、0.25MPa、0.3m/minの条件で、偏光板(日東電工(株)製、商品名「SEG1425DU」、サイズ:70mm幅×120mm長さ)上に貼り合わせた。
低汚染性良好(○):粘着シートを貼付した部分と貼付していない部分で変化が見られなかった。
低汚染性不良(×):粘着シートを貼付した部分に白化が見られた。
2EHA:アクリル酸2-エチルヘキシル
MMA:メタクリル酸メチル
AA:アクリル酸
HS-1025:第一工業製薬(株)製、商品名「アクアロンHS-1025」(反応性ノニオンアニオン系乳化剤)
TETRAD-C:三菱ガス化学(株)製、商品名「TETRAD-C」(1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4)(非水溶性架橋剤)
TETRAD-X:三菱ガス化学(株)製、商品名「TETRAD-X」(1,3-ビス(N,N-ジグリシジルアミノメチル)ベンゼン、エポキシ当量:100、官能基数:4)(非水溶性架橋剤)
EX-512:ナガセケムテックス(株)製、商品名「デナコール EX-512」(Polyglycerol Polyglycidyl Ether、エポキシ当量:168、官能基数:約4)(水溶性架橋剤)
LiCF3SO3:トリフルオロメタンスルホン酸リチウム(50重量%水溶液)、フッ素含有のアルカリ金属塩(帯電防止剤)
SF-106:ADEKA製、商品名「アデカミンSF-106」(ジメチルジアルキルオキシエチレンアンモニウムクロライド、固形分80重量%、非アルカリ金属塩)(帯電防止剤)
2 粘着シート
3 偏光板
4 アクリル板
5 サンプル固定台
Claims (14)
- 原料モノマーとして、 (メタ)アクリル酸アルキルエステル(i)70~99.5重量%、及び、カルボキシル基含有不飽和モノマー(ii)0.5~10重量%から構成されるアクリルエマルション系重合体、非水溶性架橋剤、及び、イオン性化合物を含有することを特徴とする再剥離用水分散型アクリル系粘着剤組成物。
- 前記イオン性化合物が、イオン液体、及び/又は、アルカリ金属塩であることを特徴とする請求項1に記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記イオン液体が、下記式(A)~(E)で表わされるカチオンからなる群より選択される少なくとも1種のカチオンを含有することを特徴とする請求項2に記載の再剥離用水分散型アクリル系粘着剤組成物。
[式(A)中のRaは、炭素数4から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、RbおよびRcは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。但し、窒素原子が2重結合を含む場合、Rcはない。]
[式(B)中のRdは、炭素数2から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、Re、Rf、およびRgは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。]
[式(C)中のRhは、炭素数2から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよく、Ri、Rj、およびRkは、同一または異なって、水素または炭素数1から16の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。]
[式(D)中のZは、窒素、硫黄、またはリン原子を表し、Rl、Rm、Rn、およびRoは、同一または異なって、炭素数1から20の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。但しZが硫黄原子の場合、Roはない。]
[式(E)中のRPは、炭素数1から18の炭化水素基を表し、前記炭化水素基の一部がヘテロ原子で置換された官能基であってもよい。] - 前記イオン液体のカチオンが、含イミダゾリウム塩型、含ピリジニウム塩型、含モルフォリニウム塩型、含ピロリジニウム塩型、含ピペリジニウム塩型、含アンモニウム塩型、含ホスホニウム塩型、及び、含スルホニウム塩型からなる群より選択される少なくとも1種であることを特徴とする請求項2又は3に記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記イオン液体が、下記式(a)~(d)で表わされるカチオンからなる群より選択される少なくとも1種のカチオンを含有することを特徴とする請求項2~4のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物。
[式(a)中のR1は、水素または炭素数1から3の炭化水素基を表し、R2は、水素または炭素数1から7の炭化水素基を表す。]
[式(b)中のR3は、水素または炭素数1から3の炭化水素基を表し、R4は、水素または炭素数1から7の炭化水素基を表す。]
[式(c)中のR5は、水素または炭素数1から3の炭化水素基を表し、R6は、水素または炭素数1から7の炭化水素基を表す。]
[式(d)中のR7は、水素または炭素数1から3の炭化水素基を表し、R8は、水素または炭素数1から7の炭化水素基を表す。] - 前記アクリルエマルション系重合体(固形分)100重量部に対して、前記イオン液体を4.9重量部以下含有することを特徴とする請求項2~5のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記アルカリ金属塩が、フッ素含有アニオンを有することを特徴とする請求項2に記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記アルカリ金属塩が、リチウム塩であることを特徴とする請求項2又は7に記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記アクリルエマルション系重合体の固形分100重量部に対して、前記アルカリ金属塩を3重量部以下含有することを特徴とする請求項2、7、及び8のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記アクリルエマルション系重合体が、分子中にラジカル重合性官能基を含む反応性乳化剤を用いて重合された重合体であることを特徴とする請求項1~9のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物。
- 前記カルボキシル基含有不飽和モノマー(ii)のカルボキシル基1モルに対する、非水溶性架橋剤のカルボキシル基と反応しうる官能基のモル数が、0.2~1.3モルであることを特徴とする請求項1~10のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物。
- 基材の少なくとも片面側に、請求項1~11のいずれかに記載の再剥離用水分散型アクリル系粘着剤組成物から形成された粘着剤層を有することを特徴とする粘着シート。
- 光学部材用の表面保護フィルムであることを特徴とする請求項12に記載の粘着シート。
- 請求項13に記載の粘着シートが貼り付けられていることを特徴とする光学部材。
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CN201280051068.1A CN103890123B (zh) | 2011-10-19 | 2012-10-12 | 再剥离用水分散型丙烯酸类粘合剂组合物以及粘合片 |
US14/352,533 US20140342152A1 (en) | 2011-10-19 | 2012-10-12 | Removable water-dispersible acrylic pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet |
KR1020147002396A KR101947848B1 (ko) | 2011-10-19 | 2012-10-12 | 재박리용 수분산형 아크릴계 점착제 조성물 및 점착 시트 |
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JP2012224519A JP5965814B2 (ja) | 2011-10-19 | 2012-10-09 | 再剥離用水分散型アクリル系粘着剤組成物、及び粘着シート |
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JP2018135438A (ja) * | 2017-02-21 | 2018-08-30 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、及び、粘着剤層付光学フィルム |
JP6952497B2 (ja) * | 2017-05-31 | 2021-10-20 | 日東電工株式会社 | 粘着剤組成物、表面保護シート、及び、光学部材 |
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Also Published As
Publication number | Publication date |
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JP5965814B2 (ja) | 2016-08-10 |
CN103890123A (zh) | 2014-06-25 |
KR101947848B1 (ko) | 2019-02-13 |
US20140342152A1 (en) | 2014-11-20 |
CN103890123B (zh) | 2017-06-20 |
TWI625374B (zh) | 2018-06-01 |
JP2013100482A (ja) | 2013-05-23 |
TW201331327A (zh) | 2013-08-01 |
KR20140079351A (ko) | 2014-06-26 |
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