WO2023162944A1 - Composition adhésive autocollante, couche adhésive autocollante et feuille adhésive autocollante - Google Patents

Composition adhésive autocollante, couche adhésive autocollante et feuille adhésive autocollante Download PDF

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Publication number
WO2023162944A1
WO2023162944A1 PCT/JP2023/006107 JP2023006107W WO2023162944A1 WO 2023162944 A1 WO2023162944 A1 WO 2023162944A1 JP 2023006107 W JP2023006107 W JP 2023006107W WO 2023162944 A1 WO2023162944 A1 WO 2023162944A1
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pressure
polymer
sensitive adhesive
group
meth
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PCT/JP2023/006107
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English (en)
Japanese (ja)
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大輔 水野
優吉 浪岡
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日東電工株式会社
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Publication of WO2023162944A1 publication Critical patent/WO2023162944A1/fr

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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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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]

Definitions

  • the present invention relates to an adhesive composition, an adhesive layer, and an adhesive sheet. More particularly, it relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet that are excellent in antistatic properties.
  • LCDs liquid crystal displays
  • touch panels In recent years, display devices such as liquid crystal displays (LCDs) and input devices such as touch panels have been widely used in various fields.
  • adhesive sheets are used for bonding optical members.
  • transparent adhesive sheets are used for laminating optical members in various display devices such as touch panels.
  • an adhesive polymer As a result of intensive studies by the present inventors in order to solve the above problems, it has been found that an adhesive polymer, a conductive polymer having a specific configuration, a mixture of monomer components constituting the conductive polymer, or a partially polymerized product of the mixture
  • the adhesive polymer and the conductive polymer form an interpenetrating polymer network or a semi-interpenetrating polymer network, thereby improving durability (especially, corrosion resistance stability, resistance
  • the present inventors have found that it is possible to form a pressure-sensitive adhesive layer that exhibits low surface resistivity and excellent antistatic performance, which is less likely to cause defects in value stability), and completed the present invention.
  • the first aspect of the present invention contains an adhesive polymer (A) and a conductive polymer (B), and as a monomer component constituting the conductive polymer (B), a functional group (b1)
  • (B) has a three-dimensional network structure, and the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or semi-interpenetrating polymer network.
  • a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer forming an interstitial polymer network is provided.
  • the adhesive composition of the first aspect of the present invention may be referred to as "adhesive composition (1)".
  • the second aspect of the present invention is a mixture of the adhesive polymer (A) and the monomer components constituting the conductive polymer (B) or a partially polymerized mixture of the monomer components constituting the conductive polymer (B) and as a monomer component constituting the conductive polymer (B), an ionic compound (B1) having a functional group (b1) in the molecule reacts with the functional group (b1) to form a covalent bond It contains a compound (B2) having a functional group (b2) that can be formed in the molecule, and the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2).
  • the adhesive composition of the second aspect of the present invention may be referred to as "adhesive composition (2)".
  • the adhesive composition (1) and the adhesive composition (2) may be collectively referred to as "the adhesive composition of the present invention”.
  • the 3rd aspect of this invention provides the adhesive layer formed with the adhesive composition (adhesive composition (1) or (2)) of this invention.
  • the pressure-sensitive adhesive layer of the third aspect of the present invention may be referred to as "the pressure-sensitive adhesive layer of the present invention”.
  • the 4th aspect of this invention provides the adhesive sheet which has the adhesive layer of this invention.
  • the pressure-sensitive adhesive sheet of the fourth aspect of the present invention may be referred to as "the pressure-sensitive adhesive sheet of the present invention".
  • the pressure-sensitive adhesive layer of the present invention and the pressure-sensitive adhesive sheet of the present invention are formed from the pressure-sensitive adhesive composition of the present invention (the pressure-sensitive adhesive composition (1) or (2)), durability (in particular, corrosion resistance stability, Resistance value stability) is less likely to occur, exhibits a low surface resistivity, and has excellent antistatic performance.
  • the adhesive composition (1) of the present invention is an adhesive composition for forming an adhesive layer containing an adhesive polymer (A) and a conductive polymer (B).
  • the adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention
  • the conductive polymer (B) is the adhesive of the present invention. It functions as a polymer component that imparts antistatic properties to the agent layer.
  • the pressure-sensitive adhesive composition (2) of the present invention is a mixture of monomer components constituting the adhesive polymer (A) and the conductive polymer (B), or a mixture of monomer components constituting the conductive polymer (B) is partially polymerized. contains things.
  • the pressure-sensitive adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the pressure-sensitive adhesive layer of the present invention.
  • "Mixture of” and “partially polymerized mixture of monomer components constituting the conductive polymer (B)" are precursors (raw material mixtures) for forming the conductive polymer (B) by the progress of the polymerization reaction.
  • the formed conductive polymer (B) functions as a polymer component that imparts antistatic properties to the pressure-sensitive adhesive layer of the present invention.
  • the adhesive composition of the present invention is an ionic compound (B1 ) and a compound (B2) having in its molecule a functional group (b2) capable of reacting with the functional group (b1) to form a covalent bond.
  • the ionic compound (B1) is a monomer component for imparting an antistatic function to the conductive polymer (B), and the compound (B2) constitutes the conductive polymer (B) together with the ionic compound (B1). It is a monomer component.
  • the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, the polymerization reaction proceeds, and the conductive polymer (B) is formed. It is formed.
  • the conductive polymer (B) has a three-dimensional network structure, and the three-dimensional network structure of the conductive polymer (B), It is entangled with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • the structure imparts adhesiveness to the adhesive layer of the present invention with the adhesive polymer (A), imparts antistatic properties to the adhesive layer of the present invention with the conductive polymer (B), and the conductive
  • the three-dimensional network structure of the adhesive polymer (B) and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network, whereby the antistatic agent is applied to the adhesive layer surface. Defects such as corrosion of metal wiring due to the deposition of are less likely to occur, and the migration of antistatic agents from the adhesive layer to other optical members in a moist and hot environment is suppressed, suppressing increases in surface resistance.
  • the pressure-sensitive adhesive composition (1) of the present invention is less likely to cause defects in durability (in particular, corrosion resistance stability and resistance value stability), exhibits a low surface resistivity, and has excellent antistatic performance.
  • An adhesive layer can be formed.
  • the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, resulting in a three-dimensional A conductive polymer (B) having a network structure is formed, and the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • the pressure-sensitive adhesive composition (2) of the present invention is a mixture containing the ionic compound (B1) and the compound (B2), or a partial polymer of a mixture containing the ionic compound (B1) and the compound (B2).
  • the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, the polymerization reaction proceeds, and the three-dimensional network structure can form a conductive polymer (B) having During the course of the polymerization reaction, the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network. Due to the formed interpenetrating polymer network or semi-interpenetrating polymer network, failures such as corrosion of metal wiring due to precipitation of antistatic agents on the adhesive layer surface are unlikely to occur, and charging in a moist and hot environment is prevented.
  • the pressure-sensitive adhesive composition (2) of the present invention is less likely to cause defects in durability (in particular, corrosion resistance stability and resistance value stability), exhibits a low surface resistivity, and has excellent antistatic performance.
  • An adhesive layer can be formed.
  • the ionic compound (B1) preferably has two or more functional groups (b1) in the molecule.
  • the configuration in which the ionic compound (B1) has two or more functional groups (b1) in the molecule allows the compound (B2) and the above polymerization reaction to proceed to efficiently form the conductive polymer (B). and preferred.
  • the functional group (b1) is a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a (meth)acryloyloxy group, a (meth) At least one functional group selected from the group consisting of an acryloylamino group, a vinyl group, an allyl group, and a styryl group is preferred.
  • the configuration in which the functional group (b1) is selected from these functional groups is preferable in that the functional group (b2) is easily polymerized and the conductive polymer (B) can be efficiently formed.
  • the compound (B2) preferably has 3 or more functional groups (b2) in the molecule.
  • the above polymerization reaction with the ionic compound (B1) proceeds to form the three-dimensional network structure of the conductive polymer (B). It is preferable in that it can be formed efficiently.
  • the functional group (b2) is an isocyanate group, a thioisocyanate group, an epoxy group, an aziridinyl group, an oxazolinyl group, a carbodiimide group, a (meth ) is preferably at least one functional group selected from the group consisting of an acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, and a styryl group.
  • the configuration in which the functional group (b2) is selected from these functional groups facilitates the polymerization reaction with the functional group (b1), and the three-dimensional network structure of the conductive polymer (B) can be efficiently formed. preferable.
  • the content ratio of the conductive polymer (B) to the adhesive polymer (A) is preferably 0.05 to 0.5.
  • the configuration in which the content ratio is 0.05 or more is preferable in that excellent antistatic properties can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the configuration in which the content ratio is 0.5 or less is preferable in that excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the thickness of the adhesive sheet of the present invention is preferably 10-350 ⁇ m.
  • the configuration in which the thickness of the pressure-sensitive adhesive sheet of the present invention is equal to or greater than a certain value is preferable in that peeling at a step portion is less likely to occur.
  • the configuration in which the thickness of the pressure-sensitive adhesive sheet of the present invention is equal to or less than a certain value is preferable in that an excellent appearance can be easily maintained during production.
  • the durability (especially corrosion resistance stability, resistance value stability) is less likely to occur, and the pressure-sensitive adhesive layer exhibits low surface resistivity and excellent antistatic performance. and an adhesive sheet is obtained.
  • FIG. 1 is a schematic diagram (cross-sectional view) showing one embodiment of the pressure-sensitive adhesive sheet of the present invention.
  • the adhesive composition (1) of the present invention contains an adhesive polymer (A) and a conductive polymer (B), and as a monomer component constituting the conductive polymer (B), a functional group (b1) in the molecule and a compound (B2) having in the molecule a functional group (b2) capable of reacting with the functional group (b1) to form a covalent bond, and the conductive
  • the polymer (B) has a three-dimensional network structure, and the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or semi-interpenetrating polymer network.
  • the adhesive composition (2) of the present invention is a mixture of monomer components constituting the adhesive polymer (A) and the conductive polymer (B) or a mixture of monomer components constituting the conductive polymer (B). and an ionic compound (B1) having a functional group (b1) in the molecule as a monomer component constituting the conductive polymer (B), which reacts with the functional group (b1) A compound (B2) having a functional group (b2) capable of forming a covalent bond in the molecule, wherein the functional group (b1) of the ionic compound (B1) and the functional group (b2) of the compound (B2) reacts to form a covalent bond to form the conductive polymer (B) having a three-dimensional network structure, and the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer A pressure-sensitive adhesive composition capable of forming a network or semi-interpenetrating polymer network.
  • the above-mentioned “mixture of monomer components” includes the case of being composed of a single monomer component and the case of being composed of two or more monomer components.
  • the above-mentioned “partially polymerized mixture of monomer components” means a composition in which one or more of the constituent monomer components of the above-mentioned “mixture of monomer components” is partially polymerized. do.
  • the adhesive layer of the present invention is an adhesive layer formed from the adhesive composition (1) or the adhesive composition (2) of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive composition of the present invention may have any form, and examples thereof include solvent type, emulsion type, hot melt type (hot melt type), non-solvent type (active energy ray-curable type), and the like. be done.
  • the pressure-sensitive adhesive composition of the present invention is preferably of solvent type.
  • the pressure-sensitive adhesive composition means a composition used for forming the pressure-sensitive adhesive layer, and includes the meaning of the composition used for forming the pressure-sensitive adhesive.
  • the organic solvent is not particularly limited as long as it is an organic compound used as a solvent.
  • examples include hydrocarbon solvents such as cyclohexane, hexane, and heptane; aromatic solvents such as toluene and xylene; ethyl acetate, methyl acetate, and the like.
  • ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, butanol and isopropyl alcohol.
  • the mixed solvent containing 2 or more types of organic solvents may be sufficient as the said organic solvent.
  • Adhesive polymer (A) In the adhesive composition of the present invention, the adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention.
  • the adhesive polymer (A) is not particularly limited. rubber-based polymer contained as a base polymer in a silicone-based pressure-sensitive adhesive composition, silicone-based polymer contained as a base polymer in a silicone-based pressure-sensitive adhesive composition, polyester-based polymer contained as a base polymer in a polyester-based pressure-sensitive adhesive composition, urethane Urethane-based polymer contained as a base polymer in the adhesive composition, polyamide-based polymer contained as a base polymer in the polyamide-based adhesive composition, epoxy-based polymer contained as a base polymer in the epoxy-based adhesive composition, vinyl alkyl ether vinyl alkyl ether-based polymer contained as a base polymer in the PSA composition, fluorine-based polymer contained as a base polymer in the fluorine-based PSA composition,
  • the adhesive polymer (A) is preferably an acrylic polymer from the viewpoints of transparency, weather resistance, adhesion reliability, and ease of functional design of the solvent-based composition due to a wide variety of monomers.
  • the pressure-sensitive adhesive composition of the present invention is preferably an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as the pressure-sensitive adhesive polymer (A).
  • the above base polymers can be used alone or in combination of two or more.
  • the acrylic polymer contained as the adhesive polymer (A) may be referred to as "acrylic polymer (A)".
  • the content of the adhesive polymer (A) in the adhesive composition of the present invention is not particularly limited, but is preferably 70 to 95% by weight, more preferably 75 to 93% by weight, and still more preferably 80% by weight. ⁇ 90% by weight.
  • a configuration in which the content of the adhesive polymer (A) is 70% by weight or more is preferable in that excellent adhesiveness can be imparted to the adhesive layer of the present invention.
  • the configuration in which the content of the adhesive polymer (A) is 95% by weight or less means that the adhesive layer of the present invention can be provided with excellent antistatic properties by containing the conductive polymer (B). is suitable.
  • the acrylic polymer (A) contained as the adhesive polymer (A) will be described below, but the present invention is not limited to this embodiment.
  • the content of the acrylic polymer (A) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but is 70 to 95% by weight with respect to the total weight of the pressure-sensitive adhesive composition of the present invention (total weight, 100% by weight). preferably 75 to 93% by weight, and still more preferably 80 to 90% by weight.
  • a configuration in which the content of the acrylic polymer (A) is 70% by weight or more is preferable in that excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the structure that the content of the acrylic polymer (A) is 95% by weight or less means that the adhesive layer of the present invention can be provided with excellent antistatic properties by containing the conductive polymer (B). is suitable.
  • the adhesive composition for forming the adhesive layer containing the acrylic polymer (A) as a main component is not particularly limited, but for example, a composition containing the acrylic polymer (A) as an essential component; an acrylic polymer ( Examples thereof include a mixture of monomer components constituting A) (sometimes referred to as a "monomer mixture") or a composition containing a partial polymer thereof as an essential component.
  • examples of the former include so-called solvent-based compositions and water-dispersed compositions (emulsion-type compositions), and examples of the latter include so-called active energy ray-curable compositions. be done.
  • the pressure-sensitive adhesive composition is preferably a solvent-based composition.
  • the said adhesive composition may contain the other additive agent as needed.
  • the above-mentioned "monomer mixture” includes the case where it is composed of a single monomer component that constitutes the acrylic polymer (A), and the case that it is composed of two or more monomer components that constitute the acrylic polymer (A). .
  • the above-mentioned “partially polymerized product” means a composition in which one or more of the components of the monomer mixture that constitutes the acrylic polymer (A) is partially polymerized.
  • “acrylic polymer (A)” when simply referring to "acrylic polymer (A)", unless otherwise specified, “acrylic polymer (A)", “mixture of monomer components constituting acrylic polymer (A)”, and “"partially polymerized mixture of monomer components constituting the acrylic polymer (A)” is also included.
  • the acrylic polymer (A) is a polymer (polymer) containing an acrylic monomer (acrylic monomer) as an essential monomer unit (monomer unit, monomer structural unit).
  • the acrylic polymer (A) is a polymer containing structural units derived from acrylic monomers as structural units.
  • the acrylic polymer (A) is a polymer constituted (formed) with an acrylic monomer as an essential monomer component.
  • "(meth)acryl” means either one or both of "acryl” and “methacryl", and the same applies to others.
  • the weight average molecular weight of the acrylic polymer (A) is not particularly limited, it is preferably from 100,000 to 5,000,000.
  • the acrylic polymer (A) is a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as an essential monomer unit (hereinafter sometimes simply referred to as "(meth)acrylic acid alkyl ester"). ) is preferred.
  • Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ((meth) ) n-butyl acrylate), isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate ) Decyl acryl
  • the (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group with a carbon number of 1 to 18 from the viewpoint of obtaining strong adhesion and adjusting the residual stress.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • EHA 2-ethylhexyl acrylate
  • ISA isostearyl acrylate
  • the content (percentage) of the (meth)acrylic acid alkyl ester in the total monomer units of the acrylic polymer (A) is not particularly limited, but the adhesion reliability , Especially in terms of adhesion reliability at low temperatures, it is preferably 30 to 100 parts by weight, more preferably 35 to 90 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A), More preferably 40 to 85 parts by weight.
  • the acrylic polymer (A) is a (meth)acrylic acid alkoxyalkyl ester having a linear or branched alkoxyalkyl group as an essential monomer unit (hereinafter simply referred to as "(meth)acrylic acid alkoxyalkyl ester"). It is also preferred that the polymer comprises a
  • Examples of the (meth)acrylic acid alkoxyalkyl esters include, for example, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and (meth)acrylic acid 3 - alkoxy groups having 1 to 20 carbon atoms such as methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate have 1 to 20 carbon atoms; Examples thereof include (meth)acrylic acid alkoxyalkyl esters having an alkoxyalkyl group substituted with an alkyl group. In addition, (meth)acrylic-acid alkoxyalkyl ester may be used individually or in combination of 2 or more types.
  • the above (meth)acrylic acid alkoxyalkyl ester has an alkoxy group having 1 to 18 carbon atoms substituted with an alkyl group having 1 to 18 carbon atoms from the viewpoint of obtaining strong adhesiveness and adjusting residual stress ( Meth)acrylic acid alkoxyalkyl esters are preferred, more preferably 2-methoxyethyl acrylate (MEA).
  • MEA 2-methoxyethyl acrylate
  • the content (percentage) of the (meth)acrylic acid alkoxyalkyl ester in the total monomer units of the acrylic polymer (A) is not particularly limited, but the adhesion reliability From the standpoint of adhesion reliability, especially at low temperatures, it is preferably 30 to 100 parts by weight, more preferably 35 to 90 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A). , more preferably 40 to 85 parts by weight.
  • the acrylic polymer (A) may contain copolymerizable monomers (copolymerizable monomers) in addition to the (meth)acrylic acid alkyl esters and (meth)acrylic acid alkoxyalkyl esters as monomer units. good.
  • the acrylic polymer (A) may contain a copolymerizable monomer as a constituent monomer component.
  • the copolymerizable monomers may be used alone or in combination of two or more.
  • a hydroxyl group-containing monomer is preferably mentioned.
  • the acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer unit, it becomes easy to polymerize the constituent monomer components, and it becomes easy to obtain good cohesive strength. For this reason, it becomes easy to obtain strong adhesiveness, and it becomes easy to obtain excellent anti-foaming peeling property by increasing the gel fraction. Furthermore, it becomes easy to suppress whitening of the adhesive sheet that may occur in a high-humidity environment.
  • the hydroxyl group can also serve as a reaction point with a cross-linking agent, which will be described later.
  • the content (proportion) of the hydroxyl group-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited.
  • the amount of the hydroxyl group-containing monomer is at least a certain amount, the whitening of the pressure-sensitive adhesive sheet, which may occur in a high-humidity environment, can be further suppressed, and the transparency such as resistance to humid clouding can be ensured.
  • the lower limit of the content of the hydroxyl group-containing monomer is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, more preferably 10 parts by weight or more.
  • the upper limit of the content of the hydroxyl group-containing monomer is preferably 40 parts by weight or less, and 35 parts by weight, from the viewpoint of cohesive strength, adhesiveness, and ease of obtaining adhesion reliability such as resistance to foaming and peeling. It is more preferably 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, or 31 parts by weight or less, and even more preferably 30 parts by weight or less.
  • a nitrogen atom-containing monomer is preferably mentioned.
  • the acrylic polymer (A) contains a nitrogen atom-containing monomer as a monomer unit, it becomes easy to obtain an appropriate cohesive force. For this reason, the 180° (degree) peeling adhesive force to the glass plate and the 180° peeling adhesive force to the acrylic plate are increased, making it easier to obtain strong adhesiveness, and increasing the gel fraction to achieve excellent adhesion. It becomes easy to obtain anti-foaming peeling property. Furthermore, it becomes easy to obtain appropriate flexibility in the pressure-sensitive adhesive layer, to adjust the 300% tensile residual stress within a specific range, and to obtain excellent stress relaxation properties and excellent step followability.
  • the content (proportion) of the nitrogen atom-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited, but is preferably 1 part by weight or more.
  • the lower limit of the content of the nitrogen atom-containing monomer is 2 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) from the viewpoint of cohesive strength, adhesiveness, and resistance to foaming and peeling. It is preferably at least 3 parts by weight, more preferably at least 3 parts by weight, more preferably at least 5 parts by weight, at least 7 parts by weight, at least 8 parts by weight, at least 9 parts by weight, or at least 10 parts by weight.
  • the upper limit of the content of the nitrogen atom-containing monomer is 40 parts by weight, since it becomes easier to obtain appropriate flexibility in the pressure-sensitive adhesive layer, and it becomes easier to obtain excellent stress relaxation and excellent conformability to unevenness. It is preferably 35 parts by weight or less, more preferably 30 parts by weight or less.
  • the above acrylic polymer (A) can be obtained by polymerizing the above monomer units (monomer components) by a known or commonly used polymerization method.
  • the polymerization method of the acrylic polymer (A) include solution polymerization method, emulsion polymerization method, bulk polymerization method, polymerization method by active energy ray irradiation (active energy ray polymerization method), and the like.
  • the solution polymerization method and the active energy ray polymerization method are preferable, and the active energy ray polymerization method is more preferable in terms of the transparency, water resistance, cost, etc. of the adhesive layer.
  • Examples of the active energy ray irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as ⁇ -ray, ⁇ -ray, ⁇ -ray, neutron beam, and electron beam, and ultraviolet rays, particularly ultraviolet rays. is preferred.
  • the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause the reaction of the monomer components.
  • solvents may be used in the polymerization of the acrylic polymer (A).
  • examples of such solvents include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as cyclohexane; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • a solvent may be used individually or in combination of 2 or more types.
  • a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction.
  • a polymerization initiator may be used individually or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited. Active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like can be mentioned.
  • a photoinitiator may be used individually or in combination of 2 or more types.
  • benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. Methyl ether etc. are mentioned.
  • acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. be done.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
  • Examples of the benzoin-based photopolymerization initiator include benzoin.
  • Examples of the benzyl-based photopolymerization initiator include benzyl.
  • benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
  • ketal photopolymerization initiator examples include benzyl dimethyl ketal.
  • thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
  • the amount of the photopolymerization initiator to be used is not particularly limited. 001 to 1 part by weight, more preferably 0.01 to 0.50 part by weight.
  • the thermal polymerization initiator is not particularly limited, but for example, an azo polymerization initiator, a peroxide polymerization initiator (e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator agents and the like.
  • an azo polymerization initiator e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.
  • a redox polymerization initiator agents e.g., dibenzoyl peroxide, tert-butyl permaleate, etc.
  • the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
  • azo polymerization initiator examples include 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as "AIBN”), 2,2'-azobis-2-methylbutyronitrile (hereinafter, “AMBN”), 2,2′-azobis(2-methylpropionate)dimethyl, 4,4′-azobis-4-cyanovaleric acid, and the like.
  • AIBN 2,2'-azobisisobutyronitrile
  • AMBN 2,2'-azobis-2-methylbutyronitrile
  • 2,2′-azobis(2-methylpropionate)dimethyl 2,4′-azobis-4-cyanovaleric acid
  • the amount of the thermal polymerization initiator used is not particularly limited.
  • all monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)) It is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight, per 100 parts by weight.
  • Carboxyl group-containing monomer, etc. Copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers further include carboxyl group-containing monomers.
  • the carboxyl group-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and has a carboxyl group.
  • the carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the carboxyl group-containing monomers include maleic anhydride. and anhydride group-containing monomers such as itaconic anhydride.
  • a carboxyl group-containing monomer can be used individually or in combination of 2 or more types.
  • the acrylic polymer (A) contains the carboxyl group-containing monomer as a monomer component constituting the polymer, the carboxyl group-containing monomer in all the monomer components (100% by weight) constituting the acrylic polymer (A)
  • the proportion of the monomer is not particularly limited, it is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.05% by weight or more, from the viewpoint of improving durability and obtaining high adhesion reliability. 1% by weight or more.
  • the upper limit of the ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less, from the viewpoint of obtaining a pressure-sensitive adhesive layer having appropriate flexibility. be.
  • the pressure-sensitive adhesive composition of the present invention does not contain, or substantially does not contain, a basic group-containing monomer as a monomer component constituting the base polymer.
  • a basic group-containing monomer as a base polymer
  • the pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic polymer (A) as a base polymer
  • A acrylic polymer
  • the PSA composition substantially does not contain a basic group-containing monomer.
  • the content of the basic group-containing monomer is 0.05 parts by weight or less (for example, 0 to 0.05 parts by weight), more preferably 0.01 parts by weight or less (eg, 0 to 0.01 parts by weight), still more preferably 0.001 parts by weight or less (eg, 0 to 0.001 parts by weight) can be said to be substantially free of
  • a hydroxyl group-containing monomer means a monomer having at least one hydroxyl group in the molecule. Also, a monomer having at least one hydroxyl group in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer is not particularly limited, but specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic acid hydroxyl group-containing (meth)acrylic acid esters such as hydroxyllauryl and (meth)acrylic acid (4-hydroxymethylcyclohexyl); vinyl alcohol, allyl alcohol and the like.
  • the hydroxyl group-containing monomer is preferably a hydroxyl group-containing (meth)acrylic acid ester, more preferably 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), acrylic acid 4 - hydroxybutyl (4HBA).
  • HOA 2-hydroxyethyl acrylate
  • HPA 2-hydroxypropyl (meth)acrylate
  • 4HBA acrylic acid 4 - hydroxybutyl
  • the hydroxyl group-containing monomers may be used alone or in combination of two or more.
  • a nitrogen atom-containing monomer means a monomer having at least one nitrogen atom in its molecule (in one molecule).
  • the hydroxyl group-containing monomer does not include the nitrogen atom-containing monomer. That is, in this specification, a monomer having a hydroxyl group and a nitrogen atom in its molecule is included in the nitrogen atom-containing monomer.
  • a monomer having at least one nitrogen atom in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer and is not a nitrogen atom-containing monomer.
  • N-vinyl cyclic amides, (meth)acrylamides, and the like are preferable as the nitrogen atom-containing monomer.
  • the nitrogen atom-containing monomers may be used alone or in combination of two or more.
  • N-vinyl cyclic amide an N-vinyl cyclic amide represented by the following formula (1) is preferable.
  • R 1 represents a divalent organic group
  • R 1 in the above formula (1) is a divalent organic group, preferably a divalent saturated hydrocarbon group or an unsaturated hydrocarbon group, more preferably a divalent saturated hydrocarbon group (e.g., carbon number 3 to 5 alkylene groups, etc.).
  • N-vinyl-2-pyrrolidone N-vinyl-2-pyrrolidone
  • N-vinyl-2-piperidone N-vinyl -2-caprolactam
  • N-vinyl-3-morpholinone N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione and the like
  • N-vinyl-2- pyrrolidone N-vinyl-2-caprolactam
  • N-vinyl-2-pyrrolidone N-vinyl-2-pyrrolidone
  • N-vinyl-2-caprolactam more preferably N-vinyl-2-pyrrolidone.
  • Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide.
  • Examples of the N-alkyl(meth)acrylamide include N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-octylacrylamide and the like.
  • N-alkyl(meth)acrylamides also include (meth)acrylamides having an amino group such as dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, and dimethylaminopropyl(meth)acrylamide.
  • N,N-dialkyl(meth)acrylamides examples include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl (Meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide and the like.
  • the (meth)acrylamides also include, for example, various N-hydroxyalkyl(meth)acrylamides.
  • N-hydroxyalkyl(meth)acrylamide examples include N-methylol(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N- (1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-methyl-N-2-hydroxyethyl(meth)acrylamide and the like.
  • the (meth)acrylamides also include, for example, various N-alkoxyalkyl(meth)acrylamides.
  • Examples of the N-alkoxyalkyl(meth)acrylamides include N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide.
  • Nitrogen atom-containing monomers other than the N-vinyl cyclic amides and the (meth)acrylamides include, for example, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylamino (meth)acrylate, propyl, amino group-containing monomers such as t-butylaminoethyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; (meth)acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinyl imidazole, N-vinylpyrazine, N-vinylmorpholine, N-vinylpyrazole, vinylpyridine, vinylpyrimidine, vinyloxazole, vinylisoxazole, vinylthiazole, vinylisothiazole, vinylpyridazine, (meth)acryloylpyrrolidone,
  • Aromatic ring structure-containing monomer Copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers further include aromatic ring structure-containing monomers.
  • the aromatic ring structure-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and has an aromatic ring structure.
  • an alkyl (meth)acrylate having a phenyl group is included in the aromatic ring structure-containing monomer.
  • aromatic ring structure-containing monomer examples include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.
  • the aromatic ring structure-containing monomers can be used alone or in combination of two or more.
  • the acrylic polymer (A) contains the aromatic ring structure-containing monomer as a monomer component constituting the polymer, the aromatic ring in all the monomer components (100% by weight) constituting the acrylic polymer (A)
  • the proportion of the structure-containing monomer is not particularly limited, it is preferably 5% by weight or more, more preferably 10% by weight or more, from the viewpoint of improving durability and obtaining high adhesion reliability.
  • the upper limit of the ratio of the aromatic ring structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less, from the viewpoint of obtaining a pressure-sensitive adhesive layer having appropriate flexibility. is.
  • Alicyclic Structure-Containing Monomer Copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers further include alicyclic structure-containing monomers.
  • the alicyclic structure-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and has an alicyclic structure.
  • an alkyl (meth)acrylate having a cycloalkyl group is included in the alicyclic structure-containing monomer.
  • an alicyclic structure containing monomer can be used individually or in combination of 2 or more types.
  • the alicyclic structure in the alicyclic structure-containing monomer is a cyclic hydrocarbon structure, preferably having 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, further preferably 6 to 15 carbon atoms, and 6 to 10 are particularly preferred.
  • Examples of the alicyclic structure-containing monomer include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, HPMPA represented by the following formula (2), TMA-2 represented by the following formula (3), HCPA represented by the following formula (4), etc. (Meth)acrylic monomers.
  • formula (4) there is no particular limitation on the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses. Among these, isobornyl (meth)acrylate is preferred.
  • the acrylic polymer (A) contains the alicyclic structure-containing monomer as a monomer component constituting the polymer, the alicyclic structure in all the monomer components (100% by weight) constituting the acrylic polymer (A)
  • the ratio of the structure-containing monomer is not particularly limited, it is preferably 10% by weight or more from the viewpoint of improving durability and obtaining high adhesion reliability.
  • the upper limit of the ratio of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less, from the viewpoint of obtaining a pressure-sensitive adhesive layer having appropriate flexibility. is.
  • copolymerizable monomers in the acrylic polymer (A) include, in addition to the above nitrogen atom-containing monomers and hydroxyl group-containing monomers, epoxy group-containing monomers [e.g., glycidyl (meth)acrylate, methyl (meth)acrylate, glycidyl, etc.]; sulfonic acid group-containing monomers [e.g., sodium vinyl sulfonate, etc.]; phosphoric acid group-containing monomers; vinyl esters [e.g., vinyl acetate, vinyl propionate, etc.]; toluene, etc.]; olefins or dienes [eg, ethylene, propylene, butadiene, isoprene, isobutylene, etc.]; vinyl ethers [eg, vinyl alkyl ether, etc.];
  • the copolymerizable monomers in the acrylic polymer (A) also include polyfunctional monomers.
  • a polyfunctional monomer acts as a cross-linking component.
  • the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, Allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, ure
  • the content (proportion) of the polyfunctional monomer in all monomer units of the acrylic polymer (A) is not particularly limited, but with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A), It is preferably 0.5 parts by weight or less (for example, 0 to 0.5 parts by weight), more preferably 0 to 0.35 parts by weight, still more preferably 0 to 0.3 parts by weight.
  • the content of the polyfunctional monomer is 0.5 parts by weight or less, the pressure-sensitive adhesive layer has appropriate cohesive strength, and the pressure-sensitive adhesive strength and step absorbability are easily improved, which is preferable.
  • the polyfunctional monomer when using a cross-linking agent, may not be used, but the content of the multi-functional monomer when the cross-linking agent is not used is preferably 0.001 to 0.5 parts by weight. , more preferably 0.001 to 0.35 parts by weight, more preferably 0.002 to 0.3 parts by weight.
  • the pressure-sensitive adhesive composition of the present invention contains an acrylic polymer (A) as a base polymer
  • the pressure-sensitive adhesive composition of the present invention includes an acrylic polymer having a weight average molecular weight of 1000 to 30000 together with the acrylic polymer (A). It is preferable to contain the system polymer (B).
  • the acrylic polymer (B) is contained, the adhesion to the adherend at the interface of the pressure-sensitive adhesive sheet is improved, making it easier to obtain strong adhesion and excellent resistance to foaming and peeling.
  • "acrylic polymer (B) having a weight average molecular weight of 1000 to 30000” may be simply referred to as "acrylic polymer (B)".
  • the acrylic polymer (B) is also a three-dimensional polymer (B) together with the acrylic polymer (A).
  • the network may be entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • an acrylic polymer composed of a (meth)acrylic acid ester having a cyclic structure in the molecule as an essential monomer component is preferably mentioned, and a (meth) having a cyclic structure in the molecule.
  • An acrylic polymer composed of an acrylic acid ester and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as essential monomer components is more preferable.
  • the acrylic polymer (B) preferably includes an acrylic polymer containing a (meth)acrylic acid ester having a cyclic structure in the molecule as a monomer unit, and has a cyclic structure in the molecule as a monomer unit (meth) )
  • Acrylic polymers containing acrylic acid esters and (meth)acrylic acid alkyl esters having linear or branched alkyl groups are more preferred.
  • the cyclic structure (ring) of the (meth)acrylic acid ester having a cyclic structure in the molecule (in one molecule) is an aromatic ring , a non-aromatic ring, and is not particularly limited.
  • the aromatic ring include aromatic carbocyclic rings [eg, monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.], various aromatic heterocyclic rings, and the like.
  • non-aromatic ring examples include non-aromatic aliphatic rings (non-aromatic alicyclic rings) [e.g., cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring cycloalkene rings such as cyclohexene rings], non-aromatic bridging rings [e.g., bicyclic hydrocarbon rings in pinane, pinene, bornane, norbornane, norbornene, etc.; tricyclic or higher aliphatic hydrocarbons in adamantane, etc. rings (bridged hydrocarbon rings, etc.)], non-aromatic heterocycles [eg, epoxy ring, oxolane ring, oxetane ring, etc.] and the like.
  • non-aromatic aliphatic rings e.g., cycloalkane rings such as
  • tricyclic or higher aliphatic hydrocarbon ring examples include, for example, a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b).
  • an adamantyl group represented by the following formula (5d) an adamantyl group represented by the following formula (5d)
  • a tricyclopentenyl group represented by the following formula (5e) examples include, for example, a dicyclopentanyl group represented by the following formula (5a), and a dicyclopentanyl group represented by the following formula (5b).
  • an adamantyl group represented by the following formula (5d) an adamantyl group represented by the following formula (5d)
  • examples of the ring-containing (meth)acrylic acid ester include (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.
  • Acrylic acid cycloalkyl ester (meth)acrylic acid ester having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth) Tricyclic or higher aliphatics such as acrylates, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate (Meth)acrylic acid esters having a hydrocarbon ring; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate, (meth)acrylic acid aryloxyalkyl esters such as phenoxyethyl (meth)acrylate, (meth)acrylic acid esters Examples thereof include (meth)acrylic acid esters having an aromatic ring, such as
  • the ring-containing (meth)acrylic acid ester is particularly preferably a non-aromatic ring-containing (meth)acrylic acid ester, more preferably cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), acrylic They are dicyclopentanyl acid (DCPA) and dicyclopentanyl methacrylate (DCPMA), more preferably dicyclopentanyl acrylate (DCPA) and dicyclopentanyl methacrylate (DCPMA).
  • ring-containing (meth)acrylic acid esters may be used alone or in combination of two or more.
  • non-aromatic ring-containing (meth)acrylic acid esters a (meth)acrylic acid ester having a tricyclic or higher aliphatic hydrocarbon ring (particularly, a tricyclic or higher bridging hydrocarbon ring) is used. This is particularly preferable in that polymerization inhibition is less likely to occur.
  • a dicyclopentanyl group having no unsaturated bond represented by the above formula (5a), an adamantyl group represented by the above formula (5c), and a tricyclopentanyl group represented by the above formula (5d) When using a (meth) acrylic acid ester having, it is possible to further increase the resistance to foaming and peeling, and furthermore, the adhesion to low-polar adherends such as polyethylene and polypropylene can be significantly improved. .
  • the content (percentage) of the ring-containing (meth)acrylic acid ester in all monomer units of the acrylic polymer (B) is not particularly limited, but the acrylic polymer It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting (B).
  • the content of the ring-containing (meth)acrylic acid ester is 10 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable.
  • the content is 90 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility, and the pressure-sensitive adhesive strength, step absorbability, etc. are likely to be improved, which is preferable.
  • Examples of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group as a monomer unit of the acrylic polymer (B) include methyl (meth)acrylate and ethyl (meth)acrylate. , propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Pentyl acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate ) nonyl acrylate, isononyl (me
  • Examples thereof include (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms.
  • methyl methacrylate (MMA) is preferable because it has good compatibility with the acrylic polymer (A).
  • said (meth)acrylic-acid alkylester may be used individually or in combination of 2 or more types.
  • Content (percentage) of (meth)acrylic acid alkyl ester having a linear or branched alkyl group in all monomer units of acrylic polymer (B) is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B) in terms of resistance to foaming and peeling. parts by weight, more preferably 20 to 60 parts by weight. When the content is 10 parts by weight or more, the adhesive strength to an adherend made of acrylic resin or polycarbonate tends to be improved, which is preferable.
  • the monomer unit of the acrylic polymer (B) in addition to the ring-containing (meth)acrylic acid ester and the (meth)acrylic acid alkyl ester having a linear or branched alkyl group, these monomers and A polymerizable monomer (copolymerizable monomer) may be included.
  • the content (proportion) of the copolymerizable monomer in all monomer units of the acrylic polymer (B) is not particularly limited, but the acrylic polymer (B ) is preferably 49.9 parts by weight or less (for example, 0 to 49.9 parts by weight), more preferably 30 parts by weight or less, relative to the total amount (100 parts by weight) of the monomer components constituting ). Also, the copolymerizable monomers may be used alone or in combination of two or more.
  • Examples of the copolymerizable monomer (the copolymerizable monomer constituting the acrylic polymer (B)) as monomer units of the acrylic polymer (B) include (meth)acrylic acid alkoxyalkyl esters [for example, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, (meth) ) 4-methoxybutyl acrylate, 4-ethoxybutyl (meth)acrylate, etc.]; hydroxyl group (hydroxyl group)-containing monomers [e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth
  • the acrylic polymer (B) includes, as monomer units, a (meth)acrylic acid ester having a cyclic structure in the molecule and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group.
  • Acrylic polymers are preferred. Among them, acrylic polymers containing, as monomer units, ring-containing (meth)acrylic acid esters and (meth)acrylic acid alkyl esters having the above linear or branched alkyl groups are preferred.
  • a monomer component constituting the acrylic polymer (B) The amount of the ring-containing (meth)acrylic acid ester relative to the total amount (100 parts by weight) is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight.
  • the content of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and still more preferably 20 to 60 parts by weight.
  • the monomer unit is (1) selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. and (2) an acrylic polymer containing methyl methacrylate.
  • dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and the content of cyclohexyl methacrylate is 30 to 70 parts by weight with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B), 2)
  • the content of methyl methacrylate is preferably 30 to 70 parts by weight.
  • the acrylic polymer (B) is not limited to the above specific configuration.
  • the acrylic polymer (B) can be obtained by polymerizing the above monomer components by a known or commonly used polymerization method.
  • the polymerization method of the acrylic polymer (B) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • the bulk polymerization method and the solution polymerization method are preferable, and the solution polymerization method is more preferable.
  • Various common solvents may be used in the polymerization of the acrylic polymer (B).
  • the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane, methylcyclohexane and the like. alicyclic hydrocarbons; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • such a solvent may be used individually or in combination of 2 or more types.
  • a known or commonly used polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
  • a polymerization initiator may be used individually or in combination of 2 or more types.
  • thermal polymerization initiators examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile (AMBN), 2,2′-azobis(2- methylpropionate) dimethyl, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane) and other azo initiators; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1- Examples include peroxide-based initiators such as bis(
  • the amount of the thermal polymerization initiator to be used is not particularly limited. .1 to 15 parts by weight.
  • the photopolymerization initiator is not particularly limited, but includes, for example, the same photopolymerization initiator as the photopolymerization initiator used in the polymerization of the acrylic polymer (A) mentioned above.
  • the amount of the photopolymerization initiator to be used is not particularly limited, and is appropriately selected.
  • a chain transfer agent may be used in the polymerization of the acrylic polymer (B) to adjust the molecular weight (specifically, to adjust the weight average molecular weight to 1000 to 30000).
  • the chain transfer agent include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate
  • ⁇ -thioglycerol and methyl thioglycolate are preferable, and ⁇ -thioglycerol is particularly preferable, from the viewpoint of suppressing whitening of the adhesive sheet due to humidification.
  • a chain transfer agent may be used individually or in combination of 2 or more types.
  • the content (amount used) of the chain transfer agent is not particularly limited, but is 0 per 100 parts by weight of all monomer units of the acrylic polymer (B) (total amount of monomer components constituting the acrylic polymer (B)). .1 to 20 parts by weight is preferred, more preferably 0.2 to 15 parts by weight, and still more preferably 0.3 to 10 parts by weight.
  • the weight average molecular weight (Mw) of the acrylic polymer (B) is 1,000 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. Since the acrylic polymer (B) has a weight-average molecular weight of 1000 or more, the adhesive strength and holding properties are improved, and the resistance to foaming and peeling is improved. On the other hand, since the acrylic polymer (B) has a weight-average molecular weight of 30,000 or less, the adhesive strength is easily increased, and the resistance to foaming and peeling is improved.
  • the weight-average molecular weight (Mw) of the acrylic polymer (B) can be determined by the GPC method in terms of polystyrene. For example, it can be measured under the following conditions using a high-speed GPC apparatus "HPLC-8120GPC" manufactured by Tosoh Corporation. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min
  • the glass transition temperature (Tg) of the acrylic polymer (B) is not particularly limited, but is preferably 20 to 300°C, more preferably 30 to 300°C, still more preferably 40 to 300°C.
  • the acrylic polymer (B) has a glass transition temperature of 20° C. or higher, the resistance to foaming and peeling is easily improved, which is preferable.
  • the glass transition temperature of the acrylic polymer (B) is 300° C. or less, the pressure-sensitive adhesive layer has appropriate flexibility, and it becomes easy to obtain good adhesive strength and good step absorbability, resulting in excellent adhesion. This is preferable because it makes it easier to obtain reliability.
  • Tg is the glass transition temperature (unit: K) of the acrylic polymer (B)
  • Tg is the glass transition temperature (unit: K) when the monomer i forms a homopolymer
  • Tg of the homopolymer of the monomers constituting the acrylic polymer (B) the values shown in Table 1 below can be adopted.
  • Tg of homopolymers of monomers not listed in Table 1 values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) can be used. Furthermore, as the Tg of a homopolymer of a monomer not described in the above literature, the value obtained by the above-described measuring method (tan ⁇ peak top temperature by viscoelasticity test) can be employed.
  • the content of the acrylic polymer (B) when the pressure-sensitive adhesive composition of the present invention contains the acrylic polymers (A) and (B) is not particularly limited. On the other hand, it is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 2 to 10 parts by weight. That is, the content of the acrylic polymer (B) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but 1 to 30 parts by weight per 100 parts by weight of the total monomer units of the acrylic polymer (A) It is preferably 2 to 20 parts by weight, and still more preferably 2 to 10 parts by weight. The content of the acrylic polymer (B) in the adhesive composition of the present invention is not particularly limited. parts by weight, more preferably 2 to 10 parts by weight.
  • the content of the acrylic polymer (B) is 1 part by weight or more, excellent adhesiveness and excellent resistance to foaming and peeling can be easily obtained, which is preferable. Further, when the content of the acrylic polymer (B) is 30 parts by weight or less, excellent transparency and adhesion reliability are easily obtained, which is preferable.
  • the pressure-sensitive adhesive composition (1) of the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer containing a conductive polymer (B) in addition to the pressure-sensitive adhesive polymer (A).
  • the conductive polymer (B) functions as a polymer component that imparts antistatic properties to the pressure-sensitive adhesive layer of the present invention.
  • the adhesive composition (2) of the present invention is a mixture of monomer components constituting the conductive polymer (B) or a mixture of monomer components constituting the conductive polymer (B). and a partial polymer of the mixture.
  • the "mixture of monomer components constituting the conductive polymer (B)” and the “partially polymerized mixture of the monomer components constituting the conductive polymer (B)” are It is a precursor (raw material mixture) for the progress of the polymerization reaction to form the conductive polymer (B), and the formed conductive polymer (B) imparts antistatic properties to the pressure-sensitive adhesive layer of the present invention. It functions as a polymer component.
  • the above-mentioned "monomer mixture” includes the case where it is composed of a single monomer component that constitutes the conductive polymer (B), and the case that it is composed of two or more monomer components that constitute the conductive polymer (B). .
  • the above-mentioned “partially polymerized product” means a composition in which one or more of the components of the monomer mixture that constitutes the conductive polymer (B) is partially polymerized.
  • conductive polymer (B) when simply referred to as “conductive polymer (B)", unless otherwise specified, “conductive polymer (B)”, “mixture of monomer components constituting conductive polymer (B)”, and “"Partially polymerized mixture of monomer components constituting the conductive polymer (B)” is also included.
  • the adhesive composition of the present invention is an ionic compound (B1 ) and a compound (B2) having in its molecule a functional group (b2) capable of reacting with the functional group (b1) to form a covalent bond.
  • the ionic compound (B1) is a monomer component for imparting an antistatic function to the conductive polymer (B), and the compound (B2) constitutes the conductive polymer (B) together with the ionic compound (B1). It is a monomer component.
  • the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, the polymerization reaction proceeds, and the conductive polymer (B) is formed. It is formed.
  • the conductive polymer (B) has a three-dimensional network structure.
  • the functional group (b1) of the ionic compound (B1) and the functional group (b2) of the compound (B2) react to form a covalent bond, A conductive polymer (B) having a three-dimensional network structure is formed.
  • the "three-dimensional network structure” refers to a structure in which linear or branched polymers that constitute the conductive polymer (B) are linked by a crosslinked structure to construct a three-dimensional network structure. .
  • the ionic compound (B1) preferably has two or more functional groups (b1) in the molecule.
  • the configuration in which the ionic compound (B1) has two or more functional groups (b1) in the molecule allows the compound (B2) and the above polymerization reaction to proceed to efficiently form the conductive polymer (B). and preferred.
  • the number of functional groups (b1) that the ionic compound (B1) has in the molecule is preferably 2 to 4, more preferably 2 to 3, in that the conductive polymer (B) can be efficiently formed. Two are more preferred.
  • the functional group (b1) is a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a (meth)acryloyloxy group, a (meth) At least one functional group selected from the group consisting of an acryloylamino group, a vinyl group, an allyl group, and a styryl group is preferred.
  • the configuration in which the functional group (b1) is selected from these functional groups is preferable in that the functional group (b2) is easily polymerized and the conductive polymer (B) can be efficiently formed.
  • the functional group (b1) is preferably a hydroxyl group, a carboxyl group, an amino group, or a mercapto group, more preferably a hydroxyl group or a carboxyl group, and still more preferably a hydroxyl group, in that the conductive polymer (B) can be efficiently formed.
  • the ionic compound (B1) may have one type of functional group (b1), or may have two or more types of functional groups (b1) in combination.
  • the amino group also includes --NH 2 and --NHR (R is an alkyl group having 1 to 6 carbon atoms).
  • the compound (B2) preferably has 3 or more functional groups (b2) in the molecule.
  • the above polymerization reaction with the ionic compound (B1) proceeds to form the three-dimensional network structure of the conductive polymer (B). It is preferable in that it can be formed efficiently.
  • the number of functional groups (b2) that the compound (B2) has in the molecule is preferably 3 to 8, more preferably 3 to 6, in that the three-dimensional network structure of the conductive polymer (B) can be efficiently formed. is more preferred, 3 to 5 is more preferred, and 3 or 4 is even more preferred.
  • the functional group (b2) is an isocyanate group, a thioisocyanate group, an epoxy group, an aziridinyl group, an oxazolinyl group, a carbodiimide group, a (meth ) is preferably at least one functional group selected from the group consisting of an acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, and a styryl group.
  • the configuration in which the functional group (b2) is selected from these functional groups is preferable in that the functional group (b1) is easily polymerized and the conductive polymer (B) can be efficiently formed.
  • the functional group (b2) is preferably an isocyanate group, a thioisocyanate group, or an epoxy group, more preferably an isocyanate group or an epoxy group, and an isocyanate group.
  • the compound (B2) may have one type of functional group (b2), or may have two or more types of functional groups (b2) in combination.
  • Functional group (b1) and functional group (b2) are capable of reacting to form a covalent bond. That is, the functional group (b1) of the ionic compound (B1) and the functional group (b2) of the compound (B2) react sequentially to form a covalent bond, and the polymerization reaction proceeds, resulting in a three-dimensional network structure. can form a conductive polymer (B) having The combination of the functional group (b1) and the functional group (b2) is not particularly limited as long as they can react with each other to form a covalent bond.
  • a combination of a hydroxyl group and an isocyanate group and a combination of a carboxy group and an epoxy group are preferable from the viewpoint of high reactivity and efficient formation of the conductive polymer (B).
  • a combination in which the functional group (b1) is a hydroxyl group and the functional group (b2) is an isocyanate group is most preferable from the viewpoint of easy material availability and high reactivity.
  • an ionic compound (B1) having a hydroxyl group as the functional group (b1) and a compound (B2) having an isocyanate group as the functional group (b2) will be described. is not limited to
  • the ionic compound (B1) is an essential monomer component for constituting the conductive polymer (B), and is a monomer component for imparting an antistatic function to the conductive polymer (B).
  • the ionic compound (B1) is an ionic compound having a functional group (b1) in the molecule in the cation portion and/or the anion portion (either or both) constituting the ionic compound (B1). .
  • the ionic compound (B1) is preferably a non-volatile molten salt having transparency (ionic liquid) which is liquid (liquid) at any temperature within the range of 0 to 150°C.
  • the ionic compound (B1) can be used alone or in combination of two or more.
  • the conductive polymer (B) contains the ionic compound (B1) as a monomer component, the ionic compound (B1) is incorporated into the molecule of the conductive polymer (B). Bleeding out of the antistatic component can be suppressed even under harsh conditions, and failures such as corrosion of metal wiring due to precipitation of the antistatic agent on the surface of the pressure-sensitive adhesive layer are less likely to occur. In addition, even under harsh conditions such as a moist and hot environment, the antistatic agent must be prevented from migrating from the adhesive layer to other optical members, suppressing an increase in surface resistance, and maintaining excellent antistatic properties. can be done.
  • the pressure-sensitive adhesive layer of the present invention containing a conductive polymer (B) containing an ionic compound (B1) as a monomer component has excellent antistatic properties and durability (in particular, corrosion resistance stability and resistance value stability). is satisfactory and useful.
  • the cation moiety of the ionic compound (B1) can be used without particular limitation, and includes quaternary ammonium cations, imidazolium cations, pyridinium cations, piperinidinium cations, pyrrolidinium cations, quaternary phosphonium cations, tri Alkylsulfonium cations, pyrrole cations, pyrazolium cations, guanidinium cations, and the like. Phosphonium cations, trialkylsulfonium cations are more preferred, and quaternary ammonium cations are even more preferred.
  • the anions include SCN ⁇ , BF 4 ⁇ , PF 6 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 - , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6 - , F ( HF ) n- , (CN ) 2N- , C4F9SO3- , ( C2F5SO2 ) 2N- , C3F7COO- , (CF3SO2 ) ( CF3CO )N- , B (CN) 4- , C ( CN) 3- , N (CN ) 2- , CH3OSO3- , C2H5OSO3- , C
  • an ion represented by the following general formula (B) is used in that the conductive polymer (B) can be efficiently formed. It is preferably a chemical compound.
  • X + is a cation moiety.
  • Y ⁇ is an anion.
  • Z 1 and Z 2 are the same or different and each represents a single bond, an alkylene group having 1 to 16 carbon atoms, or a polyoxyalkylene group.
  • n 1 is 1 and n 2 is an integer of 1-3. When n 2 is 2 or more, two or more Z 2 in parentheses may be the same or different.
  • the cation moiety (X + ) constituting the ionic compound represented by the general formula (B) includes a quaternary ammonium group, an imidazolium group, a pyridinium group, a piperinidinium group, a pyrrolidinium group, a pyrrole group and a quaternary phosphonium group. , a trialkylsulfonium group, a pyrazolium group, a guanidinium group, and the like.
  • a quaternary ammonium group is particularly excellent in transparency and is a preferred embodiment for electronic and optical applications.
  • quaternary ammonium groups are suitable because they are less likely to inhibit general radical polymerization reactions during ultraviolet (UV) curing and are presumed to have high curability.
  • n 1 +n 2 is 2, dimethylammonium group, diethylammonium group, dipropylammonium group, methylethylammonium group, methylpropylammonium group, methylbenzylammonium group, ethylbenzylammonium group group, methyloctadecylammonium group, ethyloctadecylammonium group, methyloleyl ammonium group, ethyl oleyl ammonium group, etc.
  • dimethyl ammonium group and methyl oleyl ammonium group are particularly preferable in terms of easy availability of inexpensive industrial materials. form.
  • the anions include SCN ⁇ , BF 4 ⁇ , PF 6 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF3COO- , CH3SO3- , CF3SO3- , ( FSO2 ) 2N- , ( CF3SO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF 6- , NbF6- , TaF6- , F ( HF ) n- , ( CN) 2N- , C4F9SO3- , (C2F5SO2 ) 2N- , C3F7COO - , ( CF3SO2 ) ( CF3CO )N- , B (CN ) 4- , C ( CN ) 3- , N(CN) 2- , CH3OSO3-
  • Z 1 and Z 2 constituting the ionic compound represented by the general formula (B) are a single bond, an alkylene group having 1 to 16 carbon atoms, or a polyoxyalkylene group.
  • the alkylene group having 1 to 16 carbon atoms is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms.
  • Specific examples include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, etc., and an ethylene group and a trimethylene group are preferable.
  • polyoxyalkylene group a polyoxyalkylene group in which oxyalkylene units having 2 to 4 carbon atoms are polymerized with a degree of polymerization of 2 to 8 is preferable.
  • Z 1 and Z 2 may be the same or different.
  • Specific examples of the group represented by -Z 1 -OH or -Z 2 -OH in the above general formula (B) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and a hydroxyhexyl group. and polyoxyalkylene groups such as a hydroxyalkyl group such as a polyoxyethylene group and a polyoxypropylene group.
  • the groups represented by -Z 1 -OH and -Z 2 -OH may be the same or different.
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 1
  • Z 1 and Z 2 are alkylene groups.
  • Specific examples of embodiments include bis(2-hydroxyethyl)-dimethylammonium bis(fluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-butylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxy Ethyl)-methyl-octylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-decylammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-dodecylammonium bis(trifluoro romethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-methyl-
  • X + is a quaternary ammonium group
  • n 1 is 1
  • n 2 is 1
  • Z 1 and Z 2 are polyoxyalkylene groups.
  • Specific examples of the aspect are bis(polyoxyethylene)-methyl-octylammonium bis(trifluoromethanesulfonyl)imide, bis(polyoxyethylene)-methyl-decylammonium bis(trifluoromethanesulfonyl)imide, bis(poly oxyethylene)-methyl-dodecylammonium bis(trifluoromethanesulfonyl)imide, bis(polyoxyethylene)-methyl-tetradecylammonium bis(trifluoromethanesulfonyl)imide, bis(polyoxyethylene)-methyl-hexadecylammonium bis( trifluoromethanesulfonyl)imide, bis(polyoxyethylene)-methyl-o
  • the content (percentage) of the ionic compound (B1) with respect to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, but the pressure-sensitive adhesive layer of the present invention has sufficient antistatic performance. From the point that it can be imparted, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and 20 parts by weight with respect to 100 parts by weight of the total amount of the monomer components constituting the conductive polymer (B). Above, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more may be included.
  • the content of the ionic compound (B1) is not particularly limited, but the conductive polymer (B) is added in order to easily ensure durability such as transparency, appearance, and adhesion reliability in the pressure-sensitive adhesive layer of the present invention.
  • the conductive polymer (B) is added in order to easily ensure durability such as transparency, appearance, and adhesion reliability in the pressure-sensitive adhesive layer of the present invention.
  • 90 parts by weight or less more preferably 85 parts by weight or less, still more preferably 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight or less per 100 parts by weight of the total amount of the constituent monomer components may contain.
  • the conductive polymer (B) contains, as a monomer component, a non-ionic compound (B1′) having two or more hydroxyl groups in the molecule as the functional group (b1) within a range that does not impair the effects of the present invention. may be
  • polyols can be used without particular limitation. Examples include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4- butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxy C2-4 alkylene glycol (polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.), bisphenol A and its Alkylene oxide adducts, bisphenol F and its alkylene oxide adducts, hydrogenated bisphenol A and its alkylene oxide adducts, hydrogenated bisphenol F and its alkylene oxide adducts, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, isosorbide , xylene glycol, xylene glycol, x
  • the content (percentage) of the ionic compound (B1′) with respect to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, but the pressure-sensitive adhesive layer of the present invention has sufficient antistatic performance.
  • the lower limit of the content (ratio) of the ionic compound (B1') is not particularly limited, but may be 0.01 parts by weight or more.
  • the compound (B2) is an essential monomer component for forming the conductive polymer (B) together with the ionic compound (B1).
  • the compound (B2) has three or more functional groups (b2) in the molecule.
  • the compound (B2) can be used alone or in combination of two or more.
  • the polyfunctional isocyanate having 3 or more isocyanate groups in the molecule may be either aromatic or aliphatic.
  • Aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates are preferable from the viewpoint of formation, and in particular, aromatic diisocyanates, aliphatic diisocyanates, or polyhydric alcohol adducts of alicyclic diisocyanates, or aromatic diisocyanates, and aliphatic diisocyanates. , or polymers of alicyclic diisocyanates are more preferred.
  • Polyhydric alcohol adducts of polyhydric alcohol adducts of aromatic diisocyanates, aliphatic diisocyanates, or alicyclic diisocyanates include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, Excess amount of aromatic diisocyanate such as isocyanate, tetramethylxylylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1 , 2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diiso
  • a terminal isocyanate-containing compound obtained by reacting an excess amount of an alicyclic diisocyanate such as dimer acid diisocyanate or norbornene diisocyanate with a polyhydric alcohol is exemplified.
  • tolylene diisocyanate xylylene diisocyanate, 1,6-hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, or A polyhydric alcohol adduct of isophorone diisocyanate is preferred.
  • polyhydric alcohols used herein include aliphatic polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol, with trimethylolpropane being preferred.
  • Polymers of aromatic diisocyanates, aliphatic diisocyanates, or alicyclic diisocyanates include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like.
  • aromatic diisocyanates 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, Aliphatic groups with 2 to 12 carbon atoms (excluding carbon in NCO) such as 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, dodecamethylene diisocyanate, and lysine diisocyanate 3 to 6 amounts of diisocyanate or alicyclic diisocyanate such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyan
  • polyfunctional isocyanate having 3 or more isocyanate groups in the molecule commercially available products can be used.
  • Propane/tolylene diisocyanate adduct [manufactured by Tosoh Corporation, trade name "Coronate L”], trimethylolpropane/hexamethylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”], trimethylolpropane/ Xylylene diisocyanate adduct [manufactured by Mitsui Chemicals, Inc., trade name “Takenate D-110N”], tolylene diisocyanate isocyanurate [manufactured by Mitsui Chemicals, trade name “Takenate D-262”], tolylene Trimethylolpropane adduct of isocyanate [manufactured by Mitsui Chemicals, Inc., trade name “Takenate D-101E
  • the content (ratio) of the compound (B2) with respect to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, but the three-dimensional network structure of the conductive polymer (B) can be efficiently formed. From the viewpoint of being able to form, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and 20 parts by weight, relative to 100 parts by weight of the total amount of the monomer components constituting the conductive polymer (B). Above, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more may be included.
  • the content of the compound (B2) is not particularly limited, but the total amount of the monomer components constituting the conductive polymer (B) is 100 parts by weight from the viewpoint of easily ensuring the flexibility and stress relaxation properties of the pressure-sensitive adhesive layer of the present invention. , preferably 90 parts by weight or less, more preferably 85 parts by weight or less, more preferably 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight or less.
  • the content (proportion) of the polyfunctional isocyanate having 3 or more isocyanate groups in the molecule with respect to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, but the conductive polymer (B) From the viewpoint of being able to efficiently form a three-dimensional network structure, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and still more preferably may comprise 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more.
  • the conductive polymer (B) Preferably 90 parts by weight or less, more preferably 85 parts by weight or less, still more preferably 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight with respect to 100 parts by weight of the total amount of the monomer components constituting the May include:
  • the conductive polymer (B) contains, as a monomer component, a non-ionic compound (B2′) having two isocyanate groups in the molecule as functional groups (b2) within a range that does not impair the effects of the present invention.
  • may be Compound (B2') includes the aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates described above.
  • the content (ratio) of the ionic compound (B2′) to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, but the three-dimensional network structure of the conductive polymer (B) is From the viewpoint of efficient formation, it is preferably 30 parts by weight or less (for example, 0 to 30 parts by weight), more preferably 20 parts by weight or less, relative to 100 parts by weight of the total amount of the monomer components constituting the conductive polymer (B). and more preferably 10 parts by weight or less, 5 parts by weight or less, 1 part by weight or less, or 0.1 parts by weight or less.
  • the lower limit of the content (ratio) of the ionic compound (B2′) is not particularly limited, but may be 0.01 parts by weight or more.
  • the ratio of the ionic compound (B1) to the compound (B2) in the conductive polymer (B) is not particularly limited, but is sufficient for the pressure-sensitive adhesive layer of the present invention. From the point of being able to impart antistatic performance, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, 0.4 or more, 0.5 or more, or 0.6 or more good too. In addition, from the viewpoint of being able to efficiently form the three-dimensional network structure of the conductive polymer (B), the ratio is preferably 4 or less, more preferably 3.5 or less, even more preferably 3 or less, 2.5 or less, Or it may be 2 or less.
  • the "mixture of monomer components constituting the conductive polymer (B)" includes the ionic compound (B1), the compound (B2), and optionally the compounds (B1') and (B2') at room temperature or It can be prepared by stirring and mixing while heating if necessary.
  • the "partially polymerized product of the mixture of monomer components constituting the conductive polymer (B)” is prepared by adding the "mixture of the monomer components constituting the conductive polymer (B)" to the presence of a crosslinking catalyst in the presence of a crosslinking retarder. It can be prepared by allowing the polymerization reaction to proceed in the presence or absence of.
  • Any appropriate catalyst can be used as the cross-linking catalyst that can be used when obtaining the partial polymer.
  • Examples of such catalysts include tertiary amine compounds and organometallic compounds.
  • tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU).
  • organometallic compounds examples include tin-based compounds and non-tin-based compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
  • DBTDL dibutyltin dilaurate
  • dibutyltin diacetate dibutyltin sulfide, tributyltin sulfide, tributyltin oxide
  • non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride
  • lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate
  • cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate
  • zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate
  • zirconium-based compounds such as zirconium naphthenate
  • the amount of the crosslinking catalyst used is preferably 0.01 to 1.0% by weight with respect to the mixture of monomer components.
  • a cross-linking retarder may be used together with the cross-linking catalyst when obtaining the partial polymer.
  • a cross-linking retarder By using a cross-linking retarder, the effect of extending the pot life of the pressure-sensitive adhesive composition can be realized.
  • the cross-linking retarder a compound that causes keto-enol tautomerism can be preferably used.
  • Various ⁇ -dicarbonyl compounds can be used as compounds that cause keto-enol tautomerism.
  • ⁇ -diketones acetylacetone, 2,4-hexanedione, etc.
  • acetoacetic esters methyl acetoacetate, ethyl acetoacetate, etc.
  • a crosslinking retarder can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the cross-linking retarder used can be, for example, 0.1 to 30 parts by weight, or 0.5 to 25 parts by weight, per 100 parts by weight of the mixture of the monomer components.
  • the reaction temperature for obtaining the partial polymer is preferably less than 100°C, more preferably 50°C to 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become difficult to obtain the partial polymer having a predetermined molecular weight.
  • the reaction time is not particularly limited, but can be selected from 1 hour to 72 hours.
  • the content of the conductive polymer (B) in the adhesive composition of the present invention is not particularly limited, but is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, still more preferably 10 to 20% by weight. % by weight.
  • a configuration in which the content of the conductive polymer (B) is 5% by weight or more is preferable from the viewpoint of imparting sufficient antistatic performance to the pressure-sensitive adhesive layer of the present invention.
  • the configuration in which the content of the conductive polymer (B) is 30% by weight or less is preferable in that excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the content ratio of the conductive polymer (B) to the adhesive polymer (A) is preferably 0.05 to 0.5.
  • the configuration in which the content ratio is 0.05 or more is preferable in that excellent antistatic properties can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the content is preferably 0.07 or more, more preferably 0.08 or more, and still more preferably 0.1 or more, from the viewpoint that excellent antistatic properties can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the configuration in which the content ratio is 0.5 or less is preferable in that excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the content ratio is preferably 0.4 or less, more preferably 0.3 or less, from the viewpoint that excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive composition of the present invention may contain an antistatic agent as long as the effects of the present invention are not impaired.
  • the antistatic agent include materials capable of imparting antistatic properties, such as ionic compounds, ionic surfactants, conductive polymers, and conductive fine particles. Among these, ionic compounds are preferred from the viewpoint of compatibility with the adhesive polymer (A) and conductive polymer (B) and transparency of the adhesive layer.
  • an inorganic cation anion salt and/or an organic cation anion salt can be preferably used, and it is particularly preferable to use an inorganic cation anion salt.
  • An ionic compound containing an inorganic cation (inorganic cation anion salt) is more preferable than an organic cation anion salt because it can suppress a decrease in adhesiveness (anchor force) of the pressure-sensitive adhesive layer when used.
  • the term "inorganic cation anion salt" as used in the present invention generally indicates an alkali metal salt formed from an alkali metal cation and an anion, and the alkali metal salt includes organic salts and inorganic salts of alkali metals. can be used.
  • organic cation anion salt as used in the present invention means an organic salt whose cation part is composed of an organic substance, and whose anion part may be an organic substance or an inorganic substance.
  • Organic cation anion salts are also referred to as ionic liquids and ionic solids.
  • anion component constituting the ionic compound it is preferable to use a fluorine-containing anion from the viewpoint of antistatic function.
  • alkali metal ions that make up the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.
  • the anion portion of the alkali metal salt may be composed of an organic substance or may be composed of an inorganic substance.
  • the anion moiety constituting the organic salt include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , C 4 F 9 SO 3 - , C3F7COO- , ( CF3SO2 ) ( CF3CO )N- , -O3S ( CF2 ) 3SO3- , PF6- , CO32- , or the following general formula ( 1) to (4), (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (where n is an integer of 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (where m is an integer of 1 to 10), (3): - O 3 S(CF 2 ) l SO 3 - (where l is an integer of
  • an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.
  • the anion portion constituting the inorganic salt include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , etc. are used.
  • fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable.
  • a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
  • alkali metal organic salts include sodium acetate , sodium alginate, sodium ligninsulfonate, sodium toluenesulfonate, LiCF3SO3 , Li( CF3SO2 ) 2N , Li( CF3SO2 ) .
  • Li(CF 3 SO 3 ) 2N Li( C2F5SO2 ) 2N , Li ( C4F9SO2 ) 2N , Li( CF3SO2 ) 3C , KO3S ( CF2 ) 3SO3K , LiO 3 S(CF 2 ) 3 SO 3 K, among others, LiCF 3 SO 3 , Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc.
  • Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N , Li(C 4 F 9 SO 2 ) 2 N and the like are preferred, and bis(trifluoromethanesulfonyl)imidelithium and bis(fluorosulfonyl)imidelithium are particularly preferred.
  • Inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
  • An organic cation anion salt is composed of a cation component and an anion component, and the cation component is composed of an organic substance.
  • cationic components include pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, Examples include pyrazolium cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and the like.
  • anion components include Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH3SO3- , CF3SO3- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , TaF6- , ( CN ) 2N- , C4F 9 SO 3 ⁇ , C 3 F 7 COO ⁇ , ((CF 3 SO 2 )(CF 3 CO) N ⁇ , —O 3 S(CF 2 ) 3 SO 3 ⁇ , and compounds represented by the following general formulas (1) to (4) ), (1): (C n F 2n+1 SO 2 ) 2 N ⁇ (where n is an integer of 1 to 10), (2): CF 2 (C m F
  • anions containing a fluorine atom are particularly preferred because they yield ionic compounds with good ion dissociation properties.
  • fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable.
  • a bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability in a humidified or heated environment.
  • the ionic compounds include inorganic compounds such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. salt. These ionic compounds can be used alone or in combination.
  • ionic surfactants examples include cationic surfactants (e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.) and anionic surfactants (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.). , Zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic (polyhydric alcohol derivative, ⁇ -cyclodextrin inclusion compound, sorbitan fatty acid monoester/diester, polyalkylene oxide derivative, amine oxide, etc.).
  • cationic surfactants e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.
  • anionic surfactants carboxylic acid type, sulfonate type, sulfate type,
  • Examples of conductive polymers include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Among these, polyaniline, polythiophene, and the like are preferably used. Polythiophene is particularly preferred.
  • Examples of conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Among these, the tin oxide type is preferable. Tin oxides include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composite, titanium oxide- Composites of tin oxide and the like can be mentioned.
  • the fine particles have an average particle size of about 1 to 100 nm, preferably 2 to 50 nm.
  • antistatic agents other than the above acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salt, etc.), amphoteric ion type (betaine compound, etc.), anionic type (sulfonic acid salts, etc.), homopolymers of monomers having nonionic (glycerin, etc.) ion-conductive groups or copolymers of the above monomers with other monomers, acrylates or methacrylates having a quaternary ammonium base Polymers having ionic conductivity such as polymers having sites of origin; and permanent antistatic agents of the type in which hydrophilic polymers such as polyethylene methacrylate copolymers are alloyed with acrylic resins or the like.
  • the content is not particularly limited, but from the viewpoint of ensuring durability such as transparency, appearance, and contact reliability of the pressure-sensitive adhesive layer of the present invention Therefore, it is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, 0.4 parts by weight or less, 0.4 part by weight or less, based on 100 parts by weight of the total amount of the adhesive polymer (A) and the conductive polymer (B). It may be 3 parts by weight or less, or 0.2 parts by weight or less.
  • the lower limit of the content is not particularly limited. , 0.01 parts by weight or more, or 0.05 parts by weight or more.
  • the pressure-sensitive adhesive composition of the present invention may optionally contain a cross-linking agent, a cross-linking accelerator, a silane coupling agent, a tackifying resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), an anti-aging agent, Known additives such as fillers, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, rust preventives, etc., can enhance the properties of the present invention. It may be included as long as it does not cause damage. In addition, such an additive may be used individually or in combination of 2 or more types.
  • the base polymer is cross-linked to increase the gel fraction, making it easier to improve the resistance to foaming and peeling.
  • the acrylic polymer (A) by cross-linking the acrylic polymer (A), the control of the gel fraction can be easily increased, so that the resistance to foaming and peeling can be easily improved.
  • the acrylic polymer (A) and the conductive polymer (B) can form a covalent bond via a cross-linking agent.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal Examples include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents.
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer containing an acrylic polymer (A) as a base polymer
  • isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable and more preferable from the viewpoint of improving resistance to foaming and peeling.
  • a crosslinking agent may be used individually or in combination of 2 or more types.
  • isocyanate-based crosslinking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate; , cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate , xylylene diisocyanate and other aromatic polyisocyanates.
  • lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate
  • cyclopentylene diisocyanate cycl
  • isocyanate-based cross-linking agent examples include trimethylolpropane/tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”], trimethylolpropane/hexamethylene diisocyanate adduct [Nippon Polyurethane Kogyo Co., Ltd., trade name “Coronate HL”], trimethylolpropane/xylylene diisocyanate adduct [Mitsui Chemicals Co., Ltd., trade name “Takenate D-110N”].
  • epoxy-based cross-linking agent examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether , glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition of the present invention is not particularly limited. Parts by weight are preferred, more preferably 0.01 to 5 parts by weight. When the content of the cross-linking agent is 0.001 parts by weight or more, the resistance to foaming and peeling is easily improved, which is preferable. On the other hand, when the content of the cross-linking agent is 10 parts by weight or less, the pressure-sensitive adhesive layer has appropriate flexibility and the pressure-sensitive adhesive strength is easily improved, which is preferable.
  • the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent, excellent adhesion to glass (in particular, excellent adhesion reliability to glass at high temperature and high humidity) can be easily obtained, which is preferable.
  • the silane coupling agent include, but are not limited to, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane. etc. Among them, ⁇ -glycidoxypropyltrimethoxysilane is preferred.
  • silane coupling agent examples include commercially available products such as the product name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a silane coupling agent may be used individually or in combination of 2 or more types.
  • the content of the silane coupling agent in the adhesive composition of the present invention is not particularly limited, but from the viewpoint of improving the adhesion reliability to glass, the total amount of the adhesive polymer (A) and the conductive polymer (B) is 100 weight. 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.
  • the pressure-sensitive adhesive composition of the present invention contains a coloring agent (pigment, dye, etc.), it prevents reflection due to metal wiring, metal oxides such as ITO, etc., and contributes to prevention of RGB color mixing and improvement of contrast. It is preferable because it is possible.
  • a coloring agent pigment, dye, etc.
  • the coloring agent may be a dye or a pigment as long as it can be dissolved or dispersed in the adhesive composition of the present invention.
  • Dyes are preferred because they can achieve a low haze even when added in small amounts, and are easy to distribute uniformly without sedimentation like pigments. Pigments are also preferred because they have high color development even when added in small amounts. If a pigment is used as the colorant, it preferably has low or no conductivity. Moreover, when a dye is used, it is preferable to use it together with an antioxidant or the like.
  • Pigments include Tokushiki's “9050BLACK”, “UVBK-0001", carbon black, and titanium black.
  • dyes include “VALIFAST BLACK 3810” and “NUBIAN Black PA-2802” manufactured by Orient Chemical Industries.
  • the content of the colorant in the adhesive composition of the present invention is, for example, about 0.01 to 20 parts by weight with respect to 100 parts by weight (total amount) of the adhesive polymer (A) and the conductive polymer (B). and may be appropriately set according to the type of coloring agent, the color tone and light transmittance of the pressure-sensitive adhesive layer, and the like. Colorants may be added to the composition as a solution or dispersion dissolved or dispersed in a suitable solvent.
  • interpenetrating polymer network or semi-interpenetrating polymer network In the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (1) of the present invention, the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or semi-interpenetrating polymer network. It forms an interpenetrating polymer network.
  • the structure imparts adhesiveness to the adhesive layer of the present invention with the adhesive polymer (A), imparts antistatic properties to the adhesive layer of the present invention with the conductive polymer (B), and the conductive
  • the three-dimensional network structure of the adhesive polymer (B) and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network, whereby the antistatic agent is applied to the adhesive layer surface. Defects such as corrosion of metal wiring due to the deposition of are less likely to occur, and the migration of antistatic agents from the adhesive layer to other optical members in a moist and hot environment is suppressed, suppressing increases in surface resistance.
  • the pressure-sensitive adhesive composition (1) of the present invention is less likely to cause defects in durability (in particular, corrosion resistance stability and resistance value stability), exhibits a low surface resistivity, and has excellent antistatic performance.
  • An adhesive layer can be formed.
  • the functional group (b1) of the ionic compound (B1) and the functional group (b2) of the compound (B2) react to form a covalent bond
  • a conductive polymer (B) having a three-dimensional network structure is formed, and the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • the pressure-sensitive adhesive composition (2) of the present invention is a mixture containing the ionic compound (B1) and the compound (B2), or a partial polymer of a mixture containing the ionic compound (B1) and the compound (B2).
  • the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, the polymerization reaction proceeds, and the three-dimensional network structure can form a conductive polymer (B) having During the course of the polymerization reaction, the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • the pressure-sensitive adhesive composition (2) of the present invention is less likely to cause defects in durability (in particular, corrosion resistance stability and resistance value stability), exhibits a low surface resistivity, and has excellent antistatic performance.
  • An adhesive layer can be formed.
  • IPN interpenetrating polymer network
  • An "interpenetrating polymer network (IPN)" is two or more highly polymerized polymers that are at least partially intertwined at the molecular level but are not covalently bonded to each other and cannot be separated unless the chemical bonds are broken. It is a material containing a molecular network structure, and refers to a form in which the crosslinked structures of two or more polymers having a crosslinked structure are entangled with each other. That is, the three-dimensional network structure of the conductive polymer (B) and the interpenetrating polymer network (IPN) formed by the entanglement of the adhesive polymer (A) means that the adhesive polymer (A) has a crosslinked structure. , and the crosslinked structure is entangled with the three-dimensional network structure of the conductive polymer (B).
  • a “semi-interpenetrating polymer network (Semi-IPN)” is a material containing one or more polymer network structures and one or more linear or branched polymers.
  • a material characterized in that at least one network structure is penetrated by at least some linear or branched macromolecules at the molecular level, and one or more macromolecules having a crosslinked structure It refers to a form in which one or more polymer chains that do not have a crosslinked structure are entangled with a crosslinked structure.
  • a semi-interpenetrating polymer network formed by entangling the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) is formed by cross-linking the adhesive polymer (A). It has no structure, and shows a form in which the chain structure is entangled with the three-dimensional network structure of the conductive polymer (B).
  • Semi-interpenetrating polymeric networks are distinguished from interpenetrating polymeric networks because the constituent linear or branched polymers can be separated from the constituent polymeric networks without breaking chemical bonds.
  • the form in which the conductive polymer (B) and the adhesive polymer (A) are further covalently crosslinked by, for example, the above-described crosslinking agent is also an interpenetrating polymer network and a semi-interpenetrating polymer network in the present invention. It shall be included in the polymer network.
  • the method of forming the "interpenetrating polymer network" in the present invention is not particularly limited.
  • the mixture is subjected to a polymerization reaction of the adhesive polymer (A) and the conductive polymer (B) in a form in which the adhesive polymer (A) and the conductive polymer (B) do not react with each other to form crosslinks due to covalent bonds. can be carried out by allowing the polymerization reactions to proceed simultaneously or sequentially.
  • the method for forming the "semi-interpenetrating polymer network" in the present invention is not particularly limited.
  • the polymerization reactions of (B) can be carried out simultaneously or sequentially.
  • the "polymerization reaction of the adhesive polymer (A)” can be carried out in the same manner as the “polymerization method of the acrylic polymer (A)” described above.
  • the “polymerization reaction of the conductive polymer (B)” can be carried out in the same manner as the above-mentioned “method of obtaining a partially polymerized mixture of monomer components constituting the conductive polymer (B)".
  • the "method for polymerizing the acrylic polymer (A)” and/or the “polymerization reaction for the conductive polymer (B)” described above may be performed after forming the pressure-sensitive adhesive layer, which will be described later.
  • a specific method for forming the "interpenetrating polymer network formed by entangling the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A)" in the present invention preferably includes: It includes the following steps. (1) A mixture containing a monomer component constituting the adhesive polymer (A) and a component capable of imparting a crosslinked structure to the adhesive polymer (A), such as the above-mentioned cross-linking agent and polyfunctional monomer, is subjected to a polymerization reaction. to form an adhesive polymer (A) having a crosslinked structure.
  • a conductive polymer (B) having a three-dimensional network structure is formed by the above-described "method for obtaining a partially polymerized product of a mixture of monomer components constituting the conductive polymer (B)".
  • the crosslinked structure of the adhesive polymer (A) formed in step (1) is entangled with the three-dimensional network structure of the conductive polymer (B) formed in step (2), resulting in the "interpenetrating polymer network” of the present invention. ” can be formed.
  • a specific method for forming a "semi-interpenetrating polymer network formed by entangling a three-dimensional network structure of a conductive polymer (B) and an adhesive polymer (A)" in the present invention is preferably , which includes the following steps.
  • (1′) A mixture containing a monomer component constituting the adhesive polymer (A) and not containing a component capable of imparting a crosslinked structure to the adhesive polymer (A), such as the above-mentioned cross-linking agent or polyfunctional monomer, is subjected to a polymerization reaction. to form a linear or branched adhesive polymer (A) having no crosslinked structure.
  • the formed adhesive polymer (A), a mixture of monomer components constituting the conductive polymer (B) or a partial polymer thereof, the above-mentioned crosslinking catalyst, and, if necessary, a crosslinking retarder are blended.
  • the conductive polymer (B) having a three-dimensional network structure is formed by the above-mentioned "method for obtaining a partially polymerized product of a mixture of monomer components constituting the conductive polymer (B)".
  • the linear or branched adhesive polymer (A) formed in step (1′) penetrates and entangles the three-dimensional network structure of the conductive polymer (B) formed in step (2′). , can form the "semi-interpenetrating polymeric network" of the present invention.
  • the pressure-sensitive adhesive layer of the present invention is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive layer of the present invention has excellent antistatic performance. Therefore, display defects due to static electricity can be suppressed when an image display device and an optical member are attached to each other via the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
  • the surface resistivity (according to JIS K 6271) of the pressure-sensitive adhesive layer of the present invention is preferably 1.0 ⁇ from the viewpoint of excellent antistatic performance. 10 13 ⁇ / ⁇ or less, more preferably 0.5 ⁇ 10 13 ⁇ / ⁇ or less, still more preferably 1.0 ⁇ 10 12 ⁇ / ⁇ or less, and 0.5 ⁇ 10 12 ⁇ / ⁇ or less or less, or 1.0 ⁇ 10 11 ⁇ / ⁇ or less.
  • the lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but may be 1.0 ⁇ 10 5 ⁇ / ⁇ or more, or 0.5 ⁇ 10 5 ⁇ / ⁇ or more.
  • the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) suppresses the migration of the antistatic agent from the pressure-sensitive adhesive layer to other optical members even in a moist and hot environment, thereby improving the surface resistance. It is possible to suppress the increase in the value and maintain excellent antistatic performance. Therefore, display defects due to static electricity can be suppressed even in a wet and hot environment after the image display device and the optical member are bonded together via the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive layer of the present invention is suitably used for manufacturing image display devices.
  • the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) was placed in an environment of 85°C and 85% RH for 168 hours and then taken out, and then placed in an environment of 23°C and 50% RH.
  • the surface resistivity of the adhesive layer surface after performing temperature and humidity control for 72 hours is preferably 1.0 ⁇ 10 13 ⁇ / ⁇ or less, and more It is preferably 0.5 ⁇ 10 13 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 12 ⁇ / ⁇ or less, 0.5 ⁇ 10 12 ⁇ / ⁇ or less, or 1.0 ⁇ 10 11 ⁇ / ⁇ or less.
  • the lower limit of the surface resistivity of the pressure-sensitive adhesive layer of the present invention after the humidification test is not particularly limited, but is 1.0 ⁇ 10 5 ⁇ / ⁇ or more, or 0.5 ⁇ 10 5 ⁇ / ⁇ or more. good too.
  • the surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after the humidification test can be measured by the method described in Examples below.
  • the surface resistivity of the pressure-sensitive adhesive layer of the present invention and the surface resistivity after a humidification test are determined by the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, and the ionic compound ( B1), the type and ratio of the compound (B2), the amount ratio of the adhesive polymer (A) and the conductive polymer (B), the type and amount of other additives, curing conditions, etc. can be adjusted.
  • the adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) is transparent or has transparency. Therefore, the visibility and appearance through the pressure-sensitive adhesive layer of the present invention are excellent. Thus, the pressure-sensitive adhesive layer of the present invention is suitable for optical applications.
  • the haze (according to JIS K7136) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 3% or less, more preferably 1%. 0.7% or less, or 0.6% or less. A haze of 3% or less is preferable because excellent transparency and appearance can be obtained.
  • the haze is, for example, an adhesive layer (thickness: 100 ⁇ m), which is allowed to stand in a normal state (23° C., 50% RH) for at least 24 hours, and then slide glass (for example, total light transmittance of 92%, Haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N").
  • HM-150N haze meter
  • the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive layer of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. may When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable.
  • the above total light transmittance is measured, for example, by using an adhesive layer (thickness: 100 ⁇ m), leaving it at normal conditions (23° C., 50% RH) for at least 24 hours, and then removing it if it has a release liner.
  • a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N”) is used as a sample, which is peeled off and laminated on a slide glass (for example, a total light transmittance of 92% and a haze of 0.2%). ”).
  • the total light transmittance and haze of the adhesive layer of the present invention can be measured according to JIS K7136 and JIS K7361-1, respectively.
  • the total light transmittance and haze of the pressure-sensitive adhesive layer of the present invention are determined by the monomer composition constituting the pressure-sensitive adhesive polymer (A), the amount of the cross-linking agent, the ionic compound (B1) constituting the conductive polymer (B), the compound ( It can be adjusted by the type and proportion of B2), the amount ratio of the adhesive polymer (A) and the conductive polymer (B), the type and amount of other additives, curing conditions, and the like.
  • the gel fraction (ratio of solvent-insoluble components) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 40-95%, more preferably 50-92%, and still more preferably 55-90%.
  • the cohesive force of the pressure-sensitive adhesive layer is improved, causing foaming and peeling at the interface with the adherend in a high-temperature environment, dents during handling, and edges during processing. Contamination of the part is suppressed, and it is easy to obtain excellent anti-foaming peeling property, which is preferable.
  • the gel fraction is 95% or less, appropriate flexibility can be obtained, and the adhesiveness and step followability are further improved, which is preferable.
  • the gel fraction (ratio of solvent-insoluble components) is, for example, a value calculated by the following "Method for measuring gel fraction".
  • Adhesive layer About 0.1 g was collected from the adhesive sheet, wrapped in a porous tetrafluoroethylene sheet (trade name “NTF1122”, manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 ⁇ m, and tied with a kite string. The weight at that time is measured, and the weight is taken as the weight before immersion. The weight before immersion is the total weight of the adhesive layer (the adhesive layer collected above), the tetrafluoroethylene sheet, and the kite string. Also, the total weight of the tetrafluoroethylene sheet and the kite string is measured, and this weight is taken as the weight of the package.
  • the gel fraction is, for example, the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, the ionic compound (B1) constituting the conductive polymer (B), the type of the compound (B2), It can be adjusted by the ratio, the amount ratio of the adhesive polymer (A) and the conductive polymer (B), the type and amount of other additives, curing conditions, and the like.
  • the storage modulus of the pressure-sensitive adhesive layer of the present invention at 25° C. and 1 Hz is not particularly limited, but is preferably 3 ⁇ 10 4 Pa or more.
  • the configuration in which the pressure-sensitive adhesive layer of the present invention has a storage elastic modulus of 3 ⁇ 10 4 Pa or more at 25° C. and 1 Hz is preferable in that dents are less likely to occur during handling.
  • the storage elastic modulus of the pressure-sensitive adhesive layer of the present invention at 25° C. and 1 Hz is more preferably 5 ⁇ 10 4 Pa or more, more preferably 1 ⁇ 10 5 Pa or more, in that dents on the pressure-sensitive adhesive layer of the present invention can be suppressed.
  • the upper limit of the storage elastic modulus at 25° C. and 1 Hz of the pressure-sensitive adhesive layer of the present invention is not particularly limited, it is preferably 5 ⁇ 10 6 Pa or less, and 1 ⁇ It may be 10 6 Pa or less.
  • the storage modulus of the pressure-sensitive adhesive sheet of the present invention at 25°C and 1 Hz can be measured by dynamic viscoelasticity measurement.
  • the storage elastic modulus at 25° C. and 1 Hz of the pressure-sensitive adhesive sheet of the present invention depends on the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, and the ionic compound (B1) constituting the conductive polymer (B). , the type and proportion of the compound (B2), the amount ratio of the adhesive polymer (A) and the conductive polymer (B), the type and amount of other additives, curing conditions, and the like.
  • the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 5 to 250 ⁇ m, more preferably 7 to 240 ⁇ m, 10 to 230 ⁇ m, 12 to 220 ⁇ m, 15 to 210 ⁇ m, 20 to 200 ⁇ m, 23 to 175 ⁇ m, or 25 to 150 ⁇ m. may be When the thickness is at least a certain value, the followability to unevenness and adhesion reliability are improved, which is preferable. In addition, when the thickness is a certain value or less, it is particularly excellent in handleability and manufacturability, which is preferable.
  • the method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited. For example, it can be produced by preparing the pressure-sensitive adhesive composition (precursor composition) of the present invention and, if necessary, performing irradiation with active energy rays, heat drying, and the like. Specifically, an additive or the like is added to the adhesive polymer (A), the conductive polymer (B), a mixture of monomer components constituting the conductive polymer (B), or a partial polymer thereof, if necessary. and mixing, and the like. After forming the pressure-sensitive adhesive layer of the present invention, the above-described "polymerization method of the acrylic polymer (A)" and/or “polymerization reaction of the conductive polymer (B)" may be performed.
  • the method for producing the pressure-sensitive adhesive layer of the present invention is not particularly limited. and curing.
  • a known coating method may be used for applying (coating) the pressure-sensitive adhesive composition.
  • coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters may be used.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it has the pressure-sensitive adhesive layer of the present invention (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention).
  • the pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet in which both sides are pressure-sensitive adhesive layer surfaces, or may be a single-sided pressure-sensitive adhesive sheet in which only one side is pressure-sensitive adhesive layer surfaces. Among them, a double-sided pressure-sensitive adhesive sheet is preferable from the viewpoint of bonding two members together.
  • the term "adhesive sheet” includes a tape-like one, that is, “adhesive tape”.
  • the adhesive layer surface may be called an "adhesive surface.”
  • the adhesive sheet of the present invention may have a release liner on the adhesive surface until use.
  • the pressure-sensitive adhesive sheet of the present invention may be a so-called “base-less type” pressure-sensitive adhesive sheet (hereinafter sometimes referred to as “base-less pressure-sensitive adhesive sheet”) that does not have a base material (base layer). , a pressure-sensitive adhesive sheet having a substrate (hereinafter sometimes referred to as a “substrate-attached pressure-sensitive adhesive sheet").
  • base-less pressure-sensitive adhesive sheet a pressure-sensitive adhesive sheet having a substrate
  • substrate-less pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet consisting of only the pressure-sensitive adhesive layer, and a pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer (sometimes referred to as “another pressure-sensitive adhesive layer”). ) and the like.
  • the pressure-sensitive adhesive sheet with a substrate includes a pressure-sensitive adhesive sheet having the above pressure-sensitive adhesive layer on at least one side of a substrate.
  • a substrate-less pressure-sensitive adhesive sheet (substrate-less double-sided pressure-sensitive adhesive sheet) is preferable, and a substrate-less double-sided pressure-sensitive adhesive sheet comprising only the above pressure-sensitive adhesive layer is more preferable.
  • base material base material layer
  • the pressure-sensitive adhesive sheet of the present invention is preferably a substrate-less pressure-sensitive adhesive sheet.
  • Fig. 1 shows one embodiment of the adhesive sheet of the present invention (base-less adhesive sheet).
  • 10 is an adhesive layer
  • 11 and 12 are release liners.
  • the 180° peeling adhesive force at 23°C to the plate is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive force is high, it is preferably 4 N / 20 mm or more, more preferably 6 N /20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more.
  • the pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive force to a glass plate at 23°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved.
  • the upper limit of the 180° peeling adhesive strength of the pressure-sensitive adhesive sheet of the present invention to a glass plate at 23°C is not particularly limited. is 25 N/20 mm, 24 N/20 mm, 23 N/20 mm, 22 N/20 mm, 21 N/20 mm or 20 N/20 mm.
  • the pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive strength at 80°C to a glass plate (especially, the pressure-sensitive adhesive surface provided by the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention) is
  • the 180° peeling adhesive strength at 80°C to the plate is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive strength is high, it is preferably 4 N / 20 mm or more, more preferably 6 N /20 mm or more, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more.
  • the pressure-sensitive adhesive sheet of the present invention has a 180° peeling adhesive force to a glass plate at 80°C of a certain value or more, the adhesiveness to glass and the ability to prevent floating on steps are further improved.
  • the upper limit of the 180° peeling adhesive strength of the pressure-sensitive adhesive sheet of the present invention to a glass plate at 80°C is not particularly limited, it is preferably 18 N/20 mm, more preferably 16 N/20 mm.
  • the 180° peeling adhesion to a glass plate at 23°C or 80°C is determined by the following method for measuring 180° peeling adhesion.
  • the glass plate is not particularly limited, for example, the product name "Soda Lime Glass #0050” (manufactured by Matsunami Glass Industry Co., Ltd.) can be mentioned.
  • non-alkali glass, chemically strengthened glass, and the like can also be used.
  • A-1. 180° peeling adhesive force measurement method The adhesive surface of the adhesive sheet is adhered to the adherend, pressed under the conditions of one reciprocation of a 2 kg roller, and aged in an atmosphere of 23° C. and 50% RH for 30 minutes or 240 hours. After aging, in accordance with JIS Z 0237, in an atmosphere of 23 ° C. or 80 ° C., 50% RH, under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °, the adhesive sheet was peeled off from the adherend and peeled off 180 °. The peel adhesion (N/20 mm) is measured.
  • the thickness (total thickness) of the adhesive sheet of the present invention is not particularly limited, but is preferably 10 to 350 ⁇ m, more preferably 12 to 350 ⁇ m, still more preferably 15 to 330 ⁇ m, 18 to 325 ⁇ m, 18 to 320 ⁇ m, 20 to 300 ⁇ m, It may be 23-300 ⁇ m, 25-275 ⁇ m, or 30-250 ⁇ m.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention includes the thickness of the base material in the case of a pressure-sensitive adhesive sheet with a base material, but does not include the thickness of the release liner.
  • the haze (according to JIS K7136) of the adhesive sheet of the present invention is not particularly limited, but is preferably 3% or less, more preferably 1% or less, 0.7% or less, or 0.6% or less. . A haze of 3% or less is preferable because excellent transparency and appearance can be obtained.
  • the haze can be measured by, for example, leaving the adhesive sheet in a normal state (23 ° C., 50% RH) for at least 24 hours, peeling off the release liner if it has, and sliding glass (for example, total light transmittance 92% haze and 0.2% haze) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N").
  • HM-150N haze meter
  • the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the adhesive sheet of the present invention is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. good too. When the total light transmittance is 90% or more, excellent transparency and excellent appearance can be obtained, which is preferable.
  • the above total light transmittance can be measured, for example, by leaving the pressure-sensitive adhesive sheet in a normal state (23° C., 50% RH) for at least 24 hours, peeling off the release liner, Light transmittance of 92%, haze of 0.2%) can be used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HM-150N"). can.
  • the adhesive strength, total light transmittance and haze of the adhesive sheet of the present invention can be measured according to JIS K7136 and JIS K7361-1.
  • the adhesive strength, total light transmittance and haze of the pressure-sensitive adhesive sheet of the present invention are determined by the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, and the ionic compound (B1) constituting the conductive polymer (B). , the type and proportion of the compound (B2), the amount ratio of the adhesive polymer (A) and the conductive polymer (B), the type and amount of other additives, curing conditions, and the like.
  • the pressure-sensitive adhesive sheet of the present invention is not particularly limited, it is preferably manufactured according to a known or commonly used manufacturing method.
  • the pressure-sensitive adhesive sheet of the present invention is a substrate-less pressure-sensitive adhesive sheet, it can be obtained by forming the pressure-sensitive adhesive layer on a release liner by the method described above.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate, it may be obtained by directly forming the above-mentioned pressure-sensitive adhesive layer on the surface of the substrate (direct transfer method), or once the above pressure-sensitive adhesive layer is formed on a release liner. After forming the pressure-sensitive adhesive layer, it may be obtained by transferring (bonding) to the substrate, or by providing the above-mentioned pressure-sensitive adhesive layer on the substrate (transfer method).
  • the pressure-sensitive adhesive sheet of the present invention may have other layers in addition to the pressure-sensitive adhesive layer.
  • Examples of other layers include other adhesive layers (adhesive layers other than the above adhesive layer (adhesive layers other than the adhesive layer formed from the adhesive composition of the present invention)), intermediate layers, and undercoats. layers and the like.
  • the pressure-sensitive adhesive sheet of the present invention may have two or more other layers.
  • the substrate is not particularly limited, but examples thereof include various optical films such as plastic films, antireflection (AR) films, polarizing plates, and retardation plates. be done.
  • Plastic film Materials for the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name "Arton (cyclic olefin polymer, manufactured by JSR Corporation)", trade name “Zeonor (cyclic olefin polymer, Nippon Zeon Co., Ltd.) plastic materials such as cyclic olefin polymers such as ". These plastic materials may be used alone or in combination of two or more.
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • TAC triacetyl cellulose
  • polysulfone polyarylate
  • polyimide polyimide
  • Polyvinyl chloride polyvinyl a
  • base material is a part that is attached to the adherend together with the adhesive layer when the pressure-sensitive adhesive sheet is applied to the adherend.
  • a release liner that is peeled off when the adhesive sheet is used (attached) is not included in the “base material”.
  • the base material is preferably transparent.
  • the total light transmittance (according to JIS K7361-1) of the base material in the visible light wavelength region is not particularly limited, but is preferably 85% or more, more preferably 88% or more.
  • the haze (according to JIS K7136) of the substrate is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less.
  • transparent substrates include PET films and non-oriented films such as the trade name "Arton" and the trade name "Zeonor".
  • the thickness of the base material is not particularly limited, it is preferably 1 to 500 ⁇ m, for example.
  • the base material may have either a single-layer structure or a multilayer structure.
  • the surface of the substrate may be appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as undercoating treatment.
  • the pressure-sensitive adhesive sheet of the present invention may be provided with a release liner on the pressure-sensitive adhesive surface until use.
  • each pressure-sensitive adhesive surface may be protected by two release liners. It may be protected in a form wound in a shape.
  • a release liner is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when applied to an adherend.
  • the release liner also serves as a support for the pressure-sensitive adhesive layer. Note that the release liner may not necessarily be provided.
  • a conventional release paper or the like can be used.
  • a fluorine-based polymer e.g., polytetrafluoro ethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.
  • a low-adhesive base material made of a polymer for example, an olefin resin such as polyethylene or polypropylene
  • an olefin resin such as polyethylene or polypropylene
  • a release liner having a release treatment layer formed on at least one surface of a release liner substrate can be suitably used.
  • Base materials for such release liners include polyester film (polyethylene terephthalate film, etc.), olefin resin film (polyethylene film, polypropylene film, etc.), polyvinyl chloride film, polyimide film, polyamide film (nylon film), and rayon film.
  • plastic base films synthetic resin films
  • papers wooden paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.
  • these are laminated or co-extruded into multiple layers (composite of 2 to 3 layers) and the like.
  • the release treatment agent that constitutes the release treatment layer is not particularly limited, but for example, a silicone-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl-based release treatment agent, or the like can be used.
  • the release agents can be used alone or in combination of two or more.
  • the thickness of the release liner is not particularly limited, and may be appropriately selected from the range of 5 to 100 ⁇ m.
  • the release liner may have an antistatic layer formed on at least one surface of the release liner substrate in order to prevent damage to adherends such as image display panels.
  • the antistatic layer may be formed on one surface (release-treated surface or untreated surface) of the release liner, or may be formed on both surfaces (release-treated surface and untreated surface) of the release liner.
  • the antistatic layer is not particularly limited, but is, for example, an antistatic layer formed by coating a release liner with a conductive coating liquid containing a conductive polymer. Specifically, for example, it is an antistatic layer formed by coating a release liner (release-treated surface and/or untreated surface) with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.
  • polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers can be used.
  • the thickness of the antistatic layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm.
  • the antistatic layer may consist of only one layer, or may consist of two or more layers.
  • the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, when it is used for bonding image display devices, display defects due to static electricity are less likely to occur. In addition, bleeding out of the antistatic component can be suppressed even under severe conditions such as a moist and hot environment, and failures such as corrosion of metal wiring due to precipitation of the antistatic agent on the surface of the adhesive layer are less likely to occur.
  • the transfer of the antistatic agent from the adhesive layer to other optical members is suppressed, suppressing the increase in surface resistance value and maintaining excellent antistatic properties. can be done.
  • a conductive path can be efficiently formed in the pressure-sensitive adhesive layer.
  • compatibility is not impaired, transparency is easily maintained, foaming and peeling on the surface of the pressure-sensitive adhesive layer are suppressed, and durability defects such as appearance and adhesion reliability are less likely to occur. Therefore, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention satisfies excellent antistatic properties, transparency, moist heat resistance, and low staining properties, and is useful for the production of image display devices.
  • the pressure-sensitive adhesive layer of the present invention is excellent in adhesiveness, resistance to foaming and peeling, and stress relaxation, as well as step followability and adhesion reliability, especially at high temperatures. Moreover, it is excellent in external appearance. Therefore, the pressure-sensitive adhesive sheet of the present invention is useful for adherends that tend to foam at the interface at high temperatures.
  • PMMA polymethyl methacrylate
  • PC Polycarbonate
  • the pressure-sensitive adhesive sheet of the present invention is excellent in anti-foaming peeling property, it is also useful for plastic adherends containing such resins.
  • the pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with a small coefficient of linear expansion, but also for adherends with a large coefficient of linear expansion.
  • the adherend having a small linear expansion coefficient is not particularly limited, but examples thereof include glass plates (linear expansion coefficient: 0.3 ⁇ 10 ⁇ 5 to 0.8 ⁇ 10 ⁇ 5 /° C.), polyethylene terephthalate groups, material (PET film, coefficient of linear expansion: 1.5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 /° C.).
  • the adherend having a large coefficient of linear expansion is not particularly limited, but examples thereof include resin substrates having a large coefficient of linear expansion.
  • the pressure-sensitive adhesive sheet of the present invention is useful for bonding an adherend with a small coefficient of linear expansion and an adherend with a large coefficient of linear expansion.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding a glass adherend (for example, a glass plate, chemically strengthened glass, glass lens, etc.) to the resin substrate having a large coefficient of linear expansion.
  • the pressure-sensitive adhesive sheet of the present invention is useful for bonding adherends made of various materials, and is particularly useful for bonding glass adherends and plastic adherends.
  • the plastic adherend may be an optical film such as a plastic film having an ITO (indium tin oxide) layer on its surface.
  • the pressure-sensitive adhesive sheet of the present invention is useful not only for adherends with smooth surfaces, but also for adherends with uneven surfaces.
  • the pressure-sensitive adhesive sheet of the present invention can be used even if at least one of the glass adherend and the resin substrate having a large coefficient of linear expansion has steps on the surface. It is useful for lamination with large resin substrates.
  • the adhesive sheet of the present invention is preferably used for manufacturing portable electronic devices.
  • portable electronic devices include mobile phones, PHS, smartphones, tablets (tablet computers), mobile computers (mobile PCs), personal digital assistants (PDA), electronic notebooks, portable televisions, portable radios, and the like. type broadcast receivers, portable game machines, portable audio players, portable DVD players, cameras such as digital cameras, and camcorder type video cameras.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used, for example, for attaching members or modules constituting a portable electronic device to each other, fixing members or modules constituting a portable electronic device to a housing, or the like. More specifically, bonding a cover glass or a lens (especially a glass lens) to a touch panel or a touch sensor, fixing a cover glass or a lens (especially a glass lens) to a housing, fixing a display panel to a housing, Fixation of input devices such as sheet keyboards and touch panels to housings, bonding of protection panels for information display parts to housings, bonding of housings to each other, bonding of housings and decorative sheets, mobile electronics Examples include fixing and pasting of various members and modules that constitute the device.
  • the display panel refers to a structure composed of at least a lens (particularly a glass lens) and a touch panel.
  • the term "lens” used herein is a concept that includes both a transparent body that exhibits light refraction and a transparent body that does not have light refraction.
  • a lens in this specification also includes a mere window panel that has no refractive effect.
  • the adhesive sheet of the present invention is preferably used for optical applications. That is, the pressure-sensitive adhesive sheet of the present invention is preferably an optical pressure-sensitive adhesive sheet for optical applications. More specifically, for example, it is preferably used for bonding optical members (for bonding optical members) or for manufacturing products (optical products) using the optical member.
  • the pressure-sensitive adhesive sheet of the present invention can be suitably used for bonding optical members.
  • the pressure-sensitive adhesive sheet may have a release liner on the pressure-sensitive adhesive surface until use.
  • An optical member refers to a member having optical properties (e.g., polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.).
  • the substrate constituting the optical member is not particularly limited.
  • transparent conductive film e.g., plastic film having an ITO layer on the surface (preferably ITO film such as PET-ITO, polycarbonate, cycloolefin polymer), etc.), design film, decorative film, surface protection plate, prism , lenses, color filters, transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates such as glass plates with transparent electrodes, etc.), and substrates on which these are laminated (these are collectively referred to as " may be referred to as "functional film”) and the like.
  • these films may have a metal nanowire layer, a conductive polymer layer, or the like. Further, these films may be mesh-printed with thin metal wires.
  • plate and film include forms such as plate-like, film-like, and sheet-like, respectively.
  • polarizing film includes “polarizing plate” and “polarizing sheet”.
  • film shall include film sensors and the like.
  • Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, and the like. Moreover, a touch panel etc. are mentioned as said input device.
  • the substrate constituting the optical member is not particularly limited. etc.).
  • the "optical member" in the present invention includes members (design films, decorative films, surface protective films, etc.) that play a role of decoration and protection while maintaining the visibility of display devices and input devices. shall be taken.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate and the pressure-sensitive adhesive sheet constitutes a member having optical properties
  • the substrate can be regarded as the substrate
  • the pressure-sensitive adhesive sheet is the optical member of the present invention. It can be said that it is.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a substrate and the functional film is used as the substrate
  • the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer on at least one side of the functional film. It can also be used as an "adhesive functional film”.
  • Production example 1 ⁇ Production of acrylic polymer P1> 100 parts by mass of n-butyl acrylate (BA) and 2,2'-azobisisobutyronitrile as a polymerization initiator in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. A mixture containing 0.2 parts by mass of (AIBN) and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). Thus, a polymer solution containing acrylic polymer P1 was obtained.
  • BA n-butyl acrylate
  • 2,2'-azobisisobutyronitrile as a polymerization initiator
  • a mixture containing 0.2 parts by mass of (AIBN) and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction).
  • Production example 2 ⁇ Production of acrylic polymer P2> 100 parts by mass of 2-methoxyethyl acrylate (2-MEA) and 2,2'-azobis as a polymerization initiator were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. A mixture containing 0.2 parts by mass of isobutyronitrile (AIBN) and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). Thus, a polymer solution containing acrylic polymer P2 was obtained.
  • 2-methoxyethyl acrylate (2-MEA) and 2,2'-azobis as a polymerization initiator were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
  • AIBN isobutyronitrile
  • PSA composition A was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the above polymer solution containing acrylic polymer P1.
  • ⁇ Multifunctional Isocyanate additive Polyhexamethylene diisocyanate (trade name "Coronate HX", manufactured by Nippon Polyurethane Co., Ltd.) 5.05 parts by mass Cross-linking catalyst: Dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 Parts by mass Crosslinking retarder: Acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Adhesive Sheet A The pressure-sensitive adhesive composition A was applied to a release liner (polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side to form a coating film. Next, this coating film was dried at 152° C. for 3 minutes to form an adhesive layer A having a thickness of 25 ⁇ m. A 38- ⁇ m-thick release liner (polyester film, 38- ⁇ m-thick, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side of a polyester film was attached to the pressure-sensitive adhesive layer. Thereafter, aging treatment was performed at 60° C. for 1 day to allow urethane reaction to proceed in the adhesive layer to obtain adhesive sheet A consisting of release liner/adhesive layer A/release liner.
  • PSA composition B was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the polymer solution containing acrylic polymer P2.
  • Multifunctional Isocyanate additive Polyhexamethylene diisocyanate (trade name "Coronate HX", manufactured by Nippon Polyurethane Co., Ltd.) 5.1 parts by mass
  • Cross-linking catalyst Dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 Parts by mass Crosslinking retarder: Acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) 3
  • PSA composition C was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the above polymer solution containing acrylic polymer P2.
  • Multifunctional Isocyanate additive Trimethylolpropane/tolylene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 8.6 parts by mass
  • Cross-linking catalyst Dibutyltin dilaurate (trade name "OL-1", Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass Crosslinking retarder: Acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.
  • PSA composition D was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the polymer solution containing acrylic polymer P2.
  • Multifunctional Isocyanate additive isocyanurate form of tolylene diisocyanate (trade name “Takenate D262”, manufactured by Mitsui Chemicals) 14.3 parts by mass
  • Cross-linking catalyst dibutyltin dilaurate (trade name “OL-1”, manufactured by Tokyo Fine Chemicals Co., Ltd.) 0.01 part by mass Crosslinking retarder: 3 parts by mass of acetylacetone (manufactured by Wako Pure Chemical
  • PSA composition E was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the above polymer solution containing acrylic polymer P1.
  • Antistatic agent: N-ethyl-N-(2-methoxyethyl)-N,N-dimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) 5.25 parts by mass ⁇ Production of Adhesive Sheet E >
  • the pressure-sensitive adhesive composition E was applied to a release liner (polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side to form a coating film.
  • this coating film was dried at 152° C. for 3 minutes to form an adhesive layer E having a thickness of 25 ⁇ m.
  • a 38- ⁇ m-thick release liner (polyester film, 38- ⁇ m-thick, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side of a polyester film was attached to the pressure-sensitive adhesive layer. Then, it was subjected to aging treatment at 60° C. for 1 day to obtain PSA sheet E consisting of release liner/PSA layer E/release liner.
  • PSA composition F was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the polymer solution containing acrylic polymer P2.
  • Antistatic agent: N-ethyl-N-(2-methoxyethyl)-N,N-dimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) 5.25 parts by mass ⁇ Production of Adhesive Sheet F > Adhesive sheet F consisting of release liner/adhesive layer F/release liner was obtained in the same manner as in Comparative Example 1, except that PSA composition F was used instead of PSA composition E.
  • PSA composition C was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the above polymer solution containing acrylic polymer P3.
  • -Hydroxyl group-containing ionic compound N-butyl-N,N-di(2-hydroxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (trade name "CIL-R10", Carlit Holdings Co., Ltd.) 3 Parts by mass Polyfunctional isocyanate additive: Trimethylolpropane/tolylene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 6.6 parts by mass Cross-linking catalyst: Dibutyltin dilaurate (trade name "OL -1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass Crosslinking retarder: Acetylacetone (manufactured by Wako Pure Chemical Industries
  • Adhesive Sheet G The pressure-sensitive adhesive composition G was applied to a release liner (polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side to form a coating film. Next, this coating film was dried at 152° C. for 3 minutes to form an adhesive layer G with a thickness of 15 ⁇ m. A 38- ⁇ m-thick release liner (polyester film, 38- ⁇ m-thick, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side of a polyester film was attached to the pressure-sensitive adhesive layer. Thereafter, aging treatment was performed at 60° C. for 1 day to allow urethane reaction to proceed in the adhesive layer, thereby obtaining an adhesive sheet G consisting of release liner/adhesive layer G/release liner.
  • PSA composition H was prepared by uniformly mixing the following components per 100 parts by mass of acrylic polymer (base polymer) with the polymer solution containing acrylic polymer P4.
  • -Hydroxyl group-containing ionic compound N-butyl-N,N-di(2-hydroxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (trade name "CIL-R10", Carlit Holdings Co., Ltd.)
  • Polyfunctional isocyanate additive Trimethylolpropane/tolylene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 9.9 parts by mass Cross-linking catalyst: Dibutyltin dilaurate (trade name "OL -1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass Crosslinking retarder: Acetylacetone (manufactured by Wako Pure Chemical Industries,
  • Adhesive Sheet H The pressure-sensitive adhesive composition H was applied to a release liner (polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side to form a coating film. Next, this coating film was dried at 152° C. for 3 minutes to form an adhesive layer H having a thickness of 15 ⁇ m. A 38- ⁇ m-thick release liner (polyester film, 38- ⁇ m-thick, manufactured by Mitsubishi Chemical Corporation, MRF#38) having a release surface on one side of a polyester film was attached to the pressure-sensitive adhesive layer. Thereafter, aging treatment was performed at 60° C. for 1 day to allow urethane reaction to proceed in the adhesive layer, thereby obtaining an adhesive sheet H consisting of release liner/adhesive layer H/release liner.
  • a sample composed of release liner/adhesive layer/triacetyl cellulose film in this order was heated at 85° C. and 85% RH. H. was stored in a constant temperature and humidity machine for 168 hours. After the storage, the surface resistance value was measured after standing for 72 hours in an atmosphere of 23° C. and 50% RH. The measurement was performed in an atmosphere of 23° C. and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical Analytic Tech. • Stability of resistance value The difference between the common logarithm Log(SR 2 ) of SR 2 and the common logarithm Log(SR 1 ) of SR 1 : Resistance value stability was evaluated from Log(SR 2 ) ⁇ Log(SR 1 ). If the difference is less than 0.5, it can be said that the resistance value stability is excellent.
  • the conductive polymer (B) has a three-dimensional network structure, The three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) are entangled to form an adhesive layer forming an interpenetrating polymer network or semi-interpenetrating polymer network.
  • an ionic compound (B1) having a functional group (b1) in the molecule and a functional group (B1) capable of forming a covalent bond by reacting with the functional group (b1) containing a compound (B2) having b2) in the molecule The functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, and the conductive polymer (B ), and the three-dimensional network structure and the adhesive polymer (A) are entangled to form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • [Appendix 3] The pressure-sensitive adhesive composition according to Appendix 1 or 2, wherein the ionic compound (B1) has two or more functional groups (b1) in the molecule.
  • the functional group (b1) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, and a styryl group. 4.
  • the functional group (b2) is an isocyanate group, a thioisocyanate group, an epoxy group, an aziridinyl group, an oxazolinyl group, a carbodiimide group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, or an allyl group. , and a styryl group.
  • [Appendix 7] The content ratio of the conductive polymer (B) to the adhesive polymer (A) (conductive polymer (B)/adhesive polymer (A)) is 0.05 to 0.5.
  • [Appendix 8] A pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of Appendices 1 to 7.
  • [Appendix 9] A pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer according to Appendix 8.
  • Appendix 10 The pressure-sensitive adhesive sheet according to Appendix 9, which has a thickness of 10 to 350 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention vise à fournir une composition adhésive autocollante capable de former une couche adhésive autocollante qui est moins apte à avoir des défaillances de durabilité (en particulier de stabilité de la non-corrosivité et de stabilité de résistivité), présente une faible résistivité de surface, et présente une excellente performance antistatique.　Cette composition adhésive autocollante comprend : un polymère adhésif autocollant (A) ; et un polymère électroconducteur (B), un mélange d'ingrédients monomères pour constituer le polymère électroconducteur (B), ou un produit de polymérisation partielle du mélange. Les ingrédients monomères pour constituer le polymère électroconducteur (B) comprennent un composé ionique (B1) ayant un groupe fonctionnel (b1) dans la molécule et un composé (B2) ayant, dans la molécule, un groupe fonctionnel (b2) capable de réagir avec le groupe fonctionnel (b1) pour former une liaison covalente. Le polymère électroconducteur (B) a une structure de réseau 3D. La couche adhésive autocollante formée à partir de cette composition adhésive sensible à la pression comporte un réseau polymère d'interpénétration ou un réseau polymère de semi-interpénétration formé par l'enchevêtrement de la structure de réseau tridimensionnel du polymère électroconducteur (B) avec le polymère adhésif autocollant (A).
PCT/JP2023/006107 2022-02-22 2023-02-21 Composition adhésive autocollante, couche adhésive autocollante et feuille adhésive autocollante WO2023162944A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013087227A (ja) * 2011-10-19 2013-05-13 Nitto Denko Corp 水分散型アクリル系粘着剤組成物、及び粘着シート
WO2014103964A1 (fr) * 2012-12-27 2014-07-03 日東電工株式会社 Couche antistatique, feuille adhésive antistatique et film optique
JP2014189787A (ja) * 2013-03-28 2014-10-06 Nitto Denko Corp 帯電防止性粘着シート、及び、光学フィルム
WO2018008712A1 (fr) * 2016-07-08 2018-01-11 日東電工株式会社 Composition adhésive, couche adhésive, film optique pourvu d'une couche adhésive, écran d'affichage d'images et affichage à cristaux liquides
JP2022179400A (ja) * 2021-05-21 2022-12-02 日東電工株式会社 光学用粘着シート、光学積層体、及び画像表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013087227A (ja) * 2011-10-19 2013-05-13 Nitto Denko Corp 水分散型アクリル系粘着剤組成物、及び粘着シート
WO2014103964A1 (fr) * 2012-12-27 2014-07-03 日東電工株式会社 Couche antistatique, feuille adhésive antistatique et film optique
JP2014189787A (ja) * 2013-03-28 2014-10-06 Nitto Denko Corp 帯電防止性粘着シート、及び、光学フィルム
WO2018008712A1 (fr) * 2016-07-08 2018-01-11 日東電工株式会社 Composition adhésive, couche adhésive, film optique pourvu d'une couche adhésive, écran d'affichage d'images et affichage à cristaux liquides
JP2022179400A (ja) * 2021-05-21 2022-12-02 日東電工株式会社 光学用粘着シート、光学積層体、及び画像表示装置

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