WO2016194891A1 - Aqueous emulsion, method for producing aqueous emulsion, aqueous adhesive composition, and adhesive sheet - Google Patents

Aqueous emulsion, method for producing aqueous emulsion, aqueous adhesive composition, and adhesive sheet Download PDF

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Publication number
WO2016194891A1
WO2016194891A1 PCT/JP2016/065986 JP2016065986W WO2016194891A1 WO 2016194891 A1 WO2016194891 A1 WO 2016194891A1 JP 2016065986 W JP2016065986 W JP 2016065986W WO 2016194891 A1 WO2016194891 A1 WO 2016194891A1
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polymerizable component
polymer
mass
aqueous emulsion
aqueous
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PCT/JP2016/065986
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French (fr)
Japanese (ja)
Inventor
健太 奥原
安井　義勝
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昭和電工株式会社
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Priority to JP2017521946A priority Critical patent/JP6929218B2/en
Priority to CN201680022013.6A priority patent/CN107428854B/en
Publication of WO2016194891A1 publication Critical patent/WO2016194891A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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

Definitions

  • the present invention relates to an aqueous emulsion, an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed using the aqueous pressure-sensitive adhesive composition.
  • Patent Document 1 describes an aqueous dispersion of a multi-stage emulsion polymer exhibiting improved water resistance and water whitening resistance.
  • Patent Document 2 describes a water-dispersed pressure-sensitive adhesive composition for an optical film that can form a pressure-sensitive adhesive layer that can suppress peeling in a humidified environment and peeling over time.
  • Patent Document 3 describes a light diffusion film produced by applying an emulsion obtained by polymerizing an unsaturated monomer in the presence of an addition-cleavage chain transfer agent to a transparent film.
  • Patent Documents 4 to 6 describe coating compositions containing an emulsion obtained by polymerizing an unsaturated monomer in the presence of an addition-cleavage chain transfer agent.
  • Patent Document 7 describes an acrylic rubber obtained by polymerizing a monomer mixture in the presence of an addition-cleavage chain transfer agent.
  • the present invention has been made in view of the above circumstances, and has a pressure-sensitive adhesive sheet that has a strong pressure-sensitive adhesive force and can be peeled off without leaving adhesive residue and sticking marks on the adherend, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet It is an object of the present invention to provide an aqueous pressure-sensitive adhesive composition used in the above, and an aqueous emulsion suitably used for the aqueous pressure-sensitive adhesive composition.
  • the present inventor has paid attention to an emulsion of a polymer containing a plurality of monomer components having different glass transition temperatures (Tg) in a homopolymer, and has intensively studied. Specifically, in the presence of an addition-cleavage type chain transfer agent, a polymer emulsion was produced using a monomer component giving a soft polymer and a monomer component giving a hard polymer.
  • the soft polymer has a low Tg and a strong adhesive force.
  • the hard polymer has a high Tg, and can be expected to reduce the amount of adhesive residue and sticking marks on the adherend. This inventor evaluated the performance of the manufactured emulsion, and repeated examination.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet may be formed using a polymer emulsion obtained by the method described below, and have conceived the present invention.
  • An aqueous emulsion obtained by a production method comprising the step (II) of polymerization and satisfying the following conditions (1) to (3):
  • the amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
  • the first polymerizable component gives a polymer having a glass transition temperature of ⁇ 20 ° C.
  • the second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
  • aqueous pressure-sensitive adhesive composition containing the aqueous emulsion according to any one of [1] to [6].
  • Step (I) of emulsion polymerization of the first polymerizable component in the presence of the addition-cleavage type chain transfer agent, and supplying the second polymerizable component to the polymer obtained in the step (I) A method of producing an aqueous emulsion comprising a step (II) of polymerization and satisfying the following conditions (1) to (3): (1) The amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component. (2) The first polymerizable component gives a polymer having a glass transition temperature of ⁇ 20 ° C.
  • the second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
  • the soft polymer has a glass transition temperature of ⁇ 20 ° C. or less, and is contained in an amount of 70 to 95% by mass in the structural unit of the polymer.
  • the hard polymer has a glass transition temperature of 50 ° C.
  • the aqueous emulsion used suitably for the aqueous adhesive composition used for the adhesion layer of an adhesive sheet can be provided.
  • the pressure-sensitive adhesive sheet formed by forming the pressure-sensitive adhesive layer on one or both sides of the substrate using the aqueous pressure-sensitive adhesive composition containing the aqueous emulsion of the present invention has a strong adhesive force, and has adhesive residue on the adherend. It can be peeled without leaving a mark.
  • the aqueous emulsion of the present embodiment includes a step (I) of emulsion-polymerizing the first polymerizable component in the presence of an addition-cleavage chain transfer agent, and a second polymerizable component in the polymer obtained in the step (I). And an aqueous emulsion of a polymer obtained by a production method satisfying the following conditions (1) to (3).
  • the polymer contained in the aqueous emulsion of this embodiment has a soft polymer obtained by polymerizing the first polymerizable component and a hard polymer obtained by polymerizing the second polymerizable component. Since the hard polymer is contained in the polymer in the aqueous emulsion, when an adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion, no adhesive residue or sticking remains on the adherend. The adhesive layer can be peeled off from the adherend. Further, since the soft polymer is present in the polymer of the aqueous emulsion, strong adhesive force to the adherend can be obtained by the flexibility of the soft polymer.
  • the amount of addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
  • the first polymerizable component gives a polymer having a Tg of ⁇ 20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
  • the second polymerizable component gives a polymer having a Tg of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
  • addition-cleavage type chain transfer agent examples include ⁇ -bromomethylstyrene, ⁇ -phenoxymethylstyrene, ⁇ -alkylthiomethylstyrene, ⁇ -t-butylperoxymethylstyrene.
  • ⁇ -benzyloxystyrene methyl- ⁇ -phenoxymethyl acrylate, methyl- ⁇ -alkylthiomethyl acrylate, methyl- ⁇ -t-butylperoxymethyl acrylate, methyl- ⁇ -benzyloxy acrylate, ⁇ -bromomethylacrylonitrile, etc.
  • ⁇ -substituted unsaturated monomers such as ⁇ -methylstyrene dimer, methyl methacrylate dimer, methacrylonitrile dimer, benzyldithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenyl-2-propyl Pinyl dithiobenzoate, 1-acetoxyethyl dithiobenzoate, benzyl dithioacetate, t-butyl dithiobenzoate, 2-cyano-2-propynyl dithiobenzoate, cumyl dithiobenzoate, dithio fatty acid ester or derivative thereof, dithiobenzoate ester or its Examples include dithio compounds such as derivatives.
  • addition-cleavage chain transfer agents it is preferable to use an ⁇ -substituted dimer because it is easy to handle due to its low odor and is relatively inexpensive and easily available industrially.
  • ⁇ -substituted dimer ⁇ -methylstyrene dimer is preferable.
  • mold chain transfer agent may be used independently, and may use 2 or more types together.
  • the addition-cleavage type chain transfer agent is added in an amount of 0.05 to 100 parts by mass with respect to 100 parts by mass of the total polymerizable component including the first polymerizable component and the second polymerizable component. 1 part by mass is used.
  • the pressure-sensitive adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, when the amount of addition-cleavage chain transfer agent used is 0.05 parts by weight or more with respect to 100 parts by weight of the total polymerizable component Furthermore, it becomes an adhesive layer in which adhesive residue and / or sticking marks are hardly left on the adherend.
  • mold chain transfer agent shall be 0.05 mass part or more with respect to 100 mass parts of all the polymeric components, and it is preferable to set it as 0.1 mass part or more.
  • the pressure-sensitive adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, when the amount of addition-cleavage chain transfer agent used is 1 part by mass or less with respect to 100 parts by mass of the total polymerizable component In addition, the adhesive layer is difficult to cohesively break.
  • mold chain transfer agent shall be 1 mass part or less with respect to 100 mass parts of all the polymeric components, it is preferable to set it as 0.6 mass part or less, and shall be 0.4 mass part or less. It is more preferable.
  • the monomer used as the first polymerizable component and / or the second polymerizable component is preferably an ethylenically unsaturated monomer.
  • (meth) acrylate means acrylate or methacrylate.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
  • Polyalkylene glycol (meth) acrylates such as ethylene glycol (meth) acrylate and butylene glycol (meth) acrylate;
  • Alkylamino (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate;
  • Vinyl ester compounds such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-methylstyrene, ethylvinylbenzene; Heterocyclic vinyl compounds such as vinylpyrrolidone; Monoolefin compounds such as ethylene, propylene, butylene, isobutylene; Conjugated diolefin compounds such as butadiene, isoprene and chloroprene; Amine-imide-containing vinyl compounds such as 1,1,1-trimethylamine methacrylamide;
  • Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Amide groups or substituted amide group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as (meth) acrylamide, N-methylacrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide; ⁇ , ⁇ -unsaturated mono or dicarboxylic such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, 2-carboxyethyl acrylate oligomer, 2-acryloyloxyethyl succinic acid acid;
  • Amide groups or substituted amide group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as (meth) acrylamide, N-methylacrylamide, N, N-dimethyl (meth) acrylamide, N, N
  • Carboxyl group-containing vinyl compounds such as monohydroxyethyl (meth) acrylate phthalate and monohydroxypropyl (meth) acrylate oxalate; Sulphonic acid group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as allyl sulfonate and sodium p-styrenesulfonate.
  • the monomer used as the first polymerizable component and / or the second polymerizable component may contain a crosslinkable monomer that forms a polymer having a crosslinked structure.
  • the crosslinkable monomer include epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, glycidyl (meth) allyl ether, and 3,4-epoxycyclohexyl (meth) acrylate.
  • Hydrolyzable alkoxysilyl group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane;
  • Polyfunctional vinyl compounds such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate;
  • Examples include carbonyl group-containing ⁇ , ⁇ -ethylenically unsaturated compounds such as diacetone acrylamide.
  • the crosslinked structure of the polymer obtained after polymerization depends on the type of the crosslinkable monomer used. For example, it may be a cross-linked structure formed by polymerizing a cross-linkable monomer, or may be formed by a bond between a functional group of the cross-linkable monomer and an active hydrogen group contained in another monomer or cross-linking agent. It may be a crosslinked structure.
  • the first polymerizable component used when producing the aqueous emulsion of the present embodiment gives a polymer having a Tg of ⁇ 20 ° C. or lower.
  • a polymer that gives a polymer having a Tg of ⁇ 20 ° C. or lower is used as the first polymerizable component, excellent adhesive strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion. It is done.
  • the first polymerizable component should give a polymer having a Tg of ⁇ 20 ° C. or lower, preferably a polymer of ⁇ 40 ° C. or lower.
  • the first polymerizable component has a Tg of ⁇ 70 ° C.
  • the first polymerizable component only needs to give a polymer having a Tg of ⁇ 20 ° C. or less, and may be a single monomer or a mixture of two or more monomers.
  • the first polymerizable component is a mixture of two or more monomers, two or more monomers giving a polymer having a Tg of ⁇ 20 ° C. or less may be used in combination.
  • a monomer that provides a polymer having two or more Tg of ⁇ 20 ° C. or less may be combined with a monomer that provides a polymer having one or more Tg exceeding ⁇ 20 ° C.
  • the first polymerizable component among the monomers used as the first polymerizable component and / or the second polymerizable component described above, ethyl acrylate, n-butyl acrylate, alkyl acrylates having an alkyl group having 2 to 10 carbon atoms such as n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, i-octyl acrylate, and the like, and methoxyethyl acrylate, 2- It is preferable to use a substituted alkyl acrylate having an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group or a hydroxy group, such as hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • the first polymerizable component it is preferable to use n-butyl acrylate and
  • the first polymerizable component is used to increase the adhesive strength of the adhesive layer formed using the aqueous adhesive composition containing an aqueous emulsion, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid. It preferably contains an unsaturated carboxylic acid having 3 to 5 carbon atoms, and particularly preferably contains one or more selected from acrylic acid, methacrylic acid and itaconic acid.
  • an aqueous emulsion such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid.
  • the first polymerizable component is mainly composed of n-butyl acrylate and / or 2-ethylhexyl acrylate (in other words, n-butyl acrylate and / or 2-ethylhexyl acrylate is a total of 50 in the first polymerizable component. It is preferably contained in an amount of more than 70% by mass, and more preferably 70% by mass or more in the first polymerizable component. Further, the first polymerizable component preferably contains an unsaturated carboxylic acid having 3 to 5 carbon atoms as a copolymer component with n-butyl acrylate and / or 2-ethylhexyl acrylate. In this case, the first polymerizable component preferably contains 0.1 to 10% by mass of an unsaturated carboxylic acid having 3 to 5 carbon atoms, more preferably 0.5 to 5% by mass. preferable.
  • the first polymerizable component contains n-butyl acrylate and / or 2-ethylhexyl acrylate and an unsaturated carboxylic acid having 3 to 5 carbon atoms
  • a copolymer obtained by polymerizing these components in the aqueous emulsion It becomes a soft polymer of the contained polymer.
  • an aqueous emulsion that can be used as an aqueous pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having strong adhesive strength can be obtained.
  • the second polymerizable component used when producing the aqueous emulsion of the present embodiment gives a polymer having a Tg of 50 ° C. or higher.
  • a polymer that gives a polymer having a Tg of 50 ° C. or higher is used as the second polymerizable component, sufficient adhesive strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion.
  • the second polymerizable component shall give a polymer having a Tg of 50 ° C. or higher, and preferably give a polymer having a Tg of 70 ° C. or higher from the viewpoint of removability (less adhesive residue).
  • the second polymerizable component is not particularly limited as long as it provides a polymer having a Tg of 50 ° C. or higher, and may be a single monomer or a mixture of two or more monomers.
  • the second polymerizable component is a mixture of two or more monomers, two or more monomers giving a polymer having a Tg of 50 ° C. or more may be used in combination. You may combine the monomer which gives the polymer whose Tg of more than seed
  • the second polymerizable component is selected from methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, and n-butyl acrylate among the monomers used as the first polymerizable component and / or the second polymerizable component described above. It is preferable to use 1 type (s) or 2 or more types.
  • the second polymerizable component is two types of monomers, it is preferably a combination of methyl methacrylate and butyl methacrylate or a combination of n-butyl acrylate and 2-ethylhexyl acrylate.
  • the second polymerizable component is mainly composed of methyl methacrylate and / or n-butyl acrylate (in other words, methyl methacrylate and / or n-butyl acrylate is contained in the second polymerizable component in total exceeding 50 mass%. It is preferable that 70% by mass or more is contained in the second polymerizable component.
  • the first polymerizable component is contained in an amount of 70 to 95% by mass in the total polymerizable component (the total of the first polymerizable component and the second polymerizable component).
  • the second polymerizable component is contained in the total polymerizable component in an amount of 5 to 30% by mass. Further, the first polymerizable component is preferably contained in 80 to 95% by mass in the total polymerizable component.
  • the second polymerizable component is preferably contained in the total polymerizable component in an amount of 5 to 20% by mass.
  • the polymer contained in the aqueous emulsion is subjected to the first polymerization.
  • a soft polymer obtained by polymerizing the active component is sufficiently formed.
  • the content of the first polymerizable component in the total polymerizable component is 95% by mass or less (the second polymerizable component is 5% by mass or more)
  • the hard material formed by polymerizing the second polymerizable component is fully formed. For this reason, when an adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, cohesive failure is less likely to occur and adhesive residue on the adherend is less likely to occur.
  • the glass transition temperature (Tg) of the polymer in the present embodiment is a theoretical value obtained by calculating from the respective monomer components constituting the polymer and the ratio thereof according to the FOX equation shown below.
  • Tg T-273
  • 1 / T (W1 / T1 + W2 / T2 + W3 / T3 +... + Wn / Tn)
  • Tg glass transition temperature (degrees Celsius) of the polymer
  • T glass transition temperature (absolute temperature) of the polymer
  • W1, W2, W3, Wn are the weight of each monomer component.
  • T1, T2, T3, and Tn are glass transition temperatures (absolute temperatures) of homopolymers of the respective monomer components.
  • calculation of Tg of the polymer obtained from the first polymerizable component (soft polymer) and the polymer obtained from the second polymerizable component (hard polymer) is calculated based on the monofunctional monomer.
  • the monofunctional monomer even if a polyfunctional monomer is contained in the first polymerizable component and / or the second polymerizable component, the content thereof is small. Therefore, the polyfunctional monomer contained in the first polymerizable component and / or the second polymerizable component has little influence on the Tg of the polymer. For this reason, calculation of Tg of a polymer does not include the influence by a polyfunctional monomer.
  • the aqueous emulsion of the present embodiment preferably has a gel fraction of 90% or more, and more preferably 93% or more.
  • An aqueous emulsion having a gel fraction of 90% or more is such that an adhesive layer formed using an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion is more unlikely to have adhesive residue and imprints on the adherend when peeled. .
  • the aqueous emulsion of the present embodiment includes a step (I) of emulsion-polymerizing the first polymerizable component in the presence of an addition-cleavage chain transfer agent, and a second polymerizable component in the polymer obtained in the step (I). It can manufacture by performing process (II) which superposes and polymerizes on said conditions.
  • step (I) for example, an addition-cleavage type chain transfer agent and water are charged into a reactor, and other components are supplied to the reactor together with the first polymerizable component (monomer) as necessary.
  • the other components include one or more selected from water, an emulsifier, a polymerization initiator, a reducing agent, a chain transfer agent that is not an addition cleavage type, and a crosslinking agent.
  • a surfactant is mentioned as an emulsifier used in process (I).
  • the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene nonylphenyl ether, cesyltrimethylammonium bromide, Examples include cationic surfactants such as lauryl pyridinium chloride, amphoteric surfactants such as lauryl bedine, and reactive surfactants such as polyexethylene-1- (allyloxyethylene) alkyl ether sulfate ammonium salt.
  • a reactive surfactant is preferably used because it is taken into the polymer by polymerization.
  • the aqueous pressure-sensitive adhesive composition containing an aqueous emulsion produced using a reactive surfactant has less ooze out of the emulsifier from the adhesive layer to the adherend when the adhesive layer is formed using this. For this reason, the adherend is less likely to be contaminated by components that have oozed from the adhesive layer, which is preferable.
  • These emulsifiers may be used alone or in combination.
  • polymerization initiator used in the step (I) examples include persulfate initiators such as potassium persulfate and ammonium persulfate, and water-soluble azo derivatives such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride.
  • persulfate initiators such as potassium persulfate and ammonium persulfate
  • water-soluble azo derivatives such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride
  • examples include initiators, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and hydrogen peroxide. These polymerization initiators may be used alone or in combination.
  • Examples of the reducing agent used in the step (I) include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salt, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite. And other reducing inorganic compounds.
  • Non-addition-cleavage chain transfer agents used in step (I) include 2-ethylhexyl thioglycolate, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-mercaptoethanol, ⁇ -mercaptopropionic acid, methyl Examples include alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, and benzyl alcohol.
  • 2-ethylhexyl thioglycolate is preferably used because of its excellent effect of adjusting the molecular weight of the polymer.
  • These non-addition cleavage type chain transfer agents may be used alone or in combination.
  • the type of the crosslinking agent used in step (I) is appropriately determined according to the type of monomer used when the aqueous emulsion is produced. Specifically, a silane coupling agent, a polyhydrazine compound, a polyfunctional epoxy compound, a polyfunctional isocyanate compound, or the like can be used as the crosslinking agent. Among these crosslinking agents, a silane coupling agent is preferably used because a crosslinked structure is formed only by copolymerization and handling is easy.
  • the crosslinkable monomer includes a carbonyl group-containing ⁇ , ⁇ -ethylenically unsaturated compound
  • the crosslinker includes two or more hydrazide groups such as oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and polyacrylic acid hydrazide. It is preferable to form a crosslinked structure using the polyhydrazine compound which has.
  • step (I) the entire amount of the first polymerizable component and / or other components used in step (I) may be charged into a reactor in advance and subjected to emulsion polymerization.
  • emulsion polymerization may be carried out while supplying the first polymerizable component and / or other components continuously or intermittently.
  • step (I) in order to obtain an aqueous emulsion containing polymer particles having a uniform particle size, emulsion polymerization is carried out while continuously or intermittently supplying the first polymerizable component and other components to the reactor. Is preferred.
  • the emulsion polymerization in the step (I) is preferably performed at a temperature in the reactor of 5 to 100 ° C., preferably 50 to 90 ° C. while stirring the solution in the reactor.
  • the step (I) when emulsion polymerization is carried out while continuously or intermittently supplying the first polymerizable component and other components to the reactor, supply of the first polymerizable component and other components into the reactor After completion of the polymerization, the polymerization may be continued for 0.5 to 5 hours at a temperature of 5 to 100 ° C., preferably 50 to 90 ° C., for example.
  • the emulsion polymerization in the step (I) can be performed in an air atmosphere or an inert atmosphere.
  • one type of emulsion is contained in the emulsion containing the polymer during or after emulsion polymerization.
  • Examples of the acid used in the step (I) for adjusting the pH of the emulsion including the polymer during or after the emulsion polymerization include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, and sulfuric acid.
  • Examples of the base used for adjusting the pH of the emulsion include amine compounds such as triethylamine, ammonia, diethanolamine, and diethylaminoethanol; and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide.
  • step (II) the second polymerizable component is supplied to the polymerization system containing the polymer obtained in step (I) for polymerization.
  • step (II) other components may be supplied together with the second polymerizable component (monomer) to the polymerization system containing the polymer obtained in step (I) as necessary.
  • the other components include one or more selected from water, an emulsifier, a polymerization initiator, a reducing agent, a chain transfer agent that is not an addition cleavage type, and a crosslinking agent.
  • step (II) when supplying the above-mentioned other components together with the second polymerizable component (monomer) to the polymerization system containing the polymer obtained in the step (I), the second polymerizable component and One or more other components described above may be mixed using a mixer or the like to form an emulsion, and then supplied to the polymerization system in step (I).
  • step (II) the emulsifier, polymerization initiator, reducing agent, non-addition-cleavage chain transfer agent, and crosslinking agent used as other components are the same as the other components used in step (I) described above. Can be used. In addition, when using another component in process (I) and process (II), all the other components in both may be the same, or a part or all may be different.
  • step (II) the entire amount of the second polymerizable component and / or other components used in step (II) may be collectively supplied to the polymerization system in step (I) for polymerization.
  • step (II) the polymerization may be carried out while continuously or intermittently supplying the second polymerizable component and / or other components.
  • step (II) in order to obtain an aqueous emulsion containing polymer particles having a uniform particle size, the second polymerizable component and other components are continuously or intermittently supplied to the polymerization system of step (I). However, it is preferable to polymerize.
  • the polymerization in the step (II) is preferably carried out while the temperature in the reactor is 5 to 100 ° C., preferably 50 to 90 ° C., and the solution in the reactor is stirred.
  • the polymerization system of the step (I) After the supply of the second polymerizable component and other components to is completed, the polymerization is preferably continued for 0.5 to 5 hours, for example, at a temperature of 5 to 100 ° C., preferably 50 to 90 ° C.
  • the emulsion polymerization in the step (II) can be performed in an air atmosphere or an inert atmosphere.
  • the reaction conditions in step (II) may all be the same as in step (I), or some or all of them may be different.
  • the pH to be 4 to 10 by adding one or more acids or bases to the aqueous emulsion obtained after the polymerization in step (II).
  • the pH of the aqueous emulsion By setting the pH of the aqueous emulsion to 4 to 10, the surface charge of the aqueous emulsion is increased and stability is imparted.
  • the acid used for adjusting the pH of the aqueous emulsion include the same acids as those used for adjusting the pH of the emulsion containing the polymer during or after emulsion polymerization in step (I).
  • a base used for adjustment of pH of an aqueous emulsion the same thing as the base used for pH adjustment in process (I) is mentioned.
  • the aqueous emulsion of the present embodiment containing particles of a polymer having a two-layer structure having a functional group derived from an addition-cleavage type chain transfer agent is obtained.
  • the polymer having the two-layer structure has, as structural units, a soft polymer obtained by polymerizing the first polymerizable component and a hard polymer obtained by polymerizing the second polymerizable component.
  • Examples of the two-layer structure of the polymer include a core shell, a snowman type, and a confetti type.
  • the two-layer structure of the polymer varies depending on the type and ratio of the first polymerizable component and / or the second polymerizable component.
  • the non-volatile fraction of the polymer in the aqueous emulsion thus obtained is usually 30 to 70% by mass, preferably 40 to 65% by mass.
  • the aqueous pressure-sensitive adhesive composition of the present embodiment contains the aqueous emulsion of the present embodiment.
  • the aqueous emulsion obtained after the polymerization in the above-described step (II) can be used as it is as an aqueous pressure-sensitive adhesive composition.
  • the solid content concentration of the aqueous emulsion obtained after the polymerization in the step (II) described above may be adjusted by diluting with a solvent or the like and used as an aqueous pressure-sensitive adhesive composition.
  • aqueous pressure-sensitive adhesive composition one prepared by the above method so that the pH of the aqueous emulsion obtained after the polymerization in the above-mentioned step (II) is 4 to 10 may be used.
  • Additives include cross-linking agents (polyfunctional epoxies, polyfunctional isocyanates, silane coupling agents, etc.), viscosity improvers, thickeners, antifoaming agents, pigments (external pigments, colored pigments, hollow balloons, etc.), dispersants , Wetting agents, light stabilizers, ultraviolet absorbers, preservatives, antibacterial agents and the like.
  • the aqueous pressure-sensitive adhesive composition of the present embodiment can be suitably used as a pressure-sensitive adhesive.
  • Examples of the adherend when the aqueous pressure-sensitive adhesive composition is used as a pressure-sensitive adhesive include paper, plastic film, metal, glass, woven fabric, nonwoven fabric, plastic and rubber foam.
  • the aqueous pressure-sensitive adhesive composition of the present embodiment is also suitable as an adhesive used for automobile products, home appliances, and electronic parts.
  • the pressure-sensitive adhesive sheet of this embodiment has a pressure-sensitive adhesive layer on one side or both sides of a substrate.
  • the pressure-sensitive adhesive layer forming the pressure-sensitive adhesive sheet is formed using the aqueous pressure-sensitive adhesive composition of the present embodiment.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the use of the pressure-sensitive adhesive sheet, the material of the adherend, and the like.
  • the thickness of the pressure-sensitive adhesive layer can be, for example, 5 to 200 ⁇ m, and preferably 10 to 100 ⁇ m.
  • the base material used for the pressure-sensitive adhesive sheet is not particularly limited, and examples thereof include paper, plastic film, resin foam, rubber foam, metal, glass, woven fabric, non-woven fabric, and inorganic plate.
  • the adhesive sheet of this embodiment may be provided with a releasable protective layer on the adhesive layer.
  • the protective layer include porous materials such as plastic film, paper, cloth, and nonwoven fabric, nets, foamed sheets, metal foils, and appropriate thin leaf bodies such as laminates thereof.
  • plastic film used for the protective layer examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples include polyurethane films and ethylene-vinyl acetate copolymer films.
  • the thickness of the plastic film used for the protective layer can be, for example, 5 to 200 ⁇ m, and preferably 5 to 100 ⁇ m.
  • the pressure-sensitive adhesive sheet of the present embodiment can be produced, for example, by a method of forming the pressure-sensitive adhesive layer by applying the aqueous pressure-sensitive adhesive composition of the present embodiment to one or both sides of a substrate and then drying it. Before applying the aqueous pressure-sensitive adhesive composition, an anchor layer may be formed on the surface of the base material on which the aqueous pressure-sensitive adhesive composition is applied in order to improve the adhesion between the base material and the pressure-sensitive adhesive layer. Further, various easy adhesion treatments such as corona treatment and plasma treatment may be performed.
  • aqueous pressure-sensitive adhesive composition Various methods can be used as a method of applying the aqueous pressure-sensitive adhesive composition.
  • an application method for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Examples thereof include an extrusion coating method using a die coater.
  • the coating amount is controlled so that the pressure-sensitive adhesive layer formed after drying has a predetermined thickness.
  • the applied aqueous pressure-sensitive adhesive composition is dried according to a conventional method to form an adhesive layer. Thereafter, an easy adhesion treatment may be performed on the surface of the pressure-sensitive adhesive layer as necessary. Moreover, you may provide a releasable protective layer on an adhesion layer as needed.
  • the pressure-sensitive adhesive sheet of this embodiment is obtained through the above steps.
  • the pressure-sensitive adhesive sheet of the present embodiment includes, for example, daily goods such as pressure-sensitive adhesive tapes, double-sided tapes, pressure-sensitive adhesive labels, wallpaper, floor tiles, floor sheets (cushion floors), carpets, ceiling materials, window pressure-sensitive adhesive sheets (for example, heat shield sheets, It can be suitably used in the field of housing materials such as reflective sheets and security sheets.
  • the pressure-sensitive adhesive sheet according to the present embodiment can be used, for example, in the manufacture of automobile products, home appliances, electronic components and the like.
  • Example 1 In a reactor of a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, ion exchange water and NOFMER MSD, which is an addition-cleavage chain transfer agent, were charged at a ratio described in Table 1 and heated. . Then, in the air atmosphere, potassium persulfate was added as described in Table 1 while maintaining the reactor internal temperature at 80 ° C. and stirring the solution in the reactor at about 120 rpm.
  • each component shown in the section of (A) Emulsion and (B) Emulsion in Table 1 is mixed in the proportions described in Table 1, and emulsified using a homomixer, whereby (A) Emulsion And (B) an emulsion was prepared.
  • Step (II) was started 30 minutes after the end of dropping of the emulsion.
  • step (II) the emulsion is continuously dropped into the reactor of the polymerization apparatus containing the emulsion obtained in step (I) and stirred at a temperature of 80 ° C. at about 120 rpm. The emulsion polymerization was carried out.
  • the dropping rate of the emulsion was about 194 parts / hour (about 194 g / hour).
  • polymerization was continued for 1 hour after completion
  • the aqueous emulsion of Example 1 was obtained through the above steps.
  • Examples 2 to 5 Comparative Examples 1 to 8 Aqueous emulsion in the same manner as in Example 1, except that the amount of addition-cleavage chain transfer agent and / or the composition of (A) emulsion and (B) emulsion was changed as shown in Table 1 or Table 2. Was prepared.
  • the numerical values of (A) emulsion and (B) emulsion, addition-cleavage chain transfer agent, polymerization initiator, dropping catalyst, and neutralizing agent shown in Tables 1 and 2 are mass, and the unit is (g). It is.
  • the ratio of the first polymerizable component (A) shown in Table 1 and Table 2 is the first polymerizable component in the total polymerizable component obtained by adding the first polymerizable component (A) and the second polymerizable component (B). It is a ratio (mass%) of a component (A).
  • the ratio of the 2nd polymeric component (B) is a ratio (mass%) of the 2nd polymeric component (B) in the said all polymeric component.
  • the values of the first polymerizable component (A) Tg and the second polymerizable component (B) Tg shown in Table 1 and Table 2 are homopolymers of the monomer components shown in Table 1, Table 2 and below.
  • Tn which is the glass transition temperature (absolute temperature) of the (homopolymer), was calculated based on the above-described FOX equation as a value shown below.
  • MMA methyl methacrylate: 378K BuA (n-butyl acrylate): 221K 2EHA (2-ethylhexyl acrylate): 203K Aa (acrylic acid): 379K ⁇ -CEA ( ⁇ -carboxyethyl acrylate): 310K 2HEMA (2-hydroxyethyl methacrylate): 328K
  • Nonvolatile content The aqueous emulsion was dried at 105 ° C. for 1 hour, and calculated according to the following formula.
  • Non-volatile fraction (%) [mass after drying / mass before drying] ⁇ 100
  • Viscosity Measured under conditions of 23 ° C. and 10 rpm using a BH viscometer.
  • C pH: Measured with a pH meter.
  • aqueous emulsions of Examples 1 to 5 and Comparative Examples 1 to 8 as aqueous adhesive compositions, adhesive sheets were prepared by the following method.
  • a polyester film having a thickness of 50 ⁇ m and having a corona treatment on one side was prepared.
  • an aqueous emulsion (aqueous adhesive composition) is applied to the surface of the polyester film that has been subjected to corona treatment so that the film thickness of the adhesive layer after drying is 35 ⁇ m, and dried at 105 ° C. for 2 minutes for adhesion. Layer formation was performed to obtain an adhesive sheet.
  • the peel strength of the obtained adhesive sheet was measured by the method shown below. The results are shown in Tables 1 and 2.
  • 180 ° peel strength (N / 25 mm) was measured for each of those left for 20 minutes and those left for 24 hours under the conditions of a peel rate of 300 mm / min.
  • peel strength when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was cohesively broken, “c” was added to the end of the 180 ° peel strength values shown in Tables 1 and 2.
  • the 180 ° peel strength (N / 25 mm) of the adherend (stainless steel plate) that was allowed to stand for 20 minutes after bonding was evaluated according to the following criteria. "Standard" ⁇ ; 12.0 (N / 25mm) or more ⁇ ; 10.0 (N / 25mm) or more ⁇ ; Less than 10.0 (N / 25mm)
  • the pressure-sensitive adhesive sheets using the aqueous emulsions (aqueous pressure-sensitive adhesive compositions) of Examples 1 to 5 were used at the initial stage of bonding (peeling force after 20 minutes) and after 24 hours. High adhesion was shown.
  • the pressure-sensitive adhesive sheets of Example 1 and Example 3 had an adhesive strength after 12.5 minutes of bonding of 12.5 (N / 25 mm) or more, and showed very high adhesive strength.
  • the adhesive sheets of Examples 1 to 5 had little adhesive residue on the adherend and could be peeled without leaving any mark.
  • the adhesive sheet using the aqueous emulsion of Comparative Example 1 produced without using an addition-cleavage type chain transfer agent (Nofmer MSD) produced an adhesive residue on the adherend.
  • the pressure-sensitive adhesive sheet of Comparative Example 1 was cohesively broken when the adhesive strength was evaluated 24 hours after bonding.
  • the pressure-sensitive adhesive sheet using the aqueous emulsion of Comparative Example 2 produced without using the addition-cleavage type chain transfer agent and the pressure-sensitive adhesive sheet using the aqueous emulsion of Comparative Example 3 with a small amount of addition-cleavage type chain transfer agent are used. Despite the gel fraction being 90% or more, a mark remained.
  • seat using the aqueous emulsion of the comparative example 4 which does not use (B) emulsion produced the adhesive residue to a to-be-adhered body.
  • the pressure-sensitive adhesive sheet of Comparative Example 4 was cohesively broken when the adhesive strength was evaluated after 20 minutes and 24 hours after bonding.
  • the pressure-sensitive adhesive sheet of Comparative Example 5 had insufficient adhesive strength at the initial stage of bonding (peeling force after 20 minutes), and cohesive failure occurred during evaluation of the adhesive strength 24 hours after bonding.
  • the adhesive sheet using the aqueous emulsion of Comparative Example 6 in which the amount of the addition-cleavage type chain transfer agent used was too large had adhesive residue on the adherend.
  • the pressure-sensitive adhesive sheet of Comparative Example 6 had insufficient adhesive strength at the initial stage of bonding (peeling force after 20 minutes), and cohesive failure occurred during evaluation of the adhesive strength after 24 hours of bonding.

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

This aqueous emulsion is obtained using a production method that includes the following steps and that satisfies the following conditions: (I) A step in which a first polymerizable component is emulsion polymerized in the presence of an addition fragmentation chain transfer agent; a step (II) in which the polymer obtained in step (I) is supplied with a second polymerizable component and polymerized. The amount of the addition fragmentation chain transfer agent is 0.05 to 1 parts by mass per 100 parts by mass of the totality of polymerizable contents obtained by adding the first polymerizable component and the second polymerizable component. The first polymerizable component gives a polymer having a glass transition temperature not exceeding -20°C, and accounts for 70-95% by mass of the totality of polymerizable components. The second polymerizable component gives a polymer having a glass transition temperature of at least 50°C, and accounts for 5-30% by mass of the totality of polymerizable components.

Description

水性エマルション、水性エマルションの製造方法、水性粘着剤組成物および粘着シートAqueous emulsion, method for producing aqueous emulsion, aqueous pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet
　本発明は、水性エマルションおよび水性エマルションを含有する水性粘着剤組成物、その水性粘着剤組成物を用いて形成された粘着層を有する粘着シートに関する。
　本出願は、２０１５年６月４日に日本に出願された特願２０１５－１１４０１２に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an aqueous emulsion, an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed using the aqueous pressure-sensitive adhesive composition.
This application claims priority based on Japanese Patent Application No. 2015-1114012 filed in Japan on June 4, 2015, the contents of which are incorporated herein by reference.
　近年、地球環境への負荷を低減するために、溶剤を用いない水性エマルションを用いた粘着剤の開発が進められている。
　粘着剤として用いられる水性エマルションとして、例えば、特許文献１には、改良された耐水性および水白化耐性を示す多段エマルションポリマーの水性分散物が記載されている。
　また、特許文献２には、加湿環境下でのハガレおよび経時ハガレを抑えることができる粘着剤層を形成できる光学フィルム用水分散型粘着剤組成物が記載されている。 In recent years, in order to reduce the burden on the global environment, development of an adhesive using an aqueous emulsion that does not use a solvent has been underway.
As an aqueous emulsion used as an adhesive, for example, Patent Document 1 describes an aqueous dispersion of a multi-stage emulsion polymer exhibiting improved water resistance and water whitening resistance.
Patent Document 2 describes a water-dispersed pressure-sensitive adhesive composition for an optical film that can form a pressure-sensitive adhesive layer that can suppress peeling in a humidified environment and peeling over time.
また、従来、付加開裂型連鎖移動剤の存在下で単量体を重合させる技術が知られている。
　例えば、特許文献３には、付加開裂型連鎖移動剤の存在下で不飽和単量体を重合して得られたエマルションを、透明フィルムに塗布することにより製造した光拡散フィルムが記載されている。
　また、特許文献４～特許文献６には、付加開裂型連鎖移動剤の存在下で、不飽和単量体を重合させて得られたエマルションを含有する塗料組成物が記載されている。
　また、特許文献７には、付加開裂型連鎖移動剤の存在下で単量体混合物を重合させて得られるアクリルゴムが記載されている。 Conventionally, a technique for polymerizing a monomer in the presence of an addition-cleavage type chain transfer agent is known.
For example, Patent Document 3 describes a light diffusion film produced by applying an emulsion obtained by polymerizing an unsaturated monomer in the presence of an addition-cleavage chain transfer agent to a transparent film. .
Patent Documents 4 to 6 describe coating compositions containing an emulsion obtained by polymerizing an unsaturated monomer in the presence of an addition-cleavage chain transfer agent.
Patent Document 7 describes an acrylic rubber obtained by polymerizing a monomer mixture in the presence of an addition-cleavage chain transfer agent.
特開２００６－２９９２６０号公報JP 2006-299260 A 特開２０１２－１２８３９１号公報JP 2012-128391 A 特開２０１４－１３４７３５号公報JP 2014-134735 A 特開２００６－１９３６８０号公報JP 2006-193680 A 特開２００６－１４３７６３号公報JP 2006-143663 A 特許第５２５８２９３号公報Japanese Patent No. 5258293 国際公開第２００７／１１４１０８号International Publication No. 2007/114108
　近年、強い粘着力を有し、かつ被着体に糊残りおよび貼り跡を残さず剥離できる粘着層を形成できる粘着剤に対する需要が高まっている。その粘着剤の原料として使用できる水性エマルションが要求されている。
　しかしながら、従来の水性エマルションを用いた強い接着力を有する粘着剤では、被着体に糊残りおよび貼り跡を残さず剥離できる粘着層を形成することは困難であった。 In recent years, there is an increasing demand for an adhesive that has a strong adhesive force and can form an adhesive layer that can be peeled off without leaving any adhesive residue or sticking on an adherend. There is a demand for an aqueous emulsion that can be used as a raw material for the pressure-sensitive adhesive.
However, it has been difficult to form a pressure-sensitive adhesive layer that can be peeled off without leaving any adhesive residue and sticking marks on an adherend with a conventional pressure-sensitive adhesive using an aqueous emulsion.
　本発明は、上記事情に鑑みてなされたものであり、強い粘着力を有し、かつ被着体に糊残りおよび貼り跡を残さず剥離できる粘着層を有する粘着シート、前記粘着シートの粘着層に使用される水性粘着剤組成物、前記水性粘着剤組成物に好適に使用される水性エマルションを提供することを課題とする。 The present invention has been made in view of the above circumstances, and has a pressure-sensitive adhesive sheet that has a strong pressure-sensitive adhesive force and can be peeled off without leaving adhesive residue and sticking marks on the adherend, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet It is an object of the present invention to provide an aqueous pressure-sensitive adhesive composition used in the above, and an aqueous emulsion suitably used for the aqueous pressure-sensitive adhesive composition.
　本発明者は、上記課題を解決するために、単独重合体でのガラス転移温度（Ｔｇ：glass　transition　temperature）が異なる複数の単量体成分を含む重合体のエマルションに着目し、鋭意検討した。具体的には、付加開裂型連鎖移動剤の存在下において、軟質重合体を与える単量体成分と、硬質重合体を与える単量体成分とを用いて、重合体のエマルションを製造した。軟質重合体は、Ｔｇが低く、強い粘着力が得られる。硬質重合体は、Ｔｇが高く、被着体への糊残りおよび貼り跡を低減できる効果が期待できる。本発明者は、製造したエマルションの性能を評価し、検討を重ねた。 In order to solve the above-mentioned problems, the present inventor has paid attention to an emulsion of a polymer containing a plurality of monomer components having different glass transition temperatures (Tg) in a homopolymer, and has intensively studied. Specifically, in the presence of an addition-cleavage type chain transfer agent, a polymer emulsion was produced using a monomer component giving a soft polymer and a monomer component giving a hard polymer. The soft polymer has a low Tg and a strong adhesive force. The hard polymer has a high Tg, and can be expected to reduce the amount of adhesive residue and sticking marks on the adherend. This inventor evaluated the performance of the manufactured emulsion, and repeated examination.
　その結果、以下に示す方法により得られた重合体のエマルションを用いて、粘着シートの粘着層を形成すればよいことを見出し、本発明を想到した。所定量の付加開裂型連鎖移動剤の存在下で、軟質重合体を与える単量体成分を乳化重合した後、所定の割合で硬質重合体を与える単量体成分を加えて重合する方法。
　すなわち、本発明は以下の事項に関する。 As a result, the inventors have found that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet may be formed using a polymer emulsion obtained by the method described below, and have conceived the present invention. A method in which a monomer component giving a soft polymer is emulsion-polymerized in the presence of a predetermined amount of addition-cleavage chain transfer agent, and then the monomer component giving a hard polymer is added at a predetermined ratio for polymerization.
That is, the present invention relates to the following matters.
［１］　付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、前記工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを含み、且つ、以下の（１）～（３）の条件を満たす製造方法により得られる水性エマルション。
（１）付加開裂型連鎖移動剤の量が、前記第一重合性成分と前記第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部である。
（２）前記第一重合性成分は、ガラス転移温度が－２０℃以下の重合体を与えるものであって前記全重合性成分中の７０～９５質量％である。
（３）前記第二重合性成分は、ガラス転移温度が５０℃以上の重合体を与えるものであって前記全重合性成分中の５～３０質量％である。 [1] Step (I) of emulsion polymerization of the first polymerizable component in the presence of an addition-cleavage chain transfer agent, and supplying the second polymerizable component to the polymer obtained in the step (I) An aqueous emulsion obtained by a production method comprising the step (II) of polymerization and satisfying the following conditions (1) to (3):
(1) The amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
(2) The first polymerizable component gives a polymer having a glass transition temperature of −20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
(3) The second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
［２］　ゲル分率が９０％以上である［１］に記載の水性エマルション。
［３］　前記第一重合性成分は、ガラス転移温度が－４０℃以下の重合体を与える［１］または［２］に記載の水性エマルション。
［４］　前記第二重合性成分は、ガラス転移温度が７０℃以上の重合体を与える［１］～［３］のいずれかに記載の水性エマルション。 [2] The aqueous emulsion according to [1], wherein the gel fraction is 90% or more.
[3] The aqueous emulsion according to [1] or [2], wherein the first polymerizable component gives a polymer having a glass transition temperature of −40 ° C. or lower.
[4] The aqueous emulsion according to any one of [1] to [3], wherein the second polymerizable component gives a polymer having a glass transition temperature of 70 ° C. or higher.
［５］　前記第二重合性成分が、メチルメタクリレートおよび／またはｎ－ブチルアクリレートを５０質量％超含む［１］～［４］のいずれかに記載の水性エマルション。
［６］　前記第一重合性成分が、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートを５０質量％超含む［１］～［５］のいずれかに記載の水性エマルション。 [5] The aqueous emulsion according to any one of [1] to [4], wherein the second polymerizable component contains more than 50% by mass of methyl methacrylate and / or n-butyl acrylate.
[6] The aqueous emulsion according to any one of [1] to [5], wherein the first polymerizable component contains more than 50% by mass of n-butyl acrylate and / or 2-ethylhexyl acrylate.
［７］　［１］～［６］のいずれかに記載の水性エマルションを含有する水性粘着剤組成物。
［８］　基材の片面または両面に粘着層を有し、前記粘着層が、［７］に記載の水性粘着剤組成物を用いて形成してなるものである粘着シート。
［９］　付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、前記工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを含み、且つ、以下の（１）～（３）の条件を満たす水性エマルションの製造方法。
（１）付加開裂型連鎖移動剤の量が、前記第一重合性成分と前記第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部である。
（２）前記第一重合性成分は、ガラス転移温度が－２０℃以下の重合体を与えるものであって前記全重合性成分中の７０～９５質量％である。
（３）前記第二重合性成分は、ガラス転移温度が５０℃以上の重合体を与えるものであって前記全重合性成分中の５～３０質量％である。
［１０］　構造単位として軟質重合体と硬質重合体とを含有し、前記両重合体は付加開裂型連鎖移動剤に由来する官能基を有し、
　前記軟質重合体はガラス転移温度が－２０℃以下であり、前記重合体の構造単位中に７０～９５質量％含まれ、
　前記硬質重合体はガラス転移温度が５０℃以上であり、前記重合体の構造単位中に５～３０質量％含まれ、
　前記軟質重合体からなる軟質重合体部分と、前記硬質重合体からなる硬質重合体部分とが二層構造を有している水性エマルション。 [7] An aqueous pressure-sensitive adhesive composition containing the aqueous emulsion according to any one of [1] to [6].
[8] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side or both sides of a substrate, wherein the pressure-sensitive adhesive layer is formed using the aqueous pressure-sensitive adhesive composition according to [7].
[9] Step (I) of emulsion polymerization of the first polymerizable component in the presence of the addition-cleavage type chain transfer agent, and supplying the second polymerizable component to the polymer obtained in the step (I) A method of producing an aqueous emulsion comprising a step (II) of polymerization and satisfying the following conditions (1) to (3):
(1) The amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
(2) The first polymerizable component gives a polymer having a glass transition temperature of −20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
(3) The second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
[10] Containing as a structural unit a soft polymer and a hard polymer, both the polymers have a functional group derived from an addition-cleavage chain transfer agent,
The soft polymer has a glass transition temperature of −20 ° C. or less, and is contained in an amount of 70 to 95% by mass in the structural unit of the polymer.
The hard polymer has a glass transition temperature of 50 ° C. or higher, and is contained in an amount of 5 to 30% by mass in the structural unit of the polymer.
An aqueous emulsion in which a soft polymer portion made of the soft polymer and a hard polymer portion made of the hard polymer have a two-layer structure.
　本発明によれば、粘着シートの粘着層に使用される水性粘着剤組成物に好適に使用される水性エマルションを提供できる。
　本発明の水性エマルションを含有する水性粘着剤組成物を用いて、基材の片面または両面に粘着層を形成してなる粘着シートは、強い粘着力を有し、かつ被着体に糊残りおよび貼り跡を残さず剥離できる。 ADVANTAGE OF THE INVENTION According to this invention, the aqueous emulsion used suitably for the aqueous adhesive composition used for the adhesion layer of an adhesive sheet can be provided.
The pressure-sensitive adhesive sheet formed by forming the pressure-sensitive adhesive layer on one or both sides of the substrate using the aqueous pressure-sensitive adhesive composition containing the aqueous emulsion of the present invention has a strong adhesive force, and has adhesive residue on the adherend. It can be peeled without leaving a mark.
　以下、本発明の水性エマルション、水性粘着剤組成物および粘着シートについて詳細に説明する。
＜水性エマルション＞
　本実施形態の水性エマルションは、付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを含み、且つ、以下の（１）～（３）の条件を満たす製造方法により得られた重合体の水性エマルションである。 Hereinafter, the aqueous emulsion, the aqueous pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of the present invention will be described in detail.
<Water-based emulsion>
The aqueous emulsion of the present embodiment includes a step (I) of emulsion-polymerizing the first polymerizable component in the presence of an addition-cleavage chain transfer agent, and a second polymerizable component in the polymer obtained in the step (I). And an aqueous emulsion of a polymer obtained by a production method satisfying the following conditions (1) to (3).
　本実施形態の水性エマルション中に含まれる重合体は、第一重合性成分が重合してなる軟質重合体と、第二重合性成分が重合してなる硬質重合体とを有する。水性エマルション中の重合体に硬質重合体が含まれているため、水性エマルションを含有する水性粘着剤組成物を用いて接着層を形成した場合、被着体に糊残りおよび貼り跡を残さずに被着体から接着層を剥離できる。また、水性エマルションの重合体中に軟質重合体が存在しているため、軟質重合体の柔軟性によって被着体に対する強い粘着力が得られる。 The polymer contained in the aqueous emulsion of this embodiment has a soft polymer obtained by polymerizing the first polymerizable component and a hard polymer obtained by polymerizing the second polymerizable component. Since the hard polymer is contained in the polymer in the aqueous emulsion, when an adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion, no adhesive residue or sticking remains on the adherend. The adhesive layer can be peeled off from the adherend. Further, since the soft polymer is present in the polymer of the aqueous emulsion, strong adhesive force to the adherend can be obtained by the flexibility of the soft polymer.
（１）付加開裂型連鎖移動剤の量が、第一重合性成分と第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部である。
（２）第一重合性成分は、Ｔｇが－２０℃以下の重合体を与えるものであって全重合性成分中の７０～９５質量％である。
（３）第二重合性成分は、Ｔｇが５０℃以上の重合体を与えるものであって全重合性成分中の５～３０質量％である。 (1) The amount of addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
(2) The first polymerizable component gives a polymer having a Tg of −20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
(3) The second polymerizable component gives a polymer having a Tg of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
（付加開裂型連鎖移動剤）
　本実施形態の水性エマルションを製造する際に使用する付加開裂型連鎖移動剤としては、例えば、α－ブロモメチルスチレン、α－フェノキシメチルスチレン、α－アルキルチオメチルスチレン、α－ｔ－ブチルペルオキシメチルスチレン、α－ベンジルオキシスチレン、メチル－α－フェノキシメチルアクリレート、メチル－α－アルキルチオメチルアクリレート、メチル－α－ｔ－ブチルペルオキシメチルアクリレート、メチル－α－ベンジルオキシアクリレート、α－ブロモメチルアクリロニトリルなどのα－置換不飽和単量体、α－メチルスチレンダイマー、メチルメタクリレートダイマー、メタクリロニトリルダイマーなどのα－置換二量体、ベンジルジチオベンゾエート、１－フェニルエチルジチオベンゾエート、２－フェニル－２－プロピニルジチオベンゾエート、１－アセトキシエチルジチオベンゾエート、ベンジルジチオアセテート、ｔ－ブチルジチオベンゾエート、２－シアノ－２－プロピニルジチオベンゾエート、クミルジチオベンゾエート、ジチオ脂肪酸エステルもしくはその誘導体、ジチオ安息香酸エステルもしくはその誘導体などのジチオ化合物などが挙げられる。 (Additional cleavage type chain transfer agent)
Examples of the addition-cleavage type chain transfer agent used for producing the aqueous emulsion of the present embodiment include α-bromomethylstyrene, α-phenoxymethylstyrene, α-alkylthiomethylstyrene, α-t-butylperoxymethylstyrene. Α-benzyloxystyrene, methyl-α-phenoxymethyl acrylate, methyl-α-alkylthiomethyl acrylate, methyl-α-t-butylperoxymethyl acrylate, methyl-α-benzyloxy acrylate, α-bromomethylacrylonitrile, etc. -Substituted unsaturated monomers, α-substituted dimers such as α-methylstyrene dimer, methyl methacrylate dimer, methacrylonitrile dimer, benzyldithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenyl-2-propyl Pinyl dithiobenzoate, 1-acetoxyethyl dithiobenzoate, benzyl dithioacetate, t-butyl dithiobenzoate, 2-cyano-2-propynyl dithiobenzoate, cumyl dithiobenzoate, dithio fatty acid ester or derivative thereof, dithiobenzoate ester or its Examples include dithio compounds such as derivatives.
　上記の付加開裂型連鎖移動剤の中でも特に、臭気が少ないために取り扱いやすく、比較的安価で工業的に入手しやすいため、α－置換二量体を用いることが好ましい。α－置換二量体としては、α－メチルスチレンダイマーが好ましい。
　上記の付加開裂型連鎖移動剤は、単独で使用してもよいし、二種以上を併用してもよい。 Among the above addition-cleavage chain transfer agents, it is preferable to use an α-substituted dimer because it is easy to handle due to its low odor and is relatively inexpensive and easily available industrially. As the α-substituted dimer, α-methylstyrene dimer is preferable.
Said addition cleavage type | mold chain transfer agent may be used independently, and may use 2 or more types together.
　本実施形態の水性エマルションを製造する際には、付加開裂型連鎖移動剤を、第一重合性成分と第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部用いる。付加開裂型連鎖移動剤の使用量が、全重合性成分１００質量部に対して０．０５質量部以上であると、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、被着体に糊残りおよび／または貼り跡が残りにくい粘着層となる。このため、付加開裂型連鎖移動剤の使用量は、全重合性成分１００質量部に対して０．０５質量部以上とし、０．１質量部以上とすることが好ましい。また、付加開裂型連鎖移動剤の使用量が、全重合性成分１００質量部に対して１質量部以下であると、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、粘着層が凝集破壊しにくい。このため、付加開裂型連鎖移動剤の使用量は、全重合性成分１００質量部に対して１質量部以下とし、０．６質量部以下とすることが好ましく、０．４質量部以下とすることがより好ましい。 When producing the aqueous emulsion of the present embodiment, the addition-cleavage type chain transfer agent is added in an amount of 0.05 to 100 parts by mass with respect to 100 parts by mass of the total polymerizable component including the first polymerizable component and the second polymerizable component. 1 part by mass is used. When the pressure-sensitive adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, when the amount of addition-cleavage chain transfer agent used is 0.05 parts by weight or more with respect to 100 parts by weight of the total polymerizable component Furthermore, it becomes an adhesive layer in which adhesive residue and / or sticking marks are hardly left on the adherend. For this reason, the usage-amount of addition cleavage type | mold chain transfer agent shall be 0.05 mass part or more with respect to 100 mass parts of all the polymeric components, and it is preferable to set it as 0.1 mass part or more. Further, when the pressure-sensitive adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, when the amount of addition-cleavage chain transfer agent used is 1 part by mass or less with respect to 100 parts by mass of the total polymerizable component In addition, the adhesive layer is difficult to cohesively break. For this reason, the usage-amount of an addition cleavage type | mold chain transfer agent shall be 1 mass part or less with respect to 100 mass parts of all the polymeric components, it is preferable to set it as 0.6 mass part or less, and shall be 0.4 mass part or less. It is more preferable.
（重合性成分）
　本実施形態の水性エマルションを製造する際に、第一重合性成分および／または第二重合性成分として用いられる単量体は、エチレン性不飽和単量体であることが好ましい。
　なお、以下の説明において、（メタ）アクリレートとは、アクリレート又はメタクリレートを意味する。 (Polymerizable component)
In producing the aqueous emulsion of the present embodiment, the monomer used as the first polymerizable component and / or the second polymerizable component is preferably an ethylenically unsaturated monomer.
In the following description, (meth) acrylate means acrylate or methacrylate.
　エチレン性不飽和単量体としては、例えば、以下に示す公知のものが挙げられる。
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボロニル（メタ）アクリレート等の（メタ）アクリレート； As an ethylenically unsaturated monomer, the well-known thing shown below is mentioned, for example.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate;
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；
　エチレングリコール（メタ）アクリレート、ブチレングリコール（メタ）アクリレート等のポリアルキレンレングリコール（メタ）アクリレート；
　Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート等のアルキルアミノ（メタ）アクリレート； Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Polyalkylene glycol (meth) acrylates such as ethylene glycol (meth) acrylate and butylene glycol (meth) acrylate;
Alkylamino (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate;
　蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチツク酸ビニル等のビニルエステル化合物；
　スチレン、α－メチルスチレン、ｐ－メチルスチレン、エチルビニルベンゼン等の芳香族ビニル化合物；
　ビニルピロリドン等の複素環式ビニル化合物；
　エチレン、プロピレン、ブチレン、イソブチレン等のモノオレフィン化合物；
　ブタジエン、イソプレン、クロロプレン等の共役ジオレフィン化合物；
　１，１，１－トリメチルアミンメタクリルイミド等のアミンイミド基含有ビニル化合物； Vinyl ester compounds such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene;
Heterocyclic vinyl compounds such as vinylpyrrolidone;
Monoolefin compounds such as ethylene, propylene, butylene, isobutylene;
Conjugated diolefin compounds such as butadiene, isoprene and chloroprene;
Amine-imide-containing vinyl compounds such as 1,1,1-trimethylamine methacrylamide;
　アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物；
　（メタ）アクリルアミド、Ｎ－メチルアクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド等のアミド基もしくは置換アミド基含有α，β－エチレン性不飽和化合物；
　アクリル酸、メタクリル酸、クロトン酸、シトラコン酸、イタコン酸、マレイン酸、無水マレイン酸、フマル酸、２－カルボキシエチルアクリレートオリゴマー、２－アクリロイルオキシエチルコハク酸等のα，β－不飽和モノまたはジカルボン酸； Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Amide groups or substituted amide group-containing α, β-ethylenically unsaturated compounds such as (meth) acrylamide, N-methylacrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide;
Α, β-unsaturated mono or dicarboxylic such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, 2-carboxyethyl acrylate oligomer, 2-acryloyloxyethyl succinic acid acid;
　フタル酸モノヒドロキシエチル（メタ）アクリレート、シュウ酸モノヒドロキシプロピル（メタ）アクリレート等のカルボキシル基含有ビニル化合物；
　スルホン酸アリル、ｐ－スチレンスルホン酸ナトリウム等のスルホン酸基含有α，β－エチレン性不飽和化合物。 Carboxyl group-containing vinyl compounds such as monohydroxyethyl (meth) acrylate phthalate and monohydroxypropyl (meth) acrylate oxalate;
Sulphonic acid group-containing α, β-ethylenically unsaturated compounds such as allyl sulfonate and sodium p-styrenesulfonate.
　第一重合性成分および／または第二重合性成分として用いられる単量体には、架橋構造を有する重合体を形成する架橋性モノマーが含まれていてもよい。
　架橋性モノマーとしては、例えば、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジルビニルエーテル、グリシジル（メタ）アリルエーテル、３，４－エポキシシクロヘキシル（メタ）アクリレート等のエポキシ基含有α，β－エチレン性不飽和化合物；
　ビニルトリエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン等の加水分解性アルコキシシリル基含有α，β－エチレン性不飽和化合物；
　エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、アリル（メタ）アクリレート、ジビニルベンゼン、ジアリルフタレート等の多官能ビニル化合物；
　ダイアセトンアクリルアミドのようなカルボニル基含有α，β－エチレン性不飽和化合物などが挙げられる。 The monomer used as the first polymerizable component and / or the second polymerizable component may contain a crosslinkable monomer that forms a polymer having a crosslinked structure.
Examples of the crosslinkable monomer include epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, glycidyl (meth) allyl ether, and 3,4-epoxycyclohexyl (meth) acrylate. Containing α, β-ethylenically unsaturated compounds;
Hydrolyzable alkoxysilyl group-containing α, β-ethylenically unsaturated compounds such as vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane;
Polyfunctional vinyl compounds such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate;
Examples include carbonyl group-containing α, β-ethylenically unsaturated compounds such as diacetone acrylamide.
　第一重合性成分および／または第二重合性成分に、架橋性モノマーが含まれている場合、重合後に得られる重合体の架橋構造は、使用した架橋性モノマーの種類に依存する。
　例えば、架橋性モノマーを重合することにより形成された架橋構造であってもよいし、架橋性モノマーの有する官能基と、他の単量体もしくは架橋剤に含まれる活性水素基との結合により形成された架橋構造であってもよい。 When a crosslinkable monomer is contained in the first polymerizable component and / or the second polymerizable component, the crosslinked structure of the polymer obtained after polymerization depends on the type of the crosslinkable monomer used.
For example, it may be a cross-linked structure formed by polymerizing a cross-linkable monomer, or may be formed by a bond between a functional group of the cross-linkable monomer and an active hydrogen group contained in another monomer or cross-linking agent. It may be a crosslinked structure.
　本実施形態の水性エマルションを製造する際に用いる第一重合性成分は、Ｔｇが－２０℃以下の重合体を与える。第一重合性成分として、Ｔｇが－２０℃以下の重合体を与えるものを用いると、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、優れた粘着力が得られる。このため、第一重合性成分は、Ｔｇが－２０℃以下の重合体、好ましくは－４０℃以下の重合体を与えるものが良い。一方で、第一重合性成分は、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に高い凝集力および強い剥離強度が得られる点から、Ｔｇが－７０℃以上の重合体を与えるものが好ましく、－５５℃以上の重合体を与えるものがより好ましい。 The first polymerizable component used when producing the aqueous emulsion of the present embodiment gives a polymer having a Tg of −20 ° C. or lower. When a polymer that gives a polymer having a Tg of −20 ° C. or lower is used as the first polymerizable component, excellent adhesive strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion. It is done. For this reason, the first polymerizable component should give a polymer having a Tg of −20 ° C. or lower, preferably a polymer of −40 ° C. or lower. On the other hand, the first polymerizable component has a Tg of −70 ° C. or higher because a high cohesive force and a strong peel strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion. Those that give a polymer are preferred, and those that give a polymer at -55 ° C. or higher are more preferred.
　第一重合性成分は、Ｔｇが－２０℃以下の重合体を与えるものであればよく、単独の単量体であっても２種以上の単量体の混合物であってもよい。第一重合性成分が２種以上の単量体の混合物である場合、Ｔｇが－２０℃以下の重合体を与える２種以上の単量体を組み合わせて使用してもよいし、１種または２種以上のＴｇが－２０℃以下の重合体を与える単量体と、１種または２種以上のＴｇが－２０℃を超える重合体を与える単量体とを組み合わせてもよい。 The first polymerizable component only needs to give a polymer having a Tg of −20 ° C. or less, and may be a single monomer or a mixture of two or more monomers. When the first polymerizable component is a mixture of two or more monomers, two or more monomers giving a polymer having a Tg of −20 ° C. or less may be used in combination. A monomer that provides a polymer having two or more Tg of −20 ° C. or less may be combined with a monomer that provides a polymer having one or more Tg exceeding −20 ° C.
　第一重合性成分としては、上述した第一重合性成分および／または第二重合性成分として用いられる単量体の中でも、重合時の安定性に優れる点で、エチルアクリレート、ｎ－ブチルアクリレート、ｎ－アミルアクリレート、イソアミルアクリレート、ｎ－ヘキシルアクリレート、２－エチルヘキシルアクリレート、ｎ－オクチルアクリレート、ｉ－オクチルアクリレートなどの炭素数２～１０を有するアルキル基を有するアルキルアクリレート、およびメトキシエチルアクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレートなどのアルコキシ基またはヒドロキシ基で置換された炭素数１～１０のアルキル基を有する置換アルキルアクリレートを用いることが好ましい。
　第一重合性成分としては、上記の単量体の中でも特に、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートを用いることが好ましい。 As the first polymerizable component, among the monomers used as the first polymerizable component and / or the second polymerizable component described above, ethyl acrylate, n-butyl acrylate, alkyl acrylates having an alkyl group having 2 to 10 carbon atoms such as n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, i-octyl acrylate, and the like, and methoxyethyl acrylate, 2- It is preferable to use a substituted alkyl acrylate having an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group or a hydroxy group, such as hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
As the first polymerizable component, it is preferable to use n-butyl acrylate and / or 2-ethylhexyl acrylate among the above monomers.
　さらに、第一重合性成分は、水性エマルションを含有する水性粘着剤組成物を用いて形成した粘着層の粘着力を高めるために、アクリル酸、メタクリル酸、フマル酸、マレイン酸、イタコン酸などの炭素数３～５の不飽和カルボン酸を含むことが好ましく、特に、アクリル酸、メタクリル酸またはイタコン酸から選ばれるいずれか一種または二種以上を含むことが好ましい。 Furthermore, the first polymerizable component is used to increase the adhesive strength of the adhesive layer formed using the aqueous adhesive composition containing an aqueous emulsion, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid. It preferably contains an unsaturated carboxylic acid having 3 to 5 carbon atoms, and particularly preferably contains one or more selected from acrylic acid, methacrylic acid and itaconic acid.
　第一重合性成分は、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートを主成分とする（言い換えると、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートが、第一重合性成分中に合計で５０質量％超含まれる）ことが好ましく、第一重合性成分中に７０質量％以上含まれていることがより好ましい。
　さらに、第一重合性成分は、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートとの共重合成分として、炭素数３～５の不飽和カルボン酸を含むことが好ましい。この場合、第一重合性成分中に炭素数３～５の不飽和カルボン酸が０．１～１０質量％含まれていることが好ましく、０．５～５質量％含まれていることがより好ましい。 The first polymerizable component is mainly composed of n-butyl acrylate and / or 2-ethylhexyl acrylate (in other words, n-butyl acrylate and / or 2-ethylhexyl acrylate is a total of 50 in the first polymerizable component. It is preferably contained in an amount of more than 70% by mass, and more preferably 70% by mass or more in the first polymerizable component.
Further, the first polymerizable component preferably contains an unsaturated carboxylic acid having 3 to 5 carbon atoms as a copolymer component with n-butyl acrylate and / or 2-ethylhexyl acrylate. In this case, the first polymerizable component preferably contains 0.1 to 10% by mass of an unsaturated carboxylic acid having 3 to 5 carbon atoms, more preferably 0.5 to 5% by mass. preferable.
　第一重合性成分が、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートと、炭素数３～５の不飽和カルボン酸とを含む場合、これらが重合してなる共重合体が、水性エマルション中に含まれる重合体の軟質重合体となる。その結果、強い粘着力を有する粘着層を形成できる水性粘着剤組成物として使用できる水性エマルションが得られる。 When the first polymerizable component contains n-butyl acrylate and / or 2-ethylhexyl acrylate and an unsaturated carboxylic acid having 3 to 5 carbon atoms, a copolymer obtained by polymerizing these components in the aqueous emulsion It becomes a soft polymer of the contained polymer. As a result, an aqueous emulsion that can be used as an aqueous pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having strong adhesive strength can be obtained.
　本実施形態の水性エマルションを製造する際に用いる第二重合性成分は、Ｔｇが５０℃以上の重合体を与える。第二重合性成分として、Ｔｇが５０℃以上の重合体を与えるものを用いると、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、十分な粘着力が得られやすい。このため、第二重合性成分は、Ｔｇが５０℃以上の重合体を与えるものとし、再剥離性（糊残りの少なさ）の点から好ましくは７０℃以上の重合体を与えるものとする。 The second polymerizable component used when producing the aqueous emulsion of the present embodiment gives a polymer having a Tg of 50 ° C. or higher. When a polymer that gives a polymer having a Tg of 50 ° C. or higher is used as the second polymerizable component, sufficient adhesive strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion. Cheap. For this reason, the second polymerizable component shall give a polymer having a Tg of 50 ° C. or higher, and preferably give a polymer having a Tg of 70 ° C. or higher from the viewpoint of removability (less adhesive residue).
　第二重合性成分は、Ｔｇが５０℃以上の重合体を与えるものであればよく、単独の単量体であっても２種以上の単量体の混合物であってもよい。第二重合性成分が２種以上の単量体の混合物である場合、Ｔｇが５０℃以上の重合体を与える２種以上の単量体を組み合わせて使用してもよいし、１種または２種以上のＴｇが５０℃以上の重合体を与える単量体と、１種または２種以上のＴｇが５０℃未満の重合体を与える重合体とを組み合わせてもよい。 The second polymerizable component is not particularly limited as long as it provides a polymer having a Tg of 50 ° C. or higher, and may be a single monomer or a mixture of two or more monomers. When the second polymerizable component is a mixture of two or more monomers, two or more monomers giving a polymer having a Tg of 50 ° C. or more may be used in combination. You may combine the monomer which gives the polymer whose Tg of more than seed | species is 50 degreeC or more, and the polymer which gives the polymer whose 1 type or 2 or more types Tg is less than 50 degreeC.
　第二重合性成分としては、上述した第一重合性成分および／または第二重合性成分として用いられる単量体の中でも、メチルメタクリレート、ブチルメタクリレート、２－エチルヘキシルアクリレート、ｎ－ブチルアクリレートから選ばれる１種または２種以上を用いることが好ましい。
　第二重合性成分が２種の単量体である場合、メチルメタクリレートとブチルメタクリレートとの組み合わせ、またはｎ－ブチルアクリレートと２－エチルヘキシルアクリレートとの組み合わせであることが好ましい。 The second polymerizable component is selected from methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, and n-butyl acrylate among the monomers used as the first polymerizable component and / or the second polymerizable component described above. It is preferable to use 1 type (s) or 2 or more types.
When the second polymerizable component is two types of monomers, it is preferably a combination of methyl methacrylate and butyl methacrylate or a combination of n-butyl acrylate and 2-ethylhexyl acrylate.
　第二重合性成分は、メチルメタクリレートおよび／またはｎ－ブチルアクリレートを主成分とする（言い換えると、メチルメタクリレートおよび／またはｎ－ブチルアクリレートが、第二重合性成分中に合計で５０質量％超含まれる）ことが好ましく、第二重合性成分中に７０質量％以上含まれていることがより好ましい。 The second polymerizable component is mainly composed of methyl methacrylate and / or n-butyl acrylate (in other words, methyl methacrylate and / or n-butyl acrylate is contained in the second polymerizable component in total exceeding 50 mass%. It is preferable that 70% by mass or more is contained in the second polymerizable component.
　第一重合性成分は、全重合性成分（第一重合性成分と第二重合性成分との合計）中に７０～９５質量％含まれている。第二重合性成分は、全重合性成分中に５～３０質量％含まれている。さらに、第一重合性成分は、全重合性成分中に８０～９５質量％含まれていることが好ましい。第二重合性成分は、全重合性成分中に５～２０質量％含まれていることが好ましい。 The first polymerizable component is contained in an amount of 70 to 95% by mass in the total polymerizable component (the total of the first polymerizable component and the second polymerizable component). The second polymerizable component is contained in the total polymerizable component in an amount of 5 to 30% by mass. Further, the first polymerizable component is preferably contained in 80 to 95% by mass in the total polymerizable component. The second polymerizable component is preferably contained in the total polymerizable component in an amount of 5 to 20% by mass.
　全重合性成分中の第一重合性成分の含有量が７０質量％以上である（第二重合性成分が３０質量％以下である）と、水性エマルション中に含まれる重合体に、第一重合性成分が重合してなる軟質重合体が十分に形成される。このため、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、十分な粘着力が得られるという利点がある。
　また、全重合性成分中の第一重合性成分の含有量が９５質量％以下である（第二重合性成分が５質量％以上である）と、第二重合性成分が重合してなる硬質重合体が十分に形成される。このため、水性エマルションを含有する水性粘着剤組成物を用いて粘着層を形成した場合に、凝集破壊が生じにくくなり、被着体への糊残りが生じにくくなる。 When the content of the first polymerizable component in the total polymerizable component is 70% by mass or more (the second polymerizable component is 30% by mass or less), the polymer contained in the aqueous emulsion is subjected to the first polymerization. A soft polymer obtained by polymerizing the active component is sufficiently formed. For this reason, there is an advantage that sufficient adhesive strength can be obtained when an adhesive layer is formed using an aqueous adhesive composition containing an aqueous emulsion.
Further, when the content of the first polymerizable component in the total polymerizable component is 95% by mass or less (the second polymerizable component is 5% by mass or more), the hard material formed by polymerizing the second polymerizable component. The polymer is fully formed. For this reason, when an adhesive layer is formed using an aqueous pressure-sensitive adhesive composition containing an aqueous emulsion, cohesive failure is less likely to occur and adhesive residue on the adherend is less likely to occur.
　なお、本実施形態における重合体のガラス転移温度（Ｔｇ）は、重合体を構成する各単量体成分とその割合から、以下に示すＦＯＸの式により計算して得た理論値である。 In addition, the glass transition temperature (Tg) of the polymer in the present embodiment is a theoretical value obtained by calculating from the respective monomer components constituting the polymer and the ratio thereof according to the FOX equation shown below.
　Ｔｇ＝Ｔ－２７３
　ただし、１／Ｔ＝（Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋Ｗ３／Ｔ３＋・・・＋Ｗｎ／Ｔｎ）
（式中、Ｔｇは重合体のガラス転移温度（摂氏温度）であり、Ｔは重合体のガラス転移温度（絶対温度）である。Ｗ１、Ｗ２、Ｗ３、Ｗｎは、各単量体成分の重量分率であり、Ｔ１、Ｔ２、Ｔ３、Ｔｎは、各単量体成分の単独重合体のガラス転移温度（絶対温度）である。） Tg = T-273
However, 1 / T = (W1 / T1 + W2 / T2 + W3 / T3 +... + Wn / Tn)
(Wherein, Tg is the glass transition temperature (degrees Celsius) of the polymer, and T is the glass transition temperature (absolute temperature) of the polymer. W1, W2, W3, Wn are the weight of each monomer component. (T1, T2, T3, and Tn are glass transition temperatures (absolute temperatures) of homopolymers of the respective monomer components.)
　本発明において、第一重合性成分から得られる重合体（軟質重合体）および第二重合性成分から得られる重合体（硬質重合体）のＴｇの算出は、単官能単量体に基づいて算出されるものとする。すなわち、第一重合性成分および／または第二重合性成分に多官能単量体が含まれていても、その含有量は少量である。したがって、第一重合性成分および／または第二重合性成分に含まれている多官能単量体による重合体のＴｇへの影響は少ない。このため、重合体のＴｇの算出には、多官能単量体による影響は含めないものとする。 In the present invention, calculation of Tg of the polymer obtained from the first polymerizable component (soft polymer) and the polymer obtained from the second polymerizable component (hard polymer) is calculated based on the monofunctional monomer. Shall be. That is, even if a polyfunctional monomer is contained in the first polymerizable component and / or the second polymerizable component, the content thereof is small. Therefore, the polyfunctional monomer contained in the first polymerizable component and / or the second polymerizable component has little influence on the Tg of the polymer. For this reason, calculation of Tg of a polymer does not include the influence by a polyfunctional monomer.
　なお、上記ＦＯＸの式により求められるＴｇの理論値は、示差走査熱量測定（ＤＳＣ）により求められる実測値に基づいて算出したガラス転移温度とよく一致する。 In addition, the theoretical value of Tg calculated | required by the said formula of FOX corresponds well with the glass transition temperature calculated based on the actual value calculated | required by differential scanning calorimetry (DSC).
（ゲル分率）
　本実施形態の水性エマルションは、ゲル分率が９０％以上のものであることが好ましく、９３％以上のものであることがより好ましい。ゲル分率が９０％以上である水性エマルションは、これを含有する水性粘着剤組成物を用いて形成した接着層が、剥離時に被着体に糊残りおよび貼り跡がより一層残りにくいものとなる。 (Gel fraction)
The aqueous emulsion of the present embodiment preferably has a gel fraction of 90% or more, and more preferably 93% or more. An aqueous emulsion having a gel fraction of 90% or more is such that an adhesive layer formed using an aqueous pressure-sensitive adhesive composition containing the aqueous emulsion is more unlikely to have adhesive residue and imprints on the adherend when peeled. .
＜水性エマルションの製造方法＞
　本実施形態の水性エマルションは、付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを、上記の条件で行うことにより製造できる。 <Method for producing aqueous emulsion>
The aqueous emulsion of the present embodiment includes a step (I) of emulsion-polymerizing the first polymerizable component in the presence of an addition-cleavage chain transfer agent, and a second polymerizable component in the polymer obtained in the step (I). It can manufacture by performing process (II) which superposes and polymerizes on said conditions.
　工程（Ｉ）では、例えば、付加開裂型連鎖移動剤と水とを反応器に仕込み、第一重合性成分（単量体）とともに、必要に応じて、その他の成分を、反応器に供給して乳化重合する。その他の成分としては、水、乳化剤、重合開始剤、還元剤、付加開裂型でない連鎖移動剤、架橋剤から選ばれる１種以上が挙げられる。 In step (I), for example, an addition-cleavage type chain transfer agent and water are charged into a reactor, and other components are supplied to the reactor together with the first polymerizable component (monomer) as necessary. To emulsion polymerize. Examples of the other components include one or more selected from water, an emulsifier, a polymerization initiator, a reducing agent, a chain transfer agent that is not an addition cleavage type, and a crosslinking agent.
　工程（Ｉ）において使用する乳化剤としては、界面活性剤が挙げられる。界面活性剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム等のアニオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンノニルフェニルエーテル等のノニオン性界面活性剤、セシルトリメチルアンモニウムブロミド、ラウリルピリジニウムクロリド等のカチオン性界面活性剤、ラウリルベダイン等の両性界面活性剤、ポリエキシエチレン－１－（アリルオキシエチレン）アルキルエーテル硫酸エステルアンモニウム塩などの反応性界面活性剤などが挙げられる。
　これらの乳化剤の中でも特に、重合により重合体内部に取り込まれるため、反応性界面活性剤を用いることが好ましい。反応性界面活性剤を用いて製造した水性エマルションを含有する水性粘着剤組成物は、これを用いて接着層を形成した場合に、接着層から被着体への乳化剤の滲み出しが少ない。このため、接着層から浸み出した成分による被着体の汚染が生じにくく、好ましい。これらの乳化剤は、単独で使用してもよいし、混合して使用してもよい。 A surfactant is mentioned as an emulsifier used in process (I). Examples of the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene nonylphenyl ether, cesyltrimethylammonium bromide, Examples include cationic surfactants such as lauryl pyridinium chloride, amphoteric surfactants such as lauryl bedine, and reactive surfactants such as polyexethylene-1- (allyloxyethylene) alkyl ether sulfate ammonium salt.
Among these emulsifiers, a reactive surfactant is preferably used because it is taken into the polymer by polymerization. The aqueous pressure-sensitive adhesive composition containing an aqueous emulsion produced using a reactive surfactant has less ooze out of the emulsifier from the adhesive layer to the adherend when the adhesive layer is formed using this. For this reason, the adherend is less likely to be contaminated by components that have oozed from the adhesive layer, which is preferable. These emulsifiers may be used alone or in combination.
　工程（Ｉ）において使用する重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩系開始剤、２，２’－アゾビス（２－メチルプロピオンアミジン）ジ塩酸塩等の水溶性アゾ系開始剤、ｔ－ブチルヒドロパーオキシド、クメンヒドロパーオキシド等の有機過酸化物類、過酸化水素等が挙げられる。これらの重合開始剤は、単独で使用してもよいし、混合して使用してもよい。 Examples of the polymerization initiator used in the step (I) include persulfate initiators such as potassium persulfate and ammonium persulfate, and water-soluble azo derivatives such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride. Examples include initiators, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and hydrogen peroxide. These polymerization initiators may be used alone or in combination.
　工程（Ｉ）において使用する還元剤としては、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラート金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の還元性無機化合物等が挙げられる。 Examples of the reducing agent used in the step (I) include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salt, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite. And other reducing inorganic compounds.
　工程（Ｉ）において使用する付加開裂型でない連鎖移動剤としては、２エチルヘキシルチオグリコレート、ｎ－ドデシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ｎ－ブチルメルカプタン、２－メルカプトエタノール、β－メルカプトプロピオン酸、メチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｔ－ブチルアルコール、ベンジルアルコールなどが挙げられる。これらの付加開裂型でない連鎖移動剤の中でも特に、重合体の分子量を調整する効果が優れているため、２エチルヘキシルチオグリコレートを用いることが好ましい。これらの付加開裂型でない連鎖移動剤は、単独で使用してもよいし、混合して使用してもよい。 Non-addition-cleavage chain transfer agents used in step (I) include 2-ethylhexyl thioglycolate, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-mercaptoethanol, β-mercaptopropionic acid, methyl Examples include alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, and benzyl alcohol. Among these chain transfer agents that are not addition-cleavage type, 2-ethylhexyl thioglycolate is preferably used because of its excellent effect of adjusting the molecular weight of the polymer. These non-addition cleavage type chain transfer agents may be used alone or in combination.
　工程（Ｉ）において使用する架橋剤の種類は、水性エマルションを製造する際に用いる単量体の種類に応じて適宜決定される。具体的には、架橋剤として、シランカップリング剤、ポリヒドラジン化合物、多官能エポキシ化合物、多官能イソシアネート化合物などを用いることができる。これらの架橋剤の中でも特に、共重合するだけで架橋構造が形成され、取扱いが容易であることからシランカップリング剤を用いることが好ましい。
　架橋性モノマーとして、カルボニル基含有α，β－エチレン性不飽和化合物を含む場合、架橋剤として、シュウ酸ジヒドラジド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、ポリアクリル酸ヒドラジド等の２つ以上のヒドラジド基を有するポリヒドラジン化合物を用いて架橋構造を形成することが好ましい。 The type of the crosslinking agent used in step (I) is appropriately determined according to the type of monomer used when the aqueous emulsion is produced. Specifically, a silane coupling agent, a polyhydrazine compound, a polyfunctional epoxy compound, a polyfunctional isocyanate compound, or the like can be used as the crosslinking agent. Among these crosslinking agents, a silane coupling agent is preferably used because a crosslinked structure is formed only by copolymerization and handling is easy.
When the crosslinkable monomer includes a carbonyl group-containing α, β-ethylenically unsaturated compound, the crosslinker includes two or more hydrazide groups such as oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and polyacrylic acid hydrazide. It is preferable to form a crosslinked structure using the polyhydrazine compound which has.
　工程（Ｉ）では、工程（Ｉ）で使用する第一重合性成分および／またはその他の成分の全量を、予め反応器に仕込んで乳化重合してもよい。工程（Ｉ）では、第一重合性成分および／またはその他の成分を連続的または断続的に供給しながら乳化重合してもよい。工程（Ｉ）では、粒径の均一な重合体の粒子を含む水性エマルション得るために、第一重合性成分およびその他の成分を、連続的または断続的に反応器に供給しながら乳化重合することが好ましい。 In step (I), the entire amount of the first polymerizable component and / or other components used in step (I) may be charged into a reactor in advance and subjected to emulsion polymerization. In the step (I), emulsion polymerization may be carried out while supplying the first polymerizable component and / or other components continuously or intermittently. In step (I), in order to obtain an aqueous emulsion containing polymer particles having a uniform particle size, emulsion polymerization is carried out while continuously or intermittently supplying the first polymerizable component and other components to the reactor. Is preferred.
　工程（Ｉ）における乳化重合は、反応器内の温度を５～１００℃、好ましくは５０～９０℃とし、反応器内の溶液を撹拌しながら行うことが好ましい。
　工程（Ｉ）において、第一重合性成分およびその他の成分を、連続的または断続的に反応器に供給しながら乳化重合する場合、反応器内への第一重合性成分およびその他の成分の供給が終了した後、例えば５～１００℃、好ましくは５０～９０℃の温度で、０．５～５時間重合を継続してもよい。
　工程（Ｉ）における乳化重合は、空気雰囲気下または不活性雰囲気下で行うことができる。 The emulsion polymerization in the step (I) is preferably performed at a temperature in the reactor of 5 to 100 ° C., preferably 50 to 90 ° C. while stirring the solution in the reactor.
In the step (I), when emulsion polymerization is carried out while continuously or intermittently supplying the first polymerizable component and other components to the reactor, supply of the first polymerizable component and other components into the reactor After completion of the polymerization, the polymerization may be continued for 0.5 to 5 hours at a temperature of 5 to 100 ° C., preferably 50 to 90 ° C., for example.
The emulsion polymerization in the step (I) can be performed in an air atmosphere or an inert atmosphere.
　本実施形態では、工程（Ｉ）において、反応器内への第一重合性成分およびその他の成分の供給が終了した後、乳化重合中または乳化重合後の重合物を含む乳化物に、１種または２種以上の酸もしくは塩基を添加して、ｐＨが６．５～９．０となるように調整することが好ましい。乳化物のｐＨを６．５～９．０とすることで、水性エマルションの安定性が高くなるとともに最終的に得られる水性エマルションの粗粒が少なくなるという効果が得られる。
　工程（Ｉ）において乳化重合中または乳化重合後の重合物を含む乳化物のｐＨ調整に使用される酸としては、酢酸、乳酸、塩酸、燐酸、硫酸などが挙げられる。また、乳化物のｐＨ調整に使用される塩基としては、トリエチルアミン、アンモニア、ジエタノールアミン、ジエチルアミノエタノール等のアミン化合物；水酸化カリウム、水酸化ナトリウム、水酸化リチウム等のアルカリ金属水酸化物が挙げられる。 In the present embodiment, in the step (I), after the supply of the first polymerizable component and other components into the reactor is completed, one type of emulsion is contained in the emulsion containing the polymer during or after emulsion polymerization. Alternatively, it is preferable to adjust the pH to be 6.5 to 9.0 by adding two or more acids or bases. By setting the pH of the emulsion to 6.5 to 9.0, the effect of increasing the stability of the aqueous emulsion and reducing the coarse particles of the finally obtained aqueous emulsion can be obtained.
Examples of the acid used in the step (I) for adjusting the pH of the emulsion including the polymer during or after the emulsion polymerization include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, and sulfuric acid. Examples of the base used for adjusting the pH of the emulsion include amine compounds such as triethylamine, ammonia, diethanolamine, and diethylaminoethanol; and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide.
　工程（ＩＩ）では、工程（Ｉ）で得られた重合物を含む重合系に第二重合性成分を供給して重合する。工程（ＩＩ）では、必要に応じて、工程（Ｉ）で得られた重合物を含む重合系に、第二重合性成分（単量体）とともに、その他の成分を供給してもよい。その他の成分としては、水、乳化剤、重合開始剤、還元剤、付加開裂型でない連鎖移動剤、架橋剤から選ばれる１種以上が挙げられる。
　工程（ＩＩ）において、工程（Ｉ）で得られた重合物を含む重合系に、第二重合性成分（単量体）とともに、上記のその他の成分を供給する場合、第二重合性成分と上記の一種以上のその他の成分とをミキサーなどを用いて混合して乳化物としてから、工程（Ｉ）の重合系に供給してもよい。 In step (II), the second polymerizable component is supplied to the polymerization system containing the polymer obtained in step (I) for polymerization. In step (II), other components may be supplied together with the second polymerizable component (monomer) to the polymerization system containing the polymer obtained in step (I) as necessary. Examples of the other components include one or more selected from water, an emulsifier, a polymerization initiator, a reducing agent, a chain transfer agent that is not an addition cleavage type, and a crosslinking agent.
In the step (II), when supplying the above-mentioned other components together with the second polymerizable component (monomer) to the polymerization system containing the polymer obtained in the step (I), the second polymerizable component and One or more other components described above may be mixed using a mixer or the like to form an emulsion, and then supplied to the polymerization system in step (I).
　工程（ＩＩ）において、その他の成分として使用する乳化剤、重合開始剤、還元剤、付加開裂型でない連鎖移動剤、架橋剤としては、上述した工程（Ｉ）において使用されるその他の成分と同じものを用いることができる。
　なお、工程（Ｉ）および工程（ＩＩ）において、その他の成分を用いる場合、両者におけるその他の成分は、全て同じであってもよいし、一部または全部が異なっていてもよい。 In step (II), the emulsifier, polymerization initiator, reducing agent, non-addition-cleavage chain transfer agent, and crosslinking agent used as other components are the same as the other components used in step (I) described above. Can be used.
In addition, when using another component in process (I) and process (II), all the other components in both may be the same, or a part or all may be different.
　工程（ＩＩ）では、工程（ＩＩ）で使用する第二重合性成分および／またはその他の成分の全量をまとめて工程（Ｉ）の重合系に供給して重合してもよい。工程（ＩＩ）では、第二重合性成分および／またはその他の成分を連続的または断続的に供給しながら重合してもよい。工程（ＩＩ）では、粒径の均一な重合体の粒子を含む水性エマルション得るために、第二重合性成分およびその他の成分を、連続的または断続的に工程（Ｉ）の重合系に供給しながら重合することが好ましい。 In step (II), the entire amount of the second polymerizable component and / or other components used in step (II) may be collectively supplied to the polymerization system in step (I) for polymerization. In step (II), the polymerization may be carried out while continuously or intermittently supplying the second polymerizable component and / or other components. In step (II), in order to obtain an aqueous emulsion containing polymer particles having a uniform particle size, the second polymerizable component and other components are continuously or intermittently supplied to the polymerization system of step (I). However, it is preferable to polymerize.
　工程（ＩＩ）における重合は、反応器内の温度を５～１００℃、好ましくは５０～９０℃とし、反応器内の溶液を撹拌しながら行うことが好ましい。
　本実施形態では、工程（ＩＩ）において、第二重合性成分およびその他の成分を、連続的または断続的に工程（Ｉ）の重合系に供給しながら重合する場合、工程（Ｉ）の重合系への第二重合性成分およびその他の成分の供給が終了した後、例えば５～１００℃、好ましくは５０～９０℃の温度で、０．５～５時間重合を継続することが好ましい。
　工程（ＩＩ）における乳化重合は、空気雰囲気下または不活性雰囲気下で行うことができる。
　工程（ＩＩ）における反応条件は、工程（Ｉ）と全て同じであってもよいし、一部または全部が異なっていてもよい。 The polymerization in the step (II) is preferably carried out while the temperature in the reactor is 5 to 100 ° C., preferably 50 to 90 ° C., and the solution in the reactor is stirred.
In the present embodiment, in the step (II), when the second polymerizable component and other components are polymerized while continuously or intermittently supplied to the polymerization system of the step (I), the polymerization system of the step (I) After the supply of the second polymerizable component and other components to is completed, the polymerization is preferably continued for 0.5 to 5 hours, for example, at a temperature of 5 to 100 ° C., preferably 50 to 90 ° C.
The emulsion polymerization in the step (II) can be performed in an air atmosphere or an inert atmosphere.
The reaction conditions in step (II) may all be the same as in step (I), or some or all of them may be different.
　本実施形態では、工程（ＩＩ）における重合後に得られた水性エマルションに、１種または２種以上の酸もしくは塩基を添加して、ｐＨが４～１０となるように調整することが好ましい。水性エマルションのｐＨを４～１０とすることで、水性エマルションの表面電荷が高くなり、安定性が付与される。
　水性エマルションのｐＨの調整に使用される酸としては、工程（Ｉ）において乳化重合中または乳化重合後の重合物を含む乳化物のｐＨ調整に用いる酸と同じものが挙げられる。また、水性エマルションのｐＨの調整に使用される塩基としては、工程（Ｉ）においてｐＨ調整に用いる塩基と同じものが挙げられる。 In this embodiment, it is preferable to adjust the pH to be 4 to 10 by adding one or more acids or bases to the aqueous emulsion obtained after the polymerization in step (II). By setting the pH of the aqueous emulsion to 4 to 10, the surface charge of the aqueous emulsion is increased and stability is imparted.
Examples of the acid used for adjusting the pH of the aqueous emulsion include the same acids as those used for adjusting the pH of the emulsion containing the polymer during or after emulsion polymerization in step (I). Moreover, as a base used for adjustment of pH of an aqueous emulsion, the same thing as the base used for pH adjustment in process (I) is mentioned.
　以上の工程を行うことにより、付加開裂型連鎖移動剤に由来する官能基を有する２層構造の重合体の粒子を含む本実施形態の水性エマルションが得られる。上記の２層構造の重合体は、構造単位として、第一重合性成分が重合してなる軟質重合体と、第二重合性成分が重合してなる硬質重合体とを有する。重合体の２層構造としては、例えばコアシェル、雪だるま型、金平糖型等が挙げられる。重合体の２層構造は、第一重合性成分および／または第二重合性成分の種類、割合などに応じて変化する。
　このようにして得られた水性エマルション中における重合体の不揮発分率は、通常３０～７０質量％となり、好ましくは４０～６５質量％である。 By performing the above steps, the aqueous emulsion of the present embodiment containing particles of a polymer having a two-layer structure having a functional group derived from an addition-cleavage type chain transfer agent is obtained. The polymer having the two-layer structure has, as structural units, a soft polymer obtained by polymerizing the first polymerizable component and a hard polymer obtained by polymerizing the second polymerizable component. Examples of the two-layer structure of the polymer include a core shell, a snowman type, and a confetti type. The two-layer structure of the polymer varies depending on the type and ratio of the first polymerizable component and / or the second polymerizable component.
The non-volatile fraction of the polymer in the aqueous emulsion thus obtained is usually 30 to 70% by mass, preferably 40 to 65% by mass.
＜水性粘着剤組成物＞
　本実施形態の水性粘着剤組成物は、本実施形態の水性エマルションを含有する。
　本実施形態においては、上述した工程（ＩＩ）における重合後に得られた水性エマルションを、そのまま水性粘着剤組成物として使用できる。また、必要に応じて、上述した工程（ＩＩ）における重合後に得られた水性エマルションの固形分濃度を溶媒等で薄めるなどして調節して、水性粘着剤組成物として使用してもよい。 <Water-based adhesive composition>
The aqueous pressure-sensitive adhesive composition of the present embodiment contains the aqueous emulsion of the present embodiment.
In this embodiment, the aqueous emulsion obtained after the polymerization in the above-described step (II) can be used as it is as an aqueous pressure-sensitive adhesive composition. Further, if necessary, the solid content concentration of the aqueous emulsion obtained after the polymerization in the step (II) described above may be adjusted by diluting with a solvent or the like and used as an aqueous pressure-sensitive adhesive composition.
　また、水性粘着剤組成物として、上述した工程（ＩＩ）における重合後に得られた水性エマルションのｐＨが４～１０となるように、上記の方法により調整したものを使用してもよい。
　また、水性粘着剤組成物として、本実施形態の水性エマルションに、ロジン系、テルペン系、石油系などの粘着付与剤を添加したものを用いてもよい。これらの粘着付与剤は、単独で使用してもよいし、２種以上を混合して使用しても良い。
　さらに、水性粘着剤組成物として、本実施形態の水性エマルションに、添加剤を、１種または２種以上添加したものを用いてもよい。添加剤としては、架橋剤（多官能エポキシ、多官能イソシアネート、シランカップリング剤等）、粘性改良剤、増粘剤、消泡剤、顔料（体質顔料、着色顔料、中空バルーンなど）、分散剤、湿潤剤、光安定剤、紫外線吸収剤、防腐剤、抗菌剤などが挙げられる。 Further, as the aqueous pressure-sensitive adhesive composition, one prepared by the above method so that the pH of the aqueous emulsion obtained after the polymerization in the above-mentioned step (II) is 4 to 10 may be used.
Moreover, you may use what added tackifiers, such as a rosin type | system | group, a terpene type | system | group, and a petroleum type, to the aqueous emulsion of this embodiment as an aqueous adhesive composition. These tackifiers may be used alone or in combination of two or more.
Furthermore, you may use what added the 1 type (s) or 2 or more types of additive to the aqueous emulsion of this embodiment as an aqueous | water-based adhesive composition. Additives include cross-linking agents (polyfunctional epoxies, polyfunctional isocyanates, silane coupling agents, etc.), viscosity improvers, thickeners, antifoaming agents, pigments (external pigments, colored pigments, hollow balloons, etc.), dispersants , Wetting agents, light stabilizers, ultraviolet absorbers, preservatives, antibacterial agents and the like.
　本実施形態の水性粘着剤組成物は、粘着剤として好適に用いることができる。
　水性粘着剤組成物を粘着剤として用いる場合の被着体としては、紙、プラスチックフィルム、金属、ガラス、織布、不織布、プラスチックやゴムの発泡体などが挙げられる。また、本実施形態の水性粘着剤組成物は、自動車用製品、家電製品、電子部品に用いられる接着剤としても好適である。 The aqueous pressure-sensitive adhesive composition of the present embodiment can be suitably used as a pressure-sensitive adhesive.
Examples of the adherend when the aqueous pressure-sensitive adhesive composition is used as a pressure-sensitive adhesive include paper, plastic film, metal, glass, woven fabric, nonwoven fabric, plastic and rubber foam. The aqueous pressure-sensitive adhesive composition of the present embodiment is also suitable as an adhesive used for automobile products, home appliances, and electronic parts.
＜粘着シート＞
　本実施形態の粘着シートは、基材の片面または両面に粘着層を有するものである。
　粘着シートを形成している粘着層は、本実施形態の水性粘着剤組成物を用いて形成したものである。粘着剤層の厚みは、粘着シートの用途、被着体の材質等に応じて、適宜決定することができる。粘着剤層の厚みは、例えば、５～２００μｍとすることができ、好ましくは１０～１００μｍとする。 <Adhesive sheet>
The pressure-sensitive adhesive sheet of this embodiment has a pressure-sensitive adhesive layer on one side or both sides of a substrate.
The pressure-sensitive adhesive layer forming the pressure-sensitive adhesive sheet is formed using the aqueous pressure-sensitive adhesive composition of the present embodiment. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the use of the pressure-sensitive adhesive sheet, the material of the adherend, and the like. The thickness of the pressure-sensitive adhesive layer can be, for example, 5 to 200 μm, and preferably 10 to 100 μm.
　粘着シートに用いられる基材としては、特に限定されるものではなく、紙、プラスチックフィルム、樹脂発砲体、ゴム発泡体、金属、ガラス、織布、不織布、無機板などが挙げられる。 The base material used for the pressure-sensitive adhesive sheet is not particularly limited, and examples thereof include paper, plastic film, resin foam, rubber foam, metal, glass, woven fabric, non-woven fabric, and inorganic plate.
　本実施形態の粘着シートは、粘着層を保護するために、粘着層の上に離型性の保護層が設けられたものであってもよい。
　保護層としては、例えば、プラスチックフィルム、紙、布、不織布などの多孔質材料、ネット、発泡シート、金属箔、およびこれらのラミネート体などの適宜な薄葉体などからなるものが挙げられる。 In order to protect the adhesive layer, the adhesive sheet of this embodiment may be provided with a releasable protective layer on the adhesive layer.
Examples of the protective layer include porous materials such as plastic film, paper, cloth, and nonwoven fabric, nets, foamed sheets, metal foils, and appropriate thin leaf bodies such as laminates thereof.
　保護層に用いられるプラスチックフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルムなどが挙げられる。
　保護層に用いられるプラスチックフィルムの厚みは、例えば、５～２００μｍとすることができ、好ましくは５～１００μｍである。 Examples of the plastic film used for the protective layer include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples include polyurethane films and ethylene-vinyl acetate copolymer films.
The thickness of the plastic film used for the protective layer can be, for example, 5 to 200 μm, and preferably 5 to 100 μm.
　本実施形態の粘着シートは、例えば、基材の片面または両面に、本実施形態の水性粘着剤組成物を塗布した後、乾燥させて粘着層を形成する方法により製造できる。
　基材の水性粘着剤組成物が塗布される面には、水性粘着剤組成物を塗布する前に、基材と粘着層との間の密着性を向上させるために、アンカー層を形成したり、コロナ処理やプラズマ処理などの各種易接着処理を施したりしてもよい。 The pressure-sensitive adhesive sheet of the present embodiment can be produced, for example, by a method of forming the pressure-sensitive adhesive layer by applying the aqueous pressure-sensitive adhesive composition of the present embodiment to one or both sides of a substrate and then drying it.
Before applying the aqueous pressure-sensitive adhesive composition, an anchor layer may be formed on the surface of the base material on which the aqueous pressure-sensitive adhesive composition is applied in order to improve the adhesion between the base material and the pressure-sensitive adhesive layer. Further, various easy adhesion treatments such as corona treatment and plasma treatment may be performed.
　水性粘着剤組成物を塗布する方法としては、各種方法を用いることができる。具体的には、塗布方法として、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーターなどによる押出しコート法などの方法が挙げられる。 Various methods can be used as a method of applying the aqueous pressure-sensitive adhesive composition. Specifically, as an application method, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Examples thereof include an extrusion coating method using a die coater.
　基材に水性粘着剤組成物を塗布する際には、乾燥後に形成される粘着層が所定の厚みになるように、塗布量を制御して行う。
　次いで、塗布した水性粘着剤組成物を常法にしたがって乾燥させて粘着層を形成する。
　その後、必要に応じて、粘着層の表面に易接着処理を行ってもよい。また、必要に応じて、粘着層の上に離型性の保護層を設けてもよい。
　以上の工程により、本実施形態の粘着シートが得られる。 When applying the aqueous pressure-sensitive adhesive composition to the substrate, the coating amount is controlled so that the pressure-sensitive adhesive layer formed after drying has a predetermined thickness.
Next, the applied aqueous pressure-sensitive adhesive composition is dried according to a conventional method to form an adhesive layer.
Thereafter, an easy adhesion treatment may be performed on the surface of the pressure-sensitive adhesive layer as necessary. Moreover, you may provide a releasable protective layer on an adhesion layer as needed.
The pressure-sensitive adhesive sheet of this embodiment is obtained through the above steps.
　本実施形態の粘着シートは、例えば、粘着テープ、両面テープ、粘着ラベルなどの日用品、壁紙、床タイル、床シート（クッションフロアー）、カーペット、天井材、窓用粘着シート（たとえば、遮熱シート、反射シート、防犯シート）などの住宅用資材などの分野で好適に使用できる。このほか、本実施形態の粘着シートは、例えば、自動車用製品、家電製品、電子部品などの製造においても利用できる。 The pressure-sensitive adhesive sheet of the present embodiment includes, for example, daily goods such as pressure-sensitive adhesive tapes, double-sided tapes, pressure-sensitive adhesive labels, wallpaper, floor tiles, floor sheets (cushion floors), carpets, ceiling materials, window pressure-sensitive adhesive sheets (for example, heat shield sheets, It can be suitably used in the field of housing materials such as reflective sheets and security sheets. In addition, the pressure-sensitive adhesive sheet according to the present embodiment can be used, for example, in the manufacture of automobile products, home appliances, electronic components and the like.
　以下、実施例により本発明を詳細に説明する。本発明は以下に示す実施例によってなんら制限を受けるものではない。
　なお、実施例、比較例中の「部」および「％」は、特に断りのない限り「質量部」および「質量％」を示す。 Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited by the following examples.
In the examples and comparative examples, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified.
「実施例１」
　撹拌機、温度計、還流凝縮機を備えた重合装置の反応器中に、表１に記載された割合で、イオン交換水と付加開裂型連鎖移動剤であるノフマーＭＳＤとを仕込み、昇温した。そして、空気雰囲気下で、反応器内温を８０℃に保ち、反応器内の溶液を約１２０ｒｐｍで撹拌しながら、重合開始剤として過硫酸カリウムを表１に記載のとおり添加した。 "Example 1"
In a reactor of a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, ion exchange water and NOFMER MSD, which is an addition-cleavage chain transfer agent, were charged at a ratio described in Table 1 and heated. . Then, in the air atmosphere, potassium persulfate was added as described in Table 1 while maintaining the reactor internal temperature at 80 ° C. and stirring the solution in the reactor at about 120 rpm.
　別途、表１の（Ａ）乳化物および（Ｂ）乳化物の項に示す各成分を、表１に記載された割合で混合し、ホモミキサーを用いて乳化することにより、（Ａ）乳化物および（Ｂ）乳化物を調製した。 Separately, each component shown in the section of (A) Emulsion and (B) Emulsion in Table 1 is mixed in the proportions described in Table 1, and emulsified using a homomixer, whereby (A) Emulsion And (B) an emulsion was prepared.
「工程（Ｉ）」
　上記の重合装置の反応器内に、（Ａ）乳化物と２．５％過硫酸カリウム水溶液（滴下用触媒）とを連続的に滴下し、８０℃の温度で約１２０ｒｐｍで撹拌しながら乳化重合した。さらに、（Ａ）乳化物の滴下終了から３０分間重合を継続し、乳化物を得た。
　なお、（Ａ）乳化物の滴下速度は約２３３部／時間（約２３３ｇ／時間）とした。また、２．５％過硫酸カリウム水溶液（滴下用触媒）の滴下速度は、約１１．１部／時間（約１１．１ｇ／時間）とした。そして、（Ａ）乳化物および滴下用触媒の滴下が終了した直後に、中和剤としてアンモニア水を添加し、ｐＨ７～８に調整した。 "Process (I)"
(A) The emulsion and 2.5% potassium persulfate aqueous solution (catalyst for dropping) are continuously dropped into the reactor of the above polymerization apparatus, and emulsion polymerization is performed while stirring at about 120 rpm at a temperature of 80 ° C. did. Further, (A) polymerization was continued for 30 minutes from the end of dropping of the emulsion to obtain an emulsion.
The dropping rate of (A) the emulsion was about 233 parts / hour (about 233 g / hour). The dropping rate of the 2.5% potassium persulfate aqueous solution (catalyst for dropping) was about 11.1 parts / hour (about 11.1 g / hour). (A) Immediately after the dropping of the emulsion and the dropping catalyst was completed, aqueous ammonia was added as a neutralizing agent to adjust the pH to 7-8.
「工程（ＩＩ）」
　（Ａ）乳化物の滴下終了から３０分後、工程（ＩＩ）を開始した。工程（ＩＩ）では、工程（Ｉ）で得られた乳化物の入れられた重合装置の反応器内に、（Ｂ）乳化物を連続的に滴下し、８０℃の温度で約１２０ｒｐｍで撹拌しながら乳化重合した。（Ｂ）乳化物の滴下速度は約１９４部／時間（約１９４ｇ／時間）とした。さらに、（Ｂ）乳化物の滴下終了から１時間重合を継続し、その後室温（２５℃）に冷却した。以上の工程により、実施例１の水性エマルションを得た。 "Process (II)"
(A) Step (II) was started 30 minutes after the end of dropping of the emulsion. In step (II), (B) the emulsion is continuously dropped into the reactor of the polymerization apparatus containing the emulsion obtained in step (I) and stirred at a temperature of 80 ° C. at about 120 rpm. The emulsion polymerization was carried out. (B) The dropping rate of the emulsion was about 194 parts / hour (about 194 g / hour). Furthermore, (B) superposition | polymerization was continued for 1 hour after completion | finish of dripping of an emulsion, and it cooled to room temperature (25 degreeC) after that. The aqueous emulsion of Example 1 was obtained through the above steps.
「実施例２～５、比較例１～８」
　付加開裂型連鎖移動剤の量および／または（Ａ）乳化物および（Ｂ）乳化物の組成を、表１または表２に示すように変更したこと以外は、実施例１と同様にして水性エマルションを調製した。 “Examples 2 to 5, Comparative Examples 1 to 8”
Aqueous emulsion in the same manner as in Example 1, except that the amount of addition-cleavage chain transfer agent and / or the composition of (A) emulsion and (B) emulsion was changed as shown in Table 1 or Table 2. Was prepared.
[規則26に基づく補充 17.06.2016]　
Figure WO-DOC-TABLE-1
 [Supplement under rule 26 17.06.2016]
Figure WO-DOC-TABLE-1
[規則26に基づく補充 17.06.2016]　
Figure WO-DOC-TABLE-2
 [Supplement under rule 26 17.06.2016]
Figure WO-DOC-TABLE-2
　表１および表２に示す（Ａ）乳化物および（Ｂ）乳化物、付加開裂型連鎖移動剤、重合開始剤、滴下用触媒、中和剤の数値は、質量であり、単位は（ｇ）である。
　表１および表２に示す第一重合性成分（Ａ）の割合は、第一重合性成分（Ａ）と第二重合性成分（Ｂ）とを合計した全重合性成分中の第一重合性成分（Ａ）の割合（質量％）である。また、第二重合性成分（Ｂ）の割合は、上記全重合性成分中の第二重合性成分（Ｂ）の割合（質量％）である。 The numerical values of (A) emulsion and (B) emulsion, addition-cleavage chain transfer agent, polymerization initiator, dropping catalyst, and neutralizing agent shown in Tables 1 and 2 are mass, and the unit is (g). It is.
The ratio of the first polymerizable component (A) shown in Table 1 and Table 2 is the first polymerizable component in the total polymerizable component obtained by adding the first polymerizable component (A) and the second polymerizable component (B). It is a ratio (mass%) of a component (A). Moreover, the ratio of the 2nd polymeric component (B) is a ratio (mass%) of the 2nd polymeric component (B) in the said all polymeric component.
　表１および表２に示す第一重合性成分（Ａ）Ｔｇの値、第二重合性成分（Ｂ）Ｔｇの値は、表１、表２および下記に示す各単量体成分の単独重合体（ホモポリマー）のガラス転移温度（絶対温度）であるＴｎを以下に示す値として、上述したＦＯＸの式に基づいて算出した。 The values of the first polymerizable component (A) Tg and the second polymerizable component (B) Tg shown in Table 1 and Table 2 are homopolymers of the monomer components shown in Table 1, Table 2 and below. Tn, which is the glass transition temperature (absolute temperature) of the (homopolymer), was calculated based on the above-described FOX equation as a value shown below.
　ＭＭＡ（メチルメタクリレート）：３７８Ｋ
　ＢｕＡ（ｎ－ブチルアクリレート）：２２１Ｋ
　２ＥＨＡ（２－エチルヘキシルアクリレート）：２０３Ｋ
　Ａａ（アクリル酸）：３７９Ｋ
　β－ＣＥＡ（β－カルボキシエチルアクリレート）：３１０Ｋ
　２ＨＥＭＡ（２－ヒドロキシエチルメタクリレート）：３２８Ｋ MMA (methyl methacrylate): 378K
BuA (n-butyl acrylate): 221K
2EHA (2-ethylhexyl acrylate): 203K
Aa (acrylic acid): 379K
β-CEA (β-carboxyethyl acrylate): 310K
2HEMA (2-hydroxyethyl methacrylate): 328K
　実施例および比較例の水性エマルションの製造に使用した単量体成分以外の表１および表２に示す材料は、以下のとおりである。
　ノフマーＭＳＤ（α－メチルスチレンダイマー）：付加開裂型連鎖移動剤（日油株式会社製）
　シリコンＳＣＡ-５０３：シランカップリング剤（Zhangjiagang　Guotai-Huarong　New　Chemical　Materials　Co.,Ltd製）
　アクアロンＫＨ－１０（ポリエキシエチレン－１－（アリルオキシエチレン）アルキルエーテル硫酸エステルアンモニウム塩）：界面活性剤（第一工業製薬製） The materials shown in Tables 1 and 2 other than the monomer components used in the production of the aqueous emulsions of Examples and Comparative Examples are as follows.
NOFMER MSD (α-methylstyrene dimer): addition-cleavage chain transfer agent (manufactured by NOF Corporation)
Silicon SCA-503: Silane coupling agent (manufactured by Zhangjiagang Guotai-Huarong New Chemical Materials Co., Ltd)
Aqualon KH-10 (Polyexethylene-1- (allyloxyethylene) alkyl ether sulfate ammonium salt): Surfactant (Daiichi Kogyo Seiyaku)
　次に、実施例１～５、比較例１～８の各水性エマルションの性状を、以下に示す方法により評価した。その結果を表１および表２に示す。 Next, the properties of the aqueous emulsions of Examples 1 to 5 and Comparative Examples 1 to 8 were evaluated by the following methods. The results are shown in Tables 1 and 2.
（水性エマルションの性状）
（イ）不揮発分率：水性エマルションを１０５℃で１時間乾燥し、下記の式により算出した。
　不揮発分率（％）＝［乾燥後の質量／乾燥前の質量］×１００
（ロ）粘度：ＢＨ型粘度計を用いて２３℃、１０ｒｐｍの条件下で測定した。
（ハ）ｐＨ：ｐＨメーターにより測定した。 (Properties of aqueous emulsion)
(I) Nonvolatile content: The aqueous emulsion was dried at 105 ° C. for 1 hour, and calculated according to the following formula.
Non-volatile fraction (%) = [mass after drying / mass before drying] × 100
(B) Viscosity: Measured under conditions of 23 ° C. and 10 rpm using a BH viscometer.
(C) pH: Measured with a pH meter.
　また、実施例１～５、比較例１～８の各水性エマルションを水性粘着剤組成物として用いて、以下に示す方法により、粘着シートを作製した。
　基材として、片面にコロナ処理を施した厚み５０μｍのポリエステルフィルムを用意した。そして、ポリエステルフィルムのコロナ処理を施した面に、水性エマルション（水性粘着剤組成物）を、乾燥後の粘着層の膜厚が３５μｍとなるように塗布し、１０５℃で２分間乾燥して粘着層形成し、粘着シートを得た。
　得られた粘着シートの剥離強度を以下に示す方法により測定した。その結果を表１および表２に示す。 Further, using the aqueous emulsions of Examples 1 to 5 and Comparative Examples 1 to 8 as aqueous adhesive compositions, adhesive sheets were prepared by the following method.
As a substrate, a polyester film having a thickness of 50 μm and having a corona treatment on one side was prepared. Then, an aqueous emulsion (aqueous adhesive composition) is applied to the surface of the polyester film that has been subjected to corona treatment so that the film thickness of the adhesive layer after drying is 35 μm, and dried at 105 ° C. for 2 minutes for adhesion. Layer formation was performed to obtain an adhesive sheet.
The peel strength of the obtained adhesive sheet was measured by the method shown below. The results are shown in Tables 1 and 2.
（剥離強度（粘着力）の測定）
　ＪＩＳ－Ｚ－０２３７に準拠した粘着力評価法を用いた。具体的には、上記の方法により作製した２５ｍｍ×２５０ｍｍの粘着シートの粘着層を、被着体であるステンレス（ＳＵＳ３０４）板に対向させて、貼合面積が２５ｍｍ×１２５ｍｍとなるように重ねた。粘着シート上に、温度２３℃、相対湿度５０％の雰囲気下で２ｋｇのローラーを１往復させることにより、粘着シートとステンレス板とを貼合し、同じ雰囲気下に放置した。貼合後、２０分間放置したものと、２４時間放置したものとを、それぞれ剥離速度３００ｍｍ／分の条件で１８０°剥離強度（Ｎ／２５ｍｍ）を測定した。
　なお、剥離強度の測定において、粘着シートの粘着層が凝集破壊した場合には、表１および表２に記載した１８０°剥離強度の数値の末尾に「ｃ」を付した。 (Measurement of peel strength (adhesive strength))
An adhesive strength evaluation method based on JIS-Z-0237 was used. Specifically, the adhesive layer of the 25 mm × 250 mm adhesive sheet produced by the above method was opposed to a stainless steel (SUS304) plate as an adherend, and was laminated so that the bonding area was 25 mm × 125 mm. . On the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet and the stainless steel plate were bonded by reciprocating a 2 kg roller in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and left in the same atmosphere. After the pasting, 180 ° peel strength (N / 25 mm) was measured for each of those left for 20 minutes and those left for 24 hours under the conditions of a peel rate of 300 mm / min.
In the measurement of peel strength, when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was cohesively broken, “c” was added to the end of the 180 ° peel strength values shown in Tables 1 and 2.
　また、貼合後２０分間放置した被着体（ステンレス板）の１８０°剥離強度（Ｎ／２５ｍｍ）について、以下に示す基準により評価した。
「基準」
　◎；１２．０（Ｎ／２５ｍｍ）以上
　○；１０．０（Ｎ／２５ｍｍ）以上
　×；１０．０（Ｎ／２５ｍｍ）未満 Further, the 180 ° peel strength (N / 25 mm) of the adherend (stainless steel plate) that was allowed to stand for 20 minutes after bonding was evaluated according to the following criteria.
"Standard"
◎; 12.0 (N / 25mm) or more ○; 10.0 (N / 25mm) or more ×; Less than 10.0 (N / 25mm)
（再剥離性（糊残り））
　粘着力の測定において使用した貼合後２４時間放置してから剥離力を測定した被着体（ステンレス板）に、糊残りが生じているか否かを、目視により判定し、以下に示す基準により評価した。
「基準」
　○；被着体に糊残り無し
　△；被着体全体の５％未満の面積に糊残りがある
　×；被着体全体の５％以上の面積に糊残りがある (Removability (adhesive residue))
Whether or not adhesive residue has occurred on the adherend (stainless steel plate) that was left to stand for 24 hours after bonding used in the measurement of adhesive strength was determined by visual inspection. evaluated.
"Standard"
○: No adhesive residue on the adherend Δ: Adhesive residue is present in an area of less than 5% of the entire adherend ×: Adhesive residue is present in an area of 5% or more of the entire adherend
（曇り（貼り跡）の有無）
　粘着力の測定において使用した貼合後２４時間放置してから剥離力を測定した被着体（ステンレス板）に、曇り（貼り跡）が生じているか否かを、目視により判定し、以下に示す基準により評価した。
「基準」
　○；被着体に曇り(貼り跡)無し
　×；被着体に曇り(貼り跡)有り (Must be cloudy (pasted))
It was visually determined whether or not the adherend (stainless steel plate) that had been left for 24 hours after the bonding used in the measurement of the adhesive force had been subjected to the peeling force measurement was cloudy (sticking marks). Evaluation was made according to the criteria shown.
"Standard"
○: No cloudiness (marks on the adherend) ×: Cloudiness (marks) on the adherend
（ゲル分率の測定）
　１０５℃で乾燥させた試料（水性エマルション）約１．０ｇを秤量し、これを約３０ｍｌのトルエン中に室温で１日浸漬した。その後、トルエン不溶分を取り出し、１１０℃にて約１時間乾燥して秤量し、以下に示す式を用いてゲル分率を算出した。
　ゲル分率（％）＝［トルエン不溶分質量／試料質量］×１００ (Measurement of gel fraction)
About 1.0 g of a sample (aqueous emulsion) dried at 105 ° C. was weighed and immersed in about 30 ml of toluene at room temperature for 1 day. Thereafter, the toluene-insoluble matter was taken out, dried at 110 ° C. for about 1 hour, weighed, and the gel fraction was calculated using the following formula.
Gel fraction (%) = [toluene insoluble mass / sample mass] × 100
　表１に示すように、実施例１～実施例５の水性エマルション（水性粘着剤組成物）を用いた粘着シートは、貼り合わせの初期（２０分後剥離力）においても、２４時間後においても高い粘着力を示した。特に、実施例１および実施例３の粘着シートは、貼り合せ２０分後の粘着力が１２．５（Ｎ／２５ｍｍ）以上であり、非常に高い粘着力を示した。
　また、実施例１～実施例５の粘着シートは、被着体への糊残りが少なく、貼り跡を残さず剥離できた。 As shown in Table 1, the pressure-sensitive adhesive sheets using the aqueous emulsions (aqueous pressure-sensitive adhesive compositions) of Examples 1 to 5 were used at the initial stage of bonding (peeling force after 20 minutes) and after 24 hours. High adhesion was shown. In particular, the pressure-sensitive adhesive sheets of Example 1 and Example 3 had an adhesive strength after 12.5 minutes of bonding of 12.5 (N / 25 mm) or more, and showed very high adhesive strength.
In addition, the adhesive sheets of Examples 1 to 5 had little adhesive residue on the adherend and could be peeled without leaving any mark.
　これに対し、表２に示すように、付加開裂型連鎖移動剤（ノフマーＭＳＤ）を使用しないで製造した比較例１の水性エマルションを用いた粘着シートは、被着体への糊残りが生じた。また、比較例１の粘着シートは、貼り合わせ２４時間後の粘着力の評価の際に凝集破壊した。
　また、付加開裂型連鎖移動剤を使用しないで製造した比較例２の水性エマルションを用いた粘着シートおよび付加開裂型連鎖移動剤の使用量が少ない比較例３の水性エマルションを用いた粘着シートは、ゲル分率が９０％以上であるにも拘らず、貼り跡が残った。 On the other hand, as shown in Table 2, the adhesive sheet using the aqueous emulsion of Comparative Example 1 produced without using an addition-cleavage type chain transfer agent (Nofmer MSD) produced an adhesive residue on the adherend. . In addition, the pressure-sensitive adhesive sheet of Comparative Example 1 was cohesively broken when the adhesive strength was evaluated 24 hours after bonding.
In addition, the pressure-sensitive adhesive sheet using the aqueous emulsion of Comparative Example 2 produced without using the addition-cleavage type chain transfer agent and the pressure-sensitive adhesive sheet using the aqueous emulsion of Comparative Example 3 with a small amount of addition-cleavage type chain transfer agent are used. Despite the gel fraction being 90% or more, a mark remained.
　また、（Ｂ）乳化物を使用しない比較例４の水性エマルションを用いた粘着シートは、被着体への糊残りが生じた。また、比較例４の粘着シートは、貼り合わせ２０分後および２４時間後の粘着力の評価の際に凝集破壊した。
　（Ｂ）乳化物のＴｇが－５２℃である比較例５の水性エマルションを用いた粘着シートは、被着体への糊残りが生じた。また、比較例５の粘着シートは、貼り合わせの初期（２０分後剥離力）の粘着力が不十分であり、貼り合わせ２４時間後の粘着力の評価の際に凝集破壊した。 Moreover, the adhesive sheet | seat using the aqueous emulsion of the comparative example 4 which does not use (B) emulsion produced the adhesive residue to a to-be-adhered body. Further, the pressure-sensitive adhesive sheet of Comparative Example 4 was cohesively broken when the adhesive strength was evaluated after 20 minutes and 24 hours after bonding.
(B) In the pressure-sensitive adhesive sheet using the aqueous emulsion of Comparative Example 5 in which the Tg of the emulsion was −52 ° C., adhesive residue was left on the adherend. The pressure-sensitive adhesive sheet of Comparative Example 5 had insufficient adhesive strength at the initial stage of bonding (peeling force after 20 minutes), and cohesive failure occurred during evaluation of the adhesive strength 24 hours after bonding.
　また、付加開裂型連鎖移動剤の使用量が多すぎる比較例６の水性エマルションを用いた粘着シートは、被着体への糊残りが生じた。また、比較例６の粘着シートは、貼り合わせの初期（２０分後剥離力）の粘着力が不十分であり、貼り合わせ２４時間後の粘着力の評価の際に凝集破壊した。 In addition, the adhesive sheet using the aqueous emulsion of Comparative Example 6 in which the amount of the addition-cleavage type chain transfer agent used was too large, had adhesive residue on the adherend. Further, the pressure-sensitive adhesive sheet of Comparative Example 6 had insufficient adhesive strength at the initial stage of bonding (peeling force after 20 minutes), and cohesive failure occurred during evaluation of the adhesive strength after 24 hours of bonding.
　また、（Ａ）乳化物を使用しない比較例７の水性エマルションを用いた粘着シートは、被着体への糊残りが生じた。また、比較例７の粘着シートは、貼り合わせ２０分後および２４時間後の粘着力の評価の際に凝集破壊した。
　また、（Ａ）乳化物のＴｇが－８℃である比較例８の水性エマルションを用いた粘着シートは、貼り合わせの初期（２０分後剥離力）の粘着力が不十分であり、貼り合わせ２４時間後の粘着力も不十分であった。 Moreover, (A) The adhesive sheet | seat using the aqueous emulsion of the comparative example 7 which does not use an emulsion produced the adhesive residue to a to-be-adhered body. In addition, the pressure-sensitive adhesive sheet of Comparative Example 7 was cohesively broken when the adhesive strength was evaluated after 20 minutes and 24 hours after bonding.
In addition, (A) the adhesive sheet using the aqueous emulsion of Comparative Example 8 in which the Tg of the emulsion is −8 ° C. has insufficient adhesive strength at the initial stage of bonding (peeling force after 20 minutes). The adhesive strength after 24 hours was also insufficient.

Claims (10)

  1. 　付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、前記工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを含み、且つ、以下の（１）～（３）の条件を満たす製造方法により得られる水性エマルション。
    （１）付加開裂型連鎖移動剤の量が、前記第一重合性成分と前記第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部である。
    （２）前記第一重合性成分は、ガラス転移温度が－２０℃以下の重合体を与えるものであって前記全重合性成分中の７０～９５質量％である。
    （３）前記第二重合性成分は、ガラス転移温度が５０℃以上の重合体を与えるものであって前記全重合性成分中の５～３０質量％である。     Step (I) of emulsion polymerization of the first polymerizable component in the presence of an addition-cleavage type chain transfer agent, and a step of supplying the second polymerizable component to the polymer obtained in the step (I) for polymerization. And an aqueous emulsion obtained by a production method that satisfies the following conditions (1) to (3).
    (1) The amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
    (2) The first polymerizable component gives a polymer having a glass transition temperature of −20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
    (3) The second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
  2. 　ゲル分率が９０％以上である請求項１に記載の水性エマルション。 The aqueous emulsion according to claim 1, wherein the gel fraction is 90% or more.
  3. 　前記第一重合性成分は、ガラス転移温度が－４０℃以下の重合体を与える請求項１または請求項２に記載の水性エマルション。 The aqueous emulsion according to claim 1 or 2, wherein the first polymerizable component gives a polymer having a glass transition temperature of -40 ° C or lower.
  4. 　前記第二重合性成分は、ガラス転移温度が７０℃以上の重合体を与える請求項１～請求項３のいずれか一項に記載の水性エマルション。 The aqueous emulsion according to any one of claims 1 to 3, wherein the second polymerizable component gives a polymer having a glass transition temperature of 70 ° C or higher.
  5. 　前記第二重合性成分が、メチルメタクリレートおよび／またはｎ－ブチルアクリレートを５０質量％超含む請求項１～請求項４のいずれか一項に記載の水性エマルション。 The aqueous emulsion according to any one of claims 1 to 4, wherein the second polymerizable component contains more than 50% by mass of methyl methacrylate and / or n-butyl acrylate.
  6. 　前記第一重合性成分が、ｎ－ブチルアクリレートおよび／または２－エチルヘキシルアクリレートを５０質量％超含む請求項１～請求項５のいずれか一項に記載の水性エマルション。 The aqueous emulsion according to any one of claims 1 to 5, wherein the first polymerizable component contains more than 50% by mass of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  7. 　請求項１～請求項６のいずれか一項に記載の水性エマルションを含有する水性粘着剤組成物。 An aqueous pressure-sensitive adhesive composition containing the aqueous emulsion according to any one of claims 1 to 6.
  8. 　基材の片面または両面に粘着層を有し、前記粘着層が、請求項７に記載の水性粘着剤組成物を用いて形成してなるものである粘着シート。 A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer on one side or both sides of a base material, wherein the pressure-sensitive adhesive layer is formed using the aqueous pressure-sensitive adhesive composition according to claim 7.
  9. 　付加開裂型連鎖移動剤の存在下で、第一重合性成分を乳化重合する工程（Ｉ）と、前記工程（Ｉ）で得られた重合物に第二重合性成分を供給して重合する工程（ＩＩ）とを含み、且つ、以下の（１）～（３）の条件を満たす水性エマルションの製造方法。
    （１）付加開裂型連鎖移動剤の量が、前記第一重合性成分と前記第二重合性成分とを合計した全重合性成分１００質量部に対して０．０５～１質量部である。
    （２）前記第一重合性成分は、ガラス転移温度が－２０℃以下の重合体を与えるものであって前記全重合性成分中の７０～９５質量％である。
    （３）前記第二重合性成分は、ガラス転移温度が５０℃以上の重合体を与えるものであって前記全重合性成分中の５～３０質量％である。     Step (I) of emulsion polymerization of the first polymerizable component in the presence of an addition-cleavage type chain transfer agent, and a step of supplying the second polymerizable component to the polymer obtained in the step (I) for polymerization. A method for producing an aqueous emulsion comprising (II) and satisfying the following conditions (1) to (3):
    (1) The amount of the addition-cleavage type chain transfer agent is 0.05 to 1 part by mass with respect to 100 parts by mass of the total polymerizable component obtained by adding the first polymerizable component and the second polymerizable component.
    (2) The first polymerizable component gives a polymer having a glass transition temperature of −20 ° C. or less, and is 70 to 95% by mass in the total polymerizable component.
    (3) The second polymerizable component gives a polymer having a glass transition temperature of 50 ° C. or more, and is 5 to 30% by mass in the total polymerizable component.
  10. 　構造単位として軟質重合体と硬質重合体とを含有し、前記両重合体は付加開裂型連鎖移動剤に由来する官能基を有し、
    　前記軟質重合体はガラス転移温度が－２０℃以下であり、前記重合体の構造単位中に７０～９５質量％含まれ、
    　前記硬質重合体はガラス転移温度が５０℃以上であり、前記重合体の構造単位中に５～３０質量％含まれ、
    　前記軟質重合体からなる軟質重合体部分と、前記硬質重合体からなる硬質重合体部分とが二層構造を有している水性エマルション。     Containing a soft polymer and a hard polymer as structural units, both the polymers have a functional group derived from an addition-cleavage chain transfer agent,
    The soft polymer has a glass transition temperature of −20 ° C. or less, and is contained in an amount of 70 to 95% by mass in the structural unit of the polymer.
    The hard polymer has a glass transition temperature of 50 ° C. or higher, and is contained in an amount of 5 to 30% by mass in the structural unit of the polymer.
    An aqueous emulsion in which a soft polymer portion made of the soft polymer and a hard polymer portion made of the hard polymer have a two-layer structure.
PCT/JP2016/065986 2015-06-04 2016-05-31 Aqueous emulsion, method for producing aqueous emulsion, aqueous adhesive composition, and adhesive sheet WO2016194891A1 (en)

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JPS6310610A (en) * 1986-03-07 1988-01-18 Kanegafuchi Chem Ind Co Ltd Production of methacrylate resin composition
US6710112B1 (en) * 1999-11-12 2004-03-23 Basf Aktiengesellschaft Aqueous polymer dispersions
JP2010006966A (en) * 2008-06-27 2010-01-14 Toray Fine Chemicals Co Ltd Manufacturing method of acrylic copolymer
JP2011529999A (en) * 2008-08-05 2011-12-15 アルケマ フランス A novel core-shell impact modifier for transparent polymer matrices

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US6710112B1 (en) * 1999-11-12 2004-03-23 Basf Aktiengesellschaft Aqueous polymer dispersions
JP2010006966A (en) * 2008-06-27 2010-01-14 Toray Fine Chemicals Co Ltd Manufacturing method of acrylic copolymer
JP2011529999A (en) * 2008-08-05 2011-12-15 アルケマ フランス A novel core-shell impact modifier for transparent polymer matrices

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