WO2019187787A1 - Adhesive tape - Google Patents

Adhesive tape Download PDF

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Publication number
WO2019187787A1
WO2019187787A1 PCT/JP2019/005982 JP2019005982W WO2019187787A1 WO 2019187787 A1 WO2019187787 A1 WO 2019187787A1 JP 2019005982 W JP2019005982 W JP 2019005982W WO 2019187787 A1 WO2019187787 A1 WO 2019187787A1
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WO
WIPO (PCT)
Prior art keywords
meth
pressure
sensitive adhesive
adhesive tape
acrylate
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PCT/JP2019/005982
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French (fr)
Japanese (ja)
Inventor
雅代 坂下
真央 山下
Original Assignee
綜研化学株式会社
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Application filed by 綜研化学株式会社 filed Critical 綜研化学株式会社
Priority to JP2020510412A priority Critical patent/JPWO2019187787A1/en
Priority to CN201980014238.0A priority patent/CN111742024B/en
Publication of WO2019187787A1 publication Critical patent/WO2019187787A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • This disclosure relates to an adhesive tape.
  • VOC volatile organic compounds
  • JP 2008-285554 A Japanese Patent No. 5142446
  • an object of this invention is to provide the adhesive tape which can make the outstanding adhesive performance and reduction of the amount of VOC compatible.
  • a pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive composition contains a polymer obtained by copolymerizing a monomer mixture containing (meth) acrylic acid,
  • the pressure-sensitive adhesive layer has a thickness of 30 ⁇ m or more, and the pressure-sensitive adhesive tape has a total volatile organic compound (TVOC) calculated using a test piece having a surface area of the pressure-sensitive adhesive layer of 100 mm ⁇ 100 mm and a 5 L sampling bag.
  • TVOC total volatile organic compound
  • an adhesive tape capable of achieving both excellent adhesive performance and a reduced VOC amount.
  • polymer is used to include homopolymers and copolymers
  • polymerization is used to include homopolymerization and copolymerization.
  • the compound represented by formula (i) (i is a formula number) is also simply referred to as “compound (i)”.
  • (meth) acryl means acryl or methacryl
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylo means acrylo or methacrylo.
  • the adhesive tape which concerns on 1 aspect of this invention is equipped with the adhesive layer containing the adhesive composition.
  • This pressure-sensitive adhesive composition contains a polymer obtained by copolymerizing a monomer mixture.
  • the pressure-sensitive adhesive composition is typically an acrylic pressure-sensitive adhesive composition.
  • the polymer is obtained by copolymerizing a monomer mixture containing (meth) acrylic acid. By adopting such a configuration, excellent adhesive performance can be achieved.
  • the total content of (meth) acrylic acid is not particularly limited, but is, for example, 0.5 to 10% by mass, preferably 0.6 to 8% by mass, and more preferably based on the total mass of all raw material monomers. Is 0.7 to 7% by mass, more preferably 0.8 to 6% by mass.
  • the VOC amount (especially alcohol amount) of the adhesive tape mentioned later may become high.
  • the content of (meth) acrylic acid is excessively small, the effect of adding (meth) acrylic acid as a monomer is slightly weakened.
  • This polymer may be synthesized by a normal radical polymerization method or may be synthesized by a living radical polymerization method.
  • the weight average molecular weight (Mw) of this polymer measured by gel permeation chromatography (GPC) method is, for example, 50,000 to 3,000,000, preferably 50,000 to 2,500,000. More preferably, it is 50,000 to 2,000,000.
  • the molecular weight distribution (Mw / Mn) measured by the GPC method of this polymer is, for example, 30.0 or less, preferably 25.0 or less, more preferably 20.0 or less.
  • This polymer is, for example, a (meth) acrylic polymer.
  • This polymer may be a random polymer or a block polymer.
  • This polymer may be, for example, a (meth) acrylic random polymer or a (meth) acrylic block polymer.
  • the type of monomer other than (meth) acrylic acid that can be contained in the monomer mixture is not particularly limited.
  • (meth) acrylic acid ester is mainly used, but other functional group-containing monomers and copolymerizable monomers may be further used.
  • (meth) acrylic acid ester examples include alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, alkoxypolyalkylene glycol mono (meth) acrylates, alicyclic groups, or aromatic group-containing (meth) acrylates. .
  • functional group-containing (meth) acrylates such as hydroxyl group-containing (meth) acrylate and carboxy group-containing (meth) acrylate are excluded from (meth) acrylic acid esters.
  • the number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1-20.
  • the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate,
  • alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
  • Examples of the alicyclic group or aromatic group-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, and phenoxyethyl (meth) acrylate. It is done.
  • (Meth) acrylic acid ester can be used alone or in combination of two or more.
  • the total amount of (meth) acrylic acid ester used is, for example, 70 to 99.9% by mass, preferably 80 to 99.5% by mass, and more preferably 85 to 98.95% by mass with respect to the total mass of all raw material monomers. %.
  • Examples of the functional group-containing monomer other than the (meth) acrylic acid include a hydroxyl group-containing monomer, an acid group-containing monomer, and a nitrogen atom-containing monomer.
  • Examples of the acid group include a carboxy group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
  • the nitrogen atom-containing monomer contains a nitrogen atom, for example, in the form of an amino group or an amide bond.
  • hydroxyl group-containing monomer examples include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
  • the number of carbon atoms in the alkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
  • carboxy group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate. , Itaconic acid, crotonic acid, fumaric acid and maleic acid.
  • acid anhydride group-containing monomer include maleic anhydride.
  • Examples of the phosphate group-containing monomer include (meth) acrylic monomers having a phosphate group in the side chain, and examples of the sulfate group-containing monomer include (meth) acrylic monomers having a sulfate group in the side chain.
  • nitrogen atom-containing monomer examples include amino group-containing monomers and amide bond-containing monomers.
  • amino group is used as a concept including not only a primary amino group but also secondary and tertiary amino groups.
  • the amino group is preferably a tertiary amino group, and the tertiary amino group may be a cyclic amino group.
  • the amide bond may be part of a lactam structure.
  • the nitrogen atom of the amino group is preferably modified with an alkyl group.
  • the alkyl group include those having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, Examples thereof include an iso-butyl group and a tert-butyl group.
  • the amino group-containing monomer is more preferably an aminoalkyl (meth) acrylic acid ester.
  • the preferable aspect of the amino group in aminoalkyl (meth) acrylic ester it is the same as that of the above.
  • the alkyl group in the aminoalkyl group include those having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Sec-butyl group, iso-butyl group, and tert-butyl group.
  • the aminoalkyl group include a tert-butylaminoethyl group, a dimethylaminoethyl group, and a diethylaminoethyl group.
  • amino group-containing monomers include tert-butylaminoethyl methacrylate (TBAEMA), dimethylaminoethyl methacrylate (DMAEMA; DM), diethylaminoethyl methacrylate (DEAEMA), and dimethylaminoethyl acrylate. (DMAEA).
  • TAAEMA tert-butylaminoethyl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • DEAEMA diethylaminoethyl methacrylate
  • DMAEA dimethylaminoethyl acrylate
  • the amide bond-containing monomer is preferably a (meth) acrylamide derivative or a lactam having a vinyl group.
  • the (meth) acrylamide derivative is, for example, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, or diacetone acrylamide.
  • alkyl group include those having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, Examples thereof include an iso-butyl group and a tert-butyl group.
  • amide bond-containing monomer examples include N, N-dimethylacrylamide (DMAA), N, N-diethylacrylamide (DEAA), N-isopropylacrylamide (NIPAM), diacetone acrylamide (DAAM), N-acryloylmorpholine ( ACMO), N-vinyl-2-pyrrolidone (NVP), N-vinyl-caprolactam (NVC), and N- (2-hydroxyethyl) acrylamide (HEAA).
  • DMAA N-dimethylacrylamide
  • DEAA N-diethylacrylamide
  • NIPAM N-isopropylacrylamide
  • DAAM diacetone acrylamide
  • ACMO N-acryloylmorpholine
  • NVP N-vinyl-2-pyrrolidone
  • NVC N-vinyl-caprolactam
  • HEAA N- (2-hydroxyethyl) acrylamide
  • the functional group-containing monomer can be used alone or in combination of two or more.
  • the total amount of the functional group-containing monomer excluding the (meth) acrylic acid is preferably 0 to 15% by mass, more preferably 0.05 to 10% by mass, based on the total mass of all raw material monomers. is there.
  • the total amount of the hydroxyl group-containing polymer is, for example, 0 to 5% by mass, preferably 0.05 to 2% by mass, and more preferably 0.00%, based on the total mass of all raw material monomers.
  • the content is 1 to 1% by mass, more preferably 0.12 to 0.8% by mass.
  • Copolymerizable monomers examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes, fluorostyrene, chlorostyrene, bromostyrene, dibromo.
  • styrene monomers such as styrene, iodostyrene, nitrostyrene, acetylstyrene and methoxystyrene, and vinyl acetate.
  • the copolymerizable monomer can be used alone or in combination of two or more.
  • the pressure-sensitive adhesive composition includes, as other components, a tackifier resin, a crosslinking agent, a silane coupling agent, an antistatic agent, an organic solvent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a plasticizer, a crosslinking accelerator, It may further contain nanoparticles and the like.
  • the pressure-sensitive adhesive composition may contain a tackifier resin.
  • a tackifying resin in addition to the above-mentioned polymer as a component constituting the pressure-sensitive adhesive composition, for example, it is generally difficult to adhere to an acrylic pressure-sensitive adhesive, such as polyethylene, polypropylene, and other olefinic adherends. Even for this, good adhesion (tackiness) can be exhibited. Moreover, the constant load peeling resistance of the obtained adhesive layer can be improved.
  • a rosin ester resin is preferably used, and a polymerized rosin ester resin may be used in combination.
  • a terpene tackifier resin or a hydrocarbon petroleum resin may be used.
  • the tackifier resin may be used alone or in combination of two or more.
  • the total content of the tackifying resin in the pressure-sensitive adhesive composition is, for example, 1 to 40 parts by mass, preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polymer.
  • Crosslinking agent examples include isocyanate compounds, epoxy compounds, metal chelate compounds, and the like.
  • an isocyanate compound having two or more isocyanate groups in one molecule is usually used.
  • the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
  • Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
  • aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
  • alicyclic diisocyanate examples include 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate.
  • Diisocyanate is mentioned.
  • aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
  • isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ′, 4 ′′ -triphenylmethane triisocyanate.
  • Diphenylmethane diisocyanate trimer polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, reaction product of trimethylolpropane with tolylene diisocyanate or xylylene diisocyanate (eg tolylene diisocyanate) Isocyanate or xylylene diisocyanate trimolecular adducts), trimethylolpropane and hexamethylene diisocyanate reaction products (eg hexamethylene diisocyanate) Over 3 molecular adduct g), polyether polyisocyanates, and polyester polyisocyanates.
  • an epoxy compound having 2 or more epoxy groups in one molecule is usually used.
  • metal chelate compound for example, alkoxide, acetylacetone, ethyl acetoacetate and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, etc.
  • a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, etc.
  • Compounds. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
  • the crosslinking agent is in the range of 0.01 to 10 parts by mass, preferably 0.01 to 8 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total with the polymer. When a crosslinking agent is included in this range, it is possible to balance the various required adhesive properties.
  • the silane coupling agent can firmly adhere the pressure-sensitive adhesive layer to an adherend such as a glass substrate, and can prevent the pressure-sensitive adhesive layer from peeling off in a high-humidity heat environment.
  • silane coupling agent examples include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3- Epoxy group-containing silane cups such as glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Ring agent; amino group-containing silane such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Coupling agent Halogen-containing si
  • an epoxy group-containing silane coupling agent is preferable in terms of stress relaxation.
  • the content of the silane coupling agent is usually 1 part by mass or less, preferably 0.01-1 part by mass, more preferably 0.05-0. 5 parts by mass. When the content is in the above range, peeling of the pressure-sensitive adhesive layer in a high-humidity heat environment and bleeding of the silane coupling agent in a high-temperature environment tend to be prevented.
  • Antistatic agent examples include a surfactant, an ionic compound, and a conductive polymer.
  • surfactant examples include cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridium salts, primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates, glycerin fatty acid esters
  • Nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyldiethanolamides It is done.
  • a reactive emulsifier having a polymerizable group is also exemplified as the surfactant, and a polymer surfactant obtained by increasing the molecular weight of the monomer component containing the above surfactant or reactive emulsifier can also be used.
  • Examples of the conductive polymer include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
  • the content of the antistatic agent is usually 3 parts by mass or less, preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass with respect to 100 parts by mass of the polymer. Part by mass.
  • the pressure-sensitive adhesive composition does not necessarily contain a solvent, but may contain an organic solvent in order to adjust its coatability.
  • the content of the organic solvent is usually 30 to 90% by mass, preferably 30 to 85% by mass.
  • solid content refers to all components excluding the organic solvent among the components contained in the pressure-sensitive adhesive composition
  • solid content concentration refers to 100% by mass of the pressure-sensitive adhesive composition. The ratio of the said solid content is said.
  • the pressure-sensitive adhesive tape according to the present invention is formed on, for example, a double-sided pressure-sensitive adhesive sheet having only an adhesive layer formed on a peeled cover film (hereinafter also referred to as a separator), a base material, and both surfaces of the base material.
  • Double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer in this case, the base material is also referred to as a core material
  • a base material in this case, the base material is also referred to as a core material
  • a base material is also referred to as a core material
  • a base material includes a pressure-sensitive adhesive sheet in which a peeled cover film is attached to a surface of the pressure-sensitive adhesive layer that is not in contact with the base material.
  • the base material examples include polyester films such as polyethylene terephthalate (PET), plastic films such as polycarbonate, polyethylene, polypropylene, polyolefin films such as ethylene-vinyl acetate copolymer, woven fabrics and non-woven fabrics.
  • PET polyethylene terephthalate
  • plastic films such as polycarbonate, polyethylene, polypropylene, polyolefin films such as ethylene-vinyl acetate copolymer, woven fabrics and non-woven fabrics.
  • the thickness of the substrate is not particularly limited, but is usually 1 to 2000 ⁇ m, particularly 3 to 500 ⁇ m, especially 10 to 100 ⁇ m.
  • cover film examples include a plastic film such as a polyester film such as polyethylene terephthalate (PET) optionally having a surface-exfoliated treatment, a polyolefin film such as polycarbonate, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • PET polyethylene terephthalate
  • polyolefin film such as polycarbonate, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the plastic film one in which various additives are blended or one in which a plurality of layers are laminated can be used.
  • a known thickness such as a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, or a gravure coating method may be used.
  • the method of applying and drying can be used, and the pressure-sensitive adhesive layer can be formed in this way.
  • the pressure-sensitive adhesive layer has a thickness formed by a single coating step of 30 ⁇ m or more, preferably 40 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • the said adhesive layer is 30 micrometers or more in thickness formed by the single application
  • the total thickness of the pressure-sensitive adhesive layer is usually 60 ⁇ m or more.
  • the upper limit of the total thickness of the said adhesive layer is not specifically limited, Usually, it is 1000 micrometers or less.
  • the pressure-sensitive adhesive tape according to the present invention has a total volatile organic compound (TVOC) concentration of 10,000 ⁇ g / m 3 or less calculated using a test piece having an area of the pressure-sensitive adhesive layer of 100 mm ⁇ 100 mm and a 5 L sampling bag. .
  • a Tedlar (registered trademark) bag manufactured by GL Sciences: model: AA-5) is used as the sampling bag.
  • the present inventors have found that the above-mentioned VOC concentration cannot be achieved with a conventional adhesive tape. And as a result of earnest examination, it discovered that the contribution of isoparaffin and alcohol had big influence on the said VOC density
  • the initiator it is preferable to use one having as little isoparaffin content as a diluent. That is, it is preferable to use an initiator having a decomposition temperature that is so high that a diluent is unnecessary.
  • the isoparaffin content in the initiator is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, based on the total solid content of the pressure-sensitive adhesive composition. More preferably, the content is 0.01% by mass or less.
  • the initiator does not substantially contain isoparaffin.
  • the “isoparaffin” means a chain saturated hydrocarbon having a side chain and having about 20 or more carbon atoms.
  • the remaining amount of the initiator in the pressure-sensitive adhesive composition is preferably as small as possible.
  • Examples of the initiator having a relatively high decomposition temperature include PBND100 [manufactured by NOF; t-butylperoxynedecanoate], V601 [manufactured by Wako Pure Chemical Industries; (2,2′-Azobis (isobutyronitrile)), V-65 [Wako Pure Chemical Industries; (2,2′-Azobis (2,4-dimethylhydrerontrile)], V-59 [Wako Pure Chemicals] (2,2′-Azobis (2-methylbutyronitrile)), and Parroyl L [manufactured by NOF; DialoylPeroxide] can be used, but these are merely examples, and other It is of course also possible to use the initiator.
  • the drying condition of the pressure-sensitive adhesive layer affects the total VOC concentration.
  • the total VOC concentration can be reduced.
  • the contribution of alcohol in the VOC becomes relatively large, so that adjustment of drying conditions is particularly important.
  • isoparaffin concentration calculated using the test piece and the sampling bag is preferably 5000 [mu] g / m 3 or less, more preferably 4000 ⁇ g / m 3 or less, is 3000 ⁇ g / m 3 or less More preferably. Further it, the alcohol concentration calculated using the test piece and the sampling bag is preferably at 3000 ⁇ g / m 3 or less, more preferably 2500 g / m 3 or less, 2000 [mu] g / m 3 or less Is more preferable. ⁇ Example>
  • an initiator was added at a rate described in Table 1, and a polymerization reaction was performed at 80 ° C. for 6 hours in a nitrogen gas atmosphere. After completion of the reaction, it was diluted with ethyl acetate to prepare a polymer solution having a solid content concentration of 50% by mass.
  • PBND100, PBND, PHPV, PBPV, and PL355 are NOF initiators, and V601 is an initiator manufactured by Wako Pure Chemical Industries.
  • the polymers obtained in Synthesis Examples 1 to 7 were mixed with a tackifying resin and a crosslinking agent as necessary to obtain a pressure-sensitive adhesive composition.
  • Table 2 shows the remaining amount of initiator and the amount of isoparaffin (IP) in the initiator together with the composition.
  • IP isoparaffin
  • the IP content and the remaining amount of initiator in Table 2 represent amounts relative to the total solid content of the pressure-sensitive adhesive composition.
  • PCJ polymerized rosin ester resin, manufactured by Harima Chemicals
  • Each obtained pressure-sensitive adhesive composition was coated on a light release film and dried to form a pressure-sensitive adhesive layer having a thickness of 55 ⁇ m.
  • the pressure-sensitive adhesive layer was transferred to one surface of a PET film having a thickness of 25 ⁇ m (Lumirror: manufactured by Toray).
  • the procedure for forming the 55 ⁇ m thick pressure-sensitive adhesive layer was performed again, and the pressure-sensitive adhesive layer was transferred to the other side of the previous PET film. That is, the pressure-sensitive adhesive tape has a structure of (pressure-sensitive adhesive layer / PET film (base material) / pressure-sensitive adhesive layer), and the total thickness of the pressure-sensitive adhesive layer is 110 ⁇ m, and the total thickness of the adhesive tape is 135 ⁇ m.
  • Total VOC concentration The above adhesive tape is cut out in an area of 100 mm ⁇ 100 mm, using a 5 L Tedlar (registered trademark) bag (manufactured by GL Sciences: model: AA-5), with total VOC, ethyl acetate, toluene, alcohol, and isoparaffin (IP ) was measured.
  • each detected amount is a value obtained by converting a peak area corresponding to each target substance analyzed in the gas chromatograph into toluene.
  • the total VOC is a value obtained by converting the sum of the detection peak areas of the gas chromatograph detected in the range from n-hexane to n-hexadecane into a toluene detection peak area.
  • the isoparaffin concentration is a value obtained by converting the total area of detection peak groups corresponding to paraffin-derived parts into a toluene detection peak area. The results are also shown in Table 2.
  • Example 1 the total VOC amount could be suppressed to 10000 ⁇ g / m 3 or less.
  • Comparative Examples 1 to 4 the total VOC amount exceeded 10000 ⁇ g / m 3 .
  • Example 1 and Comparative Example 1 were compared, it was found that the total VOC amount could be greatly reduced by using the polymer P3 and increasing the drying temperature from 90 ° C. to 120 ° C. I understand.
  • Examples 1 to 5 and Comparative Examples 2 to 4 are compared, it can be seen that the total VOC amount can be greatly reduced even by using an initiator having a low isoparaffin content.
  • Holding force is measured in accordance with JISZ1541, the adhesive sheet is cut to 20mm width, pasted so that the area of 20x20mm is in contact with the SUS plate, and a load of 1Kg is applied at a temperature of 40 ° C or 80 ° C. The presence or absence of the fall when left for 1 hour was observed.
  • the obtained adhesive tape was transferred to a 10 mm-thick polyether urethane foam material to obtain a test tape for a curved surface sticking test.
  • This test tape was cut into 20 mm ⁇ 50 mm to obtain a test piece.
  • This test piece was attached to a 50 mm ⁇ or 30 mm ⁇ SUS304 cylinder polished with No. 280 water-resistant abrasive paper. The sample was allowed to stand at 80 ° C. or 23 ° C. for 24 hours, and the test piece edge portion or the peeling distance was measured.
  • the adhesive tape of Example 5 had sufficient adhesive performance.
  • the pressure-sensitive adhesive tape of Example 5 was more excellent in holding power at 80 ° C. and curved surface stickiness at 23 ° C. than the pressure-sensitive adhesive tape of Reference Example 3. This difference is considered to be due to the fact that the pressure-sensitive adhesive tape of Example 5 includes a pressure-sensitive adhesive composition containing a copolymer having acrylic acid as a monomer component.

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  • Adhesive Tapes (AREA)

Abstract

The present invention provides an adhesive tape capable of achieving both good adhesion and a reduced amount of VOC. This adhesive tape is provided with an adhesive layer having an adhesive composition. The adhesive composition comprises a polymer obtained from high-polymerization of a monomer mixture containing a (meth)acrylic acid. The thickness of the adhesive layer is 30μm or more. In the adhesive tape, the adhesive layer has a total volatile organic compound (TVOC) concentration of 10000 μg/m3 or less, as calculated by using a specimen having an adhesive layer area of 100 mm X 100 mm and a 5L sampling bag.

Description

粘着テープAdhesive tape
　本開示は、粘着テープに関する。 This disclosure relates to an adhesive tape.
　近年、環境意識の高まりから、工業材料から生じる揮発性有機化合物（ＶＯＣ）量の低減が要求されている。このような要求は、自動車産業において特に顕著であり、アジアに拠点を有するメーカを中心に、厳しいＶＯＣ量管理が課されている。そのため、自動車製造に用いられる粘着テープについても、ＶＯＣ量を抑制することが必要である。 In recent years, due to increasing environmental awareness, there is a demand for a reduction in the amount of volatile organic compounds (VOC) generated from industrial materials. Such a requirement is particularly remarkable in the automobile industry, and strict VOC amount management is imposed mainly on manufacturers having bases in Asia. Therefore, it is necessary to suppress the amount of VOC also about the adhesive tape used for automobile manufacture.
特開２００８－２８５５５４号公報JP 2008-285554 A 特許第５１４２４４６号公報Japanese Patent No. 5142446
　しかしながら、従来の粘着テープでは、工業用途で要求される性能を満足しつつＶＯＣ量を低減させることは困難であった。そこで、本発明は、優れた粘着性能とＶＯＣ量の低減とが両立可能な粘着テープを提供することを目的とする。 However, with conventional adhesive tapes, it has been difficult to reduce the amount of VOC while satisfying the performance required for industrial applications. Then, an object of this invention is to provide the adhesive tape which can make the outstanding adhesive performance and reduction of the amount of VOC compatible.
　本発明の態様は、例えば、以下の通りである。
　［１］粘着剤組成物を含んだ粘着剤層を備えた粘着テープであって、前記粘着剤組成物は、（メタ）アクリル酸を含んだモノマー混合物を共重合させて得られるポリマーを含み、前記粘着剤層は厚さが３０μｍ以上であり、前記粘着テープは、前記粘着剤層の面積が１００ｍｍ×１００ｍｍである試験片及び５Ｌのサンプリングバッグを用いて算出される総揮発性有機化合物（ＴＶＯＣ）濃度が１００００μｇ／ｍ３以下である、粘着テープ。
　［２］前記試験片及び前記サンプリングバッグを用いて算出されるアルコール濃度が３０００μｇ／ｍ３以下である、［１］に記載の粘着テープ。
　［３］前記試験片及び前記サンプリングバッグを用いて算出されるイソパラフィン濃度が５０００μｇ／ｍ３以下である、［１］又は［２］に記載の粘着テープ。
　［４］前記共重合に用いる開始剤中のイソパラフィン含有量が、前記粘着剤組成物の全固形分に対して０．０３質量％以下である、［１］～［３］の何れかに記載の粘着テープ。
　［５］前記共重合に用いる開始剤は、イソパラフィンを実質的に含んでいない、［１］～［４］の何れかに記載の粘着テープ。 Aspects of the present invention are as follows, for example.
[1] A pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive composition contains a polymer obtained by copolymerizing a monomer mixture containing (meth) acrylic acid, The pressure-sensitive adhesive layer has a thickness of 30 μm or more, and the pressure-sensitive adhesive tape has a total volatile organic compound (TVOC) calculated using a test piece having a surface area of the pressure-sensitive adhesive layer of 100 mm × 100 mm and a 5 L sampling bag. ) An adhesive tape having a concentration of 10,000 μg / m 3 or less.
[2] The adhesive tape according to [1], wherein the alcohol concentration calculated using the test piece and the sampling bag is 3000 μg / m 3 or less.
[3] The pressure-sensitive adhesive tape according to [1] or [2], wherein the isoparaffin concentration calculated using the test piece and the sampling bag is 5000 μg / m 3 or less.
[4] The isoparaffin content in the initiator used for the copolymerization is 0.03% by mass or less based on the total solid content of the pressure-sensitive adhesive composition, according to any one of [1] to [3] Adhesive tape.
[5] The pressure-sensitive adhesive tape according to any one of [1] to [4], wherein the initiator used for the copolymerization does not substantially contain isoparaffin.
　本発明によると、優れた粘着性能とＶＯＣ量の低減とが両立可能な粘着テープを提供することができる。 According to the present invention, it is possible to provide an adhesive tape capable of achieving both excellent adhesive performance and a reduced VOC amount.
　以下、本発明の一態様に係る粘着テープについて説明する。 Hereinafter, the adhesive tape according to one embodiment of the present invention will be described.
　なお、本明細書において、「ポリマー」とはホモポリマー及びコポリマーを包含する意味で用い、「重合」とは単独重合及び共重合を包含する意味で用いる。また、式（ｉ）で表される化合物（ｉは式番号である）を単に「化合物（ｉ）」ともいう。更に、本明細書において、（メタ）アクリルとは、アクリル又はメタクリルを意味し、（メタ）アクリレートはアクリレート又はメタクリレートを意味し、（メタ）アクリロはアクリロ又はメタクリロを意味する。 In this specification, “polymer” is used to include homopolymers and copolymers, and “polymerization” is used to include homopolymerization and copolymerization. The compound represented by formula (i) (i is a formula number) is also simply referred to as “compound (i)”. Furthermore, in this specification, (meth) acryl means acryl or methacryl, (meth) acrylate means acrylate or methacrylate, and (meth) acrylo means acrylo or methacrylo.
　〔粘着剤組成物〕
　本発明の一態様に係る粘着テープは、粘着剤組成物を含んだ粘着剤層を備えている。この粘着剤組成物は、モノマー混合物を共重合させて得られるポリマーを含んでいる。粘着剤組成物は、典型的には、アクリル系粘着剤組成物である。 [Adhesive composition]
The adhesive tape which concerns on 1 aspect of this invention is equipped with the adhesive layer containing the adhesive composition. This pressure-sensitive adhesive composition contains a polymer obtained by copolymerizing a monomer mixture. The pressure-sensitive adhesive composition is typically an acrylic pressure-sensitive adhesive composition.
　［ポリマー］
　上記ポリマーは、（メタ）アクリル酸を含んだモノマー混合物を共重合させて得られる。このような構成を採用することにより、優れた粘着性能を達成することができる。 [polymer]
The polymer is obtained by copolymerizing a monomer mixture containing (meth) acrylic acid. By adopting such a configuration, excellent adhesive performance can be achieved.
　（メタ）アクリル酸の合計含有量に特に制限はないが、例えば、全原料モノマーの総質量に対して、０．５～１０質量％とし、好ましくは０．６～８質量％とし、より好ましくは０．７～７質量％とし、更に好ましくは０．８～６質量％とする。（メタ）アクリル酸の含有量が過度に多いと、後述する粘着テープのＶＯＣ量（特にアルコール量）が高くなり得る。（メタ）アクリル酸の含有量が過度に少ないと、モノマーとして（メタ）アクリル酸を添加する効果がやや弱くなる。 The total content of (meth) acrylic acid is not particularly limited, but is, for example, 0.5 to 10% by mass, preferably 0.6 to 8% by mass, and more preferably based on the total mass of all raw material monomers. Is 0.7 to 7% by mass, more preferably 0.8 to 6% by mass. When there is too much content of (meth) acrylic acid, the VOC amount (especially alcohol amount) of the adhesive tape mentioned later may become high. When the content of (meth) acrylic acid is excessively small, the effect of adding (meth) acrylic acid as a monomer is slightly weakened.
　このポリマーは、通常のラジカル重合法で合成したものであってもよいし、リビングラジカル重合法で合成したものであってもよい。このポリマーのゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定される重量平均分子量（Ｍｗ）は、例えば５０，０００～３，０００，０００であり、好ましくは５０，０００～２，５００，０００であり、より好ましくは５０，０００～２，０００，０００である。このポリマーのＧＰＣ法により測定される分子量分布（Ｍｗ／Ｍｎ）は、例えば３０．０以下であり、好ましくは２５．０以下であり、より好ましくは２０．０以下である。 This polymer may be synthesized by a normal radical polymerization method or may be synthesized by a living radical polymerization method. The weight average molecular weight (Mw) of this polymer measured by gel permeation chromatography (GPC) method is, for example, 50,000 to 3,000,000, preferably 50,000 to 2,500,000. More preferably, it is 50,000 to 2,000,000. The molecular weight distribution (Mw / Mn) measured by the GPC method of this polymer is, for example, 30.0 or less, preferably 25.0 or less, more preferably 20.0 or less.
　このポリマーは、例えば、（メタ）アクリル系ポリマーである。このポリマーは、ランダムポリマーであってもよく、ブロックポリマーであってもよい。このポリマーは、例えば、（メタ）アクリル系ランダムポリマーであってもよく、（メタ）アクリル系ブロックポリマーであってもよい。 This polymer is, for example, a (meth) acrylic polymer. This polymer may be a random polymer or a block polymer. This polymer may be, for example, a (meth) acrylic random polymer or a (meth) acrylic block polymer.
　上記モノマー混合物に含まれ得る（メタ）アクリル酸以外のモノマーの種類については、特に制限はない。このようなモノマーとしては、（メタ）アクリル酸エステルが主に用いられるが、それ以外の官能基含有モノマー及び共重合性モノマーなどを更に用いることもできる。 The type of monomer other than (meth) acrylic acid that can be contained in the monomer mixture is not particularly limited. As such a monomer, (meth) acrylic acid ester is mainly used, but other functional group-containing monomers and copolymerizable monomers may be further used.
　《（メタ）アクリル酸エステル》
　（メタ）アクリル酸エステルとしては、例えば、アルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート、アルコキシポリアルキレングリコールモノ（メタ）アクリレート、脂環式基又は芳香族基含有（メタ）アクリレートが挙げられる。ただし、（メタ）アクリル酸エステルからは、水酸基含有（メタ）アクリレート及びカルボキシ基含有（メタ）アクリレート等の官能基含有（メタ）アクリレートを除く。 << (Meth) acrylic acid ester >>
Examples of (meth) acrylic acid esters include alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, alkoxypolyalkylene glycol mono (meth) acrylates, alicyclic groups, or aromatic group-containing (meth) acrylates. . However, functional group-containing (meth) acrylates such as hydroxyl group-containing (meth) acrylate and carboxy group-containing (meth) acrylate are excluded from (meth) acrylic acid esters.
　アルキル（メタ）アクリレートでのアルキル基の炭素数は、１～２０であることが好ましい。アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉｓｏ－プロピル（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、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、オレイル（メタ）アクリレート、ｎ－ステアリル（メタ）アクリレート、ｉｓｏ－ステアリル（メタ）アクリレート、ドデシル（メタ）アクリレートが挙げられる。 The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1-20. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, n-stearyl (meth) acrylate, iso-stearyl (meth) acrylate, Sil (meth) acrylate.
　アルコキシアルキル（メタ）アクリレートとしては、例えば、メトキシメチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレートが挙げられる。 Examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
　アルコキシポリアルキレングリコールモノ（メタ）アクリレートとしては、例えば、メトキシジエチレングリコールモノ（メタ）アクリレート、メトキシジプロピレングリコールモノ（メタ）アクリレート、エトキシトリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコールモノ（メタ）アクリレート、メトキシトリエチレングリコールモノ（メタ）アクリレートが挙げられる。 Examples of the alkoxypolyalkylene glycol mono (meth) acrylate include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
　脂環式基又は芳香族基含有（メタ）アクリレートとしては、例えば、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートが挙げられる。 Examples of the alicyclic group or aromatic group-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, and phenoxyethyl (meth) acrylate. It is done.
　（メタ）アクリル酸エステルは１種単独で、又は２種以上を使用することができる。（メタ）アクリル酸エステルの全使用量は、全原料モノマーの総質量に対して、例えば７０～９９．９質量％、好ましくは８０～９９．５質量％、より好ましくは８５～９８．９５質量％である。 (Meth) acrylic acid ester can be used alone or in combination of two or more. The total amount of (meth) acrylic acid ester used is, for example, 70 to 99.9% by mass, preferably 80 to 99.5% by mass, and more preferably 85 to 98.95% by mass with respect to the total mass of all raw material monomers. %.
　《官能基含有モノマー》
　上記（メタ）アクリル酸以外の官能基含有モノマーとしては、例えば、水酸基含有モノマー、酸基含有モノマー、及び窒素原子含有モノマーが挙げられる。酸基としては、例えば、カルボキシ基、酸無水物基、リン酸基、硫酸基が挙げられる。窒素原子含有モノマーは、例えば、アミノ基又はアミド結合の形態で窒素原子を含んでいる。 《Functional group-containing monomer》
Examples of the functional group-containing monomer other than the (meth) acrylic acid include a hydroxyl group-containing monomer, an acid group-containing monomer, and a nitrogen atom-containing monomer. Examples of the acid group include a carboxy group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group. The nitrogen atom-containing monomer contains a nitrogen atom, for example, in the form of an amino group or an amide bond.
　水酸基含有モノマーとしては、例えば、水酸基含有（メタ）アクリレートが挙げられ、具体的には、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロシキブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが挙げられる。ヒドロキシアルキル（メタ）アクリレートでのアルキル基の炭素数は、通常２～８、好ましくは２～６である。 Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate. The number of carbon atoms in the alkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
　カルボキシ基含有モノマーとしては、例えば、（メタ）アクリル酸β－カルボキシエチル、（メタ）アクリル酸５－カルボキシペンチル、コハク酸モノ（メタ）アクリロイルオキシエチルエステル、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート、イタコン酸、クロトン酸、フマル酸、マレイン酸が挙げられる。酸無水物基含有モノマーとしては、例えば、無水マレイン酸が挙げられる。リン酸基含有モノマーとしては、側鎖にリン酸基を有する（メタ）アクリル系モノマーが挙げられ、硫酸基含有モノマーとしては、側鎖に硫酸基を有する（メタ）アクリル系モノマーが挙げられる。 Examples of the carboxy group-containing monomer include β-carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ω-carboxypolycaprolactone mono (meth) acrylate. , Itaconic acid, crotonic acid, fumaric acid and maleic acid. Examples of the acid anhydride group-containing monomer include maleic anhydride. Examples of the phosphate group-containing monomer include (meth) acrylic monomers having a phosphate group in the side chain, and examples of the sulfate group-containing monomer include (meth) acrylic monomers having a sulfate group in the side chain.
　窒素原子含有モノマーとしては、例えば、アミノ基含有モノマー及びアミド結合含有モノマーが挙げられる。なお、ここで「アミノ基」とは、１級アミノ基のみならず、２級及び３級アミノ基を含む概念として用いている。上記アミノ基は、３級アミノ基であることが好ましく、３級アミノ基は、環状アミノ基であってもよい。また、上記アミド結合は、ラクタム構造の一部であってもよい。 Examples of the nitrogen atom-containing monomer include amino group-containing monomers and amide bond-containing monomers. Here, the “amino group” is used as a concept including not only a primary amino group but also secondary and tertiary amino groups. The amino group is preferably a tertiary amino group, and the tertiary amino group may be a cyclic amino group. The amide bond may be part of a lactam structure.
　アミノ基含有モノマーが２級又は３級アミノ基を含んでいる場合、アミノ基の窒素原子は、アルキル基によって修飾されていることが好ましい。このアルキル基としては、例えば、炭素数１～６のものが挙げられ、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、及びｔｅｒｔ－ブチル基が挙げられる。 When the amino group-containing monomer contains a secondary or tertiary amino group, the nitrogen atom of the amino group is preferably modified with an alkyl group. Examples of the alkyl group include those having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, Examples thereof include an iso-butyl group and a tert-butyl group.
　アミノ基含有モノマーは、より好ましくは、アミノアルキル（メタ）アクリル酸エステルである。アミノアルキル（メタ）アクリル酸エステル中のアミノ基の好ましい態様については、上記と同様である。また、アミノアルキル基中のアルキル基としては、例えば、炭素数１～６のものが挙げられ、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、及びｔｅｒｔ－ブチル基が挙げられる。アミノアルキル基としては、例えば、ｔｅｒｔ－ブチルアミノエチル基、ジメチルアミノエチル基、及びジエチルアミノエチル基が挙げられる。 The amino group-containing monomer is more preferably an aminoalkyl (meth) acrylic acid ester. About the preferable aspect of the amino group in aminoalkyl (meth) acrylic ester, it is the same as that of the above. Examples of the alkyl group in the aminoalkyl group include those having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Sec-butyl group, iso-butyl group, and tert-butyl group. Examples of the aminoalkyl group include a tert-butylaminoethyl group, a dimethylaminoethyl group, and a diethylaminoethyl group.
　アミノ基含有モノマーの具体例としては、ｔｅｒｔ－ブチルアミノエチルメタクリル酸エステル（ＴＢＡＥＭＡ）、ジメチルアミノエチルメタクリル酸エステル（ＤＭＡＥＭＡ；ＤＭ）、ジエチルアミノエチルメタクリル酸エステル（ＤＥＡＥＭＡ）、及びジメチルアミノエチルアクリル酸エステル（ＤＭＡＥＡ）が挙げられる。 Specific examples of amino group-containing monomers include tert-butylaminoethyl methacrylate (TBAEMA), dimethylaminoethyl methacrylate (DMAEMA; DM), diethylaminoethyl methacrylate (DEAEMA), and dimethylaminoethyl acrylate. (DMAEA).
　アミド結合含有モノマーは、好ましくは、（メタ）アクリルアミド誘導体、又は、ビニル基を備えたラクタムである。 The amide bond-containing monomer is preferably a (meth) acrylamide derivative or a lactam having a vinyl group.
　上記（メタ）アクリルアミド誘導体は、例えば、Ｎ－アルキル（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド、又は、ジアセトンアクリルアミドである。このアルキル基としては、例えば、炭素数１～６のものが挙げられ、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、及びｔｅｒｔ－ブチル基が挙げられる。 The (meth) acrylamide derivative is, for example, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, or diacetone acrylamide. Examples of the alkyl group include those having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, Examples thereof include an iso-butyl group and a tert-butyl group.
　アミド結合含有モノマーの具体例としては、Ｎ，Ｎ－ジメチルアクリルアミド（ＤＭＡA）、Ｎ，Ｎ－ジエチルアクリルアミド（ＤＥＡA）、Ｎ－イソプロピルアクリルアミド（ＮＩＰＡＭ）、ジアセトンアクリルアミド（ＤＡＡＭ）、Ｎ－アクリロイルモルホリン（ＡＣＭＯ）、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）、Ｎ－ビニル－カプロラクタム（ＮＶＣ）、及びＮ－（２－ヒドロキシエチル）アクリルアミド（ＨＥＡA）が挙げられる。 Specific examples of the amide bond-containing monomer include N, N-dimethylacrylamide (DMAA), N, N-diethylacrylamide (DEAA), N-isopropylacrylamide (NIPAM), diacetone acrylamide (DAAM), N-acryloylmorpholine ( ACMO), N-vinyl-2-pyrrolidone (NVP), N-vinyl-caprolactam (NVC), and N- (2-hydroxyethyl) acrylamide (HEAA).
　官能基含有モノマーは１種単独で、または２種以上を使用することができる。上記（メタ）アクリル酸を除く官能基含有モノマーの全使用量は、全原料モノマーの総質量に対して、０～１５質量％であることが好ましく、より好ましくは０．０５～１０質量％である。 The functional group-containing monomer can be used alone or in combination of two or more. The total amount of the functional group-containing monomer excluding the (meth) acrylic acid is preferably 0 to 15% by mass, more preferably 0.05 to 10% by mass, based on the total mass of all raw material monomers. is there.
　官能基含有モノマーのうち、水酸基含有ポリマーの合計量は、例えば、全原料モノマーの総質量に対して、０～５質量％とし、好ましくは０．０５～２質量％とし、より好ましくは０．１～１質量％とし、更に好ましくは０．１２～０．８質量％とする。 Of the functional group-containing monomers, the total amount of the hydroxyl group-containing polymer is, for example, 0 to 5% by mass, preferably 0.05 to 2% by mass, and more preferably 0.00%, based on the total mass of all raw material monomers. The content is 1 to 1% by mass, more preferably 0.12 to 0.8% by mass.
　《共重合性モノマー》
　共重合性モノマーとしては、例えば、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレン及びオクチルスチレン等のアルキルスチレン、フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレン、ニトロスチレン、アセチルスチレン及びメトキシスチレン等のスチレン系モノマー、酢酸ビニルが挙げられる。共重合性モノマーは、１種単独で、又は２種以上を使用することができる。 《Copolymerizable monomer》
Examples of copolymerizable monomers include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes, fluorostyrene, chlorostyrene, bromostyrene, dibromo. Examples thereof include styrene monomers such as styrene, iodostyrene, nitrostyrene, acetylstyrene and methoxystyrene, and vinyl acetate. The copolymerizable monomer can be used alone or in combination of two or more.
　［その他の成分］
　粘着剤組成物は、その他の成分として、粘着付与樹脂、架橋剤、シランカップリング剤、帯電防止剤、有機溶媒、酸化防止剤、光安定剤、金属腐蝕防止剤、可塑剤、架橋促進剤、ナノ粒子などを更に含有していてもよい。 [Other ingredients]
The pressure-sensitive adhesive composition includes, as other components, a tackifier resin, a crosslinking agent, a silane coupling agent, an antistatic agent, an organic solvent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a plasticizer, a crosslinking accelerator, It may further contain nanoparticles and the like.
　〈粘着付与樹脂〉
　上記粘着剤組成物は、粘着付与樹脂を含んでいてもよい。粘着剤組成物を構成する成分として上記ポリマー以外に粘着付与樹脂を併用することで、例えば、一般にアクリル系粘着剤にとっての難接着被着体である、ポリエチレン、ポリプロピレン等のオレフィン系被着体に対しても良好な接着性（粘着性）を発揮することができる。また、得られる粘着剤層の定荷重剥離耐性を向上させることができる。 <Tackifying resin>
The pressure-sensitive adhesive composition may contain a tackifier resin. By using a tackifying resin in addition to the above-mentioned polymer as a component constituting the pressure-sensitive adhesive composition, for example, it is generally difficult to adhere to an acrylic pressure-sensitive adhesive, such as polyethylene, polypropylene, and other olefinic adherends. Even for this, good adhesion (tackiness) can be exhibited. Moreover, the constant load peeling resistance of the obtained adhesive layer can be improved.
　粘着付与樹脂としては、ロジンエステル樹脂を用いることが好ましく、特に重合ロジンエステル樹脂を併用してもよい。粘着付与樹脂としては、例えば、テルペン系粘着付与樹脂又は炭化水素系石油樹脂を用いてもよい。 As the tackifier resin, a rosin ester resin is preferably used, and a polymerized rosin ester resin may be used in combination. As the tackifier resin, for example, a terpene tackifier resin or a hydrocarbon petroleum resin may be used.
　粘着付与樹脂は、１種単独で用いてもよく、２種類以上を併用してもよい。粘着剤組成物中の粘着付与樹脂の合計含有量は、ポリマー１００質量部に対して、例えば１～４０質量部、好ましくは５～３５質量部、より好ましくは１０～３０質量部とする。 The tackifier resin may be used alone or in combination of two or more. The total content of the tackifying resin in the pressure-sensitive adhesive composition is, for example, 1 to 40 parts by mass, preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polymer.
　〈架橋剤〉
　架橋剤としては、イソシアネート系化合物、エポキシ系化合物、金属キレート系化合物などが挙げられる。 <Crosslinking agent>
Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, metal chelate compounds, and the like.
　イソシアネート系化合物としては、１分子中のイソシアネート基数が２以上のイソシアネート化合物が通常用いられる。イソシアネート化合物としては、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネートが挙げられる。脂肪族ジイソシアネートとしては、エチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２－メチル－１，５－ペンタンジイソシアネート、３－メチル－１，５－ペンタンジイソシアネート、２，２，４－トリメチル－１，６－ヘキサメチレンジイソシアネート等の炭素数４～３０の脂肪族ジイソシアネートが挙げられる。脂環族ジイソシアネートとしては、イソホロンジイソシアネート、シクロペンチルジイソシアネート、シクロヘキシルジイソシアネート、水素添加キシリレンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の炭素数７～３０の脂環族ジイソシアネートが挙げられる。芳香族ジイソシアネートとしては、例えば、フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ナフチレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルメタンジイソシアネート、ジフェニルプロパンジイソシアネート等の炭素数８～３０の芳香族ジイソシアネートが挙げられる。 As the isocyanate compound, an isocyanate compound having two or more isocyanate groups in one molecule is usually used. Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate. Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl And aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Diisocyanate is mentioned. Examples of the aromatic diisocyanate include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
　１分子中のイソシアネート基数が３以上のイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環族ポリイソシアネートが挙げられる。具体的には、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートベンゼン、４，４´，４″－トリフェニルメタントリイソシアネートが挙げられる。さらに、イソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネートの３量体、ポリメチレンポリフェニルポリイソシアネート、ヘキサメチレンジイソシアネートまたはトリレンジイソシアネートのビウレット体またはイソシアヌレート体、トリメチロールプロパンとトリレンジイソシアネートまたはキシリレンジイソシアネートとの反応生成物（例えばトリレンジイソシアネートまたはキシリレンジイソシアネートの３分子付加物）、トリメチロールプロパンとヘキサメチレンジイソシアネートとの反応生成物（例えばヘキサメチレンジイソシアネートの３分子付加物）、ポリエーテルポリイソシアネート、ポリエステルポリイソシアネートが挙げられる。 Examples of the isocyanate compound having 3 or more isocyanate groups in one molecule include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ′, 4 ″ -triphenylmethane triisocyanate. , Diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, reaction product of trimethylolpropane with tolylene diisocyanate or xylylene diisocyanate (eg tolylene diisocyanate) Isocyanate or xylylene diisocyanate trimolecular adducts), trimethylolpropane and hexamethylene diisocyanate reaction products (eg hexamethylene diisocyanate) Over 3 molecular adduct g), polyether polyisocyanates, and polyester polyisocyanates.
　エポキシ系化合物としては、例えば、１分子中のエポキシ基数が２以上のエポキシ化合物が通常用いられる。例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ´，Ｎ´－テトラグリシジル－ｍ－キシリレンジアミン、Ｎ，Ｎ，Ｎ´，Ｎ´－テトラグリシジルアミノフェニルメタン、トリグリシジルイソシアヌレート、ｍ－Ｎ，Ｎ－ジグリシジルアミノフェニルグリシジルエーテル、Ｎ，Ｎ－ジグリシジルトルイジン、Ｎ，Ｎ－ジグリシジルアニリンが挙げられる。 As the epoxy compound, for example, an epoxy compound having 2 or more epoxy groups in one molecule is usually used. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′ -Tetraglycidyl-m-xylylenediamine, N, N, N ', N'-tetraglycidylaminophenylmethane, triglycidyl isocyanurate, mN, N-diglycidylaminophenyl glycidyl ether, N, N-diglycidyl Examples include toluidine and N, N-diglycidylaniline.
　金属キレート化合物としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属に、アルコキシド、アセチルアセトン、アセト酢酸エチル等が配位した化合物が挙げられる。具体的には、アルミニウムイソプロピレート、アルミニウムセカンダリーブチレート、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネートが挙げられる。 As the metal chelate compound, for example, alkoxide, acetylacetone, ethyl acetoacetate and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, etc. Compounds. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
　架橋剤は、上記ポリマーとの合計１００質量部に対して０．０１～１０質量部、好ましくは、０．０１～８質量部、さらに好ましくは０．０１～５質量部の範囲にある。この範囲で架橋剤を含むと、要求される種々の粘着物性間のバランスを取ることができる。 The crosslinking agent is in the range of 0.01 to 10 parts by mass, preferably 0.01 to 8 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total with the polymer. When a crosslinking agent is included in this range, it is possible to balance the various required adhesive properties.
　〈シランカップリング剤〉
　シランカップリング剤は、粘着剤層を特にガラス基板等の被着体に対して強固に接着させ、高湿熱環境下における粘着層の剥がれを防止することができる。 <Silane coupling agent>
The silane coupling agent can firmly adhere the pressure-sensitive adhesive layer to an adherend such as a glass substrate, and can prevent the pressure-sensitive adhesive layer from peeling off in a high-humidity heat environment.
　シランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有シランカップリング剤；３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤；３－アミノプロピルトリメトキシシラン，Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン等のアミノ基含有シランカップリング剤；３－クロロプロピルトリメトキシシラン等のハロゲン含有シランカップリング剤が挙げられる。 Examples of the silane coupling agent include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3- Epoxy group-containing silane cups such as glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Ring agent; amino group-containing silane such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Coupling agent Halogen-containing silane coupling agents such as 3-chloropropyl trimethoxysilane.
　このうち、応力緩和性などの点でエポキシ基含有シランカップリング剤が好ましい。本発明の組成物において、シランカップリング剤の含有量は、上記ポリマー１００質量部に対して、通常１質量部以下、好ましくは０．０１～１質量部、より好ましくは０．０５～０．５質量部である。含有量が前記範囲にあると、高湿熱環境下における粘着層の剥がれや、高温環境下におけるシランカップリング剤のブリードが防止される傾向にある。 Of these, an epoxy group-containing silane coupling agent is preferable in terms of stress relaxation. In the composition of the present invention, the content of the silane coupling agent is usually 1 part by mass or less, preferably 0.01-1 part by mass, more preferably 0.05-0. 5 parts by mass. When the content is in the above range, peeling of the pressure-sensitive adhesive layer in a high-humidity heat environment and bleeding of the silane coupling agent in a high-temperature environment tend to be prevented.
　〈帯電防止剤〉
　帯電防止剤としては、例えば、界面活性剤、イオン性化合物、導電性ポリマーが挙げられる。 <Antistatic agent>
Examples of the antistatic agent include a surfactant, an ionic compound, and a conductive polymer.
　界面活性剤としては、例えば、４級アンモニウム塩類、アミド４級アンモニウム塩類、ピリジウム塩類、第１級～第３級アミノ基等のカチオン性基を有するカチオン性界面活性剤；スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基等のアニオン性基を有するアニオン性界面活性剤；アルキルベタイン類、アルキルイミダゾリニウムベタイン類、アルキルアミンオキサイド類、アミノ酸硫酸エステル類等の両性界面活性剤、グリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンアルキルアミン類、ポリオキシエチレンアルキルアミン脂肪酸エステル類、Ｎ－ヒドロキシエチル－Ｎ－２－ヒドロキシアルキルアミン類、アルキルジエタノールアミド類等の非イオン性界面活性剤が挙げられる。 Examples of the surfactant include cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridium salts, primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates, glycerin fatty acid esters Nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyldiethanolamides It is done.
　また、界面活性剤として重合性基を有する反応型乳化剤も挙げられ、上記の界面活性剤または反応性乳化剤を含むモノマー成分を高分子量化したポリマー系界面活性剤を用いることもできる。 In addition, a reactive emulsifier having a polymerizable group is also exemplified as the surfactant, and a polymer surfactant obtained by increasing the molecular weight of the monomer component containing the above surfactant or reactive emulsifier can also be used.
　導電性ポリマーとしては、例えば、ポリチオフェン、ポリアニリン、ポリピロール及びこれらの誘導体が挙げられる。 Examples of the conductive polymer include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
　上記粘着剤組成物において、帯電防止剤の含有量は、上記ポリマー１００質量部に対して、通常３質量部以下、好ましくは０．０１～３質量部、より好ましくは０．０５～２．５質量部である。 In the pressure-sensitive adhesive composition, the content of the antistatic agent is usually 3 parts by mass or less, preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass with respect to 100 parts by mass of the polymer. Part by mass.
　〈有機溶媒〉
　粘着剤組成物は、必ずしも溶媒を含まなくともよいが、その塗工性を調整するため、有機溶媒を含有していてもよい。上記粘着剤組成物において、有機溶媒の含有量は、通常３０～９０質量％、好ましくは３０～８５質量％である。なお、本明細書において「固形分」とは、粘着剤組成物中の含有成分のうち上記有機溶媒を除いた全成分をいい、「固形分濃度」とは、粘着剤組成物１００質量％に対する前記固形分の割合をいう。 <Organic solvent>
The pressure-sensitive adhesive composition does not necessarily contain a solvent, but may contain an organic solvent in order to adjust its coatability. In the pressure-sensitive adhesive composition, the content of the organic solvent is usually 30 to 90% by mass, preferably 30 to 85% by mass. In the present specification, “solid content” refers to all components excluding the organic solvent among the components contained in the pressure-sensitive adhesive composition, and “solid content concentration” refers to 100% by mass of the pressure-sensitive adhesive composition. The ratio of the said solid content is said.
　〔粘着テープ〕
　本発明に係る粘着テープは、例えば、剥離処理されたカバーフィルム（以下でセパレータとも称する）上に形成された粘着剤層のみを有する両面粘着シート、基材と、基材の両面に形成された上記粘着剤層とを有する両面粘着シート（この場合、基材を芯材とも称する）、基材と、基材の一方の面に形成された上記粘着剤層を有する片面粘着シート、及びそれら粘着シートの粘着剤層の基材と接していない面に剥離処理されたカバーフィルムが貼付された粘着シートを含む。 〔Adhesive tape〕
The pressure-sensitive adhesive tape according to the present invention is formed on, for example, a double-sided pressure-sensitive adhesive sheet having only an adhesive layer formed on a peeled cover film (hereinafter also referred to as a separator), a base material, and both surfaces of the base material. Double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer (in this case, the base material is also referred to as a core material), a base material, and a single-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on one surface of the base material, and their pressure-sensitive adhesives It includes a pressure-sensitive adhesive sheet in which a peeled cover film is attached to a surface of the pressure-sensitive adhesive layer that is not in contact with the base material.
　基材としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）などのポリエステルフィルム、ポリカーボネート、ポリエチレン、ポリプロピレン、エチレン－酢酸ビニルコポリマー等のポリオレフィンフィルムなどのプラスチックフィルム、織布及び不織布が挙げられる。また、プラスチックフィルム、織布及び不織布は、各種添加剤を配合したものや複数の層が積層されたものなどを用いることができる。基材の厚さは特に限定されないが、通常１～２０００μｍ、特に３～５００μｍ、殊に１０～１００μｍである。 Examples of the base material include polyester films such as polyethylene terephthalate (PET), plastic films such as polycarbonate, polyethylene, polypropylene, polyolefin films such as ethylene-vinyl acetate copolymer, woven fabrics and non-woven fabrics. As the plastic film, woven fabric, and non-woven fabric, those in which various additives are blended or those in which a plurality of layers are laminated can be used. The thickness of the substrate is not particularly limited, but is usually 1 to 2000 μm, particularly 3 to 500 μm, especially 10 to 100 μm.
　カバーフィルムとしては、例えば、任意で表面に剥離処理がされたポリエチレンテレフタレート（ＰＥＴ）などのポリエステルフィルム、ポリカーボネート、ポリエチレン、ポリプロピレン、エチレン－酢酸ビニルコポリマー等のポリオレフィンフィルムなどのプラスチックフィルムが挙げられる。また、プラスチックフィルムは、各種添加剤を配合したものや複数の層が積層されたものなどを用いることができる。 Examples of the cover film include a plastic film such as a polyester film such as polyethylene terephthalate (PET) optionally having a surface-exfoliated treatment, a polyolefin film such as polycarbonate, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. As the plastic film, one in which various additives are blended or one in which a plurality of layers are laminated can be used.
　粘着剤組成物の塗布方法としては、公知の方法、例えばスピンコート法、ナイフコート法、ロールコート法、バーコート法、ブレードコート法、ダイコート法、グラビアコート法により、所定の厚さになるように塗布・乾燥する方法を用いることができ、このようにして粘着剤層を形成することができる。
　当該粘着剤層は、単回の塗布工程で形成される厚さが３０μｍ以上であり、４０μｍ以上が好ましく、５０μｍ以上がより好ましい。また、当該粘着剤層は、単回の塗布工程で形成される厚さが３０μｍ以上であるが、例えばこれを複数積層してもよい。特に、粘着剤層が複数層で形成される場合、通常、当該粘着剤層の総厚は６０μｍ以上である。当該粘着剤層の総厚の上限は特に限定されないが、通常は１０００μｍ以下である。なお、粘着剤層が複数層で形成される場合、粘着剤層の間に基材を設けてもよいし、基材を設けずに複数の粘着剤層を直接積層してもよい。 As a method for applying the pressure-sensitive adhesive composition, a known thickness such as a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, or a gravure coating method may be used. The method of applying and drying can be used, and the pressure-sensitive adhesive layer can be formed in this way.
The pressure-sensitive adhesive layer has a thickness formed by a single coating step of 30 μm or more, preferably 40 μm or more, and more preferably 50 μm or more. Moreover, although the said adhesive layer is 30 micrometers or more in thickness formed by the single application | coating process, you may laminate this, for example. Particularly, when the pressure-sensitive adhesive layer is formed of a plurality of layers, the total thickness of the pressure-sensitive adhesive layer is usually 60 μm or more. Although the upper limit of the total thickness of the said adhesive layer is not specifically limited, Usually, it is 1000 micrometers or less. In addition, when an adhesive layer is formed with multiple layers, you may provide a base material between adhesive layers, and may laminate | stack a some adhesive layer directly, without providing a base material.
　［総ＶＯＣ濃度］
　本発明に係る粘着テープは、当該粘着剤層の面積が１００ｍｍ×１００ｍｍである試験片及び５Ｌのサンプリングバッグを用いて算出される総揮発性有機化合物（ＴＶＯＣ）濃度が１００００μｇ／ｍ３以下である。なお、本明細書では、サンプリングバッグとして、テドラー（登録商標）バッグ（ジーエルサイエンス製：型式；AA－５）を用いている。 [Total VOC concentration]
The pressure-sensitive adhesive tape according to the present invention has a total volatile organic compound (TVOC) concentration of 10,000 μg / m 3 or less calculated using a test piece having an area of the pressure-sensitive adhesive layer of 100 mm × 100 mm and a 5 L sampling bag. . In the present specification, a Tedlar (registered trademark) bag (manufactured by GL Sciences: model: AA-5) is used as the sampling bag.
　本発明者らは、従来の粘着テープでは、上述のＶＯＣ濃度を達成できないことを見出した。そして、鋭意検討の結果、上記ＶＯＣ濃度に、イソパラフィン及びアルコールの寄与が大きな影響を与えていることを見出した。更に、本発明者らは、上記ポリマーの組成、上記ポリマーを合成する際に用いる開始剤の種類、粘着剤組成物における当該開始剤の残量、及び粘着剤層の乾燥条件などを調整することにより、必要な物性を担保しつつ、総ＶＯＣ濃度を１００００μｇ／ｍ３以下に抑えることができることを見出した。 The present inventors have found that the above-mentioned VOC concentration cannot be achieved with a conventional adhesive tape. And as a result of earnest examination, it discovered that the contribution of isoparaffin and alcohol had big influence on the said VOC density | concentration. Furthermore, the inventors adjust the composition of the polymer, the type of initiator used when synthesizing the polymer, the remaining amount of the initiator in the pressure-sensitive adhesive composition, the drying conditions of the pressure-sensitive adhesive layer, and the like. Thus, it was found that the total VOC concentration can be suppressed to 10,000 μg / m 3 or less while ensuring the necessary physical properties.
　まず、上記開始剤としては、希釈剤としてのイソパラフィン含有量ができるだけ少ないものを用いることが好ましい。即ち、開始剤としては、希釈剤が不要なほど分解温度が高いものを用いることが好ましい。具体的には、開始剤中のイソパラフィン含有量が、前記粘着剤組成物の全固形分に対して０．０３質量％以下であることが好ましく、０．０２質量％以下であることがより好ましく、０．０１質量％以下であることが更に好ましい。また、開始剤がイソパラフィンを実質的に含まないことが特に好ましい。なお、ここで「イソパラフィン」とは、側鎖を有する炭素数２０程度以上の鎖式飽和炭化水素を意味している。 First, as the initiator, it is preferable to use one having as little isoparaffin content as a diluent. That is, it is preferable to use an initiator having a decomposition temperature that is so high that a diluent is unnecessary. Specifically, the isoparaffin content in the initiator is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, based on the total solid content of the pressure-sensitive adhesive composition. More preferably, the content is 0.01% by mass or less. Further, it is particularly preferable that the initiator does not substantially contain isoparaffin. Here, the “isoparaffin” means a chain saturated hydrocarbon having a side chain and having about 20 or more carbon atoms.
　次に、粘着剤組成物における上記開始剤の残量は、できるだけ少なくすることが好ましい。そのためには、例えば、開始剤の使用量を減らしたり、分解温度の低い開始剤を使用したり、重合終期温度を高くしたりすることが好ましい。 Next, the remaining amount of the initiator in the pressure-sensitive adhesive composition is preferably as small as possible. For this purpose, for example, it is preferable to reduce the amount of initiator used, use an initiator having a low decomposition temperature, or increase the polymerization end temperature.
　上述した分解温度が比較的高い開始剤としては、例えば、ＰＢＮＤ１００［日油製；ｔ－ｂｕｔｙｌｐｅｒｏｘｙｎｅｏｄｅｃａｎｏａｔｅ］、Ｖ６０１［和光純薬工業製；Ｄｉｍｅｔｈｙｌ２，２′－ａｚｏｂｉｓ（２－ｍｅｔｈｙｌｐｒｏｐｉｏｎａｔｅ）］、ＡＩＢＮ［和光純薬工業製；（２，２’－Ａｚｏｂｉｓ（ｉｓｏｂｕｔｙｒｏｎｉｔｒｉｌｅ）］、Ｖ－６５［和光純薬工業製；（２，２’－Ａｚｏｂｉｓ（２，４－ｄｉｍｅｙｈｙｌｖａｌｅｒｏｎｉｔｒｉｌｅ）］、Ｖ－５９［和光純薬工業製；（２，２’－Ａｚｏｂｉｓ（２－ｍｅｔｈｙｌｂｕｔｙｒｏｎｉｔｒｉｌｅ）］、及びパーロイルＬ［日油製；ＤｉｌａｕｌｏｙｌＰｅｒｏｘｉｄｅ］などを使用することができる。ただし、これらは単なる例示であり、他の開始剤を使用することももちろん可能である。 Examples of the initiator having a relatively high decomposition temperature include PBND100 [manufactured by NOF; t-butylperoxynedecanoate], V601 [manufactured by Wako Pure Chemical Industries; (2,2′-Azobis (isobutyronitrile)), V-65 [Wako Pure Chemical Industries; (2,2′-Azobis (2,4-dimethylhydrerontrile)], V-59 [Wako Pure Chemicals] (2,2′-Azobis (2-methylbutyronitrile)), and Parroyl L [manufactured by NOF; DialoylPeroxide] can be used, but these are merely examples, and other It is of course also possible to use the initiator.
　また、粘着剤層の乾燥条件も、総ＶＯＣ濃度に影響を与える。粘着剤層の乾燥を高い温度で長く行うことにより、総ＶＯＣ濃度を低減させることができる。本発明に係る系のように、（メタ）アクリル酸を含んだポリマーを使用する場合には、ＶＯＣ中のアルコールの寄与が比較的大きくなるため、乾燥条件の調整が特に重要となる。 Also, the drying condition of the pressure-sensitive adhesive layer affects the total VOC concentration. By drying the pressure-sensitive adhesive layer for a long time at a high temperature, the total VOC concentration can be reduced. When using a polymer containing (meth) acrylic acid as in the system according to the present invention, the contribution of alcohol in the VOC becomes relatively large, so that adjustment of drying conditions is particularly important.
　ここで、前記試験片及び前記サンプリングバッグを用いて算出されるイソパラフィン濃度は、５０００μｇ／ｍ３以下であることが好ましく、４０００μｇ／ｍ３以下であることがより好ましく、３０００μｇ／ｍ３以下であることが更に好ましい。また、前記試験片及び前記サンプリングバッグを用いて算出されるアルコール濃度は、３０００μｇ／ｍ３以下であることが好ましく、２５００μｇ／ｍ３以下であることがより好ましく、２０００μｇ／ｍ３以下であることが更に好ましい。
　　＜実施例＞ Here, isoparaffin concentration calculated using the test piece and the sampling bag is preferably 5000 [mu] g / m 3 or less, more preferably 4000μg / m 3 or less, is 3000μg / m 3 or less More preferably. Further it, the alcohol concentration calculated using the test piece and the sampling bag is preferably at 3000μg / m 3 or less, more preferably 2500 g / m 3 or less, 2000 [mu] g / m 3 or less Is more preferable.
<Example>
　以下、本発明を実施例に基づいて更に具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」を意味する。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “parts” means “parts by mass” unless otherwise specified.
　［ポリマーの合成］
　［合成例１～７］
　撹拌機、還流冷却器、温度計および窒素導入管を備えた反応装置に、ｎ－ブチルアクリレート（ＢＡ）、２－ヒドロキシエチルアクリレート（２ＨＥＡ）、アクリル酸（ＡＡ）、ジメチルアミノエチルメタクリル酸エステル（ＤＭ）、Ｎ－イソプロピルアクリルアミド（ＮＩＰＡＭ）、ヒドロキシエチルアクリレート（ＨＥＡ）、酢酸ビニル（ＶＡｃ）を表１の割合とし、酢酸エチルを１００部仕込み、窒素ガスを導入しながら８０℃に昇温した。次いで、表１に記載した割合で開始剤を加え、窒素ガス雰囲気下、８０℃で６時間重合反応を行った。反応終了後、酢酸エチルにて希釈し固形分濃度５０質量％のポリマー溶液を調製した。なお、ＰＢＮＤ１００、ＰＢＮＤ、ＰＨＰＶ、ＰBＰＶ、及びＰＬ３５５は日油製の開始剤であり、Ｖ６０１は和光純薬工業製の開始剤である。 [Polymer synthesis]
[Synthesis Examples 1 to 7]
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with n-butyl acrylate (BA), 2-hydroxyethyl acrylate (2HEA), acrylic acid (AA), dimethylaminoethyl methacrylate ( DM), N-isopropylacrylamide (NIPAM), hydroxyethyl acrylate (HEA), and vinyl acetate (VAc) in the proportions shown in Table 1, 100 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. while introducing nitrogen gas. Next, an initiator was added at a rate described in Table 1, and a polymerization reaction was performed at 80 ° C. for 6 hours in a nitrogen gas atmosphere. After completion of the reaction, it was diluted with ethyl acetate to prepare a polymer solution having a solid content concentration of 50% by mass. PBND100, PBND, PHPV, PBPV, and PL355 are NOF initiators, and V601 is an initiator manufactured by Wako Pure Chemical Industries.
　
Figure JPOXMLDOC01-appb-I000001
　
Figure JPOXMLDOC01-appb-I000001
　合成例１～７で得られたポリマーを、必要に応じて粘着付与樹脂及び架橋剤などと混合し、粘着剤組成物を得た。下記表2に、その組成と共に、開始剤残量及び開始剤中のイソパラフィン（ＩＰ）量を示す。ここで、表2中のＩＰ含有量及び開始剤残量は、粘着剤組成物の全固形分に対しての量を表している。なお、実施例５及び参考例３では、粘着付与樹脂として、ＰＣＪ（重合ロジンエステル樹脂、ハリマ化成製）を用いた。 The polymers obtained in Synthesis Examples 1 to 7 were mixed with a tackifying resin and a crosslinking agent as necessary to obtain a pressure-sensitive adhesive composition. Table 2 below shows the remaining amount of initiator and the amount of isoparaffin (IP) in the initiator together with the composition. Here, the IP content and the remaining amount of initiator in Table 2 represent amounts relative to the total solid content of the pressure-sensitive adhesive composition. In Example 5 and Reference Example 3, PCJ (polymerized rosin ester resin, manufactured by Harima Chemicals) was used as the tackifier resin.
　
Figure JPOXMLDOC01-appb-I000002
　
Figure JPOXMLDOC01-appb-I000002
　得られた各粘着剤組成物を、軽剥離フィルムに塗工、乾燥させ、厚さ５５μｍの粘着剤層を形成した。当該粘着剤層を厚さが２５μｍのＰＥＴフィルム（ルミラー：東レ製）の一方の面に転写した。上記の厚さ５５μｍの粘着剤層の形成手順を再度実行し、当該粘着剤層を先のPETフィルムの他方の面に転写した。即ち、当該粘着テープは、（粘着剤層／PETフィルム（基材）／粘着剤層）の構成であって、粘着剤層の総厚は１１０μｍ、 粘着テープの総厚は１３５μｍである。 Each obtained pressure-sensitive adhesive composition was coated on a light release film and dried to form a pressure-sensitive adhesive layer having a thickness of 55 μm. The pressure-sensitive adhesive layer was transferred to one surface of a PET film having a thickness of 25 μm (Lumirror: manufactured by Toray). The procedure for forming the 55 μm thick pressure-sensitive adhesive layer was performed again, and the pressure-sensitive adhesive layer was transferred to the other side of the previous PET film. That is, the pressure-sensitive adhesive tape has a structure of (pressure-sensitive adhesive layer / PET film (base material) / pressure-sensitive adhesive layer), and the total thickness of the pressure-sensitive adhesive layer is 110 μm, and the total thickness of the adhesive tape is 135 μm.
　［総ＶＯＣ濃度］
　上記の粘着テープを１００ｍｍ×１００ｍｍの面積で切り出し、５Ｌのテドラー（登録商標）バッグ（ジーエルサイエンス製：型式；AA－５）を用いて、総ＶＯＣ、酢酸エチル、トルエン、アルコール、及びイソパラフィン（ＩＰ）の検出量をそれぞれ測定した。ここで、各検出量は、ガスクロマトグラフにおいて分析した各対象物質に相当するピークの面積をトルエンに換算して求めた値である。総ＶＯＣについては、ｎ－ヘキサンからｎ－ヘキサデカンまでの範囲で検出されたガスクロマトグラフの検出ピーク面積の総和をトルエン検出ピーク面積に換算して求めた値である。また、イソパラフィン濃度については、パラフィン起因部に相当する検出ピーク群面積の総和を、トルエン検出ピーク面積に換算して求めた値である。それらの結果を表２に合わせて示す。 [Total VOC concentration]
The above adhesive tape is cut out in an area of 100 mm × 100 mm, using a 5 L Tedlar (registered trademark) bag (manufactured by GL Sciences: model: AA-5), with total VOC, ethyl acetate, toluene, alcohol, and isoparaffin (IP ) Was measured. Here, each detected amount is a value obtained by converting a peak area corresponding to each target substance analyzed in the gas chromatograph into toluene. The total VOC is a value obtained by converting the sum of the detection peak areas of the gas chromatograph detected in the range from n-hexane to n-hexadecane into a toluene detection peak area. Further, the isoparaffin concentration is a value obtained by converting the total area of detection peak groups corresponding to paraffin-derived parts into a toluene detection peak area. The results are also shown in Table 2.
　表２に示す通り、実施例１乃至５では、総ＶＯＣ量を１００００μｇ／ｍ３以下に抑えることができた。これに対し、比較例１乃至４では、総ＶＯＣ量が１００００μｇ／ｍ３を超えてしまった。ここで、例えば、実施例１と比較例１とを比較すると、ポリマーＰ３を用いた上で、乾燥温度を９０℃から１２０℃に上昇させることにより、総ＶＯＣ量を大幅に低減できたことが分かる。また、実施例１乃至５と比較例２乃至４とを比較すると、イソパラフィン含有量が少ない開始剤を使用することによっても、総ＶＯＣ量を大幅に低減できたことが分かる。 As shown in Table 2, in Examples 1 to 5, the total VOC amount could be suppressed to 10000 μg / m 3 or less. On the other hand, in Comparative Examples 1 to 4, the total VOC amount exceeded 10000 μg / m 3 . Here, for example, when Example 1 and Comparative Example 1 were compared, it was found that the total VOC amount could be greatly reduced by using the polymer P3 and increasing the drying temperature from 90 ° C. to 120 ° C. I understand. Further, when Examples 1 to 5 and Comparative Examples 2 to 4 are compared, it can be seen that the total VOC amount can be greatly reduced even by using an initiator having a low isoparaffin content.
　［粘着物性］
　実施例５及び参考例３について、粘着物性についての測定も行った。なお、下記表3に示すように、架橋剤（硬化剤）としては、Ｌ－４５（綜研化学製；トリレンジイソシアネート）及びＴＤ－７５（綜研化学製；トリレンジイソシアネートのトリメチロールプロパン付加体）を用いた。 [Adhesive properties]
About Example 5 and Reference Example 3, the measurement about the adhesive physical property was also performed. As shown in Table 3 below, as the crosslinking agent (curing agent), L-45 (manufactured by Soken Chemical; Tolylene diisocyanate) and TD-75 (manufactured by Soken Chemical; trimethylolpropane adduct of tolylene diisocyanate) Was used.
　
Figure JPOXMLDOC01-appb-I000003
　
Figure JPOXMLDOC01-appb-I000003
　（保持力）
　保持力の測定は、ＪＩＳＺ１５４１に準拠して行い、粘着シートを２０ｍｍ幅に裁断し、ＳＵＳ板に２０×２０ｍｍの面積が接するように貼付け、温度４０℃又は８０℃の条件で１Ｋｇの荷重をかけ、１時間放置したときの落下の有無を観察した。 (Holding power)
Holding force is measured in accordance with JISZ1541, the adhesive sheet is cut to 20mm width, pasted so that the area of 20x20mm is in contact with the SUS plate, and a load of 1Kg is applied at a temperature of 40 ° C or 80 ° C. The presence or absence of the fall when left for 1 hour was observed.
　（曲面貼付試験）
　得られた粘着テープを、１０mm厚のポリエーテル系ウレタンフォーム材に転写して曲面貼付試験用の試験テープとした。この試験テープを２０ｍｍ×５０ｍｍに裁断し試験片とした。この試験片を２８０番の耐水研磨紙で研磨した５０ｍｍφ又は３０ｍｍφのＳＵＳ３０４円筒に貼り付けた。８０℃又は２３℃で２４時間静置して、試験片エッジ部のウキ又は剥がれ距離を測定した。 (Curved surface test)
The obtained adhesive tape was transferred to a 10 mm-thick polyether urethane foam material to obtain a test tape for a curved surface sticking test. This test tape was cut into 20 mm × 50 mm to obtain a test piece. This test piece was attached to a 50 mmφ or 30 mmφ SUS304 cylinder polished with No. 280 water-resistant abrasive paper. The sample was allowed to stand at 80 ° C. or 23 ° C. for 24 hours, and the test piece edge portion or the peeling distance was measured.
　（ボールタック試験）
　Ｊ．Ｄｏｗ法により測定した。具体的には、幅１０ｃｍに裁断した試験片からＰＥＴ剥離フィルムを剥がした粘着テープを、粘着剤層が露出するように傾斜角３０度の傾斜面に取り付けた。次に、スチールボールを傾斜面の上側から助走させた後に、粘着面（粘着剤層表面）上を滑走させた。この際の助走距離は１０ｃｍ、滑走距離は１０ｃｍとした。また、温度は２３℃又は１０℃とし、湿度は５０％ＲＨ又は１０％ＲＨとした。そして、スチールボールの径を変えながら滑走テストを行い、粘着面内で滑走を停止したスチールボールの最大径を求めた。なお、使用したスチールボールの径は、Ｘ／３２インチ（但し、Ｘは１～３２の範囲内の整数）であり、表３中に示す数値はＸの値を意味する。 (Ball tack test)
J. et al. It was measured by the Dow method. Specifically, the adhesive tape from which the PET release film was peeled from the test piece cut to a width of 10 cm was attached to an inclined surface with an inclination angle of 30 degrees so that the adhesive layer was exposed. Next, the steel ball was run from the upper side of the inclined surface, and then slid on the adhesive surface (adhesive layer surface). The running distance at this time was 10 cm, and the running distance was 10 cm. The temperature was 23 ° C. or 10 ° C., and the humidity was 50% RH or 10% RH. Then, a sliding test was performed while changing the diameter of the steel ball, and the maximum diameter of the steel ball that stopped sliding in the adhesive surface was obtained. The diameter of the steel ball used is X / 32 inches (where X is an integer in the range of 1 to 32), and the numerical values shown in Table 3 mean the value of X.
　表３に示す通り、実施例５の粘着テープは、充分な粘着性能を有していた。また、実施例５の粘着テープは、参考例３の粘着テープと比較して、８０℃における保持力及び２３℃における曲面貼付性がより優れていた。この差異は、実施例５の粘着テープが、アクリル酸をモノマー成分とする共重合ポリマーを含んだ粘着剤組成物を備えていることに起因していると考えられる。 As shown in Table 3, the adhesive tape of Example 5 had sufficient adhesive performance. In addition, the pressure-sensitive adhesive tape of Example 5 was more excellent in holding power at 80 ° C. and curved surface stickiness at 23 ° C. than the pressure-sensitive adhesive tape of Reference Example 3. This difference is considered to be due to the fact that the pressure-sensitive adhesive tape of Example 5 includes a pressure-sensitive adhesive composition containing a copolymer having acrylic acid as a monomer component.

Claims (5)

  1. 　粘着剤組成物を含んだ粘着剤層を備えた粘着テープであって、前記粘着剤組成物は、（メタ）アクリル酸を含んだモノマー混合物を共重合させて得られるポリマーを含み、前記粘着剤層は厚さが３０μｍ以上であり、前記粘着テープは、前記粘着剤層の面積が１００ｍｍ×１００ｍｍである試験片及び５Ｌのサンプリングバッグを用いて算出される総揮発性有機化合物（ＴＶＯＣ）濃度が１００００μｇ／ｍ３以下である、粘着テープ。 An adhesive tape comprising an adhesive layer containing an adhesive composition, wherein the adhesive composition comprises a polymer obtained by copolymerizing a monomer mixture containing (meth) acrylic acid, and the adhesive The layer has a thickness of 30 μm or more, and the adhesive tape has a total volatile organic compound (TVOC) concentration calculated using a test piece having an area of the adhesive layer of 100 mm × 100 mm and a 5 L sampling bag. An adhesive tape that is 10,000 μg / m 3 or less.
  2. 　前記試験片及び前記サンプリングバッグを用いて算出されるアルコール濃度が３０００μｇ／ｍ３以下である、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the alcohol concentration calculated using the test piece and the sampling bag is 3000 µg / m 3 or less.
  3. 　前記試験片及び前記サンプリングバッグを用いて算出されるイソパラフィン濃度が５０００μｇ／ｍ３以下である、請求項１又は２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1 or 2, wherein an isoparaffin concentration calculated using the test piece and the sampling bag is 5000 µg / m 3 or less.
  4. 　前記共重合に用いる開始剤中のイソパラフィン含有量が、前記粘着剤組成物の全固形分に対して０．０３質量％以下である、請求項１乃至３の何れか１項に記載の粘着テープ。 The pressure-sensitive adhesive tape according to any one of claims 1 to 3, wherein an isoparaffin content in the initiator used for the copolymerization is 0.03% by mass or less based on the total solid content of the pressure-sensitive adhesive composition. .
  5. 　前記共重合に用いる開始剤は、イソパラフィンを実質的に含んでいない、請求項１乃至４の何れか１項に記載の粘着テープ。 The pressure-sensitive adhesive tape according to any one of claims 1 to 4, wherein the initiator used for the copolymerization does not substantially contain isoparaffin.
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