WO2020170827A1 - Adhésif autocollant et feuille adhésive autocollante et procédé d'utilisation de ceux-ci - Google Patents

Adhésif autocollant et feuille adhésive autocollante et procédé d'utilisation de ceux-ci Download PDF

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Publication number
WO2020170827A1
WO2020170827A1 PCT/JP2020/004428 JP2020004428W WO2020170827A1 WO 2020170827 A1 WO2020170827 A1 WO 2020170827A1 JP 2020004428 W JP2020004428 W JP 2020004428W WO 2020170827 A1 WO2020170827 A1 WO 2020170827A1
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Prior art keywords
pressure
sensitive adhesive
sheet
meth
irradiation
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PCT/JP2020/004428
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English (en)
Japanese (ja)
Inventor
慎吾 田邉
志幸 松帆
慎治 石崎
中村　尚稔
Original Assignee
東洋インキＳｃホールディングス株式会社
トーヨーケム株式会社
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Priority to CN202080015700.1A priority Critical patent/CN113474428B/zh
Publication of WO2020170827A1 publication Critical patent/WO2020170827A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive, an adhesive sheet and a method of using the same.
  • an adhesive sheet having an adhesive layer formed on a base material sheet has been widely used as a surface protection sheet for various members.
  • the pressure sensitive adhesive include acrylic pressure sensitive adhesive, silicone pressure sensitive adhesive, and urethane pressure sensitive adhesive.
  • Acrylic pressure-sensitive adhesives have excellent adhesive strength, but due to their high adhesive strength, their removability after being adhered to an adherend is poor.
  • the silicone-based pressure-sensitive adhesive tends to cause contamination of the adherend, and further, the silicone resin having a relatively low molecular weight may volatilize and be adsorbed on the surface of equipment such as an electronic device to cause a problem.
  • the urethane-based pressure-sensitive adhesive has good adhesiveness to the adherend, is relatively excellent in removability, and is hard to volatilize.
  • the “adhesive” is an adhesive having removability (removable adhesive)
  • the “adhesive sheet” is an adhesive sheet having removability (removable adhesive sheet).
  • a method for producing a urethane-based pressure-sensitive adhesive a method using a hydroxyl-terminated urethane prepolymer and a polyfunctional isocyanate compound which are reaction products of an active hydrogen group-containing compound such as polyol and polyisocyanate, and a hydroxyl-terminated urethane prepolymer are used.
  • a method one-shot method in which a polyol and a polyfunctional isocyanate compound are reacted at once without the use.
  • a general method for producing a pressure-sensitive adhesive sheet is a coating step of coating a pressure-sensitive adhesive on a substrate sheet, and heat-drying the formed coating layer to form a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive. It includes a heating step, a winding step of winding the obtained pressure-sensitive adhesive sheet around a winding core to form a pressure-sensitive adhesive sheet roll, and a curing step of curing the pressure-sensitive adhesive sheet roll.
  • a flat panel display such as a liquid crystal display (LCD) and an organic electroluminescence display (OELD), and a touch panel display in which such a flat panel display and a touch panel are combined are used in a television (TV), a personal computer (PC), a mobile phone, and Widely used in electronic devices such as personal digital assistants.
  • the urethane-based pressure-sensitive adhesive sheet is a flat panel display, a touch panel display, and a substrate (glass substrate, and an ITO/glass substrate having an ITO (indium tin oxide) film formed on the glass substrate, which are manufactured or used in the manufacturing process thereof. Etc.) and a surface protection sheet for optical members and the like.
  • the adherend with an adhesive sheet can be transported at high speed to a processing section that performs the necessary steps in order to improve productivity.
  • a processing section that performs the necessary steps in order to improve productivity.
  • an automatic high-speed transfer has been studied in which an adherend with an adhesive sheet is adsorbed from the adhesive sheet side by using a vacuum adsorption member, lifted, and conveyed to a desired location.
  • the adherend with an adhesive sheet preferably has a relatively high adhesive force so that the adhesive sheet does not peel off from the adherend while being adsorbed by the vacuum adsorbing member.
  • the adhesive sheet in an adherend with an adhesive sheet that has undergone the necessary steps, the adhesive sheet preferably has a relatively low adhesive force so that the adhesive sheet can be peeled off at high speed.
  • Patent Document 1 discloses a convertible pressure-sensitive composition containing a base adhesive polymer, a curable molecule curable by free radical polymerization, a photoinitiator, and an internal crosslinking agent curable by a mechanism other than free radical polymerization.
  • An adhesive composition is disclosed (Claim 1).
  • the peeling strength decreases due to the polymerization of the curable molecule by the light irradiation.
  • the reduction rate of peeling strength after light irradiation is, for example, 30 to 98%, preferably 50 to 95% (claims 15 and 16).
  • the composition described in Patent Document 1 is preferably for medical adhesive dressing (claim 25).
  • the base adhesive polymer is preferably polyacrylate (claim 8).
  • Patent Document 2 discloses a urethane resin (A) having a hydroxyl group and a (meth)acryloyl group, a polyisocyanate crosslinking agent (B), a (meth)acrylic compound (C) having two or more (meth)acryloyl groups, an organic compound.
  • An ultraviolet-curable pressure-sensitive adhesive composition containing a solvent (D) and a photopolymerization initiator (E) is disclosed (Claim 1).
  • Patent Document 2 discloses a method for producing an ultraviolet-curable pressure-sensitive adhesive sheet, which comprises coating the substrate with the ultraviolet-curable pressure-sensitive adhesive composition described above and then drying the organic solvent (D) (claim 9). ..
  • a method for producing a laminate in which two or more adherends are bonded together using the ultraviolet-curable pressure-sensitive adhesive sheet and then irradiated with ultraviolet rays (claim 10).
  • the pressure-sensitive adhesive described in Patent Document 2 is intended for OCA (Optical Clear Adhesive) applications (paragraph 0002) and is not intended for re-peeling applications.
  • a pressure-sensitive adhesive sheet for OCA is required to have high step followability when attached to an adherend, but is required not to be peeled again after two or more adherends are attached.
  • Patent Document 2 prior to the irradiation of ultraviolet rays, the cross-linking density is designed to be low with emphasis on the step followability, and the crosslinking density is increased by the irradiation of ultraviolet rays to reduce the removability.
  • a bifunctional polyol is used as a raw material polyol of the urethane resin (A) in order to suppress the crosslink density before ultraviolet irradiation.
  • the urethane resin (A) and the (meth)acrylic compound (C) which is a photopolymerizable monomer both have a (meth)acryloyl group, the crosslink density of the adhesive layer after ultraviolet irradiation is increased.
  • Patent Document 3 30 to 80 parts by weight of a photopolymerizable monomer (B) having one (meth)acryloyl group, 100 parts by weight of a urethane resin (A), a photopolymerization initiator (C)
  • An adhesive containing 0.05 to 3 parts by weight of silane coupling agent and 0.1 to 5 parts by weight of silane coupling agent (D) is disclosed (Claim 1).
  • the number of functional groups of the photopolymerizable monomer (B) used is 1 to 2.
  • the crosslinking of the adhesive layer due to light irradiation is insufficient, and the decrease in the adhesive force after light irradiation may be insufficient for high-speed peeling.
  • the reference numerals of the components described in Patent Documents 1 to 3 are the reference numerals described in these references and have no relation to the reference numerals used for the components of the present invention.
  • the present invention has been made in view of the above circumstances, and has good wettability and spreadability to an adherend before irradiation with active energy rays such as ultraviolet rays, and can be reattached to the adherend. It has removability and can be attached to the adherend with an adhesive force that does not easily peel off, and after irradiation with active energy rays, the adhesive force is effectively reduced and easily adhered from the adherend.
  • An object is to provide an adhesive capable of forming an adhesive layer that can be peeled off.
  • the present invention also has good wettability and spreadability to an adherend before irradiation with active energy rays such as ultraviolet rays, and has removability capable of being reattached to the adherend,
  • a pressure-sensitive adhesive sheet that can be attached to an adherend with an adhesive force that does not easily peel off and that can be easily peeled off from an adherend by effectively reducing the adhesive force after irradiation with active energy rays. The purpose is to provide.
  • the adhesive of the present invention is A hydroxyl group which is a reaction product of one or more active hydrogen group-containing compound (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanate (N), and does not contain a (meth)acryloyl group.
  • HX active hydrogen group-containing compound
  • N polyisocyanate
  • UHP urethane prepolymer
  • MX radical-polymerizable monomer containing three or more (meth)acryloyl groups in one molecule
  • the pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive has a pressure-sensitive adhesive force reduced by irradiation with active energy rays.
  • the pressure-sensitive adhesive sheet of the present invention comprises a substrate sheet and a pressure-sensitive adhesive layer made of the cured product of the pressure-sensitive adhesive of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention is suitable for a surface protection sheet.
  • the method of using the pressure-sensitive adhesive sheet of the present invention is A step of attaching the pressure-sensitive adhesive sheet to the surface of the adherend, Irradiating active energy rays to the pressure-sensitive adhesive sheet attached to the surface of the adherend, to reduce the adhesive force of the pressure-sensitive adhesive sheet, And a step of peeling the pressure-sensitive adhesive sheet having reduced adhesive strength from the adherend.
  • the “adhesive strength” is obtained by the method described in the section “Example”.
  • an adhesive layer that can be attached to an adherend with an adhesive force that does not easily peel off and that can be easily peeled off from an adherend after the irradiation of active energy rays effectively reduces the adhesive force.
  • An adhesive that can be formed can be provided.
  • Adhesion that can be attached to an adherend with an adhesive force that does not easily peel off, and that the adhesive force is effectively reduced after irradiation with active energy rays and can be easily peeled from the adherend. Sheets can be provided.
  • the adhesive of the present invention is A hydroxyl group which is a reaction product of one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanate (N), and does not contain a (meth)acryloyl group.
  • HX active hydrogen group-containing compounds
  • N polyisocyanate
  • a re-peelable urethane-based pressure-sensitive adhesive containing a radically polymerizable monomer (MX) containing three or more (meth)acryloyl groups in one molecule.
  • the pressure-sensitive adhesive sheet of the present invention is a urethane-based pressure-sensitive adhesive sheet including a base sheet and a pressure-sensitive adhesive layer formed of a cured product of the pressure-sensitive adhesive of the present invention.
  • the pressure-sensitive adhesive layer made of the cured product of the pressure-sensitive adhesive of the present invention can have reduced adhesive strength before and after irradiation with active energy rays.
  • the hydroxyl group-terminated urethane prepolymer (UPH) is a reaction product obtained by copolymerizing one or more active hydrogen group-containing compounds (HX) and one or more polyisocyanates (N).
  • the copolymerization reaction can be carried out in the presence of one or more catalysts, if necessary. If necessary, one or more solvents can be used in the copolymerization reaction.
  • Hydroxyl terminated urethane prepolymer (UPH) does not contain (meth)acryloyl groups.
  • the active hydrogen group-containing compound (HX) is a compound having a plurality of active hydrogen groups in one molecule.
  • the active hydrogen group include a hydroxyl group, a mercapto group, and an amino group (in this specification, unless otherwise specified, the amino group includes an imino group) and the like.
  • the active hydrogen group-containing compound (HX) a polyol having a plurality of hydroxyl groups in one molecule, a polyamine having a plurality of amino groups in one molecule, an amino alcohol having an amino group and a hydroxyl group in one molecule, and one molecule
  • examples thereof include polythiols having a plurality of mercapto groups.
  • the active hydrogen group-containing compound (HX) may be a non-polymer or a polymer. These may be used alone or in combination of two or more. Among them, polyol is preferable. Since polyamine and polythiol have high reactivity with polyisocyanate and short pot life, when they are used, it is preferable to use them in combination with a polyol.
  • polyols that can be used as the active hydrogen group-containing compound (HX) include polyester polyols, polyether polyols, polyacryl polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols. Of these, polyester polyols, polyether polyols, and combinations thereof are preferable.
  • the one or more active hydrogen group-containing compounds (HX) preferably include a polyether polyol.
  • polyester polyols can be used as the active hydrogen group-containing compound (HX).
  • the polyester polyol include a compound (esterified product) obtained by an esterification reaction of one or more kinds of polyol components and one or more kinds of acid components.
  • polyol component of the raw material examples include ethylene glycol (EG), propylene glycol (PG), diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3- Examples include hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, and pentaerythritol.
  • Examples of the acid component of the raw material include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and acid anhydrides thereof Etc.
  • the polyether polyol that can be used as the active hydrogen group-containing compound (HX) known ones can be used.
  • the polyether polyol include a compound (addition polymer) obtained by addition-polymerizing one or more oxirane compounds using an active hydrogen group-containing compound having a plurality of active hydrogen groups in one molecule as an initiator. ..
  • the initiator examples include a hydroxyl group-containing compound and amines. Specifically, 2 such as ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol, neopentyl glycol, butylethylpentanediol, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.
  • Functional initiators trifunctional initiators such as glycerin, trimethylolpropane, and triethanolamine; tetrafunctional initiators such as pentaerythritol, ethylenediamine, and aromatic diamines.
  • the oxirane compound examples include alkylene oxide (AO) such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO); tetrahydrofuran (THF) and the like.
  • an alkylene oxide adduct of an active hydrogen-containing compound (also referred to as polyoxyalkylene polyol) is preferable.
  • polyethylene glycol (PEG), polypropylene glycol (PPG), PPG (PPG-EO) having ethylene oxide (EO) added to the terminal and bifunctional polyether polyol such as polyalkylene glycol such as polytetramethylene glycol;
  • a trifunctional polyether polyol such as an alkylene oxide adduct of glycerin is preferable.
  • Polyamines usable as the active hydrogen group-containing compound (HX) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6. -Hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecane Diamine, hexamethylenediamine, trimethylhexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino- 3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, dimethyleneamine with nor
  • Amino alcohols that can be used as the active hydrogen group-containing compound (HX) include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri(hydroxymethyl)aminomethane, and 2-amino-2. Examples thereof include monoamines having a hydroxyl group such as -ethyl-1,3-propanediol; diamines having a hydroxyl group such as N-(2-hydroxypropyl)ethanolamine.
  • polythiol examples include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1, 3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5 -Pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,5-naphthalenedithiol, 1,2- Benzenedimethanethiol, 1,3-benzenedimethanethiol, 1,4-benzened
  • the one or more active hydrogen group-containing compounds (HX) may include a bifunctional active hydrogen group-containing compound and/or a trifunctional or higher functional hydrogen group-containing compound.
  • the bifunctional active hydrogen group-containing compound has a two-dimensional crosslinkability and can impart appropriate flexibility to the adhesive layer.
  • the trifunctional or higher functional hydrogen-containing compound has three-dimensional crosslinkability and can impart appropriate hardness to the adhesive layer.
  • the number of functional groups of each material can be selected so that the properties such as adhesive strength, cohesive strength, and removability are in a preferable range depending on the application and the like. Since it is easy to make adhesive strength and removability compatible, the one or more active hydrogen group-containing compound (HX) contains a bifunctional active hydrogen group-containing compound and a trifunctional or more functional hydrogen group-containing compound. Is preferred.
  • the number average molecular weight (Mn) of the active hydrogen group-containing compound (HX) is not particularly limited.
  • the Mn of the active hydrogen group-containing compound (HX) is preferably 50 to 20,000, more preferably 100 to 7,000, and particularly preferably 400 to 5,000, since the adhesive force and wettability of the adhesive layer are suitable.
  • Polyisocyanate (N) can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tridiene Diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4 “-Triphenylmethane triisocyanate, ⁇ , ⁇ ′-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetra
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate. , And 2,4,4-trimethylhexamethylene diisocyanate.
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6.
  • IPDI isophorone diisocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • 1,4-cyclohexane diisocyanate methyl-2,4-cyclohexane diisocyanate
  • methyl-2,6 methyl-2,6.
  • -Cyclohexane diisocyanate 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane and the like can be mentioned.
  • polyisocyanates include trimethylolpropane adducts, biurets, allophanates, and trimers of the above polyisocyanates (the trimers include an isocyanurate ring).
  • the preferable raw material compounding ratio of the hydroxyl group-terminated urethane prepolymer (UPH) is as follows.
  • the ratio (NCO/H ratio) of the number of moles of the isocyanate group (NCO) of the polyisocyanate (N) to the total number of moles of the active hydrogen group (H) of the plurality of active hydrogen group-containing compounds (HX) is 0.
  • the raw material mixture ratio is preferably determined so as to be 20 to 0.95, and more preferably 0.40 to 0.80. As the NCO/H ratio approaches 1, the gelation tends to occur more easily during the synthesis of the hydroxyl group-terminated urethane prepolymer (UPH). When the NCO/H ratio is 0.95 or less, gelation during synthesis of the hydroxyl group-terminated urethane prepolymer (UPH) can be effectively suppressed.
  • Catalyst> One or more kinds of catalysts can be used for the polymerization of the hydroxyl-terminated urethane prepolymer (UPH), if necessary.
  • Known catalysts can be used, and examples thereof include tertiary amine compounds and organic metal compounds.
  • the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) and the like.
  • the organometallic compound include tin compounds and non-tin compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dioctyltin dilaurate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide.
  • DBTDL dibutyltin diacetate
  • dioctyltin dilaurate dibutyltin sulfide
  • tributyltin sulfide tributyltin oxide.
  • Tributyltin acetate triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
  • Non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; 2 -Iron-based iron such as iron ethylhexanoate and iron acetylacetonate; cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium naphthenate and the like A zirconium type is mentioned. The type and amount of the catalyst can be appropriately designed within a range where the reaction proceeds well.
  • the combination of two or more catalysts is not particularly limited, and examples thereof include tertiary amine/organometallic system, tin system/non-tin system, and tin system/tin system. Preferred are tin-based/tin-based, more preferably dioctyltin dilaurate and tin 2-ethylhexanoate.
  • the mass ratio of tin 2-ethylhexanoate to dioctyltin dilaurate (tin 2-ethylhexanoate/dioctyltin dilaurate) is not particularly limited and is preferably more than 0 and less than 1, more preferably 0.2 to 0.8. is there. When the mass ratio is less than 1, the catalyst activity is well balanced, gelation and cloudiness of the reaction solution are effectively suppressed, and the polymerization stability is further improved.
  • the amount of the one or more catalysts used is not particularly limited, and is preferably 0.01 to, based on the total amount of the one or more active hydrogen group-containing compounds (HX) and the one or more polyisocyanates (N). It is 1.0 mass %.
  • one or more solvents can be used for the polymerization of the hydroxyl-terminated urethane prepolymer (UPH).
  • solvents can be used, and examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Ethyl acetate, toluene and the like are particularly preferable in view of the solubility of the hydroxyl group-terminated urethane prepolymer (UPH) and the boiling point of the solvent.
  • the polymerization method of the hydroxyl group-terminated urethane prepolymer (UPH) is not particularly limited, and known polymerization methods such as bulk polymerization method and solution polymerization method can be applied.
  • the polymerization procedure of the hydroxyl-terminated urethane prepolymer (UPH) is as follows. Procedure 1) Collectively one or more active hydrogen group-containing compounds (HX), one or more polyisocyanates (N), one or more catalysts if necessary, and one or more solvents if necessary.
  • Procedure for charging a flask Procedure 2) One or more active hydrogen group-containing compounds (HX), one or more catalysts, if necessary, and one or more solvents, if necessary, were charged to a flask, and one or more polyisocyanates ( N) may be added dropwise.
  • HX active hydrogen group-containing compounds
  • N polyisocyanates
  • the reaction temperature is preferably less than 100°C, more preferably 50 to 95°C, and particularly preferably 60 to 85°C.
  • the reaction temperature is 100° C. or higher, it becomes difficult to control the reaction rate, polymerization stability and the like, and it may be difficult to form a hydroxyl group-terminated urethane prepolymer (UPH) having a desired molecular weight.
  • the reaction temperature when a catalyst is not used is preferably 100°C or higher, more preferably 110°C or higher.
  • Polyfunctional isocyanate compound (I) Known compounds can be used as the polyfunctional isocyanate compound (I), and the compounds exemplified as the polyisocyanate (N) which is a raw material for the hydroxyl group-terminated urethane prepolymer (UPH) (specifically, aromatic polyisocyanate, aliphatic compound) Polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and trimethylolpropane adduct/biuret/allophanate/trimer) thereof can be used.
  • UHP hydroxyl group-terminated urethane prepolymer
  • the pressure-sensitive adhesive of the present invention contains a radical-polymerizable monomer (MX) containing three or more (meth)acryloyl groups in one molecule.
  • the “(meth)acryloyl group” means an acryloyl group and a methacryloyl group.
  • the radical-polymerizable monomer (MX) is a material that is polymerized and cured by irradiation with active energy rays such as ultraviolet rays and electron beams in the presence of a radical polymerization initiator (R) as necessary.
  • the radical-polymerizable monomer (MX) is preferably UV-curable, which is cured by UV irradiation.
  • the radical-polymerizable monomer (MX) By the polymerization of 1), the pressure-sensitive adhesive layer is cured and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer is reduced, and the pressure-sensitive adhesive sheet can be easily peeled from the adherend.
  • MX radical-polymerizable monomer
  • a crosslinking reaction proceeds during polymerization of the radical-polymerizable monomer (MX), resulting in adhesion.
  • the number of (meth)acryloyl groups contained in the radical-polymerizable monomer (MX) is preferably 4 or more, and more preferably, because the curing of the adhesive layer and the resulting decrease in adhesive strength can be more effectively caused. It is preferably 5 or more.
  • the amount of the radically polymerizable monomer (MX) containing 5 or more (meth)acryloyl groups is used because the amount of the radically polymerizable monomer (MX) to be used is more effective because the curing of the adhesive layer and the decrease in the adhesive force due to it can be caused more effectively. It is preferably 20% by mass or more, more preferably 40% by mass or more, particularly preferably 60% by mass or more, and most preferably 80% by mass or more based on the total amount of the monomer (MX).
  • the radical polymerizable monomer (MX) containing three or more (meth)acryloyl groups in one molecule is not particularly limited, and known ones can be used. Specifically, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth) ) Acrylate, tris(acryloxyethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone-modified tris(acryloxyethyl) isocyanurate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra (Meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipent
  • the radical polymerizable monomer (MX) preferably contains a hydroxyl group and an active hydrogen group such as amino.
  • an active hydrogen group such as amino.
  • a part of the radical-polymerizable monomer (MX) can be bonded to the urethane resin via the polyfunctional isocyanate compound (I), and the adhesive layer It is possible to more effectively cause the curing of the resin and the decrease in the adhesive force thereof.
  • the radical polymerizable monomer (MX) particularly preferably contains a hydroxyl group.
  • radical polymerizable monomer (MX) containing three or more (meth)acryloyl groups and hydroxyl groups include tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipenta. Examples thereof include erythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate. These may be used alone or in combination of two or more.
  • the urethane resin (A) and the (meth)acrylic compound (C), which is a photopolymerizable monomer have a (meth)acryloyl group
  • the reactivity becomes too high and the light of a fluorescent lamp and the sun Irradiation with a small amount of ultraviolet rays contained in ambient light such as light may easily initiate and progress the reaction, resulting in a decrease in adhesive strength.
  • the adhesive strength of the adhesive layer be reduced by irradiation with a small amount of ultraviolet rays contained in the ambient light during vacuum adsorption conveyance of the adherend.
  • the hydroxyl group-terminated urethane prepolymer does not contain a (meth)acryloyl group, it is possible to suppress the crosslinking reaction due to the irradiation of a small amount of ultraviolet rays contained in ambient light, and to vacuum-adsorb and convey the adherend. It is possible to prevent the adherend from being peeled off from the pressure-sensitive adhesive sheet at the time.
  • the pressure-sensitive adhesive of the present invention can optionally contain a radical polymerization initiator (R) that initiates the polymerization of the radically polymerizable monomer (MX) when irradiated with an active energy ray.
  • a radical polymerization initiator (R) that initiates the polymerization of the radically polymerizable monomer (MX) when irradiated with an active energy ray.
  • the pressure-sensitive adhesive of the present invention has a radical polymerization initiator (R) (in this case, the radical polymerization initiator (R) is also a photopolymerization initiator (RL)). It is preferable to include).
  • the radical polymerization initiator (R) is not particularly limited, and known ones can be used.
  • acetophenone-based polymerization initiators benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, and other benzoin polymerization initiators; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-methylbenzo
  • the adhesive of the present invention may further contain one or more plasticizers (P), if necessary.
  • the plasticizer (P) is not particularly limited, and an organic acid ester is preferable from the viewpoint of compatibility with other components.
  • ester of a monobasic acid or polybasic acid and an alcohol examples include, for example, isostearyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isostearyl palmitate, isocetyl stearate, octyldodecyl oleate, phthalate.
  • esters of other acids and alcohols include unsaturated fatty acids or branched acids such as myristoleic acid, oleic acid, linoleic acid, linolenic acid, isopalmitic acid, and isostearic acid, and ethylene glycol, propylene glycol, and glycerin. , Trimethylolpropane, pentaerythritol, and esters with alcohols such as sorbitan.
  • ester of monobasic acid or polybasic acid and polyalkylene glycol examples include, for example, polyethylene glycol dihexylate, polyethylene glycol di-2-ethylhexylate, polyethylene glycol dilaurate, polyethylene glycol dioleate, and dipolyethylene glycol methyl adipate.
  • ester of monobasic acid or polybasic acid and polyalkylene glycol examples include, for example, polyethylene glycol dihexylate, polyethylene glycol di-2-ethylhexylate, polyethylene glycol dilaurate, polyethylene glycol dioleate, and dipolyethylene glycol methyl adipate.
  • the molecular weight (formula weight or Mn) of the organic acid ester is preferably 250 to 1,000, more preferably 400 to 900, and particularly preferably 500 to 850.
  • the molecular weight is 250 or more, the heat resistance of the adhesive layer is good, and when the molecular weight is 1,000 or less, the wettability of the adhesive is good.
  • the pressure-sensitive adhesive of the present invention may contain one or more solvents, if necessary.
  • solvents can be used, and examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. From the viewpoint of the solubility of the hydroxyl group-terminated urethane prepolymer (UPH) and the boiling point of the solvent, ethyl acetate, toluene and the like are particularly preferable.
  • the pressure-sensitive adhesive of the present invention may contain one or more alteration preventing agents, if necessary. As a result, it is possible to suppress deterioration of various characteristics due to long-term use of the adhesive layer.
  • the deterioration preventing agent include a hydrolysis resistant agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.
  • a hydrolysis-resistant agent When a hydrolysis reaction occurs in the adhesive layer in a (wet) heat environment to generate a carboxy group, a hydrolysis-resistant agent can be used to block the carboxy group.
  • the anti-hydrolysis agent include carbodiimide type, oxazoline type, and epoxy type. Among them, the carbodiimide type is preferable from the viewpoint of the effect of suppressing hydrolysis.
  • the carbodiimide-based hydrolysis inhibitor is a compound having one or more carbodiimide groups in one molecule.
  • the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide.
  • the polycarbodiimide compound can be produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst.
  • examples of the diisocyanate include 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4 '-Diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and the like can be mentioned.
  • Carbodiimidization catalysts include 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2-phosphorene-1-oxide, 1-ethyl- Examples thereof include 2-phospholen-1-oxide and phospholene oxides such as 3-phospholene isomers thereof.
  • oxazoline-based hydrolysis inhibitor examples include 2,2'-o-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline), and 2,2'-p-phenylenebis.
  • epoxy hydrolyzing agent examples include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycol; sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, And polyglycidyl ethers of aliphatic polyols such as trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid Diglycidyl or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids; resorcinol, bis-(p-hydroxyphenyl)methane, 2,2-bis-(p-(
  • the addition amount of the hydrolysis resistant agent is not particularly limited, and is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4.5 parts by mass with respect to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH). And particularly preferably 0.5 to 3 parts by mass.
  • antioxidants include radical scavengers and peroxide decomposers.
  • radical scavenger include phenol compounds and amine compounds.
  • peroxide decomposer include sulfur compounds and phosphorus compounds.
  • phenol compound examples include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin- ⁇ -(3,5 -Di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2- [ ⁇ -(3-t-Butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, benzenepropanoic acid,3,5- Bis(1,1-bis
  • sulfur-based antioxidants examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.
  • Examples of phosphorus compounds include triphenylphosphite, diphenylisodecylphosphite, 4,4′-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl)phosphite, cyclic neopentanetetrayl Bis(octadecylphosphite), tris(nonylphenyl)phosphite, tris(monononylphenyl)phosphite, tris(dinonylphenyl)phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -
  • the antioxidant it is possible to prevent thermal deterioration of the hydroxyl group-terminated urethane prepolymer (UPH).
  • the addition amount of the antioxidant is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, particularly preferably 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH). Is 0.2 to 2 parts by mass.
  • At least one phenolic compound that is a radical scavenger as the antioxidant, and at least one phenolic compound that is a radical scavenger and a peroxide decomposing agent are used. It is more preferable to use one or more phosphorus compounds in combination. In addition, it is particularly preferable to use a phenolic compound that is a radical scavenger and a phosphorus compound that is a peroxide decomposing agent as antioxidants in combination, and to use these antioxidants and the aforementioned hydrolysis resistant agent in combination. ..
  • UV absorber examples include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and triazine compounds.
  • the amount of the ultraviolet absorber added is such that the initiation and progress of the polymerization of the radical-polymerizable monomer (MX) by irradiation with active energy rays is not hindered, and the radicals can be easily radicalized by the environmental light such as fluorescent light and sunlight. It can be appropriately designed within a range in which the reaction of the polymerizable monomer (MX) is not started.
  • the amount of the UV absorber added is designed according to the type of the UV absorber, the wavelength range of UV rays irradiated on the adhesive layer, and the cumulative light amount. To be done.
  • the addition amount of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2.5 parts by mass, and particularly preferably 0 based on 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH). 0.2 to 2 parts by mass.
  • Light stabilizer examples include hindered amine compounds and hindered piperidine compounds.
  • the amount of the light stabilizer added is not particularly limited, and is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH). It is particularly preferably 0.2 to 1 part by mass.
  • the pressure-sensitive adhesive of the present invention can optionally contain one or more antistatic agents (AS).
  • AS antistatic agent
  • examples of the antistatic agent (AS) include inorganic salts, ionic liquids, ionic solids, and surfactants, and among them, ionic liquids and ionic solids are preferable.
  • the "ionic liquid” is also called a room temperature molten salt, and is a salt that has fluidity at 25°C.
  • inorganic salt examples include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium nitrate. , Sodium carbonate, sodium thiocyanate and the like.
  • Examples of the ionic liquid containing imidazolium ions include 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-butyl. -3-Methylimidazolium bis(trifluoromethylsulfonyl)imide and the like can be mentioned.
  • Examples of the ionic liquid containing a pyridinium ion include 1-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4- Methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methylpyridinium bis(perfluoroethylsulfonyl
  • Examples of the ionic liquid containing ammonium ions include 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, trimethylheptyl ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N- Propyl ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethane sulfonyl)imide, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethane Sulfonyl)imide, tri-n-butylmethylammonium bistrifluoromethanesulfonimide, and the like.
  • ionic liquids such as pyrrolidinium salts, phosphonium salts, and sulfonium salts can be appropriately used.
  • ionic solids are salts of cations and anions, but they are solid substances at 25°C under normal pressure.
  • cation for example, alkali metal ion, phosphonium ion, pyridinium ion, ammonium ion and the like are preferable.
  • Examples of the ionic solid containing an alkali metal ion include lithium bisfluorosulfonylimide, lithium bistrifluoromethylsulfonylimide, lithium bispentafluoroethylsulfonylimide, lithium bisheptafluoropropylsulfonylimide, lithium bisnonanefluorobutylsulfonylimide, and sodium bis.
  • Fluorosulfonylimide sodium bistrifluoromethylsulfonylimide, sodium bispentafluoroethylsulfonylimide, sodium bisheptafluoropropylsulfonylimide, sodium bisnonanefluorobutylsulfonylimide, potassium bisfluorosulfonylimide, potassium bistrifluoromethylsulfonylimide, potassium bis Pentafluoroethyl sulfonylimide, potassium bisheptafluoropropyl sulfonyl imide, potassium bisnonane fluorobutyl sulfonyl imide, etc. are mentioned.
  • ionic solids containing phosphonium ions include tetrabutylphosphonium bisfluorosulfonylimide, tetrabutylphosphonium bistrifluoromethylsulfonylimide, tetrabutylphosphonium bispentafluoroethylsulfonylimide, tetrabutylphosphonium bisheptafluoropropylsulfonylimide, tetrabutylphosphonium.
  • Examples of the ionic solid containing a pyridinium ion include 1-hexadecyl-4-methylpyridinium bisfluorosulfonylimide, 1-hexadecyl-4-methylpyridinium bistrifluoromethylsulfonylimide, 1-hexadecyl-4-methylpyridinium bispentafluoroethylsulfonyl. Examples thereof include imide, 1-hexadecyl-4-methylpyridinium bisheptafluoropropylsulfonylimide, and 1-hexadecyl-4-methylpyridinium bisnonanefluorobutylsulfonylimide.
  • Examples of the ionic solid containing ammonium ions include lauryltrimethylammonium chloride, tributylmethylbistrifluoromethylsulfonylimide, tributylmethylbispentafluoroethylsulfonylimide, tributylmethylbisheptafluoropropylsulfonylimide, tributylmethylmubisnonanefluorobutylsulfonylimide.
  • Octyltributylbistrifluoromethylsulfonylimide Octyltributylbispentafluoroethylsulfonylimide, Octyltributylbisheptafluoropropylsulfonylimide, Octyltributylmubisnonanefluorobutylsulfonylimide, Tetrabutylbisfluorosulfonylimide, Tetrabutylbistrifluoromethylsulfonyl
  • imide tetrabutylbispentafluoroethylsulfonylimide, tetrabutylbisheptafluoropropylsulfonylimide, and tetrabutylmubisnonanefluorobutylsulfonylimide.
  • ionic solids whose cations are pyrrolidinium ions, imidazolium ions, sulfonium ions, etc. can be used as appropriate.
  • the surfactants include nonionic surfactants and anionic surfactants, and both types are classified into low molecular surfactants and high molecular surfactants.
  • nonionic low molecular weight surfactant examples include glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, and fatty acid diethanolamide.
  • anionic low molecular weight surfactant examples include alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates.
  • amphoteric low-molecular-weight surfactant examples include alkyl betaine and alkyl imidazolium betaine.
  • nonionic polymer surfactant examples include polyether ester amide type, ethylene oxide-epichlorohydrin type, and polyether ester type.
  • anionic polymer surfactant examples include polystyrene sulfonic acid type and the like.
  • amphoteric polymer surfactant examples include amino acid type amphoteric surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine type amphoteric surfactants such as higher alkyldihydroxyethylbetaine.
  • the amount of the antistatic agent (AS) added is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH).
  • the pressure-sensitive adhesive of the present invention may contain a leveling agent, if necessary.
  • the leveling property of the adhesive layer can be improved by adding the leveling agent.
  • the leveling agent include acrylic leveling agents, fluorine leveling agents, and silicone leveling agents. From the viewpoint of suppressing contamination of the adherend after repeeling the pressure-sensitive adhesive sheet, acrylic leveling agents and the like are preferable.
  • the amount of the leveling agent added is not particularly limited, and from the viewpoint of suppressing contamination of the adherend after re-peeling the pressure-sensitive adhesive sheet and improving the leveling property of the pressure-sensitive adhesive layer, preferably 100 parts by mass of the hydroxyl group-terminated urethane prepolymer (UPH), The amount is 0.001 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, and particularly preferably 0.1 to 1 part by mass.
  • UHP hydroxyl group-terminated urethane prepolymer
  • the pressure-sensitive adhesive of the present invention may contain other optional components, if necessary, within a range that does not impair the effects of the present invention.
  • Other optional components include catalysts, resins other than urethane resins, fillers (talc, calcium carbonate, titanium oxide, etc.), metal powders, colorants (pigments, etc.), foils, softeners, conductive materials.
  • a catalyst inhibitor such as acetylacetone for the purpose of improving the pot life of the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive of the present invention includes one or more hydroxyl-terminated urethane prepolymers (UPH), one or more polyfunctional isocyanate compound (I), and one type containing three or more (meth)acryloyl groups in one molecule. It contains the above radical-polymerizable monomer (MX) as an essential component, and further contains one or more optional components as necessary.
  • the compounding ratio of these is not particularly limited, but the preferable compounding ratio is as follows.
  • the amount of the one or more polyfunctional isocyanate compound (I) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, particularly preferably 100 parts by mass of the one or more kinds of hydroxyl-terminated urethane prepolymers (UPH). Is 5 to 15 parts by mass. If the amount of the one or more polyfunctional isocyanate compound (I) is 1 part by mass or more, the cohesive force of the adhesive layer will be good, and if it is 30 parts by mass or less, the pot life will be good.
  • the amount of the one or more radically polymerizable monomer (MX) is preferably 1 with respect to 100 parts by mass of the one or more hydroxyl group-terminated urethane prepolymer (UPH). To 100 parts by mass, more preferably 3 to 70 parts by mass, particularly preferably 5 to 50 parts by mass, most preferably 10 to 50 parts by mass.
  • the method for producing the pressure-sensitive adhesive of the present invention is not particularly limited.
  • UHP hydroxyl-terminated urethane prepolymers
  • I polyfunctional isocyanate compound
  • MX radically polymerizable monomers containing one or more (meth)acryloyl groups, and optionally one or more other optional components are added and mixed to give the pressure-sensitive adhesive of the present invention.
  • MX radically polymerizable monomers
  • the pressure-sensitive adhesive sheet of the present invention includes a substrate sheet and a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive of the present invention.
  • the adhesive layer can be formed on one side or both sides of the base sheet. If necessary, the exposed surface of the adhesive layer can be covered with a release sheet. The release sheet is released before the adhesive sheet is attached to the adherend.
  • FIG. 1 shows a schematic cross-sectional view of the adhesive sheet according to the first embodiment of the present invention.
  • reference numeral 10 is an adhesive sheet
  • reference numeral 11 is a base sheet
  • reference numeral 12 is an adhesive layer
  • reference numeral 13 is a release sheet.
  • the adhesive sheet 10 is a single-sided adhesive sheet in which an adhesive layer is formed on one surface of a base material sheet.
  • FIG. 2 shows a schematic cross-sectional view of the adhesive sheet according to the second embodiment of the present invention.
  • reference numeral 20 is an adhesive sheet
  • reference numeral 21 is a base material sheet
  • reference numerals 22A and 22B are adhesive layers
  • reference numerals 23A and 23B are release sheets.
  • the pressure-sensitive adhesive sheet 20 is a double-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on both sides of a base material sheet.
  • the base material sheet is not particularly limited, and examples include resin sheets, paper, metal foil, and the like.
  • the base sheet may be a laminated sheet in which any one or more layers are laminated on at least one surface of these base sheets. If necessary, the surface of the base material sheet on which the adhesive layer is formed may be subjected to an easy adhesion treatment such as corona discharge treatment and application of an anchor coating agent.
  • the constituent resin of the resin sheet is not particularly limited, and ester resins such as polyethylene terephthalate (PET); olefin resins such as polyethylene (PE) and polypropylene (PP); vinyl resins such as polyvinyl chloride; nylon 66, etc. Examples include amide-based resins; urethane-based resins (including foams); and combinations thereof.
  • the thickness of the resin sheet excluding the polyurethane sheet is not particularly limited and is preferably 15 to 300 ⁇ m.
  • the thickness of the polyurethane sheet (including the foam) is not particularly limited and is preferably 20 to 50,000 ⁇ m.
  • the paper is not particularly limited, and examples thereof include plain paper, coated paper, and art paper.
  • the constituent metal of the metal foil is not particularly limited, and examples thereof include aluminum, copper, and combinations thereof.
  • the release sheet is not particularly limited, and a known release sheet in which a surface of a base material sheet such as a resin sheet or paper is subjected to a known release treatment such as application of a release agent can be used.
  • the pressure-sensitive adhesive sheet can be manufactured by a known method.
  • the pressure-sensitive adhesive of the present invention is applied to the surface of the substrate sheet to form a coating layer made of the pressure-sensitive adhesive of the present invention.
  • a coating method a known method can be applied, and examples thereof include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method.
  • the coating layer is dried and cured to form an adhesive layer made of the cured product of the adhesive of the present invention.
  • the heating and drying temperature is not particularly limited and is preferably about 60 to 150°C.
  • the thickness of the adhesive layer (thickness after drying) varies depending on the application, but is preferably 0.1 to 200 ⁇ m.
  • a release sheet is attached to the exposed surface of the adhesive layer by a known method.
  • a single-sided pressure-sensitive adhesive sheet can be manufactured as described above.
  • a double-sided pressure-sensitive adhesive sheet can be manufactured by performing the above operation on both sides.
  • the pressure-sensitive adhesive of the present invention is applied to the surface of the release sheet to form a coating layer comprising the pressure-sensitive adhesive of the present invention, and then the coating layer is dried and cured to give the present invention.
  • the method for producing the pressure-sensitive adhesive sheet is preferably a coating step of coating the pressure-sensitive adhesive on the base sheet, and a heating step of heating and drying the formed coating layer to form a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive. It includes a step, a winding step of winding the obtained pressure-sensitive adhesive sheet on a winding core to form a pressure-sensitive adhesive sheet roll, and a curing step of curing the pressure-sensitive adhesive sheet roll.
  • the method of using the pressure-sensitive adhesive sheet of the present invention is A step of attaching the pressure-sensitive adhesive sheet of the present invention to the surface of an adherend, Irradiating active energy rays such as ultraviolet rays and electron beams to the pressure-sensitive adhesive sheet attached to the surface of the adherend, and reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet, And a step of peeling the pressure-sensitive adhesive sheet having reduced adhesive strength from the adherend.
  • the pressure-sensitive adhesive of the present invention contains a radical polymerizable monomer (MX) and, if necessary, a radical polymerization initiator (R). Therefore, the pressure-sensitive adhesive layer made of the cured product of the pressure-sensitive adhesive of the present invention can be polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and the adhesive force is effectively reduced after irradiation with respect to before irradiation with active energy rays. be able to.
  • MX radical polymerizable monomer
  • R radical polymerization initiator
  • the pressure-sensitive adhesive layer made of the cured product of the pressure-sensitive adhesive of the present invention has a suitable pressure-sensitive adhesive force before irradiation with active energy rays such as ultraviolet rays, has good wettability and spreadability to an adherend, While it has removability that allows it to be reattached to the body, it can be attached to the adherend with an adhesive force that does not easily peel off during vacuum suction conveyance of the adherend.
  • the adhesive layer made of the cured product of the adhesive of the present invention is easily peeled from the adherend after irradiation with active energy rays, because the adhesive force is effectively reduced by the polymerization of the radically polymerizable monomer (MX). can do.
  • an adherend with an adhesive sheet can be transported at high speed to a processing section for performing necessary steps in order to improve productivity.
  • a processing section for performing necessary steps in order to improve productivity.
  • an automatic high-speed transfer has been studied in which an adherend with an adhesive sheet is adsorbed from the adhesive sheet side by using a vacuum adsorption member, lifted, and conveyed to a desired location.
  • the adherend with an adhesive sheet preferably has a relatively high adhesive force so that the adhesive sheet does not peel off from the adherend while being adsorbed by the vacuum adsorbing member.
  • the adhesive sheet in an adherend with an adhesive sheet that has undergone the necessary steps, the adhesive sheet preferably has a relatively low adhesive force so that the adhesive sheet can be peeled off at high speed.
  • the "adhesive with an adhesive sheet” means an adhesive sheet for the surface of an adherend such as a glass substrate, an ITO/glass substrate having an ITO (indium tin oxide) film formed on the glass substrate, and optical members. It is a laminated body stuck.
  • the active energy such as ultraviolet rays is applied to the pressure-sensitive adhesive sheet stuck to the surface of the adherend.
  • the adhesive force of the pressure-sensitive adhesive sheet can be reduced by irradiating with a line, and the pressure-sensitive adhesive sheet having the reduced pressure-sensitive adhesive force can be easily peeled off from the adherend.
  • the adhesive force of the adhesive layer before and after irradiation with active energy rays, and the decrease rate of the adhesive force after irradiation of the adhesive layer before and after irradiation with active energy rays may be appropriately designed according to the application and use conditions. it can.
  • the rate of decrease in the adhesive strength of the adhesive layer after irradiation with the active energy ray is not particularly limited and is preferably 2/3 or less, more preferably 1/2 or less, and particularly preferably 1/3 or less.
  • the adhesive strength of the adhesive layer before irradiation with active energy rays is preferably 100 gf/25 mm or less, more preferably 50 gf/25 mm or less, particularly preferably 26 gf/25 mm or less, and most preferably 20 gf/25 mm or less.
  • the adhesive strength of the adhesive layer before irradiation with active energy rays is preferably 8 gf/25 mm or more, more preferably 10 gf/25 mm or more, and particularly preferably 15 gf/25 mm or more.
  • the adhesive strength of the adhesive layer after irradiation with active energy rays is preferably 10 gf/25 mm or less, more preferably 8 gf/25 mm or less, further preferably 6 gf/25 mm or less, particularly preferably 5 gf/25 mm or less, most preferably 5 gf/ It is less than 25 mm.
  • the present invention before the irradiation with the active energy ray such as ultraviolet rays, it has a good wettability and spreadability to the adherend, and can be re-separated so that it can be reattached to the adherend. It can be adhered to the adherend with good adhesiveness and does not easily peel off, and after irradiation with active energy rays, the adhesive force is effectively reduced and easily peels from the adherend. It is possible to provide a pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer.
  • Adhesion that can be attached to an adherend with an adhesive force that does not easily peel off, and that the adhesive force is effectively reduced after irradiation with active energy rays and can be easily peeled from the adherend. Sheets can be provided.
  • the pressure-sensitive adhesive sheet of the present invention can be used in the form of a tape, a label, a seal, a double-sided tape or the like.
  • the pressure-sensitive adhesive sheet of the present invention is suitably used as a surface protective sheet, a cosmetic sheet, a non-slip sheet, and the like.
  • the "sheet” includes “film” and “tape” unless otherwise specified.
  • a flat panel display such as a liquid crystal display (LCD) and an organic electroluminescence display (OELD), and a touch panel display in which the flat panel display and a touch panel are combined are used in a television (TV), a personal computer (PC), a mobile phone, It is also widely used in electronic devices such as portable information terminals.
  • the pressure-sensitive adhesive sheet of the present invention includes a flat panel display and a touch panel display (collectively referred to simply as “display”), and a substrate (glass substrate and ITO on the glass substrate) manufactured or used in the manufacturing process thereof. It is preferably used as a surface protective sheet for (ITO/glass substrate etc. on which (indium tin oxide) film is formed) and optical members.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Device SHIMADZU Prominence (manufactured by Shimadzu Corporation), Column: 3 SHODEX LF-804 (Showa Denko KK) connected in series, Detector: differential refractive index detector, Solvent: tetrahydrofuran (THF), Flow rate: 1 mL/min, Solvent temperature: 40°C Sample concentration: 0.2%, Sample injection volume: 200 ⁇ L.
  • HX-1 Kuraray polyol P-2010, polyester polyol, number average molecular weight Mn2000, hydroxyl group number 2, manufactured by Kuraray Co.
  • HX-2) Sannix GP-3000
  • polyether polyol number average molecular weight Mn3000, hydroxyl group number 3, manufactured by Sanyo Chemical Industries
  • HX-3) Sannix GL-3000
  • polyether polyol number average molecular weight Mn3000, hydroxyl group 3, Sanyo Chemical Industries, Ltd.
  • HX-4 Exenol 851, polyether polyol, number average molecular weight Mn6700, hydroxyl group number 3, manufactured by AGC Co.
  • HX-5 Sannix PP-1000
  • polyether polyol number average molecular weight Mn1000, hydroxyl group number 2, manufactured by Sanyo Chemical Industries
  • HX-6 1,4-hexol 851, polyether polyol, number average molecular weight Mn6700, hydroxyl group number 3, manufactured by A
  • HY-1 2-hydroxyethyl acrylate (HEA).
  • N Polyisocyanate
  • N-1 Desmodur H, hexamethylene diisocyanate (HDI), manufactured by Sumika Covestro Urethane Co.
  • N-2 Desmodur I, isophorone diisocyanate (IPDI), manufactured by Sumika Covestro Urethane Co.
  • N-3 Desmodur T-80, tolylene diisocyanate (TDI), manufactured by Sumika Covestro Urethane Co.
  • ⁇ Polyfunctional isocyanate compound (I)> (I-1): Sumidule HT, hexamethylenediisocyanate trimethylolpropane adduct, nonvolatile content 75%, manufactured by Sumika Covestrourethane Co., (I-2): Takenate D-110N, trimethylolpropane adduct of xylylene diisocyanate, nonvolatile content 75%, manufactured by Mitsui Chemicals, Inc.
  • MX-1 MIRAMER M500, dipentaerythritol pentaacrylate, 5 acryloyl groups, 1 hydroxyl group, manufactured by MIWON (MX-2): MIRAMER M600, dipentaerythritol hexaacrylate, 6 acryloyl groups, 0 hydroxyl group, manufactured by MIWON, (MX-3): MIRAMER M300, trimethylolpropane triacrylate, 3 acryloyl groups, 0 hydroxyl group, manufactured by MIWON (MX-4): MIRAMER M340, pentaerythritol triacrylate, 3 acryloyl groups, 1 hydroxyl group, manufactured by MIWON, (MX-5): Sartomer CN925, aliphatic urethane tetraacrylate, 4 acryloyl groups, 0 hydroxyl group, manufactured by Arkema.
  • RL-1 Irgacure TPO, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, manufactured by BASF Corporation
  • RL-2 SB-PI 712, 4-methylbenzophenone, manufactured by Sanyo Trading Co., Ltd.
  • P ⁇ Plasticizer (P)>
  • P-1 Acetyl citrate tributyl (ATBC), manufactured by Mitsubishi Chemical Corporation
  • P-2) Monosizer W262, ether ester plasticizer, manufactured by DIC.
  • O-1 Irganox 1010, hindered phenolic antioxidant, manufactured by BASF.
  • AS-1 IL-P14, ionic liquid, manufactured by Koei Chemical Industry Co., Ltd.
  • Synthetic Examples 2 to 7 were the same as Synthetic Example 1 except that the type of active hydrogen group-containing compound (HX), the type of polyisocyanate (N), and the mixing ratio thereof were changed, and a colorless and transparent hydroxyl group terminal was used.
  • a solution of urethane prepolymers (UPH-2) to (UPH-7) was obtained.
  • Table 1 shows the compounding composition and Mw of the obtained hydroxyl group-terminated urethane prepolymer in each synthesis example.
  • Synthetic Example 11 was prepared in the same manner as in Synthetic Example 7 except that an active hydrogen group-containing compound (HY) having one active hydrogen group and one (meth)acryloyl group in one molecule was added to the charged composition. A transparent hydroxyl-terminated urethane prepolymer (UPA-1) solution was obtained. Table 1 shows the compounding composition and Mw of the obtained hydroxyl group-terminated urethane prepolymer.
  • HY active hydrogen group-containing compound having one active hydrogen group and one (meth)acryloyl group in one molecule
  • O-1) 0.1 part antioxidant
  • AS-1) 0.1 part antistatic agent
  • solvent solvent
  • the compounding amount of each material other than the solvent is shown by the amount of non-volatile components (the same applies to other examples and comparative examples).
  • the compounding composition is shown in Table 2.
  • a 75 ⁇ m thick polyethylene terephthalate sheet (double-sided easy-adhesion PET sheet, Cosmoshine A-4300, manufactured by Toyobo Co., Ltd.) was prepared as a base sheet.
  • the obtained pressure-sensitive adhesive was applied onto one surface of this substrate sheet so that the thickness after drying was 75 ⁇ m, and dried at 100° C. for 5 minutes to form a pressure-sensitive adhesive layer.
  • a release sheet having a thickness of 38 ⁇ m Super Stick SP-PET38, manufactured by Lintec Co., Ltd. was attached to the adhesive layer to obtain an adhesive sheet. After curing for 1 week in an atmosphere of 23° C. and 50% RH, various evaluations were performed.
  • Examples 2-35, Comparative Examples 1-3 In each of Examples 2 to 35 and Comparative Examples 1 to 3, a urethane type or acrylic type was prepared in the same manner as in Example 1 except that the composition of the adhesive was changed as shown in Tables 2 to 6. An adhesive and an adhesive sheet using the same were produced.
  • the evaluation items and evaluation methods of the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet are as follows. (Wet spreadability) A test piece having a width of 100 mm and a length of 200 mm was cut out from the obtained pressure-sensitive adhesive sheet, left for 30 minutes in an atmosphere of 23° C. and 50% RH, and then the release sheet was peeled from the test piece. While holding both ends of the test piece with both hands, the exposed central portion of the adhesive layer was brought into contact with the glass plate, and then both hands were released. The wettability and spreadability of the pressure-sensitive adhesive was evaluated by measuring the time taken for the entire pressure-sensitive adhesive layer to adhere to the glass plate due to the weight of the test piece.
  • Adhesion is excellent in less than 6 seconds.
  • Adhesion time is 6 seconds or more and less than 8 seconds, which is good.
  • Adhesion time is 8 seconds or more and less than 10 seconds, which is practical.
  • X The time until adhesion is 10 seconds or more, which is not practical.
  • a test piece having a width of 25 mm and a length of 100 mm was cut out from the obtained pressure-sensitive adhesive sheet, left for 30 minutes in an atmosphere of 23° C. and 50% RH, and then the release sheet was peeled from the test piece. Under an atmosphere of 23° C. and 50% RH, the exposed adhesive layer side of the test piece was attached to a stainless (SUS) plate and pressure-bonded using a 2 kg roll. After standing for 24 hours, using a tensile tester (Tensilon: manufactured by Orientec Co., Ltd.) in accordance with JIS Z0237, the peeling speed was 0.3 m/min, and the peeling force was 180°.
  • the evaluation criteria are as follows. A: Less than 20 gf/25 mm, excellent. Good: 20 gf/25 mm or more and less than 50 gf/25 mm, good. ⁇ : 50 gf/25 mm or more and 100 gf/25 mm or less, acceptable for practical use. X: Over 100 gf/25 mm, not practical.
  • a test piece with a width of 70 mm and a length of 100 mm was cut out from the obtained adhesive sheet, and a general fluorescent lamp that emits light including ultraviolet rays was included, and the test piece was prepared in an atmosphere adjusted to 23° C. and 50% RH. After being left for a time, the release sheet was released from the test piece. Under an atmosphere of 23° C. and 50% RH, the exposed adhesive layer side of the test piece was attached to a caustic soda glass plate and pressure-bonded using a 2 kg roll. Then, after leaving it for 24 hours under the condition of 60° C.-90% RH, it was air-cooled in an atmosphere of 23° C.-50% RH for 1 hour.
  • a weight of 0.5 kg was attached to the back surface of the glass plate (the surface on which the test piece was not attached).
  • For the test piece/glass plate/weight stack from the top surface (base material sheet surface, PET sheet surface) side of the test piece, use a vacuum suction member to adsorb and hold it, lift for 1 minute, and place a 0.5 kg weight on the back surface. It was confirmed whether or not the glass plate to which was adhered was peeled off from the test piece and dropped. The test was conducted 20 times and the number of drops was examined. It should be noted that the smaller the number of drops, the higher the vacuum suction retention suitability, and the better, and it is most preferable that there is no drop.
  • the evaluation criteria are as follows. ⁇ : Excellent, no fall. ⁇ : The number of drops is one, which is good. ⁇ : Practical acceptable, with 2 to 3 drops. ⁇ : The number of drops is four or more, which is not practical.
  • a test piece with a width of 25 mm and a length of 100 mm was cut out from the obtained adhesive sheet, left for 30 minutes in an atmosphere of 23° C. and 50% RH, and then the release sheet was peeled off from the test piece to expose the test piece.
  • the prepared adhesive layer side was adhered to a stainless (SUS) plate and pressure-bonded using a 2 kg roll. After leaving it in an atmosphere of 23° C. and 50% RH for 24 hours, a high pressure mercury lamp (peak wavelength: 254 nm, 365 nm, 405 nm, and 435 nm, output: 120 W) was used, and the accumulated light amount was 1000 mJ for the test piece.
  • UV irradiation Ultraviolet (UV) irradiation was performed under the following conditions. After air-cooling for 1 hour in an atmosphere of 23° C.-50% RH, using a tensile tester (Tensilon: manufactured by Orientec Co., Ltd.), a peeling speed of 0.3 m/min, a peeling angle of 180°, and an adhesive strength ( The adhesive force after UV irradiation) was measured. Further, the rate of decrease in adhesive strength before UV irradiation was determined. It is preferable that the adhesive force after UV irradiation and the decrease rate of the adhesive force are low because high-speed peeling is possible.
  • the evaluation criteria are as follows.
  • ⁇ The adhesive strength is less than 5 gf/25 mm, and the decrease rate of the adhesive strength is 2/3 or less, which is excellent.
  • Adhesive strength is 5 gf/25 mm or more and less than 8 gf/25 mm, and the decrease rate of adhesive strength is 2/3 or less, which is good.
  • Adhesive force is 8 gf/25 mm or more and 10 gf/25 mm or less, and adhesive force reduction rate is 2/3 or less, which is acceptable for practical use.
  • X Adhesive force is more than 10 gf/25 mm, or adhesive force reduction rate is more than 2/3, which is not practical.
  • Examples 1 to 35 are reaction products of one or more active hydrogen group-containing compound (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanate (N), ) Hydroxyl-terminated urethane prepolymer (UPH) containing no acryloyl group, polyfunctional isocyanate compound (I), and radically polymerizable monomer (MX) containing three or more (meth)acryloyl groups in one molecule.
  • HX active hydrogen group-containing compound
  • N polyisocyanate
  • UHP Hydroxyl-terminated urethane prepolymer
  • I polyfunctional isocyanate compound
  • MX radically polymerizable monomer
  • the adhesive layers of the obtained adhesive sheets had good wettability and spreadability on the adherend.
  • Each of the pressure-sensitive adhesive sheets obtained in these examples had an appropriate pressure-sensitive adhesive force before UV irradiation and had removability capable of being re-attached to an adherend while being adhered to the adherend. It was possible to attach with an adhesive force that does not easily peel off, and the vacuum adsorption retention suitability was good. All of the pressure-sensitive adhesive sheets obtained in these examples became effective in reducing the pressure-sensitive adhesive force after UV irradiation and could be easily peeled from the adherend, and were suitable for high-speed peeling. ..
  • the pressure-sensitive adhesive sheet obtained in Comparative Example 1 using the acrylic resin (AR) instead of the hydroxyl group-terminated urethane prepolymer (UPH) has a very high adhesive force before UV irradiation and has a wettability and spreadability to an adherend. It was poor and the removability was poor.
  • the pressure-sensitive adhesive sheet obtained in Comparative Example 1 had a high adhesive force even after UV irradiation, and was not suitable for high-speed peeling.
  • one or more active hydrogen group-containing compound (HX) having a plurality of active hydrogen groups in one molecule, and one active hydrogen group and one ( Comparative Example 2 using a hydroxyl-terminated urethane prepolymer (UPA) which is a reaction product of one or more active hydrogen group-containing compounds (HY) having a (meth)acryloyl group and one or more polyisocyanates (N) Then, the obtained pressure-sensitive adhesive sheet had a poor vacuum adsorption retention suitability before UV irradiation.
  • UPA hydroxyl-terminated urethane prepolymer
  • the adhesive layer absorbs a small amount of UV emitted from the fluorescent lamp, the reaction of the radical-polymerizable monomer (MX) starts, and the adhesive strength decreases before UV irradiation, resulting in poor vacuum adsorption retention suitability. It is thought that it became.
  • Comparative Example 3 a conventional urethane-based pressure-sensitive adhesive that was not designed for vacuum adsorption conveyance was manufactured.
  • the pressure-sensitive adhesive sheet thus obtained had a low level of pressure-sensitive adhesive strength before irradiation with UV, and had poor vacuum adsorption retention suitability.
  • Comparative Example 3 since the radical-polymerizable monomer (MX) was not used, the decrease in the adhesive force after UV irradiation was small and the result was poor.
  • MX radical-polymerizable monomer

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

Abstract

La présente invention concerne un adhésif autocollant qui permet de former une couche adhésive autocollante qui, avant exposition à un rayonnement d'énergie active, présente une bonne aptitude à l'étalement à l'état humide sur des supports, a une bonne aptitude à l'élimination qui permet une ré-application sur des supports et en même temps peut être appliquée avec une résistance au pelage qui empêche un pelage facile à partir de supports ; et qui, après exposition à un rayonnement d'énergie active, a une résistance au pelage efficacement réduite et peut être facilement décollée à partir de supports. Un adhésif autocollant selon la présente invention comprend : un prépolymère d'uréthane terminé par des groupes hydroxy et dépourvu de groupes (méth)acryloyle (UPH), qui est le produit de réaction d'au moins un polyisocyanate (N) avec au moins un composé à teneur en groupes à hydrogène actif (HX) qui comprend une pluralité de groupes à hydrogène actif dans chaque molécule ; un composé isocyanate polyfonctionnel (I) ; et un monomère polymérisable par voie radicalaire (MX) qui contient au moins trois groupes (méth)acryloyle dans chaque molécule. Une couche adhésive autocollante (12) comprenant le produit durci de l'adhésif autocollant selon la présente invention subit une diminution de résistance au pelage lors de l'exposition à un rayonnement d'énergie active.
PCT/JP2020/004428 2019-02-22 2020-02-05 Adhésif autocollant et feuille adhésive autocollante et procédé d'utilisation de ceux-ci WO2020170827A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2006022313A (ja) * 2004-06-11 2006-01-26 Toyo Ink Mfg Co Ltd 粘着剤組成物及びこれを用いた粘着シート
JP2008024848A (ja) * 2006-07-21 2008-02-07 Toyo Ink Mfg Co Ltd 活性エネルギー線粘着力消失型感圧接着剤、それを塗布した活性エネルギー線粘着力消失型粘着シート
JP2016108487A (ja) * 2014-12-09 2016-06-20 Dic株式会社 紫外線硬化型粘着剤組成物、紫外線硬化型粘着シート、及び、積層体
JP2016186064A (ja) * 2015-11-12 2016-10-27 東洋インキＳｃホールディングス株式会社 再剥離型粘着剤
WO2016175112A1 (fr) * 2015-04-30 2016-11-03 リンテック株式会社 Bande adhésive pour le traitement de tâches
WO2019130741A1 (fr) * 2017-12-26 2019-07-04 日東電工株式会社 Feuille de protection de surface pour élément optique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6323580B1 (ja) * 2017-02-14 2018-05-16 東洋インキＳｃホールディングス株式会社 粘着剤および粘着シート
JP6256648B1 (ja) * 2017-06-12 2018-01-10 東洋インキＳｃホールディングス株式会社 粘着剤およびそれを用いた粘着シート、積層体、表示装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006022313A (ja) * 2004-06-11 2006-01-26 Toyo Ink Mfg Co Ltd 粘着剤組成物及びこれを用いた粘着シート
JP2008024848A (ja) * 2006-07-21 2008-02-07 Toyo Ink Mfg Co Ltd 活性エネルギー線粘着力消失型感圧接着剤、それを塗布した活性エネルギー線粘着力消失型粘着シート
JP2016108487A (ja) * 2014-12-09 2016-06-20 Dic株式会社 紫外線硬化型粘着剤組成物、紫外線硬化型粘着シート、及び、積層体
WO2016175112A1 (fr) * 2015-04-30 2016-11-03 リンテック株式会社 Bande adhésive pour le traitement de tâches
JP2016186064A (ja) * 2015-11-12 2016-10-27 東洋インキＳｃホールディングス株式会社 再剥離型粘着剤
WO2019130741A1 (fr) * 2017-12-26 2019-07-04 日東電工株式会社 Feuille de protection de surface pour élément optique

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