WO2007029783A1 - Composition adhésive acrylique et produit adhésif - Google Patents

Composition adhésive acrylique et produit adhésif Download PDF

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Publication number
WO2007029783A1
WO2007029783A1 PCT/JP2006/317767 JP2006317767W WO2007029783A1 WO 2007029783 A1 WO2007029783 A1 WO 2007029783A1 JP 2006317767 W JP2006317767 W JP 2006317767W WO 2007029783 A1 WO2007029783 A1 WO 2007029783A1
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Prior art keywords
adhesive composition
adhesive
polymer
pressure
sensitive adhesive
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PCT/JP2006/317767
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English (en)
Japanese (ja)
Inventor
Yoshihiro Morishita
Tetsuya Kunimune
Kenichi Hamada
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Kuraray Co., Ltd.
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Priority to JP2006534507A priority Critical patent/JPWO2007029783A1/ja
Publication of WO2007029783A1 publication Critical patent/WO2007029783A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising a specific (meth) acrylic block copolymer and excellent in weather resistance, heat resistance, and water resistance.
  • Acrylic adhesives are widely used in adhesive tapes, adhesive sheets, and the like because they have superior weather resistance and heat resistance compared to rubber adhesives.
  • the acrylic copolymer used as the base polymer of the acrylic adhesive is usually a random copolymer produced by a radical polymerization method.
  • the molecular weight distribution [weight average molecular weight (Mw) Z number average molecular weight (Mn) ] Is generally as wide as about 2.0 to 5.0. Therefore, a low molecular weight component is mixed, and the pressure-sensitive adhesive containing the acrylic copolymer has a problem that the cohesive force is insufficient under a high temperature condition or adhesive residue is generated on the adherend due to cohesive failure. It was.
  • Patent Document 1 an iniferter such as xylylene-bis (N, N-jetyldithiocarbamate), xylylenebis (N-carbazolyldithiocarbamate) is used.
  • a block copolymer having a polymer block having an alkyl ester power and a polymer block having an alkyl ester power is synthesized by a fy-fater polymerization method, and the block copolymer is used as a base for an adhesive.
  • Patent Document 2 and Patent Document 3 a polymer block having mainly a methacrylic acid alkyl ester power, a glass transition temperature of + 110 ° C or higher, and a syndiotacticity of 70% or higher is mainly used.
  • a block copolymer having a polymer block having a glass transition temperature of + 30 ° C. or lower and a polymer block having a glass transition temperature of + 30 ° C. or less has been proposed as a base polymer for pressure-sensitive adhesives.
  • Patent Document 4 an acrylic block copolymer is synthesized by performing an ester exchange reaction in the presence of an acid on a polymer synthesized by a char-on polymerization method, and the block copolymer is tackified.
  • a pressure-sensitive adhesive composition made of a resin has been proposed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2-103277
  • Patent Document 2 JP-A-11-302617
  • Patent Document 3 Japanese Patent Laid-Open No. 11-323072
  • Patent Document 4 U.S. Patent No. 6734256
  • an object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive product having excellent weather resistance and heat resistance.
  • the present inventors have intensively studied to solve the above problems. As a result, it was found that by using a specific acrylic block copolymer, an adhesive composition and an adhesive product excellent in weather resistance and heat resistance could be provided, and the present invention was completed.
  • the present invention provides:
  • At least one polymer block (A) composed of methacrylic acid alkyl ester units (A) 23 to 98% by mass, and alkyl acrylate ester having 6 to 18 carbon atoms
  • At least one polymer block (B) having a potential of 77 to 2% by mass, a weight average molecular weight force of 5,000 to 1,000,000, and a molecular weight force of S1.0 to 1.5 100 parts by weight of an alkynele block copolymer;
  • a tackifier resin having a solubility parameter value of from 8.0 to 11.0;
  • the present invention is an adhesive product having an adhesive layer comprising the above-mentioned adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention contains a specific acrylic block copolymer and a specific tackifier resin, and has excellent weather resistance, heat resistance, water resistance, and transparency. Furthermore, the pressure-sensitive adhesive composition of the present invention can use a tackified resin that has been conventionally restricted in use due to different compatibility, and is intended for use such as the type of adherend and required transparency. Many types of tackifiers can be selected depending on. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive product that can have excellent adhesive performance over a long period of time even under an environment exposed to ultraviolet rays or under high temperature and high humidity usage conditions.
  • the acrylic block copolymer used in the present invention is an at least one polymer block (A) composed of alkyl ester methacrylate units, and an alkyl group having 6 to 18 carbon atoms. It has at least one polymer block (B) having an acrylic acid alkyl ester unit strength.
  • the acrylic block copolymer has a polymer block (A) composed of alkyl methacrylate units of “A”; a polymer block (B) composed of alkyl acrylate units of “B”; General formula;
  • the glass transition temperature of the polymer block (A) increases, and when it is used as a pressure-sensitive adhesive composition, it exhibits high cohesive strength at high temperatures. preferable. Further, in the case of methyl methacrylate, the phase separation between the polymer block (A) and the polymer block (B) becomes clear. preferable. These can be used alone or in combination.
  • Examples of the acrylic acid alkyl ester having an alkyl group having 618 carbon atoms which is a structural unit of the polymer block (B) in the above general formula, include, for example, n-xyl acrylate, cyclohexyl acrylate, acrylic Examples include 2-ethylhexyl acid, n-octyl acrylate, lauryl acrylate, tridecyl acrylate, and stearyl acrylate. Among them, when selected from 2-ethylhexyl acrylate, n-octyl acrylate, and tridecyl acrylate, the adhesive block having a low glass transition temperature of the polymer block (B) is highly adhesive.
  • the glass transition temperature of the polymer block (B) is 50 ° C or lower, and adhesion at low temperatures (10 ° C 40 ° C) is achieved. It is preferable in terms of excellent properties (tack, adhesive strength, etc.).
  • Examples of the block copolymer represented by the above general formula include, for example, polymethyl methacrylate b poly n-hexyl acrylate, polymethyl methacrylate b 2-ethylhexyl acrylate, polymethacrylic acid Methyl b-polyacrylate lauryl, polymethyl methacrylate b Polyacrylate 2-ethylhexyl b Polymethyl methacrylate, polyethyl acrylate 2-ethylhexyl b Polymethyl methacrylate b Polyethyl acrylate 2-ethylhexyl Etc.
  • the polymer block (A) and the polymer block (B) represented by the general formula described above have a small proportion (20% by mass or less in the polymer block) without impairing the effects of the present invention. ),
  • Other monomer units may be included. Examples of the monomer unit that may be contained include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) Acrylic acid 2-aminoethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid tetrahydrofurfuryl, etc.
  • (meth) acrylic acid ester (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride Bull monomers having a carboxyl group such as acid, fumaric acid and (meth) acrylamide; Aromatic bullet monomers such as styrene, ⁇ -methylstyrene and ⁇ -methylstyrene; Conjugated monomers such as butadiene and isoprene; Ethylene, Olefin monomers such as propylene; ⁇ -force prolatate , Rataton-based monomers such as Barerorataton and the like.
  • the method for producing the block copolymer used in the present invention employs a method according to a known method without particular limitation as long as a polymer satisfying the conditions of the present invention concerning the chemical structure is obtained. can do.
  • a method for obtaining a block copolymer having a narrow molecular weight distribution a method in which a monomer as a constituent unit is subjected to living polymerization is employed.
  • living polymerization techniques include a method of polymerizing using an organic rare earth metal complex as a polymerization initiator, and a mineral salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator.
  • Method of polymerizing in the presence of an organic alkali metal examples thereof include a method in which a compound is used as a polymerization initiator and anion polymerization in the presence of an organoaluminum compound, an atom transfer radical polymerization (ATRP) method, and the like.
  • a compound is used as a polymerization initiator and anion polymerization in the presence of an organoaluminum compound, an atom transfer radical polymerization (ATRP) method, and the like.
  • ATRP atom transfer radical polymerization
  • the block copolymer used in the present invention is produced by a method for polymerizing in the presence of an organoaluminum compound.
  • a method for producing the block copolymer used in the present invention a method in which a monomer which is a constituent unit of the block copolymer is directly polymerized is preferable.
  • a method for polymerizing an alkyl (meth) acrylate having an alkyl group capable of transesterification after a polymerization reaction of t-butyl (meth) acrylate, etc. p With any alcohol in the presence of an acid such as toluenesulfonic acid Although it can be synthesized by a transesterification reaction, a hydrolysis reaction that occurs as a side reaction of the transesterification reaction may generate a carboxylic acid group in the polymer, resulting in a decrease in water resistance.
  • Examples of the polymerization method in the presence of the above organoaluminum compound include an organolithium compound and the following general formula:
  • R 1 R 2 and R 3 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.
  • An aralkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent or an N, N disubstituted amino group, or R 1 is As described above, it represents any group, and R 2 and R 3 together have a substituent and may represent a arylene dioxy group.
  • an ether such as dimethyl ether, dimethoxyethane, diethoxyethane, 12 crown 4; Ethynoleamine, N, N, ⁇ ', ⁇ , monotetramethyleneethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ ", ⁇ ,, -pentamethyljetylenetriamine, 1, 1, 4, 7, 10 , 10
  • a method of polymerizing a (meth) acrylic acid ester by further using a nitrogen-containing compound such as hexamethyltriethylenetetramine, pyridine, 2,2′-dipyridyl, etc. can be employed.
  • Examples of the organic lithium compound include methyllithium, ethyllithium, ⁇ -propyl lithium, isopropyllithium, ⁇ -butynolethium, sec butynolelithium, isobutyllithium, tert-butyllithium, and n pentyllithium. , N-hexyllithium, tetramethylenedilithium, pentamethylenedilithium, hexamethylenedilithium, etc., alkyllithium and alkyldilithium; phenol lithium, mtrilyllithium, ptrilyllithium, xylyllithium, lithium naphthalene, etc.
  • organoaluminum compounds represented by the above general formula include, for example, trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, tri-s-butyl aluminum, tri-t-butyl aluminum, triisobutyl.
  • organoaluminum compounds isobutylbis (2,6 di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6 di-tert-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-) 6-tert butylphenoxy)] aluminum isotonic This is particularly preferred because it is easy to handle and allows the polymerization of the acrylate ester to proceed without deactivation under relatively mild temperature conditions. These may be used alone or in combination of two or more.
  • the overall weight average molecular weight (Mw) of the acrylic block copolymer used in the present invention is 5,000 to 1,000,000.
  • Mw weight average molecular weight
  • the ratio (MwZMn) of the total weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic block copolymer used in the present invention is 1.0 to 1.5.
  • a pressure-sensitive adhesive composition it is preferably 1.0 to 1.4, more preferably 1.0 to 1.3, from the viewpoint of high cohesive strength at high temperatures.
  • the mass ratio of all the polymer blocks (A) and all the polymer blocks (B) in the acrylic block copolymer used in the present invention is excellent when a pressure-sensitive adhesive composition is used. From the point that it is possible to supply a block copolymer and a pressure-sensitive adhesive using the block copolymer in a form that has adhesiveness and is easy to handle, B) It is more preferable that the polymer block (A) is 30 to 70% by mass and the polymer block (B) 70 to 30% by mass is preferably 77 to 2% by mass! /. When the mass ratio of the polymer block (B) is less than 2%, it is preferable that the pressure-sensitive adhesive composition has low adhesiveness! / ⁇ .
  • the block copolymer becomes a bale-like product, which is handled in the production of the block copolymer and an adhesive using the block copolymer. It becomes difficult.
  • the block copolymer used in the present invention can be processed into a form that is easy to handle. For example, by using a device in which an underwater cutter or a center hot cutter device is connected to a twin-screw extruder. Process and provide polymer in pellet form Is possible. Moreover, after cooling the strand which also produces the twin-screw extruder power, it can be cut with a strand cutter to obtain pellets. Polymers that are in the form of these pellets can be quantitatively fed by a pellet feeder and can increase the production efficiency of adhesives and adhesive products.
  • the pressure-sensitive adhesive composition of the present invention is mixed with a tackifier resin, it is easy to adjust the tack, the adhesive force, and the holding force.
  • a tackifier resin include natural resin such as rosin resin and terpene resin; petroleum resin, hydrogenated (hereinafter sometimes referred to as “hydrogenated”) petroleum resin, styrene resin Examples thereof include synthetic resins such as fat, coumarone indene resin, phenol resin, and xylene resin.
  • rosin-based rosin examples include rosins such as gum rosin, tall oil rosin and wood rosin; modified rosins such as hydrogenated rosin, disproportionated rosin and polymerized rosin; glycerin esters of these rosins and modified rosins, Examples thereof include rosin esters such as pentaerythritol ester.
  • terpene resin examples include terpene resin mainly composed of a-vinene, j8-vinene, dipentene, aromatic modified terpene resin, hydrogenated terpene resin, terpene phenol resin, etc. Can be given.
  • hydrogenated petroleum resin examples include, for example, (hydrogenated) aliphatic (C) petroleum resin, (hydrogenated)
  • Examples include pentagen-based petroleum resin and alicyclic saturated hydrocarbon resin.
  • styrene resin examples include poly ⁇ -methyl styrene, ⁇ -methyl styrene styrene copolymer, styrene monomer ⁇ ⁇ ⁇ ⁇ aliphatic monomer copolymer, styrene monomer ⁇ ⁇ -methyl styrene ⁇ aliphatic monomer Copolymers, styrene monomer copolymers, styrene monomers, and aromatic monomer copolymers.
  • tackifying resins terpene resin, rosin resin, (hydrogenated) petroleum resin, and styrene resin are particularly preferable because they exhibit high adhesive strength. From the viewpoint of excellent transparency, (hydrogenated) petroleum resin and styrene-based resin are more preferable. These may be used alone or in combination of two or more.
  • the softening point of the tackifying resin is preferably 50 ° C. to 150 ° C. from the viewpoint of developing high adhesive strength.
  • the solubility parameter value of the tackifying resin that can be used in the present invention is a viewpoint power that achieves both adhesive properties and high water resistance as an adhesive composition 8.0 to: L 1.0, and 8.0. -10. 4 is preferred 8.5 to 9.4 is more preferred.
  • a method for determining the solubility parameter value of the tackifying resin for example, a method of calculating from physical characteristics such as heat of evaporation, refractive index, Kauri-butanol number, surface tension, dipole efficiency, Fedors' formula, Examples include the method of calculating chemical yarns using the Small equation, the Hoy equation, etc., the method of measuring by a solubility test in a solvent whose solubility parameter value is known, and the cloud point titration method. In particular, a method of actual measurement by a point solubility test that is applicable even when the chemical structure is not single or unknown is preferable.
  • the tackifier resin when the tackifier resin is soluble in a solvent having a solubility parameter value of X, insoluble in a solvent having a solubility parameter value of power, and Y is a value greater than X.
  • the solubility parameter value of the tackifier resin can be determined by rounding off the second decimal place, where X is Y.
  • a known literature value can be adopted as the solubility parameter value of the solvent to be used. For example, the value described in Journal of Paint Technology, 42 (541), pages 76-118 (1970) is adopted. be able to.
  • the solvent to be used is preferably selected from hydrocarbon compounds, aromatic compounds, ester compounds, ketone compounds, nitrile compounds, alcohols, amines, etc.
  • a solvent containing a functional group having an active proton is not preferable because the solubility is changed by hydrogen bonding.
  • the compounding amount of the tackifying resin can be appropriately selected according to the use of the pressure-sensitive adhesive, the type of adherend, and the like. From the viewpoint of improving the adhesive force and improving the coatability.
  • the agent composition it is 1 part by mass or more and 400 parts by mass or less, and preferably 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the acryl-based block copolymer.
  • the pressure-sensitive adhesive composition of the present invention may contain various plasticizers as required!
  • plasticizers include, for example, phthalates such as dibutino phthalate, di n-octino phthalate, bis 2-ethylhexyl phthalate, di n-decyl phthalate, diisodecyl phthalate, bis 2 —Adipate esters such as ethylhexyl adipate and di n-octyl adipate, bis 2-ethylhexyl sebacate, di n-butyl sebacate Sebacic acid esters such as bis-2-ethylhexylazelate, etc.
  • Fatty acid esters such as azelineic acid esters such as bis-2-ethylhexylase; Norafins such as chlorinated paraffin; Glycols such as polypropylene glycol; Epoxidized soybean oil, Epoxy Epoxy polymer plasticizers such as modified amide oil; Phosphate esters such as trioctyl phosphate and triphenyl phosphate; Phosphites such as triphenyl phosphite; Adipic acid and 1,3-butylene glyco —Ester oligomers such as esters with poly (ethylene); acrylic oligomers such as poly (meth) acrylic acid n -butyl and poly (meth) acrylic acid 2-ethylhexyl; polybutene; polyisobutylene; polyisoprene; process Oils, such as naphthenic oils, which can be used alone or in a mixture I can.
  • the amount of plasticizer used is generally 80% by mass or less of the plasticizer in the
  • the pressure-sensitive adhesive composition of the present invention may contain various additives as necessary.
  • additives include antioxidants and ultraviolet absorbers for further improving weather resistance, heat resistance, and acid resistance; inorganic powders such as calcium carbonate, titanium oxide, my strength, and talc.
  • inorganic powders such as calcium carbonate, titanium oxide, my strength, and talc.
  • fillers include fibrous fillers such as glass fibers and organic reinforcing fibers.
  • each component is usually used by using a known mixing or kneading apparatus such as a kneader-louder, an extruder, a mixing roll, a Banbury mixer, or the like. It can be produced by mixing at a temperature in the range of 100 ° C to 250 ° C. Alternatively, the components may be prepared by dissolving and mixing each component in an organic solvent and then distilling off the organic solvent.
  • a known mixing or kneading apparatus such as a kneader-louder, an extruder, a mixing roll, a Banbury mixer, or the like. It can be produced by mixing at a temperature in the range of 100 ° C to 250 ° C.
  • the components may be prepared by dissolving and mixing each component in an organic solvent and then distilling off the organic solvent.
  • An adhesive product obtained by forming an adhesive layer comprising the adhesive composition of the present invention on a substrate includes an adhesive sheet (including an adhesive film), an adhesive tape, a pressure sensitive tape, and masking.
  • an adhesive sheet including an adhesive film
  • an adhesive tape including an adhesive film
  • an adhesive tape including an adhesive film
  • a pressure sensitive tape and masking.
  • Examples include tapes, electrical insulating tapes, laminating films, medical poultices, decorative adhesive sheets, and adhesive optical films.
  • the pressure-sensitive adhesive composition of the present invention When the pressure-sensitive adhesive composition of the present invention is in a molten state, it has a film shape, a sheet shape, a tape shape or other desired shape, paper, paper board, cellophane, organic polymer film 'sheet, cloth, wood,
  • the adhesive product can be produced by coating on a substrate such as metal and then cooling.
  • the pressure-sensitive adhesive composition of the present invention can be dissolved in a solvent such as toluene to form a solution and used as a solvent-type pressure-sensitive adhesive. You may manufacture said adhesive product by making it emit.
  • the reaction solution lg was collected in a sampling container containing a small amount of methanol for analysis.
  • the conversion rate of methyl methacrylate was 100%.
  • the internal temperature of the polymerization solution was cooled to ⁇ 30 ° C., and 234 g of 2-ethylhexyl acrylate was added dropwise over 2 hours.
  • 1 g of the reaction solution was collected in a sampling container containing a small amount of methanol.
  • the conversion rate of 2-ethylhexyl acrylate was 100%.
  • the finally obtained polymer 1 was polymethyl methacrylate-b polyacrylic acid 2- Tylhexyl b
  • Polymethylmethacrylate triblock copolymer Mn of polymethyl methacrylate block taken during the reaction is 6,300, Mw is 7,030, MwZMn is 1 Mn of polymethyl methacrylate-b polyhexyl acrylate collected during the reaction is 42,300, Mw is 43,800, and Mw ZMn is 1.04.
  • the Mn of the finally obtained triblock body was 48,000, Mw was 50, 200, and MwZMn was 1.05.
  • the reaction solution lg was collected in a sampling container containing a small amount of methanol for analysis.
  • the conversion rate of methyl methacrylate was 100%.
  • the internal temperature of the polymerization solution was cooled to ⁇ 30 ° C., and 312.8 g of 2-ethylhexyl acrylate was added dropwise over 2 hours.
  • the reaction solution lg was collected in a sampling container containing a small amount of methanol.
  • the conversion rate of 2-ethylhexyl acrylate was 100%.
  • the finally obtained polymer 1 was polymethyl methacrylate-b polyacrylic acid 2- Tylhexyl b
  • Polymethyl methacrylate triblock copolymer Mn of polymethyl methacrylate block taken during the reaction is 9,850, Mw is 11,000, and MwZMn is 1.
  • Mn of polymethyl methacrylate-b-polyethylhexyl acrylate collected during the reaction was 51,000, Mw was 51,900, MwZMn was 1.02, and the final The Mn of the triblock obtained as a result was 59,000, Mw was 60,600, and MwZMn was 1.03.
  • a 3 L three-necked flask was fitted with a three-way cock, and the inside was replaced with nitrogen.
  • 1040 g of toluene, 1, 1, 4, 7, 10, 10 2.45 g of hexamethylpolyethyleneteramine, isobutyl bis (2, 6 Di-t-butyl-4-methylphenoxy) aluminum solution containing 35.5 mmol of toluene 52.9 g was added, and then, butyllithium 7. 8. 87 mmol of cyclohexane and n-hexane mixed solution 5. 20g was added. Subsequently, 71.8 g of methyl methacrylate (1) was added thereto.
  • the reaction solution was initially colored yellow and became colorless after stirring for 60 minutes at room temperature. At this point, the reaction solution lg was collected in a sampling container containing a small amount of methanol for analysis. As a result of GC measurement of the reaction solution, the conversion rate of methyl metatalate was 100%. Subsequently, the internal temperature of the polymerization solution was cooled to ⁇ 30 ° C., and 468 g of 2-ethylhexyl acrylate was added dropwise over 3 hours. After completion of dropping, the reaction solution lg was collected in a sampling container containing a small amount of methanol. As a result of GC measurement of the reaction solution, the conversion rate of 2-ethylhexyl acrylate was 100%.
  • the finally obtained polymer 4 was polymethyl methacrylate-b-polyacrylic acid n- Petroleum b—polymethyl methacrylate triblock copolymer.
  • Mn of polymethyl methacrylate block collected during the reaction is 6,700, Mw is 7,300, Mw / M n
  • Mn of polymethyl methacrylate-b-polyacrylate n-butyl collected during the reaction is 58,000, Mw is 61,000, and Mw / Mn3 ⁇ 4l.05.
  • the resulting triblock Mn was 64,900, Mw was 68,100, and Mw ZMn was 1.03.
  • the finally obtained polymer 5 was polymethyl methacrylate-b-polyacrylic acid n- Petroleum b—polymethyl methacrylate triblock copolymer.
  • Mn of the polymethyl methacrylate block collected during the reaction is 9,720, Mw is 10,400, MwZ Mn is 1 Mn of poly (methyl methacrylate) -b-polytalylate n-butyl collected during the reaction was 61, 100, Mw was 67, 200, and Mw / Mn was 1.10.
  • the Mn of the finally obtained triblock body was 69,600, Mw was 76,900, and MwZMn was 1.11.
  • the proportion of each block is polymethyl methacrylate (14.9 mass. / 0 ) —b—poly (n-butyl acrylate) (70.2 mass%) — b—polymethyl methacrylate (14.9 mass%) It turned out to be.
  • the finally obtained polymer 6 was polymethyl methacrylate-b-polyacrylic acid n- Petroleum b—polymethyl methacrylate triblock copolymer.
  • Mn of polymethyl methacrylate block collected during the reaction is 7,600, Mw is 8,800, and MwZMn is 1 15 and poly (methyl methacrylate) b-polyacrylic acid n-butynole collected in the middle of reaction 61, 400, Mwi 69, 100, Mw / Mni 1. 13.
  • the resulting triblock Mn was 64,000, Mw was 76,100, and Mw ZMn was 1.19.
  • the 2 kg roller was applied by reciprocating twice at a speed of 10 mm / min, and the evaluation was performed after storing at room temperature for 24 hours.
  • the prepared adhesive tape was affixed to a stainless steel (SU S304) plate at 25mm x 25mm, and then the sample was stored for 24 hours at room temperature, then the load lkg was suspended at 120 ° C and the drop time was determined. It was.
  • the prepared adhesive tape is affixed to a stainless steel (SUS304) plate at 25 mm x 25 mm, and then the sample is stored at room temperature for 24 hours, then a load of 500 g is suspended at a temperature of 80 ° C and a humidity of 90% for 94 hours. The length of the later shift was measured.
  • SUS304 stainless steel
  • the prepared adhesive tape with a width of 25 mm and a length of 100 mm was affixed to a stainless steel (SUS304) plate and a polyethylene sheet of about 1 mm thickness, and then the sample was stored at room temperature for 24 hours. Measurement was performed by peeling in the direction of 180 ° at a speed of 300 mm Z at ° C.
  • SAFT shear bond failure temperature
  • the block copolymer and tackifier resin having the blending mass ratio shown in Table 2 were dissolved in toluene to prepare a 40% by weight concentration adhesive toluene solution, and a cast sheet having a thickness of about 1 mm was prepared. From the transparency of the obtained cast sheet and the presence or absence of the phenomenon of tensile whitening, ⁇ : transparent and without tensile whitening;
  • ⁇ Slightly transparent and with tensile whitening
  • ⁇ Opaque and tensile whitening
  • Example 13 the composition of Example 13, Example 49, and Example 10 correspond to the composition of Comparative Example 13, Comparative Example 49, and Comparative Example 10, respectively.
  • Examples 1 to 3 [Reference Examples 1 and 2]
  • the pressure-sensitive adhesive composition containing block copolymer 3 and blended with tackifier resin having a low solubility parameter value in the examples was evaluated.
  • Table 6 shows the composition and evaluation results.
  • Block copolymer 6 100 100 100 100 Adhesive composition
  • the pressure-sensitive adhesive of the present invention is particularly excellent in cohesive force and transparency at high temperatures.
  • a pressure-sensitive adhesive having a good balance between adhesive strength and adhesive strength can be obtained.
  • Example 2 and Example 3 are more adhesive than Comparative Example 2 and Comparative Example 3 of the corresponding composition shown in Table 3, and are transparent and have high holding power at high temperatures. You can see that it has.
  • the block copolymer used in the pressure-sensitive adhesive of the present invention is compatible with many types of tackifying resins.
  • adhesive properties such as adhesive strength and cohesive strength, Facilitates response to various plant requirements ranging from odor and raw material costs.
  • the pressure-sensitive adhesive composition of the present invention has high cohesive strength even under high humidity, and the transparency is impaired even under conditions immersed in water. This indicates that the water resistance is excellent.
  • the pressure-sensitive adhesive composition of the present invention contains a specific acrylic block copolymer and has excellent weather resistance, heat resistance, water resistance, and transparency.
  • INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive product that can have excellent pressure-sensitive adhesive performance over a long period of time even under an environment exposed to ultraviolet rays or under high temperature and high humidity usage conditions.
  • the specific acrylic block copolymer used in the present invention has a form excellent in handling properties such as pellets. It is possible provided in state, c which can increase the production efficiency of the adhesive

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition adhésive ayant d'excellentes résistance aux agents atmosphériques, résistance à la chaleur et résistance à l'eau ; et un produit adhésif. L'invention concerne précisément une composition adhésive contenant un copolymère acrylique en blocs et une résine conférant de l'adhésivité ayant une valeur de paramètre de solubilité de 8-11. Le copolymère acrylique en blocs contient 23-98 % en poids d'au moins un bloc de polymère (A) composé d'une unité méthacrylate d'alkyle telle qu'une unité méthacrylate de méthyle et 77-2 % en poids d'au moins un bloc de polymère (B) composé d'une unité acrylate d'alkyle telle qu'une unité acrylate d'octyle, le groupe alkyle ayant 6-18 atomes de carbone, tout en ayant un poids moléculaire moyen en poids de 5 000-1 000 000 et une distribution du poids moléculaire de 1,0-1,5. L'invention concerne également spécifiquement un produit adhésif ayant une couche adhésive composée d'une telle composition adhésive.
PCT/JP2006/317767 2005-09-07 2006-09-07 Composition adhésive acrylique et produit adhésif WO2007029783A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2007118592A (ja) * 2005-09-29 2007-05-17 Kokuyo S&T Co Ltd 製本用感圧性接着剤およびそれを用いる製本方法
WO2011048802A1 (fr) 2009-10-23 2011-04-28 クラレメディカル株式会社 Composition polymérisable et matériau dentaire
JP2012077177A (ja) * 2010-09-30 2012-04-19 Dainippon Printing Co Ltd 成形品加飾用粘着シート
WO2013162056A1 (fr) 2012-04-27 2013-10-31 Kuraray Co., Ltd. Composition adhésive acrylique sensible à la pression et produits adhésifs sensibles à la pression associés
US8637595B2 (en) 2008-12-30 2014-01-28 3M Innovative Properties Company Acrylic block copolymers for aerosols and aerosol adhesives
EP2688969A2 (fr) * 2011-03-24 2014-01-29 3M Innovative Properties Company Adhésifs ignifuges
JP2015010142A (ja) * 2013-06-27 2015-01-19 積水フーラー株式会社 粘着剤組成物
WO2015111646A1 (fr) * 2014-01-24 2015-07-30 ニチバン株式会社 Composition adhésive acrylique sensible à la pression et bande adhésive sensible à la pression
JP2015536371A (ja) * 2012-11-02 2015-12-21 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 電子デバイスのための成形およびオーバーモールド組成物
JP2016044203A (ja) * 2014-08-20 2016-04-04 株式会社クラレ アクリル系粘着剤組成物及び粘着製品
WO2016140285A1 (fr) * 2015-03-03 2016-09-09 株式会社クラレ Film décoratif
JP2016183275A (ja) * 2015-03-26 2016-10-20 積水化学工業株式会社 粘着剤組成物及び粘着テープ
WO2017168869A1 (fr) * 2016-03-30 2017-10-05 住友理工株式会社 Composition adhésive autocollante pour film optique et film optique
JP2017190463A (ja) * 2017-07-21 2017-10-19 株式会社クラレ 粘接着剤組成物
JP2019189871A (ja) * 2015-09-29 2019-10-31 協立化学産業株式会社 相溶組成物、接着剤組成物、複合構造物並びに複合構造物の製造方法及び解体方法
WO2021172398A1 (fr) 2020-02-28 2021-09-02 株式会社クラレ Copolymère acrylique tribloc à poids moléculaire élevé et composition adhésive sensible à la pression le contenant
CN114929826A (zh) * 2020-01-21 2022-08-19 Dic株式会社 粘合带
CN114945642A (zh) * 2020-01-21 2022-08-26 Dic株式会社 粘合带

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Publication number Priority date Publication date Assignee Title
JP2007118592A (ja) * 2005-09-29 2007-05-17 Kokuyo S&T Co Ltd 製本用感圧性接着剤およびそれを用いる製本方法
US8637595B2 (en) 2008-12-30 2014-01-28 3M Innovative Properties Company Acrylic block copolymers for aerosols and aerosol adhesives
US8993663B2 (en) 2008-12-30 2015-03-31 3M Innovative Properties Company Acrylic block copolymers for aerosols and aerosol adhesives
WO2011048802A1 (fr) 2009-10-23 2011-04-28 クラレメディカル株式会社 Composition polymérisable et matériau dentaire
US9333148B2 (en) 2009-10-23 2016-05-10 Kuraray Noritake Dental Inc. Polymerizable composition and dental material
EP2918258A1 (fr) 2009-10-23 2015-09-16 Kuraray Noritake Dental Inc. Composition polymérisable et matériau dentaire
JP2012077177A (ja) * 2010-09-30 2012-04-19 Dainippon Printing Co Ltd 成形品加飾用粘着シート
EP2688969A4 (fr) * 2011-03-24 2014-11-05 3M Innovative Properties Co Adhésifs ignifuges
JP2017206700A (ja) * 2011-03-24 2017-11-24 スリーエム イノベイティブ プロパティズ カンパニー 難燃接着剤
EP2688969A2 (fr) * 2011-03-24 2014-01-29 3M Innovative Properties Company Adhésifs ignifuges
KR20150003780A (ko) 2012-04-27 2015-01-09 가부시키가이샤 구라레 아크릴계 점착제 조성물 및 점착 제품
US10519347B2 (en) 2012-04-27 2019-12-31 Kuraray Co., Ltd. Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive products
US9963617B2 (en) 2012-04-27 2018-05-08 Kuraray Co., Ltd. Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive products
WO2013162056A1 (fr) 2012-04-27 2013-10-31 Kuraray Co., Ltd. Composition adhésive acrylique sensible à la pression et produits adhésifs sensibles à la pression associés
JP2015536371A (ja) * 2012-11-02 2015-12-21 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 電子デバイスのための成形およびオーバーモールド組成物
JP2015010142A (ja) * 2013-06-27 2015-01-19 積水フーラー株式会社 粘着剤組成物
WO2015111646A1 (fr) * 2014-01-24 2015-07-30 ニチバン株式会社 Composition adhésive acrylique sensible à la pression et bande adhésive sensible à la pression
KR20160113159A (ko) * 2014-01-24 2016-09-28 니찌방 가부시기가이샤 아크릴계 점착제 조성물 및 점착 테이프
JPWO2015111646A1 (ja) * 2014-01-24 2017-03-23 ニチバン株式会社 アクリル系粘着剤組成物及び粘着テープ
KR102228806B1 (ko) 2014-01-24 2021-03-18 니찌방 가부시기가이샤 아크릴계 점착제 조성물 및 점착 테이프
CN105829479A (zh) * 2014-01-24 2016-08-03 日绊株式会社 丙烯酸系粘合剂组合物及粘合带
JP2016044203A (ja) * 2014-08-20 2016-04-04 株式会社クラレ アクリル系粘着剤組成物及び粘着製品
WO2016140285A1 (fr) * 2015-03-03 2016-09-09 株式会社クラレ Film décoratif
JPWO2016140285A1 (ja) * 2015-03-03 2018-02-15 株式会社クラレ 加飾フィルム
JP2016183275A (ja) * 2015-03-26 2016-10-20 積水化学工業株式会社 粘着剤組成物及び粘着テープ
JP2019189871A (ja) * 2015-09-29 2019-10-31 協立化学産業株式会社 相溶組成物、接着剤組成物、複合構造物並びに複合構造物の製造方法及び解体方法
WO2017168869A1 (fr) * 2016-03-30 2017-10-05 住友理工株式会社 Composition adhésive autocollante pour film optique et film optique
JP2017190463A (ja) * 2017-07-21 2017-10-19 株式会社クラレ 粘接着剤組成物
CN114929826A (zh) * 2020-01-21 2022-08-19 Dic株式会社 粘合带
CN114945642A (zh) * 2020-01-21 2022-08-26 Dic株式会社 粘合带
WO2021172398A1 (fr) 2020-02-28 2021-09-02 株式会社クラレ Copolymère acrylique tribloc à poids moléculaire élevé et composition adhésive sensible à la pression le contenant
KR20220149663A (ko) 2020-02-28 2022-11-08 주식회사 쿠라레 고분자량 아크릴계 트리블록 공중합체 및 그것을 포함하는 점접착제 조성물

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