WO2021145253A1 - Résine de polyoléfine chlorée, amorce, liant, adhésif, stratifié, matériau d'emballage alimentaire utilisant ladite résine de polyoléfine chlorée et son procédé de fabrication - Google Patents

Résine de polyoléfine chlorée, amorce, liant, adhésif, stratifié, matériau d'emballage alimentaire utilisant ladite résine de polyoléfine chlorée et son procédé de fabrication Download PDF

Info

Publication number
WO2021145253A1
WO2021145253A1 PCT/JP2021/000211 JP2021000211W WO2021145253A1 WO 2021145253 A1 WO2021145253 A1 WO 2021145253A1 JP 2021000211 W JP2021000211 W JP 2021000211W WO 2021145253 A1 WO2021145253 A1 WO 2021145253A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin resin
chlorinated polyolefin
polyolefin
acid
chlorinated
Prior art date
Application number
PCT/JP2021/000211
Other languages
English (en)
Japanese (ja)
Inventor
実 矢田
高本　直輔
Original Assignee
日本製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to CN202180009355.5A priority Critical patent/CN114945603A/zh
Priority to JP2021522559A priority patent/JP6940722B1/ja
Publication of WO2021145253A1 publication Critical patent/WO2021145253A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the present invention relates to a chlorinated polyolefin resin, a primer, a binder, an adhesive, a laminate, a food packaging material using the chlorinated polyolefin resin, and a method for producing the same.
  • Chlorinated polyolefin is generally produced by dissolving polyolefin in an organic solvent and then performing a chlorination addition reaction (see, for example, Patent Document 1). During the chlorination reaction, chlorination of the organic solvent also occurs, producing a large amount of by-products. Therefore, in this step, a chlorine-based solvent (chlorine-based low molecular weight compound) such as chloroform, which is particularly unlikely to cause a chlorine addition reaction, is used among the organic solvents. The chlorine-based solvent used in the chlorine addition reaction step is effectively removed and recovered from the chlorinated polyolefin by vacuum distillation or the like. Therefore, the chlorinated polyolefin, which is a product, contains almost no chlorinated solvent.
  • a chlorine-based solvent chlorine-based low molecular weight compound
  • An object of the present invention is to provide a chlorinated polyolefin resin having excellent adhesiveness in which chlorine-based low molecular weight compounds are not detected by gas chromatogram analysis under predetermined conditions.
  • a chlorinated polyolefin resin containing 1 to 45% by weight of chlorine A chlorinated polyolefin resin characterized in that no peak derived from a chlorine-based low molecular weight compound appearing in a retention time of 4 to 7 minutes is detected when gas chromatogram analysis is performed under the following conditions.
  • ⁇ Gas chromatogram analysis conditions Gas chromatograph GC-2010plus Tracella (using BID detector) manufactured by Shimadzu Corporation, carrier gas: helium (linear flow velocity: 40 cm / sec), capillary column (Rtx-624 manufactured by Restek (inner diameter: 0.32 mm, film thickness: 1.8 ⁇ m)) Length: 30 m), sample injection temperature (injection temperature): 160 ° C, column temperature: 60 ° C), and the chlorinated polyolefin resin was adjusted to a concentration of 5% by weight in a p-xylene solvent in the device. And analyze it.
  • the raw material composition contains at least the polyolefin A and the acid-modified product of the polyolefin B, or at least the acid-modified product of the polyolefin A and the acid-modified product of the polyolefin B
  • the chlorinated polyolefin resin [4] The chlorinated polyolefin resin according to any one of [1] to [3], wherein the melt viscosity at 80 ° C. is less than 100,000 mPa ⁇ s.
  • a binder for paints which comprises the chlorinated polyolefin resin according to any one of [1] to [5].
  • a binder for ink containing the chlorinated polyolefin resin according to any one of [1] to [5].
  • having fluidity at 40 ° C. or lower means that the viscosity at 40 ° C. measured by a cylindrical rotary viscometer or a cone plate type viscometer is 100,000 mPa or less. To say. Further, the notation “AA to BB%” indicates AA% or more and BB% or less.
  • the chlorinated polyolefin resin of the present invention comprises a resin obtained by chlorinating polyolefin A having fluidity at 40 ° C. or lower or an acid-modified product thereof, and polyolefin B having a melting point of more than 40 ° C. and 150 ° C. or lower thereof. Includes a resin obtained by chlorinating an acid-modified product.
  • the chlorine content is 1 to 45% by weight.
  • the chlorinated polyolefin resin of the present invention comprises polyolefin A having fluidity at 40 ° C. or lower or an acid-modified product thereof, and polyolefin B having a melting point of more than 40 ° C. and 150 ° C. or lower or an acid-modified product thereof. It is obtained by chlorinating the raw material composition containing at least the raw material in the absence of an organic solvent. The chlorine content is 1 to 45% by weight.
  • the chlorinated polyolefin resin of the present invention can be chlorinated in the absence of an organic solvent. Further, the chlorinated polyolefin resin of the present invention can be a chlorinated polyolefin resin that can be used for ink applications and the like because the raw material composition before chlorination contains polyolefin B or an acid-modified product thereof.
  • the chlorinated polyolefin resin of the present invention may be a chlorinated polyolefin resin obtained through an acid modification treatment (hereinafter, referred to as "acid-modified chlorinated polyolefin resin" for convenience).
  • acid-modified chlorinated polyolefin resin obtained through an acid modification treatment
  • the polarity of the chlorinated polyolefin resin obtained can be adjusted by the amount of acid modification (hereinafter, also referred to as “graft weight”). Therefore, the chlorinated polyolefin resin of the present invention can be applied to adherends having various polarities.
  • the acid modification treatment may be carried out independently for (1) polyolefin A and / or polyolefin B, respectively, and (2) a mixture of polyolefin A and polyolefin B before the chlorination treatment (hereinafter, for convenience, "polyolefin mixture"). It may be carried out for (3) the chlorinated polyolefin resin after the chlorination treatment.
  • the acid denaturation treatment may be any one of (1) to (3), and may be a combination of (1) and (2) or a combination of (1) and (3). Above all, the acid denaturation treatment is preferably the treatment of (1) or (2), and in particular, the treatment performed on polyolefin B alone or a mixture of polyolefins.
  • the raw material composition containing the acid-modified polyolefin mixture or the acid-modified polyolefin B is also referred to as "acid-modified raw material composition".
  • the acid denaturation treatment will be described below.
  • the method of acid denaturation treatment is not particularly limited, and a known method can be used.
  • a solution method in which polyolefin B or a polyolefin mixture, ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof is dissolved by heating in a solvent such as toluene and a radical generator is added; using a Banbury mixer, kneader, extruder or the like.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, and the like.
  • Examples include maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid ester. Of these, maleic anhydride is preferred.
  • the ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof may be any one or more compounds selected from the ⁇ , ⁇ -unsaturated carboxylic acid and its derivatives, and one or more ⁇ , ⁇ -unsaturated carboxylic acids. And a combination of one or more derivatives thereof, a combination of two or more kinds of ⁇ , ⁇ -unsaturated carboxylic acid, and a combination of two or more kinds of derivatives of ⁇ , ⁇ -unsaturated carboxylic acid.
  • the amount of ⁇ , ⁇ -unsaturated carboxylic acid or its derivative introduced is preferably 0.1 to 10% by weight, preferably 0.5 to 5% by weight, when the acid-modified raw material composition is 100% by weight. % Is more preferable.
  • the graft weight is 0.1% by weight or more, the adhesiveness of the obtained acid-modified chlorinated polyolefin resin to a material such as a metal adherend can be maintained.
  • the graft weight is 10% by weight or less, it is possible to prevent the generation of unreacted graft products, and it is possible to obtain sufficient adhesiveness to the resin adherend.
  • the amount of ⁇ , ⁇ -unsaturated carboxylic acid or its derivative introduced is a value measured by the alkaline titration method.
  • the radical generator can be appropriately selected from known radical generators.
  • organic peroxide compounds are preferable.
  • the amount of the radical generator added is preferably 1 to 100% by weight, preferably 10 to 100% by weight, based on the total (weight) of the amount of ⁇ , ⁇ -unsaturated carboxylic acid or its derivative added and the amount of (meth) acrylic acid ester added. 50% by weight is more preferable. When it is 1% by weight or more, sufficient graft efficiency can be maintained. When it is 100% by weight or less, it is possible to prevent a decrease in the weight average molecular weight of the acid-modified raw material composition.
  • the chlorinated polyolefin resin of the present invention is a raw material composition containing at least a polyolefin A having fluidity at 40 ° C. or lower or an acid-modified product thereof, and a polyolefin B having a melting point of more than 40 ° C. and 150 ° C. or lower or an acid-modified product thereof.
  • the chlorinated polyolefin resin of the present invention includes a resin obtained by chlorinating polyolefin A having fluidity at 40 ° C. or lower or an acid-modified product thereof, and polyolefin B having a melting point of more than 40 ° C. and 150 ° C. or lower or an acid-modified product thereof.
  • the adhesiveness to the non-polar resin base material and the compatibility with other components can be improved.
  • polyolefin A having fluidity at 40 ° C. or lower or an acid-modified product thereof contained in the raw material composition by blowing chlorine gas into the raw material composition and having a melting point of more than 40 ° C. and 150 ° C. or lower.
  • a method of introducing a chlorine atom into each of the polyolefin B or the acid-modified product thereof can be mentioned.
  • a chlorinating solvent such as chloroform or methylene chloride or another organic solvent when blowing chlorine gas.
  • Chlorine gas can be blown in under the irradiation of ultraviolet rays, and can be performed in the presence or absence of the radical reaction initiator.
  • the pressure at which chlorine gas is blown is not limited and may be normal pressure or pressurized.
  • the temperature at which chlorine gas is blown is not particularly limited, but is usually 50 to 140 ° C.
  • organic peroxide compounds and azonitriles such as 2,2-azobisisobutyronitrile can be used.
  • the details of the organic peroxide compound will be described later.
  • the chlorinated polyolefin resin of the present invention can be obtained by introducing a chlorine atom into a polyolefin mixture or an acid-modified product thereof, a mixture of an acid-modified product of polyolefin A and polyolefin B, or a mixture of an acid-modified product of polyolefin A and polyolefin B. Can be done.
  • the chlorine content of the chlorinated polyolefin resin of the present invention is 1 to 45% by mass, preferably 10 to 45% by mass, and more preferably 20 to 45% by weight.
  • the polarity of the chlorinated polyolefin resin can be adjusted in a certain range. Therefore, the compatibility with other resins in the coating material is improved, and sufficient adhesiveness to a non-polar substrate such as a polyolefin substrate can be obtained.
  • the chlorine content of the chlorinated polyolefin resin is a value measured based on JIS-K7229.
  • the chlorine content varies depending on the type of polyolefin resin, reaction scale, reaction device, and other factors. Therefore, the chlorine content can be adjusted while monitoring the amount of chlorine blown and the time.
  • organic peroxide compound examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroper.
  • Oxide 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoctate can be mentioned. Of these, di-t-butyl peroxide, dicumyl peroxide, and dilauryl peroxide are preferable.
  • the radical generator may be a single radical generator or a combination of a plurality of radical generators.
  • the lower limit of the weight average molecular weight of the chlorinated polyolefin resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 8,000 or more. When it is 5,000 or more, the resin has a cohesive force and can exhibit adhesion to an adherend.
  • the upper limit is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 40,000 or less. When it is 100,000 or less, it has compatibility with other resins and solubility in a solvent, and can be applied to paints, inks and the like.
  • the weight average molecular weight of the chlorinated polyolefin resin is preferably 5,000 to 100,000, more preferably 7,000 to 60,000, and even more preferably 8,000 to 40,000.
  • the weight average molecular weight is a value obtained from a standard polystyrene calibration curve by a gel permeation chromatography (GPC) method.
  • the chlorinated polyolefin resin of the present invention does not detect a peak derived from a chlorinated low molecular weight compound that appears in the retention time range of 4 to 7 minutes when gas chromatogram analysis is performed under the following conditions.
  • the chlorine-based low molecular weight compound that can be detected under such conditions can be, for example, chloroform or methylene chloride.
  • the chlorinated polyolefin resin of the present invention does not detect a peak derived from a chlorine-based low molecular weight compound appearing in the retention time range of 4 to 7 minutes, it can be distinguished from such a conventional chlorinated polyolefin resin, and chlorine. It can be suitably used as a chlorinated polyolefin resin having extremely little residue of the system solvent and by-products due to chlorination.
  • Polyolefin A is a polyolefin having fluidity at 40 ° C. or lower. By containing the polyolefin A, the melt viscosity during the chlorination reaction can be lowered, and chlorination can be performed without using an organic solvent.
  • a polyolefin having a viscosity at 40 ° C. of 100,000 mPa ⁇ s or less is preferable, and a polyolefin having a viscosity of 60,000 mPa ⁇ s or less is more preferable.
  • the lower limit of the viscosity is not particularly limited, but is usually 100 mPa ⁇ s or more.
  • the viscosity at 40 ° C. is a value measured by a cone plate type viscometer (manufactured by BROOKFIELD, model: CAP200H).
  • Polyolefin A may be any as long as it satisfies the above physical characteristics. Examples thereof include ethylene-propylene copolymers, hydride polybutadienes, ethylene-butene copolymers, ethylene-octene copolymers, propylene-butene copolymers and ⁇ -olefin derivatives.
  • polyolefin A may be used alone or in combination of two or more.
  • Polyolefin B is a polyolefin having a melting point of more than 40 ° C. and 150 ° C. or lower. By containing polyolefin B, it can be a chlorinated polyolefin resin that can be used for ink applications and the like.
  • the melting point is a value measured using a DSC measuring device (eg, "DISCOVERY DSC2500", manufactured by TA Instruments Japan) in accordance with JIS K7121 (1987). More specifically, a sample of about 5 mg is kept in a heat-melted state at 200 ° C. for 10 minutes. The temperature is lowered at a rate of 10 ° C./min, and after reaching -50 ° C., the temperature is kept stable for 5 minutes. After that, it is the melting peak temperature when the temperature is raised to 200 ° C. at 10 ° C./min and melted.
  • a DSC measuring device eg, "DISCOVERY DSC2500", manufactured by TA Instruments Japan
  • polyolefin B a polyolefin having a weight average molecular weight of 8,000 or more and less than 250,000 is preferable, a polyolefin having a weight average molecular weight of 8,000 or more and less than 200,000 is more preferable, and a polyolefin having a weight average molecular weight of 10,000 or more and less than 100,000 is preferable. Is even more preferable.
  • the weight average molecular weight is a value obtained from a standard polystyrene calibration curve by a gel permeation chromatography (GPC) method.
  • Polyolefin B may be any as long as it satisfies the above physical characteristics.
  • polyolefins using a Cheegler-Natta catalyst or a metallocene catalyst as the polymerization catalyst are preferable, and polypropylene resins or propylene and ⁇ -olefins (eg, ethylene, butene, 3) using a Cheegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst are preferable.
  • Polyolefins obtained by copolymerizing are more preferable, propylene-based random copolymers using a metallocene catalyst as a polymerization catalyst are more preferable, and a metallocene catalyst as a polymerization catalyst.
  • Polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, or ethylene-propylene-butene copolymer using the above is even more preferable.
  • the obtained polyolefin has the characteristics that the molecular weight distribution is narrow, the random copolymerizability is excellent, the composition distribution is narrow, and the range of copolymers that can be copolymerized is wide. In addition, these may be commercial products.
  • the propylene-based random copolymer refers to a polyolefin obtained by randomly copolymerizing polypropylene, propylene, and ⁇ -olefin, for example, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, or ethylene. Examples thereof include a propylene-diene copolymer and an ethylene-propylene-butene copolymer.
  • the (co) polymer constituting the polyolefin B may be a single type or a combination of a plurality of (co) polymers.
  • the metallocene catalyst known ones can be used.
  • a catalyst obtained by combining the following components (1) and (2) and, if necessary, the component (3) can be mentioned.
  • the metallocene catalyst is preferably a catalyst obtained by combining the following components (1) and (2), and further, if necessary, the component (3).
  • Component (1) A metallocene complex which is a transition metal compound of Groups 4 to 6 of the Periodic Table having at least one conjugated five-membered ring ligand.
  • Ingredient (2) Ion-exchangeable layered silicate.
  • the structure of the polyolefin may be any of an isotactic structure, an atactic structure, a syndiotactic structure and the like that can be obtained by a normal polymer compound.
  • a polyolefin having an isotactic structure which can be obtained when a metallocene catalyst is used, is preferable in consideration of the adhesion to the polyolefin base material, particularly the adhesion at low temperature drying.
  • the propylene constituent unit content is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more.
  • the adhesiveness (adhesiveness) to the polypropylene base material can be improved.
  • the propylene structural unit content of the polyolefin may be the ratio of the raw materials used, or may be a value calculated by NMR analysis.
  • an acid-modified product obtained by subjecting the above-mentioned polyolefin B to an acid modification treatment may be used instead of the polyolefin B.
  • the acid denaturation treatment By performing the acid denaturation treatment, the polarity of the chlorinated polyolefin resin can be adjusted by adjusting the graft weight. Therefore, the chlorinated polyolefin resin can be applied to adherends of various polarities.
  • the ratio (mass ratio) (A / B) of polyolefin A or its acid-modified product to polyolefin B or its acid-modified product in the raw material composition or the acid-modified raw material composition is not particularly limited and is usually used. It is 10/90 to 90/10. When the amount of polyolefin A or its acid-modified product is less than 10, and the amount of polyolefin B or its acid-modified product is more than 90, polyolefin B or its acid-modified product is not completely dissolved in polyolefin A or its acid-modified product, resulting in chlorination. May be non-uniform.
  • the obtained chlorinated polyolefin resin has insufficient cohesive force and has poor adhesion to the polyolefin substrate. It may not be obtained.
  • the melt viscosity of the chlorinated polyolefin resin at 80 ° C. is preferably less than 100,000 mPa ⁇ s, more preferably less than 70,000 mPa ⁇ s.
  • the higher the chlorine content of the chlorinated polyolefin resin of the present invention the higher the viscosity, and the viscosity increases in the reaction vessel as the chlorination progresses.
  • the melt viscosity at 80 ° C. is 100,000 mPa ⁇ s or more, the flow stops at the end of the chlorination reaction, the share by the stirrer increases, the dehydrochlorination reaction proceeds, and the chlorinated polyolefin resin is significantly colored. It becomes.
  • the lower limit of the melt viscosity is preferably more than 1,000 mPa ⁇ s, more preferably 1,500 mPa ⁇ s or more, and even more preferably 1800 mPa ⁇ s or more. If the melt viscosity is 1,000 mPa ⁇ s or less, the chlorinated polyolefin resin is not preferable because it relatively shows physical properties such as low molecular weight and low melting point and affects the adhesiveness inferior.
  • the melt viscosity at 80 ° C. can be measured with a cone plate type viscometer (manufactured by BROOKFIELD, model: CAP200H).
  • the chlorinated polypropylene resin obtained by using a conventionally known chlorinated solvent does not sufficiently melt at 80 ° C. and does not show melt viscosity.
  • the raw material composition may contain any component other than polyolefin A or an acid-modified product thereof and polyolefin B or an acid-modified product thereof.
  • the optional component include water, which may be capable of preventing resin coloring during a chlorination reaction and reducing the melt viscosity.
  • the resin composition of the present invention contains the above-mentioned chlorinated polyolefin resin and an organic solvent.
  • the resin composition of the present invention may contain a stabilizer in order to suppress the release of chlorine.
  • organic solvent examples include aromatic solvents such as toluene and xylene; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; hydrocarbon solvents such as hexane, heptane and octane; acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • Ketone-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and the like; glycol-based solvents such as ethylene glycol, ethyl cellosolve, butyl cellosolve and the like can be mentioned.
  • toluene, methylcyclohexane, ethyl acetate, propyl acetate and butyl acetate are preferable.
  • the concentration of the resin composition may be appropriately selected depending on the intended use. However, if the concentration of the resin composition is too high or too low, the coating workability is impaired, so that the concentration is preferably 15 to 70% by weight.
  • Epoxy compounds are preferable as stabilizers.
  • the epoxy compound is preferably one that is compatible with the chlorinated polyolefin resin.
  • Examples of the epoxy compound include an epoxy compound having an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule.
  • Epoxidized soybean oil or epoxidized linseed oil made by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid; epoxidizing an unsaturated fatty acid such as oleic acid, tall oil fatty acid, soybean oil fatty acid Fatty acid esters; epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; bisphenol A or polyhydric alcohol condensed with epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol Polyglycidyl ether, sorbitol polyglycidyl ether; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycid
  • the stabilizer only one of these may be used, or two or more thereof may be used in combination.
  • the aqueous dispersion of the present invention contains the above-mentioned chlorinated polyolefin resin and water.
  • the aqueous dispersion of the present invention may contain an amphipathic solvent such as an emulsifier or butyl cellosolve for the purpose of improving dispersion stability.
  • the concentration of the aqueous dispersion may be appropriately selected depending on the intended use. However, if the concentration of the aqueous dispersion is too high or too low, the coating workability is impaired. Therefore, the solid content concentration is preferably 15 to 50% by weight.
  • the pH of the aqueous dispersion is preferably 5 or more, more preferably 7 to 12.
  • the pH is 5 or higher, neutralization is sufficiently performed to prevent the modified polyolefin resin from being dispersed in other components, or even if dispersed, precipitation and separation are likely to occur over time, and storage stability is prevented from deteriorating. Can be done. Further, when the pH is 12 or less, compatibility with other components and work safety can be ensured.
  • the viscosity of the aqueous dispersion at 25 ° C. by a B-type viscometer is preferably 0.1 to 1000 mPa ⁇ s, more preferably 1 to 700 mPa ⁇ s, and even more preferably 2 to 400 mPa ⁇ s.
  • the viscosity can be measured using a B-type viscometer, the rotation speed is 60 rpm, and a # 1 or # 2 rotor is used.
  • the viscosity is measured using an aqueous dispersion having a solid content concentration of 10 to 60% by mass.
  • the method for producing a chlorinated polyolefin resin of the present invention is a method including a step of chlorinating a raw material composition containing at least polyolefin A or an acid-modified product thereof and polyolefin B or an acid-modified product thereof in the absence of an organic solvent. be.
  • the steps of polyolefin A, polyolefin B, raw material composition, and chlorination are as described above.
  • Organic solvent contained in refers to an organic solvent produced by decomposition of organic peroxide.
  • the present invention will be described in detail by way of examples.
  • the following examples are for the purpose of preferably explaining the present invention, and do not limit the present invention.
  • the method for measuring the physical property value or the like is the measurement method described above.
  • the “part” means a mass part unless otherwise specified.
  • Example 1 As polyolefin A, 5 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. of 340 mPa ⁇ s) liquid at room temperature, and as polyolefin B, the polyolefin obtained in Production Example 1 (weight average molecular weight is 20,000, melting point is 20,000). About 60 ° C.) 5 kg was put into a glass-lined reaction kettle, and after sufficiently melting at a temperature of 95 ° C., stirring was started.
  • polyolefin A 5 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. of 340 mPa ⁇ s) liquid at room temperature
  • polyolefin B the polyolefin obtained in Production Example 1 (weight average molecular weight is 20,000, melting point is 20,000). About 60 ° C.) 5 kg was put into a glass-lined reaction kettle, and after sufficiently melting at a temperature of 95 ° C., stirring was started.
  • Chlorinated polyolefin resin was obtained.
  • the melt viscosity of the obtained chlorinated polyolefin resin at 80 ° C. was 2,000 mPa ⁇ s.
  • 400 g of epoxidized soybean oil and 24 kg of toluene were added and cooled to room temperature to obtain a chlorinated polyolefin resin composition having a chlorine content of 4%.
  • Example 2 1 kg of ethylene-propylene copolymer (viscosity at 40 ° C. is 1,100 mPa ⁇ s) liquid at room temperature as polyolefin A, and about 12% by weight of ethylene produced using a metallocene catalyst as a polymerization catalyst as polyolefin B. 9 kg of the ethylene-propylene copolymer (weight average molecular weight of 12,000, melting point of about 60 ° C.) was put into a glass-lined reaction kettle, and after sufficiently melting at a temperature of 95 ° C., stirring was started.
  • Chlorinated polyolefin resin was obtained.
  • the melt viscosity of the obtained chlorinated polyolefin resin at 80 ° C. was 67,000 mPa ⁇ s.
  • 400 g of epoxidized soybean oil and 24 kg of n-propyl acetate were added and cooled to room temperature to obtain a chlorinated polyolefin resin composition having a chlorine content of 28%.
  • Example 3 As polyolefin A, 9 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. of 150 mPa ⁇ s) liquid at room temperature, and as an acid-modified product of polyolefin B, maleic anhydride-modified polyolefin obtained in Production Example 2 (weight average). An acid-modified chlorinated polyolefin resin having a chlorine content of 43% (melting at 80 ° C.) was carried out in the same manner as in Example 2 except that 1 kg having a molecular weight of 50,000 and a melting point of about 125 ° C. was used. The viscosity was 93,000 mPa ⁇ s) and the composition thereof was obtained.
  • Example 4 An ethylene-propylene copolymer having 7 kg of polybutadiene hydride (viscosity at 40 ° C. of 8,000 mPa ⁇ s) as polyolefin A and about 12% by weight of ethylene produced using a metallocene catalyst as a polymerization catalyst as polyolefin B.
  • the melt viscosity was 40,000 mPa ⁇ s) and its composition was obtained.
  • Example 5 8 kg of ethylene-propylene copolymer (thickness at 40 ° C. is 3,500 mPa ⁇ s) as polyolefin A, and ethylene-propylene having an ethylene content of about 12% by weight produced using a metallocene catalyst as a polymerization catalyst as polyolefin B. 2 kg of the copolymer (weight average molecular weight of 12,000, melting point of about 60 ° C.) was put into a glass-lined reaction vessel, and after sufficiently melting at a temperature of 130 ° C., stirring was started.
  • Example 1 As the polyolefin A, 10 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. of 150 mPa ⁇ s) liquid at room temperature was used, and the same operation as in Example 2 was performed except that nothing was used as the polyolefin B.
  • a chlorinated polyolefin resin having a chlorine content of 22% (melt viscosity at 80 ° C. was 1,000 mPa ⁇ s) and a composition thereof were obtained.
  • Example 2 As polyolefin A, 1 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. is 1,100 mPa ⁇ s) liquid at room temperature, and as polyolefin B, an ethylene content produced using a metallocene catalyst as a polymerization catalyst is about 12% by weight. The same operation as in Example 2 was carried out using 9 kg of the ethylene-propylene copolymer (weight average molecular weight of 12,000, melting point of about 60 ° C.). Although remarkable coloring occurred at the end of the chlorination reaction, a chlorinated polyolefin resin having a chlorine content of 46% (melt viscosity at 80 ° C. was 124,000 mPa ⁇ s) and a composition thereof were obtained.
  • Example 6 As polyolefin A, 9 kg of an ethylene-propylene copolymer (viscosity at 40 ° C. of 150 mPa ⁇ s) liquid at room temperature, and as polyolefin B, ethylene having an ethylene content of about 11% by weight produced using a metallocene catalyst as a polymerization catalyst. -A chlorinated polyolefin resin having a chlorine content of 32% by performing the same operation as in Example 2 except that 1 kg of a propylene copolymer (weight average molecular weight: 220,000, melting point: about 65 ° C.) was used. (The melt viscosity at 80 ° C. was 78,000 mPa ⁇ s) and its composition were obtained.
  • the OPP film corona-treated surface (Futamura Chemical Co., Ltd., 80 ⁇ m) was coated with ink and dried with a dryer. After allowing to stand at room temperature for one day, cellophane tape (24 mm manufactured by Nichiban Co., Ltd.) was attached to the ink-coated surface, and the peeled state of the coated surface when peeled off at once was examined. The peeled state was evaluated as follows. The evaluation results are shown in Table 1. A: No peeling B: Peeling area is less than 50% C: Peeling area is 50% or more D: Almost all peeling
  • a chlorinated polyolefin resin could be produced from the raw material composition containing polyolefin A and polyolefin B in the absence of an organic solvent (Examples 1 to 6).
  • the adhesion of the chlorinated polyolefin resin was inferior only with the polyolefin A (Comparative Example 1). Further, from the raw material composition containing polyolefin A and polyolefin B, even if chlorinated in the absence of an organic solvent, the adhesiveness was inferior when the chlorine content was more than 45% by weight (Comparative Example 2). ..
  • the chlorinated polyolefin resin of the present invention has excellent adhesiveness, it is suitable for a laminate having an adhesive layer containing a primer, a binder (for paints and inks), an adhesive, and a chlorinated polyolefin resin. ..
  • a primer for paints and inks
  • an adhesive for paints and inks
  • a chlorinated polyolefin resin since it can be produced without using a halogen-based solvent, it is desired to have specifications that do not use a chlorine-based solvent and do not generate by-products, and are used for food packaging and precision industrial applications (for example, automobile applications). , Base applications, packaging materials for batteries, etc.)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une résine de polyoléfine chlorée qui fait preuve d'une excellente adhésion, un composé à petite molécule à base de chlore n'étant pas détecté par la chromatographie en phase gazeuse effectuée dans des conditions spécifiées. La présente invention est une résine de polyoléfine chlorée ayant une teneur en chlore de 1 à 45 % en pds et comprenant : une polyoléfine A qui présente une fluidité à 40 °C ou moins, ou une résine obtenue par chloration de son produit modifié par un acide ; une polyoléfine B qui présente un point de fusion supérieur à 40 °C et inférieur ou égal à 150 °C, ou une résine obtenue par chloration de son produit modifié par un acide. La résine de polyoléfine chlorée est caractérisée en ce que sa chromatographie en phase gazeuse ne détecte pas de pic provenant d'un composé à petite molécule à base de chlore qui apparaît dans les limites d'un éventail temporel de maintien de 4 à 7 minutes.
PCT/JP2021/000211 2020-01-17 2021-01-06 Résine de polyoléfine chlorée, amorce, liant, adhésif, stratifié, matériau d'emballage alimentaire utilisant ladite résine de polyoléfine chlorée et son procédé de fabrication WO2021145253A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202180009355.5A CN114945603A (zh) 2020-01-17 2021-01-06 氯化聚烯烃树脂和使用该树脂的底漆、粘合剂、粘接剂、层叠体、食品包装材料以及该树脂的制造方法
JP2021522559A JP6940722B1 (ja) 2020-01-17 2021-01-06 塩素化ポリオレフィン樹脂及び、それを用いたプライマー、バインダー、接着剤、積層体、食品包装材と、その製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-005794 2020-01-17
JP2020005794 2020-01-17

Publications (1)

Publication Number Publication Date
WO2021145253A1 true WO2021145253A1 (fr) 2021-07-22

Family

ID=76864609

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/000211 WO2021145253A1 (fr) 2020-01-17 2021-01-06 Résine de polyoléfine chlorée, amorce, liant, adhésif, stratifié, matériau d'emballage alimentaire utilisant ladite résine de polyoléfine chlorée et son procédé de fabrication

Country Status (3)

Country Link
JP (1) JP6940722B1 (fr)
CN (1) CN114945603A (fr)
WO (1) WO2021145253A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05320223A (ja) * 1991-07-08 1993-12-03 Daiso Co Ltd 塩素化ポリオレフィンの製造法
JPH06248013A (ja) * 1993-02-23 1994-09-06 Sekisui Chem Co Ltd 塩素化ポリオレフィンの製造方法
JPH0827220A (ja) * 1994-07-20 1996-01-30 Sekisui Chem Co Ltd 塩素化ポリオレフィンの製造方法
WO2013146728A1 (fr) * 2012-03-28 2013-10-03 日本製紙株式会社 Composition de résine polyoléfinique chlorée
WO2020022251A1 (fr) * 2018-07-25 2020-01-30 日本製紙株式会社 Résine de polyoléfine chlorée et son procédé de production

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0633327B2 (ja) * 1989-12-26 1994-05-02 日本製紙株式会社 塩素化ポリオレフィンの製造方法
JP2001114843A (ja) * 1999-10-13 2001-04-24 Nippon Paper Industries Co Ltd 耐溶剤性良好な酸変性塩素化ポリオレフィン
JP4168228B2 (ja) * 2001-06-29 2008-10-22 東洋化成工業株式会社 低温流動性が良好なバインダー樹脂溶液組成物
WO2018168753A1 (fr) * 2017-03-17 2018-09-20 日本製紙株式会社 Composition de résine à base de polyoléfine chlorée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05320223A (ja) * 1991-07-08 1993-12-03 Daiso Co Ltd 塩素化ポリオレフィンの製造法
JPH06248013A (ja) * 1993-02-23 1994-09-06 Sekisui Chem Co Ltd 塩素化ポリオレフィンの製造方法
JPH0827220A (ja) * 1994-07-20 1996-01-30 Sekisui Chem Co Ltd 塩素化ポリオレフィンの製造方法
WO2013146728A1 (fr) * 2012-03-28 2013-10-03 日本製紙株式会社 Composition de résine polyoléfinique chlorée
WO2020022251A1 (fr) * 2018-07-25 2020-01-30 日本製紙株式会社 Résine de polyoléfine chlorée et son procédé de production

Also Published As

Publication number Publication date
JPWO2021145253A1 (fr) 2021-07-22
CN114945603A (zh) 2022-08-26
JP6940722B1 (ja) 2021-09-29

Similar Documents

Publication Publication Date Title
JP7368245B2 (ja) 塩素化ポリオレフィン樹脂及びその製造方法
JP4987473B2 (ja) 塩素化プロピレン系ランダム共重合体及びこれを含む組成物
JP4055995B2 (ja) 水性分散液、その製造方法及び用途
JP6976260B2 (ja) 変性ポリオレフィン系樹脂
JP6943882B2 (ja) 変性ポリオレフィン系樹脂
WO2000026310A1 (fr) Resine de liaison pour resine polyolefinique, son procede de production et ses utilisations
KR100656110B1 (ko) 결합제 수지 조성물, 이의 제조방법 및 이의 용도
JP6940722B1 (ja) 塩素化ポリオレフィン樹脂及び、それを用いたプライマー、バインダー、接着剤、積層体、食品包装材と、その製造方法
JP3898636B2 (ja) バインダー樹脂組成物と製造方法及びその用途
JP6166564B2 (ja) 塩素化ポリオレフィン樹脂組成物
US6555621B1 (en) Binder resin composition and process for the production thereof
JP2000007979A (ja) ポリオレフィン用塗料樹脂組成物及びその製造方法
JP2001114961A (ja) バインダー樹脂組成物及びその製造方法
JP2001114843A (ja) 耐溶剤性良好な酸変性塩素化ポリオレフィン
JPH11315185A (ja) バインダ―樹脂組成物及びその製造方法
CN111770962B (zh) 树脂组合物
JP2004161952A (ja) バインダー樹脂組成物及びその用途
WO2020213528A1 (fr) Composition de résine polyoléfinique modifiée
JP2022117819A (ja) 酸変性塩素化ポリオレフィン樹脂の製造方法
WO2021054304A1 (fr) Composition de résine et utilisation de celle-ci
JP2015209450A (ja) 塩素化ポリオレフィン樹脂組成物
JP2015067719A (ja) 塩素化ポリオレフィン樹脂組成物
JP2013072047A (ja) プライマー樹脂組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021522559

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21741069

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21741069

Country of ref document: EP

Kind code of ref document: A1