WO2022254993A1 - Agent de revêtement d'ancrage pour stratifié extrudé à l'état fondu et article en couches - Google Patents

Agent de revêtement d'ancrage pour stratifié extrudé à l'état fondu et article en couches Download PDF

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Publication number
WO2022254993A1
WO2022254993A1 PCT/JP2022/018450 JP2022018450W WO2022254993A1 WO 2022254993 A1 WO2022254993 A1 WO 2022254993A1 JP 2022018450 W JP2022018450 W JP 2022018450W WO 2022254993 A1 WO2022254993 A1 WO 2022254993A1
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Prior art keywords
polyol composition
polyisocyanate
coating agent
melt extrusion
anchor coating
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PCT/JP2022/018450
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English (en)
Japanese (ja)
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将郁 大内
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大日精化工業株式会社
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Publication of WO2022254993A1 publication Critical patent/WO2022254993A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to an anchor coating agent for melt extrusion lamination and a laminate.
  • film materials and sheet materials may be required to have various properties depending on their intended use. Satisfaction is often difficult. Therefore, laminates that satisfy various characteristics by laminating a plurality of types of film materials or the like to take advantage of the advantages and compensate for the disadvantages of each material are widely used in various fields.
  • packaging materials packaging containers, packaging materials, etc.
  • packaging materials for packaging foods, medicines, cosmetics, etc. are film-like or sheet-like laminates in which multiple layers selected from plastic films, papers, cloths, metal foils, etc. are laminated.
  • a body laminate film is often used.
  • a melt extrusion lamination method in which a film material such as a plastic film is laminated by extruding a resin in a molten state.
  • a laminate film laminate film
  • laminated material the material on which the extruded resin is laminated
  • resin layer formed by the extruded resin A high adhesive strength is required between them. Therefore, an adhesive layer called an anchor coat layer is sometimes provided between the material to be laminated and the resin to be extruded so as to exhibit good adhesive strength.
  • an anchor coat agent used for forming an anchor coat layer in the production of a melt-extruded laminated film one containing a polyol and a polyisocyanate is known (Patent Document 1).
  • Cashew nut shell liquids and derivatives thereof are known as one of raw materials derived from biomass.
  • a cashew nut shell liquid converted into a polyol resin is known (Patent Documents 2 and 3).
  • An object of the present invention is to provide an anchor coating agent for melt-extrusion lamination, which uses a biomass-derived raw material and provides a laminate having good adhesive strength, and a laminate using the same.
  • the present invention has the following aspects.
  • the polyol composition (A) comprises a biomass polyol composition containing a polyol (a1) represented by the following formula (1) and a compound (a2) represented by the following formula (2), The ratio of the compound (a2) to the entire biomass polyol composition by gel permeation chromatography is 3 to 30 area%,
  • the polyisocyanate (B) contains an aliphatic polyisocyanate (b1), The ratio of the aliphatic polyisocyanate (b1) to the total mass of the polyisocyanate (B) is 20% by mass or more,
  • An anchor coating agent for melt extrusion lamination wherein the mass ratio represented by the polyol composition (A)/the polyisocyanate (B) is 1/99 to 90/10.
  • R 1 represents a linear hydrocarbon group having 15 carbon atoms
  • R 2 represents a hydrogen atom or a substituent
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • n represents a number of 0 or more.
  • Anchor coating agent. [9] A base material, an anchor coat layer provided on the base material, and a resin layer provided on the anchor coat layer by melt extrusion lamination, A laminate, wherein the anchor coat layer is a layer formed from the anchor coat agent for melt extrusion lamination according to any one of [1] to [8].
  • an anchor coating agent for melt extrusion lamination and a laminate using the same which uses biomass-derived raw materials and provides a laminate having good adhesive strength.
  • An anchor coating agent for melt extrusion lamination includes a polyol composition (A) and a polyisocyanate (B).
  • the anchor coating agent of this aspect may further contain components other than the polyol composition (A) and the polyisocyanate (B), if necessary.
  • Polyol composition (A) includes a specific biomass polyol composition.
  • the "polyol composition” is a composition consisting of polyol only, or a composition consisting of polyol and monool.
  • a “biomass polyol composition” is a polyol composition whose constituent components (polyol, monool) are derived from biomass.
  • the polyol composition (A) may contain a non-biomass-derived polyol (hereinafter also referred to as "another polyol”) in addition to the biomass polyol composition.
  • the content of the biomass polyol composition is preferably 10% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass, relative to the total mass of the polyol composition (A).
  • the above is more preferable, and 100% by mass is particularly preferable.
  • biomass polyol composition contains a polyol (a1) represented by the following formula (1) and a compound (a2) represented by the following formula (2).
  • Compound (a2) is cardanol.
  • R 1 represents a linear hydrocarbon group having 15 carbon atoms.
  • a straight chain hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • unsaturated hydrocarbon groups include those having 1 to 3 double bonds.
  • R 1 's in formula (1) may be the same or different.
  • R2 represents a hydrogen atom or a substituent.
  • a substituent indicates an atom or atomic group other than a hydrogen atom.
  • the substituent for R 2 is not particularly limited, and includes a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), optionally substituted hydrocarbon group, hydroxy group, alkoxy group, ether group, ester group, aldehyde group, ketone group, carboxyl group, cyano group, carbamoyl group, imide group, nitro group, amino group, amide group, azo group, urea group, urethane group, sulfo group, thiol group, silyl group, A phosphino group etc.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (phenyl groups, naphthyl groups, etc.), aralkyl groups (benzyl groups, etc.), and the like.
  • Substituents that the hydrocarbon group may have include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy groups, alkoxy groups, ether groups, ester groups, aldehyde groups, ketone groups, carboxyl groups, group, cyano group, carbamoyl group, imido group, nitro group, amino group, amido group, azo group, urea group, urethane group, sulfo group, thiol group, silyl group, phosphino group and the like.
  • the hydrocarbon group may have one or two or more substituents. (n+2) R 2 in formula (1) may be the same or different.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • n represents a number of 0 or more. 1 or more is preferable and, as for n, 2 or more is more preferable. n is preferably 1000 or less, more preferably 500 or less.
  • n is at least the above lower limit, the number average molecular weight of the biomass polyol composition tends to be at least the preferred lower limit described below.
  • n is equal to or less than the above upper limit, the number average molecular weight of the biomass polyol composition tends to be equal to or less than the preferable upper limit described below.
  • the lower limit value and the upper limit value can be appropriately combined.
  • the polyol (a1) is, for example, a condensate (formula (4) below) obtained by reacting (condensation reaction) a compound (a2) with an aldehyde (formula (3) below), as shown in the reaction formula below. and an epoxy compound (the following formula (5)) are synthesized by a method of reacting (addition reaction). Condensation reaction and addition reaction can be carried out by known methods.
  • the biomass polyol composition may further contain a polyol other than the polyol (a1) and a monool other than the compound (a2).
  • Polyols other than the polyol (a1) may be those derived from biomass, such as cardol and 2-methylcardol.
  • Monools other than the compound (a2) may be those derived from biomass, such as anacardic acid.
  • the ratio of the compound (a2) to the entire biomass polyol composition (100 area%) measured by gel permeation chromatography is 3 to 30 area%, preferably 5 to 20 area%. , 7 to 15 area % is more preferred. If the ratio of the compound (a2) is within the above range, a laminate having good adhesive strength can be obtained.
  • the measurement conditions of GPC are as described in Examples below.
  • the ratio of the polyol (a1) to the entire biomass polyol composition by GPC is preferably 10 to 97 area%, more preferably 50 to 96 area%, and even more preferably 75 to 95 area%, from the viewpoint of the adhesive strength of the laminate. , 80 to 93 area % are particularly preferred.
  • the total ratio of the polyol (a1) and the compound (a2) to the entire biomass polyol composition by GPC is preferably 70 area% or more, more preferably 80 area% or more, and 90 area% from the viewpoint of the adhesive strength of the laminate.
  • the above is more preferable, and it may be 100 area %.
  • the viscosity of the biomass polyol composition at 25° C. is preferably 1500 mPa ⁇ s or more, more preferably 2000 mPa ⁇ s or more, and even more preferably 10000 mPa ⁇ s or more. When the viscosity is at least the above lower limit, there is a tendency for the easy tearing property of the laminate to be more excellent.
  • the viscosity of the biomass polyol composition at 25° C. is preferably 150000 mPa ⁇ s or less, more preferably 130000 mPa ⁇ s or less, still more preferably 90000 mPa ⁇ s or less, and particularly preferably 50000 mPa ⁇ s or less.
  • the viscosity is equal to or less than the above upper limit, there is a tendency for the cutting property of the packaging material to be more excellent.
  • the lower limit value and the upper limit value can be appropriately combined.
  • the viscosity of the biomass polyol composition is measured with a Brookfield viscometer. In the following, unless otherwise specified, the viscosity indicates the value at 25°C.
  • the viscosity of the biomass polyol composition can be adjusted by adjusting the proportion of the compound (a2), the number average molecular weight, and the like.
  • the number average molecular weight (hereinafter also referred to as “Mn”) of the biomass polyol composition is preferably 500 or more, more preferably 750 or more, and even more preferably 1000 or more. If the Mn is at least the above lower limit, there is a tendency for the adhesion to the substrate to be more excellent.
  • the Mn of the biomass polyol composition is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 100,000 or less, particularly preferably 10,000 or less, and most preferably 5,000 or less. When Mn is equal to or less than the above upper limit, the cuttability tends to be more excellent when made into a laminate film.
  • the lower limit value and the upper limit value can be appropriately combined.
  • Mn of the biomass polyol composition is a standard polystyrene conversion value measured by GPC.
  • the biomass polyol composition preferably satisfies both the above-described preferred viscosity and preferred Mn.
  • the viscosity is 1500 mPa ⁇ s or more and the number average molecular weight is 1000 or more.
  • the hydroxyl value of the biomass polyol composition is preferably 130 mgKOH/g or more, more preferably 145 mgKOH/g or more, and even more preferably 160 mgKOH/g or more. When the hydroxyl value is at least the above lower limit, the adhesive strength of the laminate tends to be more excellent.
  • the hydroxyl value of the biomass polyol composition is preferably 250 mgKOH/g or less, more preferably 230 mgKOH/g or less, and even more preferably 210 mgKOH/g or less. If the hydroxyl value is equal to or less than the above upper limit, the hydrolysis resistance tends to be more excellent.
  • the lower limit value and the upper limit value can be appropriately combined. Hydroxyl value is determined according to ASTM D4274.
  • the biomass polyol composition preferably uses cashew nut shell liquid (hereinafter also referred to as "CNSL") as a raw material from the viewpoint of reducing raw material costs and carbon dioxide emissions.
  • CNSL is an oily liquid obtained from cashew nut shells.
  • CNSL herein is generally obtained by distilling crude CNSL shelled from cashew nuts, and contains compound (a2). Cardol, methyl cardol, anacardic acid and the like may be contained in addition to compound (a2).
  • Various grades of CNSL are commercially available, and they are available at a lower price than the compound (a2) alone.
  • a reactant containing the polyol (a1) is obtained.
  • the reactant contains the unreacted compound (a2) in the above ratio
  • the obtained reactant can be used as it is as a biomass polyol composition.
  • a biomass polyol composition may be obtained by adding the compound (a2) or the like to the reactant.
  • Other polyols include low-molecular-weight polyols, high-molecular-weight polyols, and the like.
  • Examples of low-molecular-weight polyols include polyhydric alcohols (dihydric or higher alcohols).
  • Polymer polyols include polyether polyols, polyester polyols, polycarbonate polyols, and the like. These polyols can be used singly or in combination of two or more.
  • Polyhydric alcohols include ethylene glycol, 1,2-propanediol (also known as propylene glycol), 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1 ,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1, diols having an alicyclic structure such as 3-cyclohexanedimethanol and 1,4-cyclohexanedio
  • Polyester polyols include, for example, polyester polyols and polyester amide polyols obtained by a dehydration polycondensation reaction between a polyhydric carboxylic acid and a polyhydric alcohol or secondary or tertiary amines.
  • Polyvalent carboxylic acids that can be used in the production of polyester polyols include, for example, succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroortho phthalic acid, naphthalenedicarboxylic acid; and polycarboxylic acids such as trimellitic acid; acid esters thereof; and acid anhydrides thereof.
  • Examples of the polyhydric alcohol that can be used for producing the polyester polyol include the specific examples of the polyhydric alcohol described above.
  • polyesteramide polyols include low-molecular-weight amine compounds such as hexamethylenediamine, xylylenediamine, and isophoronediamine.
  • Polyester polyols include, for example, lactone-based polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ⁇ -caprolactone and ⁇ -valerolactone using low-molecular-weight alcohol compounds and low-molecular-weight aminoalcohol compounds as initiators. Polyols can also be used.
  • polyether polyols examples include those obtained by addition polymerization (ring-opening polymerization) of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and tetrahydrofuran, etc., as initiators.
  • alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and tetrahydrofuran, etc.
  • initiators examples include the polyhydric alcohols described above, as well as low-molecular-weight amine compounds such as triethanolamine, ethylenediamine, and diethylenetriamine.
  • polyether polyols examples include polyoxyethylene diol (also known as polyethylene glycol), polyoxypropylene diol (also known as polypropylene glycol), polyoxypropylene triol, ethylene oxide-propylene oxide copolymer, and polytetramethylene ether glycol (PTMEG). , polytetraethylene glycol, and sorbitol polyols.
  • Polycarbonate polyols include, for example, those obtained by the dehydrochlorination reaction of the above-mentioned polyhydric alcohol and phosgene, and those obtained by the transesterification reaction of a low-molecular-weight alcohol compound with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What can be done is mentioned.
  • the weight average molecular weight (hereinafter also referred to as "Mw") of the polymer polyol is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, and even more preferably 10,000 to 60,000. .
  • Mw of polyol is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
  • Polyisocyanate (B) includes aliphatic polyisocyanate (b1).
  • the polyisocyanate (B) may further contain polyisocyanates other than the aliphatic polyisocyanate (b1).
  • the ratio of the aliphatic polyisocyanate (b1) to the total mass of the polyisocyanate (B) is 20% by mass or more.
  • the ratio of the aliphatic polyisocyanate (b1) to the total mass of the polyisocyanate (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass. That is, it is particularly preferred that the polyisocyanate (B) consists only of the aliphatic polyisocyanate (b1).
  • the ratio of the other polyisocyanate to the total mass of the polyisocyanate (B) is preferably 0-50% by mass, more preferably 0-30% by mass.
  • aliphatic polyisocyanate (b1) examples include bifunctional aliphatic polyisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate (HDI); bifunctional aliphatic polyisocyanate adducts, isocyanurates, biuret and allophanate forms. These aliphatic polyisocyanates can be used singly or in combination of two or more.
  • Trifunctional aliphatic isocyanates include, for example, trimethylolpropane (TMP) adducts, isocyanurates, biurets and allophanates of HDI.
  • polyisocyanates include, for example, aromatic polyisocyanates and alicyclic polyisocyanates. These polyisocyanates can be used singly or in combination of two or more.
  • aromatic polyisocyanates examples include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl ether diisocyanate, and 3, Aromatic diisocyanates such as 3'-dimethyldiphenylmethane-4,4'-diisocyanate; adducts, isocyanurates, biurets and allophanates of aromatic diisocyanates.
  • alicyclic polyisocyanates examples include isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated xylene diisocyanate (H 6 XDI), and hydrogenated diphenylmethane diisocyanate (water alicyclic diisocyanates such as MDI); adducts, isocyanurates, biurets and allophanates of alicyclic isocyanates;
  • trifunctional isocyanates trifunctional aromatic isocyanates, trifunctional alicyclic isocyanates, etc.
  • the adhesive strength and easy tearability of the laminate tend to be more excellent.
  • Trifunctional isocyanate compounds include, for example, TMP adducts of TDI, XDI, IPDI or H 6 XDI.
  • the anchor coating agent may contain a liquid medium.
  • the anchor coating agent is usually applied to the material to be laminated while containing a liquid medium.
  • the liquid medium is not particularly limited, and can be appropriately selected according to the material of the material to be laminated on which the anchor coat layer is to be provided, the application of the laminate produced using the anchor coat agent, and the like.
  • liquid medium examples include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane; ethyl acetate, propyl acetate, and acetic acid; ester solvents such as butyl; ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PM), tetrahydrofuran, and dioxane; alcohol solvents such as methanol, ethanol, and isopropanol (IPA); be done.
  • ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone
  • hydrocarbon solvents such as toluene, xylene, cyclohex
  • the anchor coating agent may contain various additives.
  • additives include catalysts, tackifiers, tackifiers, surface conditioners, silane coupling agents, pigments, dyes, dispersants, antifoaming agents, leveling agents, thickeners, cross-linking agents, inorganic particles, Examples include ultraviolet absorbers, light stabilizers, surfactants, preservatives, antirust agents, and the like. These additives may be used singly or in combination of two or more.
  • the mass ratio represented by polyol composition (A)/polyisocyanate (B) (hereinafter also referred to as “A/B ratio”) is 1/99 to 90/10, and 5/ 95 to 60/40 is preferred, and 10/90 to 40/60 is more preferred. If the A/B ratio is within the above range, the laminate will be excellent in adhesive strength and tearability.
  • the total content of the polyol composition (A) and the polyisocyanate (B) is preferably 10% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass, based on the total mass of the solid content of the anchor coating agent.
  • the above is more preferable, and it may be 100% by mass.
  • the content of the liquid medium in the anchor coating agent is not particularly limited, and can be adjusted according to the solid content concentration of the anchor coating agent.
  • the content of the additive in the anchor coating agent may be, for example, 0 to 90% by mass, or may be 0 to 70% by mass, based on the mass of the total solid content of the anchor coating agent.
  • the solid content concentration of the anchor coating agent is not particularly limited, and can be adjusted so as to have an appropriate viscosity according to the method such as printing when providing the anchor coating layer on the material to be laminated.
  • a concentrated (thick) anchor coating agent may be prepared and diluted with the liquid medium described above when applied to the material to be laminated.
  • the solid content concentration of the anchor coating agent when applied to the material to be laminated is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and further 7 to 12% by mass, relative to the total mass of the anchor coating agent. preferable.
  • the anchor coating agent of this embodiment is for melt extrusion lamination, and can be used for producing a laminate by a melt extrusion lamination method.
  • a resin is melted and extruded, and the extruded resin is laminated on a material to be laminated.
  • the anchor coat agent forms an anchor coat layer provided between the extruded resin and the material to be laminated.
  • an anchor coating agent is applied to the material to be laminated to form an anchor coat layer.
  • a laminate obtained using the anchor coating agent of this embodiment exhibits good adhesive strength.
  • the easy tearability is also good, and the laminate can be easily torn by hand. If the easy tearability is good, for example, a packaging bag composed of a laminate can be easily opened by hand.
  • FIG. 1 shows an example of the laminate of this embodiment. Note that the dimensional ratios in FIG. 1 are different from the actual ones for convenience of explanation.
  • the laminate 10 of this example includes a substrate 11, an anchor coat layer 13 provided on the substrate 11, and a resin layer 15 provided on the anchor coat layer 13 by melt extrusion lamination.
  • the laminate of this embodiment may have an ink layer between the substrate 11 and the anchor coat layer 13 and may have a resin film on the resin layer 15 .
  • the base material 11 is a laminated material on which the extruded resin is laminated.
  • various film materials such as plastic film, paper, cloth, and metal foil can be used, and a plastic film is preferable.
  • plastic films include polyester films such as polyethylene terephthalate (PET), amorphous polyethylene terephthalate (A-PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polylactic acid; low-density polyethylene ( LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polyolefin films such as polypropylene (PP); cellulose films such as cellophane; polystyrene (PS) films; ethylene-vinyl acetate copolymer resin films ethylene-vinyl alcohol copolymer resin film; polyamide (Ny) film; polycarbonate film; polyimide film; Among these, polyester films and Ny films are examples of plastic films and Ny films
  • Both stretched and unstretched plastic films such as biaxially stretched PP films and non-stretched PP films, can be used as the plastic film described above.
  • the surface of the plastic film may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment and solvent treatment.
  • Substrate 11 may be multi-layered.
  • multilayer base materials include those in which another layer is provided on a film material such as a plastic film, and those in which a plurality of film materials are laminated.
  • Other layers include, for example, vapor deposition layers, ink layers, and various other coating layers.
  • vapor deposition layers include metal vapor deposition layers such as aluminum vapor deposition layers, and transparent vapor deposition layers such as alumina and silica vapor deposition layers.
  • the ink layer is provided by printing or the like for the purpose of decoration or the like.
  • the ink that forms the ink layer include urethane resin ink, acrylic resin ink, silicone resin ink, acrylic urethane resin ink, and acrylic silicone resin ink.
  • the ink forming the ink layer may be a one-component ink or a two-component curable ink.
  • urethane resin-based one-component ink and urethane resin-based two-component curable ink are preferable.
  • the thickness of the base material 11 is preferably 5-500 ⁇ m, more preferably 10-100 ⁇ m, even more preferably 10-60 ⁇ m.
  • the anchor coat layer 13 is a layer formed from the anchor coat agent described above.
  • the anchor coat layer 13 can be formed by applying an anchor coat agent onto the base material 11 and drying it. A method for forming the anchor coat layer 13 will be described later in detail.
  • the amount of the anchor coating agent to be applied is not particularly limited, but is preferably 0.01 to 2 g/m 2 , more preferably 0.05 to 1 g/m 2 in terms of dry (solid content) mass per unit area of the application surface. , 0.1 to 0.5 g/m 2 are more preferred.
  • the above coating amount corresponds to the mass per unit area of the anchor coat layer 13 .
  • the thickness of the anchor coat layer 13 is not particularly limited, and can be, for example, about 0.01 to 1 ⁇ m, preferably about 0.01 to 0.5 ⁇ m.
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE high-density polyethylene
  • PP polypropylene
  • the thickness of the resin layer 15 is preferably 1 to 300 ⁇ m, more preferably 5 to 200 ⁇ m, even more preferably 10 to 100 ⁇ m.
  • the laminate 10 is formed by, for example, applying an anchor coating agent onto the substrate 11, drying it to form the anchor coating layer 13, and forming the resin layer 15 on the anchor coating layer 13 by melt extrusion lamination. can be manufactured.
  • Examples of methods of applying the anchor coating agent include gravure roll coating, reverse roll coating, air knife coating, wire bar coating, curtain flow coating, spray coating, and dip coating.
  • the anchor coating agent is preferably applied by a coater (for example, a roll coater, etc.) attached to melt extrusion lamination equipment used when manufacturing the laminate 10 .
  • the drying temperature of the applied anchor coating agent is not particularly limited, and can be in the range of 40 to 200° C., for example.
  • the drying time is also not particularly limited, and can be in the range of 1 to 600 seconds, for example.
  • Formation of the resin layer 15 on the anchor coat layer 13 provided on the substrate 11 can be performed by a known melt extrusion lamination method.
  • a resin (thermoplastic resin) forming a resin layer is heated and melted, extruded into a film, the extruded melt is laminated on the anchor coat layer 13, and cooled.
  • a method of laminating the extruded melt on the anchor coat layer 13 and further laminating another resin film thereon can also be used.
  • the resin forming the resin film the same resin as that forming the resin layer 15 can be used.
  • the laminate 10 can be used, for example, as a packaging material.
  • packaging materials include various packaging containers containing food, beverages, pharmaceuticals, quasi-drugs, cosmetics, detergents, and chemicals, and various packaging materials such as films and paper. be done. Applications in which packaging materials are used further include electronic parts, electrical parts, electrical products, automobile parts, various sheets and cards, labels and tags provided on products, and the like. Specific examples of packaging materials include paper boxes, wrapping paper, packaging films, packaging labels, packaging bags, and plastic containers such as plastic cases and plastic bottles. Among these, packaging bags are more preferable. Suitable uses of the packaging bag include, for example, food packaging bags, pharmaceutical packaging bags, and cosmetic packaging bags.
  • laminated body of this aspect is not limited to the illustrated example, and additions, omissions, substitutions, and other modifications of the configuration are possible without departing from the scope of the present invention.
  • A-8 "Cardlite LITE-9001” manufactured by Cardlite.
  • A-9 "Cardlite NX-9005" manufactured by Cardlite.
  • Each of these biomass polyol compositions was used after being diluted with ethyl acetate to a final solids concentration of 50%.
  • ⁇ Polyisocyanate (B)> Adduct of hexamethylene diisocyanate (HDI) (bifunctional, trade name “Duranate D101”, manufactured by Asahi Kasei Corporation) b1-2: TMP adduct of hexamethylene diisocyanate (HDI) (trifunctional, trade name “Takenate D-160N”, manufactured by Mitsui Chemicals, Inc.). b2-1: TMP adduct of tolylene diisocyanate (TDI) (trifunctional, trade name “Takenate D-103”, manufactured by Mitsui Chemicals, Inc.).
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • TMP adduct of xylylene diisocyanate (XDI) trifunctional, trade name “Takenate D-110N”, manufactured by Mitsui Chemicals, Inc.
  • XDI xylylene diisocyanate
  • a laminate having the following laminate structure was produced by a melt extrusion lamination method (melt extrusion sandwich lamination method). Specifically, using melt extrusion lamination equipment, the AC agent is applied to the entire surface of one side of the laminated material in the laminated structure described below at a coating amount of 0.3 g (dry mass) / m 2 , and then dried. Ethyl acetate was evaporated in a furnace (at a temperature of 80° C.) to dry the AC agent to form an anchor coat layer (hereinafter also referred to as “AC layer”).
  • LLDPE linear low-density polyethylene
  • ⁇ Ny plain The material to be laminated is a Ny film (trade name “Harden Film N1102”, manufactured by Toyobo Co., Ltd., thickness 15 ⁇ m), and the LLDPE layer and the LLDPE film are laminated to this material (Ny film) through the AC layer.
  • ⁇ Ny white The material to be laminated is a white ink layer provided by solid printing on the Ny film, and the LLDPE layer and the LLDPE film are laminated on this material to be laminated (white ink layer I1) via the AC layer. Constitution.
  • ⁇ PET plain The material to be laminated is a PET film (trade name “Toyobo Ester Film E5102”, manufactured by Toyobo Co., Ltd., thickness 12 ⁇ m), and the LLDPE layer and the LLDPE film are laminated to this material (PET film) through the AC layer. is laminated.
  • PET film trade name “Toyobo Ester Film E5102”, manufactured by Toyobo Co., Ltd., thickness 12 ⁇ m
  • White ink layer 1-component urethane ink (8.5 parts of urethane resin, 3.0 parts of vinyl chloride-vinyl acetate copolymer resin, 0.4 parts of cellulose acetate butyrate (CAB) resin, 22.0 parts of ethyl acetate part, 25.0 parts of MEK, 5.5 parts of IPA, 1.5 parts of PM, 0.1 part of dispersant, and 34.0 parts of titanium oxide).
  • 1-component urethane ink 8.5 parts of urethane resin, 3.0 parts of vinyl chloride-vinyl acetate copolymer resin, 0.4 parts of cellulose acetate butyrate (CAB) resin, 22.0 parts of ethyl acetate part, 25.0 parts of MEK, 5.5 parts of IPA, 1.5 parts of PM, 0.1 part of dispersant, and 34.0 parts of titanium oxide).
  • the resulting laminate was evaluated for adhesion and easy tearability according to the following procedure. The results are shown in Tables 2-5.
  • T-peel test sample A rectangular sample having a width of 15 mm and a length of 100 mm was cut from each of the obtained laminates, and a T-peel test sample was prepared as a sample for adhesive strength measurement.
  • a T-type peel test sample was performed using a tensile tester (trade name "Tensilon RTG-1225", manufactured by A&D Co., Ltd.) at a tensile speed of 300 mm / min.
  • the adhesive strength (T-peel strength) between the laminated material and the LLDPE layer in the sample was measured. Moreover, the peeling state after the peeling test was visually evaluated.
  • One sheet of laminate film was cut into a rectangular shape having a width of 100 mm and a length of 150 mm from each laminate film obtained.
  • the laminated film is folded in half lengthwise with the LLDPE film on the inside and overlapped, and the edges along two adjacent sides (10 mm area from the edge) are heat-sealed to produce a sealed bag having an opening. did. After that, the opening was heat-sealed in the same manner as described above to prepare a three-sided seal bag.
  • This 3-side sealed bag was stored in a constant temperature room at 40° C. for 48 hours. After that, tearing lines were made in each of the sealed portions along two adjacent sides of the sealed bag (two places in total), and horizontal and vertical tears were performed.
  • the easy tearability at this time was evaluated on a scale of 5 according to the following evaluation criteria. It should be noted that the horizontal tear is to hold the upper edge of the cut line and tear it so that it is pulled in the left and right direction around the cut line (also called crotch tear), and the vertical tear is to hold the upper edge of the cut line. It is to tear in a straight line downwards so as to tear back and forth from the cut line. 5 points: The seal bag could be torn cleanly. 4 points: The sealed bag could be torn, but slight elongation of the LLDPE layer was observed when the bag was torn slowly during the tearing. 3 points: Elongation of the LLDPE layer was observed, but the seal bag could be torn.
  • the laminates using the AC agents of Examples 1-13 were superior in adhesive strength to the laminates using the AC agents of Comparative Examples 1-15.
  • Examples 1 to 12 were also excellent in easy tearability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'agent de revêtement d'ancrage pour un stratifié extrudé à l'état fondu selon un mode de réalisation de la présente invention contient une composition de polyol (A) et un polyisocyanate (B). La composition de polyol (A) contient un polyol (a1) représenté par la formule (1), et un composé (a2) représenté par la formule (2). La proportion du composé (a2) par rapport à la totalité d'une composition de polyol de biomasse produite par CPG va de 3 à 30 % en surface. Le polyisocyanate (B) comprend un polyisocyanate aliphatique (b1). La proportion du polyisocyanate aliphatique (b1) par rapport à la masse totale du polyisocyanate (B) est supérieure ou égale à 20 % en masse. Le rapport massique représenté par [composition de polyol (A)]/[polyisocyanate (B)] va de 1/99 à 90/10.
PCT/JP2022/018450 2021-06-02 2022-04-21 Agent de revêtement d'ancrage pour stratifié extrudé à l'état fondu et article en couches WO2022254993A1 (fr)

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