WO2015178360A1 - Composition adhésive stratifiée de polyuréthane durcissable à 2 constituants, film stratifié et matériau d'emballage alimentaire - Google Patents

Composition adhésive stratifiée de polyuréthane durcissable à 2 constituants, film stratifié et matériau d'emballage alimentaire Download PDF

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Publication number
WO2015178360A1
WO2015178360A1 PCT/JP2015/064263 JP2015064263W WO2015178360A1 WO 2015178360 A1 WO2015178360 A1 WO 2015178360A1 JP 2015064263 W JP2015064263 W JP 2015064263W WO 2015178360 A1 WO2015178360 A1 WO 2015178360A1
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Prior art keywords
polyol
adhesive composition
laminate
component curable
polyether
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PCT/JP2015/064263
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English (en)
Japanese (ja)
Inventor
竜二 木村
健一 島村
正光 新居
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Dic株式会社
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Publication of WO2015178360A1 publication Critical patent/WO2015178360A1/fr

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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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a two-component curable polyurethane laminate adhesive composition that is optimal for food packaging applications in which a plastic film or the like is bonded, in particular, a two-component curable polyurethane laminate adhesive composition for digital print packaging for soft packaging,
  • the present invention relates to a laminate film using the same, and a food packaging material using the laminate film.
  • the number average molecular weight is 10,000 or less, and 1.4 to 1. It comprises a polyol component having 8 hydroxyl groups and an isocyanate curing agent component.
  • the polyol component and the isocyanate curing agent component have an isocyanate group in the isocyanate curing agent of 0.8 to 0.8 with respect to the hydroxyl group in the polyol component.
  • a technique is disclosed in which the adhesive strength is increased by using an adhesive composition two-component curable laminate adhesive composition formulated so as to have a ratio of 5.0 equivalents.
  • Patent Document 2 discloses a problem such as delamination when a high-solid type laminating adhesive has an initial adhesive strength that does not cause tunneling when laminated, and is subjected to high-temperature sterilization treatment such as boiling and retort.
  • a two-component curable laminate adhesive composition that does not cause generation it has a maximum value of one or more molecular weight distributions in a number average molecular weight range of 50 or more and less than 4,000 and a range of 4,000 or more and 100,000 or less, respectively.
  • a two-component curable laminate adhesive composition having a polyol component as a main component and a polyisocyanate component as a curing agent is described.
  • the packaging design can be easily changed, and only the required quantity can be printed when needed, making it ideal for small lots, multiple varieties, and short-term delivery.
  • digital printing for soft packaging is required to increase the printing speed and further improve the physical properties of the laminate.
  • improvement of the printing press has been promoted in recent years, and a maximum of 60 m / min is possible with a digital printing press.
  • the laminate physical properties there has been a problem that the target adhesive strength cannot be obtained when the conventional conventional high solid type laminate adhesive is used.
  • the problem to be solved by the present invention is a two-component curable polyurethane laminate adhesive composition that exhibits good adhesive strength in the lamination of a digitally printed plastic film and another film, and a laminate that exhibits such performance.
  • the object is to provide a film and a food packaging material using the laminate film.
  • the present inventors have found a two-component curable polyurethane laminate adhesive composition comprising a polyol (A) and a polyisocyanate (B) as essential components, It was found that the above problems can be solved by using an adhesive composition in which the amount of the aromatic ring component relative to the total mass of the component (B) and the component (B) falls within a specific range, and the present invention has been completed.
  • the polyol (A) and the polyisocyanate (B) are essential components, and the number of moles of the aromatic ring component relative to the total mass of the polyol (A) and the polyisocyanate (B) is
  • the present invention relates to a two-component curable polyurethane laminate adhesive composition characterized by being in a range of 1.0 to 2.3 mmol / g.
  • the present invention further relates to a laminate film having a cured film obtained by using a two-component curable polyurethane laminate adhesive composition.
  • the present invention further relates to a food packaging material using the laminate film.
  • a two-component curable polyurethane laminate adhesive composition that exhibits good adhesive strength in laminating a digitally printed plastic film and another film, a laminate film that exhibits such performance, and the A food packaging material using a laminate film can be provided.
  • the two-component curable polyurethane laminate adhesive composition of the present invention can be used as a solvent type adhesive or a solventless type adhesive.
  • the polyol (A) that can be used is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bis Glycols such as hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol; bisphenol A, bisphenol F, hydrogenated bisphenol A Bisphenol such as hydrogenated bisphenol F; dimer diol; polyether obtained by addition
  • Polyol A urethane polyol-containing polyether polyol obtained by further polymerizing the polyether polyol with the aromatic or aliphatic polyisocyanate; propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valero Polyester obtained by ring-opening polymerization reaction of a cyclic ester compound such as lactone and the glycol, glycerin, trimethylolpropane, pentaerythritol, etc.
  • a cyclic ester compound such as lactone and the glycol, glycerin, trimethylolpropane, pentaerythritol, etc.
  • Polyester polyol which is a reaction product with polyhydric alcohol; Polyester polyol obtained by reacting bifunctional polyol such as glycol, dimer diol or bisphenol with polycarboxylic acid: The polyester polyol and the polyether Polyurethane bond-containing polyester polyether polyols obtained by reacting polyols with aromatic or aliphatic polyisocyanates; polyester polyurethane polyols obtained by polymerizing the polyester polyols with aromatic or aliphatic polyisocyanates; Examples thereof include mixtures with ether polyols.
  • polyvalent carboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid.
  • Acid terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) Ethane-p, p′-dicarboxylic acid and anhydride or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, Examples include polybasic acids such as dimer acid.
  • polyester polyol obtained by reacting a bifunctional polyol and a polyvalent carboxylic acid is used in combination with a trifunctional or higher polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol as an alcohol component. Also good.
  • aromatic or aliphatic polyisocyanate described above examples include aromatic or aliphatic polyisocyanates in the polyisocyanate (B) described later.
  • polyether polyols as solvent-free adhesives for soft packaging, polyether polyols, urethane bond-containing polyether polyols, or mixtures of these and polyester polyols can impart moderate flexibility to the cured product. It is preferable from the point.
  • the polyether polyol, urethane bond-containing polyether polyol, polyester polyol, and urethane bond-containing polyester polyether polyol used in the case of a solvent-free soft packaging adhesive have a hydroxyl value of 50 to 300 mgKOH / g. It is preferable from the point of being excellent in wettability during coating.
  • the polyisocyanate (B) that can be used in the case of a solventless adhesive is, for example, an aromatic such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, etc.
  • Polyisocyanates aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; Polyisocyanate which is a reaction product of these aromatic or aliphatic polyisocyanates and the polyol (A), and these aromatic or aliphatic polyisocyanates.
  • aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane
  • Polyisocyanate which is a reaction product of
  • Polyisocyanate derivatives such as biurets of isocyanate, or isocyanurates of aromatic or aliphatic polyisocyanates (modified products), adducts obtained by modifying these aromatic or aliphatic polyisocyanates with trimethylolpropane, etc. Can be mentioned.
  • a reaction product of an aromatic polyisocyanate and a polyol (A) is preferable for soft packaging, and particularly obtained by reacting an aromatic polyisocyanate with a polyether polyol or a urethane bond-containing polyether polyol.
  • the polyisocyanate obtained by reacting an aromatic polyisocyanate, an aromatic polyisocyanate, a polyether polyol and a polyester polyol is preferable from the viewpoint of imparting appropriate flexibility to the cured product.
  • a titration method di-n Those having an isocyanate content of 5 to 20% by mass (using butylamine) are preferred from the viewpoint of having an appropriate resin viscosity and excellent coating properties.
  • the reaction ratio between the aromatic polyisocyanate and the polyol (A) is such that the equivalent ratio [isocyanate / hydroxyl group] of the isocyanate in the aromatic polyisocyanate and the hydroxyl group in the polyol (A) is 1.5 to 5.0. It is preferable that the viscosity of the adhesive is in an appropriate range from the viewpoint that the coatability is good.
  • examples of the polyol (A) that can be used include polyether polyol, polyester polyol, and polyester urethane polyol. It is done.
  • polyester polyols having terminal hydroxyl groups obtained from polyvalent carboxylic acids and polyhydric alcohols polyester polyurethane polyols obtained from polyester polyols and organic diisocyanates, polyether polyurethane polyols obtained from polyether polyols and organic diisocyanates, polyesters Examples thereof include a polyester polyether polyurethane polyol obtained from a mixture of a polyol and a polyether polyol and an organic diisocyanate, and a polyol selected from polyether polyols.
  • examples of the polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexane.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, , 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4- Cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol, polycaprolactone diol, dimer diol, bisphenol A, hydrogenated bisphenol A, etc.
  • Polyester diol obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol , One or more compounds having two active hydrogen atoms such as trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.
  • cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone
  • ethylene glycol diethylene glycol, triethylene glycol, propylene glycol
  • One or more compounds having two active hydrogen atoms such as trimethylene glycol, 1,3-butanediol, 1,
  • the Tg of the cured coating film is preferably in the range of ⁇ 5 ° C. to 30 ° C. from the viewpoint of flexibility.
  • the polyisocyanate (B) that can be used when the two-component curable polyurethane laminate adhesive composition of the present invention is used as a solvent-type adhesive is not particularly limited.
  • Aromatic polyisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), lysine diisocyanate
  • Aliphatic polyisocyanates such as trimethylhexamethylene diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; these aromatic or aliphatic polyisocyanates
  • a polyisocyanate such as a polyisocyanate, a biuret of these aromatic or aliphatic polyisocyanates, or an is
  • aromatic polyisocyanate polyisocyanate which is a reaction product of aromatic polyisocyanate and polyol (A) has a high reaction rate with polyol (A), and is an adhesive curing step after lamination. It is preferable because the aging time can be shortened and the heat resistance and strength after adhesive curing are excellent. Moreover, adhesive performance can also be adjusted according to a use by selection of the polyol (A) made to react with aromatic polyisocyanate.
  • the number of moles of the aromatic ring component relative to the total mass of the polyol (A) and the polyisocyanate (B) in the adhesive composition is 1.0 to 2.3 mmol / g.
  • the method for calculating the amount of the aromatic ring component contained in the cured coating film of the adhesive composition of the present invention is the method of calculating the aromatic content in the polyol (A) constituting the adhesive composition in 1 g of the polyol (A).
  • the number of moles of the aromatic ring derived from the raw material having an aromatic ring among the components contained in the above is calculated, and the amount of aromatic in the polyisocyanate (B) is similarly calculated by 1 g of the polyisocyanate (B).
  • the number of moles of an aromatic ring derived from a raw material having an aromatic ring is calculated. Then, what is necessary is just to calculate the aromatic amount with respect to the total mass of (A) and (B) according to the mixture ratio of (A) component and (B) component.
  • the polyester polyol component contains an aromatic ring derived from orthophthalic acid or phthalic anhydride (OPA) raw material
  • the amount of the aromatic ring component in the polyester polyol component is:
  • an aromatic ring derived from a TDI raw material is contained in the isocyanate component, such as a trimethylolpropane (TMP) adduct of tolylene diisocyanate (TDI)
  • TMP trimethylolpropane
  • TDI tolylene diisocyanate
  • Aromatic ring component amount (mmol / g) in the adduct body 1 g ⁇ NCO% / 100 / 42.1 ⁇ 1000 It can be calculated by the following formula.
  • the total amount of aromatic ring components (mmol / g) may be calculated according to the blending ratio of the polyester polyol component and the trimethylolpropane (TMP) adduct of tolylene diisocyanate (TDI).
  • the amount of the aromatic ring component relative to the total mass of the component (A) and the component (B) is less than 1.0 mmol / g, the heat resistance of the cured coating film is lowered, while 2.3 mmol / When it exceeds g, sufficient adhesive strength will not be expressed.
  • the amount of the aromatic ring component in 1 g of the polyol (A) is preferably in the range of 5.0 (mmol / g) or less, and the aromatic ring component in 1 g of the polyisocyanate (B).
  • the amount is preferably in the range of 5.0 (mmol / g) or less.
  • the blending ratio of the polyol (A) and the polyisocyanate (B) may be adjusted so that the total amount of aromatic ring components of both is in the range of 1.0 to 2.3 (mmol / g).
  • the blending ratio (mass basis) [(A) / (B)] is preferably in the range of 20/1 to 1/20.
  • the two-component curable laminate adhesive of the present invention can use an adhesion promoter in addition to the components (A) and (B) described above.
  • adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins, and the like.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl) - ⁇ .
  • Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris ( ⁇ -methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, ⁇ -Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, ⁇ -Me It can be mentioned mercaptopropyl trimethoxysilane.
  • titanate coupling agents examples include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.
  • epoxy resins commercially available epi-bis type, novolak type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester
  • epoxy resins such as a mold, a polycarboxylic acid ester type, an aminoglycidyl type, and a resorcinol type are included.
  • a known and commonly used acid anhydride can be used in combination as a method for improving the acid resistance of the adhesive layer.
  • the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and the like.
  • usable diluent solvents include, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone.
  • Ketones such as tetrahydrofuran, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate.
  • the two-component non-drying type adhesive of the present invention can be obtained by, for example, a roll coater coating method. It can manufacture by apply
  • the coating conditions are preferably about 500 to 2500 mPa ⁇ s when heated to about 25 ° C. to 120 ° C. in a normal roll coater.
  • the coating amount is preferably 0.5 to 5 g / m 2 , more preferably about 1.0 to 4.0 g / m 2 .
  • the adhesive is cured in 12 to 48 hours at room temperature or under heating, and practical physical properties can be expressed.
  • the two-component curable laminate adhesive composition is a solvent-type adhesive
  • the two-component curable laminate adhesive composition of the present invention is applied to the first plastic film by a gravure roll coating method. Then, the solvent is removed by evaporation, and the laminate film of the present invention can be obtained by bonding by dry lamination in which other materials are laminated while heating and pressure bonding.
  • the coating amount is 0.5 to 5.0 g / m 2 , preferably 1.0 to 4.0 g / m 2 in terms of solid content.
  • the two-part curable laminate adhesive composition of the present invention exhibits excellent adhesive strength when the first plastic film is digitally printed.
  • the digital printing method include an inkjet method, a UV inkjet method, and a digital offset method.
  • digital printing may be performed directly on the first plastic film, but it is usually preferable because a printing primer is coated on the first plastic film and digital printing is performed thereon.
  • a known primer can be appropriately used according to the printing ink to be used.
  • the adhesive layer itself composed of the two-component curable polyurethane laminate adhesive composition exhibits moderately good flexibility
  • the digital printing layer and the first plastic film particularly in flexible packaging applications, are used.
  • the peeling between the primer and the first plastic film can be satisfactorily suppressed, and the strength of the laminate film itself can be dramatically improved. Can be increased.
  • first plastic film used here examples include base films such as PET (polyethylene terephthalate) film, nylon film, OPP (biaxially stretched polypropylene) film, various deposited films, aluminum foil, and the like.
  • base films such as PET (polyethylene terephthalate) film, nylon film, OPP (biaxially stretched polypropylene) film, various deposited films, aluminum foil, and the like.
  • examples of the other base material include sealant films such as CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), and LLDPE (linear low density polyethylene) film.
  • sealant films such as CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), and LLDPE (linear low density polyethylene) film.
  • the laminated film thus obtained can be used industrially as a packaging material mainly filled with foods, detergents, and drugs. Specific applications include snack packaging, frozen food packaging, boil Examples include retort food packaging materials and refill packaging materials. Examples of the refill packaging material include laundry liquid detergent, kitchen liquid detergent, bath liquid detergent, bath liquid soap, liquid shampoo, liquid conditioner and the like.
  • the two-component curable laminate adhesive composition of the present invention can freely bond arbitrary films together and can obtain a composite film having performance according to the purpose, high performance is required. It can be widely used in the manufacture of food packaging materials.
  • the two-component curable laminate adhesive composition of the present invention is called (1) tunneling immediately after lamination in the laminate of the first plastic film subjected to digital printing and the other substrate. Initial adhesion to prevent floating, (2) High normal adhesion to various plastic films, metal vapor deposition films and metal foils, (3) Boil that does not cause delamination during high temperature sterilization treatment such as boil and retort, resistance to retort Therefore, it is useful in food packaging material applications that require these performances.
  • Adjustment Example 1 Adjustment of polyol A (aromatic concentration: 2.5 mmol / g polyester resin) In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, rectification tube, water separator, etc., 32.9 parts of phthalic anhydride, 29.5 parts of adipic acid, 11.9 parts of ethylene glycol, Diethylene glycol (12.3 parts) and neopentyl glycol (13.4 parts) were charged, and the inner temperature was kept at 240 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C.
  • polyester polyol having a hydroxyl value of about 15 (mgKOH / g).
  • the obtained polyester polyol is diluted with ethyl acetate to a non-volatile content of 60%, and this is designated as polyol A.
  • polyester polyol B When the acid value became 2.0 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a hydroxyl value of about 15 (mgKOH / g).
  • the obtained polyester polyol is diluted with ethyl acetate to a non-volatile content of 60%, and this is designated as polyol B.
  • polyester polyol having a hydroxyl value of about 15 (mgKOH / g).
  • the obtained polyester polyol is diluted with ethyl acetate to a non-volatile content of 60%, and this is designated as polyol C.
  • polyester polyol having a hydroxyl value of about 15 (mgKOH / g).
  • the obtained polyester polyol is diluted with ethyl acetate to a non-volatile content of 60%.
  • Example 1 Polyol A and polyisocyanate A are blended, diluted with ethyl acetate, and softly wrapped using a test laminator (manufactured by Musashino Machine Co., Ltd.) so that the coating amount is 3.0 g (non-volatile content) / m 2.
  • the adhesive surface of the OPP film coated with the adhesive composition and the LLDPE film were coated on the printed surface of the OPP film printed with a digital printer, dried by volatilizing the diluting solvent with a dryer set at a temperature of 70 ° C.
  • a composite film made of OPP / digital printing / adhesive / LLDPE was produced. Next, this composite film was aged at 40 ° C. for 3 days, and the adhesive composition was cured to obtain a two-layer composite film.
  • Example 2 shows the results obtained in the same manner as in Example 1 except that the polyols and polyisocyanates listed in Table 1 were used in the formulation described in Table 2.
  • Polyisocyanate A Desmodur N-3210 (aliphatic polyisocyanate HDI biuret manufactured by Sumika Bayer Urethane Co., Ltd.)
  • Polyisocyanate B Desmodur L-75 (C) (Aromatic polyisocyanate TDI-trimethylolpropane modified product manufactured by Sumika Bayer Urethane Co., Ltd.)
  • the two-component curable polyurethane laminate adhesive composition of the present invention can be used as a laminate adhesive for digital print packaging for soft packaging, and can be used as a laminate film and a food packaging material using the laminate film. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition adhésive stratifiée de polyuréthane durcissable à 2 constituants qui présente une bonne force d'adhésion lors de la liaison d'un film plastique imprimé numériquement à un autre film ; un film stratifié qui présente de telles performances ; et un matériau d'emballage alimentaire qui utilise le film stratifié. Une composition adhésive stratifiée de polyuréthane durcissable à 2 constituants est utilisée, la composition étant caractérisée en ce qu'elle contient un polyol (A) et un polyisocyanate (B) en tant que constituants essentiels et caractérisée en ce que le nombre de moles de constituants à cycle aromatique est de 1,0 à 2,3 mmoles/g par rapport à la masse totale du polyol (A) et du polyuréthane (B).
PCT/JP2015/064263 2014-05-20 2015-05-19 Composition adhésive stratifiée de polyuréthane durcissable à 2 constituants, film stratifié et matériau d'emballage alimentaire WO2015178360A1 (fr)

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CN113845651A (zh) * 2021-11-18 2021-12-28 万华化学集团股份有限公司 一种聚酯多元醇及由其制备的聚氨酯胶黏剂
CN115052745A (zh) * 2020-02-28 2022-09-13 三井化学株式会社 层叠体
JP2022542739A (ja) * 2019-04-24 2022-10-07 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ２成分無溶剤ポリウレタンラミネート接着剤組成物
US11746266B2 (en) 2020-10-01 2023-09-05 The Dow Chemical Company Adhesive composition

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CN115052745A (zh) * 2020-02-28 2022-09-13 三井化学株式会社 层叠体
US11746266B2 (en) 2020-10-01 2023-09-05 The Dow Chemical Company Adhesive composition
CN113845651A (zh) * 2021-11-18 2021-12-28 万华化学集团股份有限公司 一种聚酯多元醇及由其制备的聚氨酯胶黏剂

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