WO2018043469A1 - Method for producing film for soft packaging - Google Patents

Method for producing film for soft packaging Download PDF

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Publication number
WO2018043469A1
WO2018043469A1 PCT/JP2017/030886 JP2017030886W WO2018043469A1 WO 2018043469 A1 WO2018043469 A1 WO 2018043469A1 JP 2017030886 W JP2017030886 W JP 2017030886W WO 2018043469 A1 WO2018043469 A1 WO 2018043469A1
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WO
WIPO (PCT)
Prior art keywords
agent
film
polyol
compound
polyisocyanate compound
Prior art date
Application number
PCT/JP2017/030886
Other languages
French (fr)
Japanese (ja)
Inventor
雅彦 小川
茂和 高橋
長一 高田
直樹 市村
Original Assignee
Dic株式会社
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Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Publication of WO2018043469A1 publication Critical patent/WO2018043469A1/en

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined

Definitions

  • the present invention relates to a method for producing a flexible packaging film, and more particularly to a production method having a two-liquid fractionation coating step.
  • Two-component curable polyurethane resin adhesives are widely used as adhesives for soft packaging films.
  • the plastic film is printed on the back side, and the ink is applied to the ink surface and the other plastic film is bonded together. There is a need for improved appearance. Furthermore, since a soft packaging material using a plastic laminate is preferred to have a hard texture, and a harder adhesive coating film has a better texture, such a product is desired.
  • a method of coating the substrate with a composition in which two components mainly composed of an isocyanate component and a polyol component are mixed is the mainstream, but it is fast-curing.
  • a method for providing a two-component fractionation-applied urethane adhesive that expresses initial adhesive force quickly and exhibits excellent elasticity, adhesive strength, heat resistance, cold resistance, etc. after curing a two-component fractionation coating step A coating method having the following is also known.
  • the adhesive used in this method is composed of agent A and agent B, and agent A applied to one substrate and agent B applied to the other substrate.
  • the agent A is a non-solvent agent A which is liquid at room temperature and mainly comprises a compound having an isocyanate group at both molecular ends.
  • the B agent is a solvent-free B agent which is liquid at room temperature and contains a compound having an amino group at both molecular ends, a compound having a tertiary amine in the molecule, and a tackifying resin.
  • a two-part fractionation-type urethane adhesive is described.
  • An object of the present invention is to provide a method for producing a flexible packaging film that improves the packaging texture.
  • the present invention relates to a method for producing a flexible packaging film in which a polyurethane adhesive is applied to a base material, wherein the polyurethane adhesive uses the A agent and the B agent as reaction raw materials, and the A agent applied to one base material It has a two-component fractionation coating process in which the B agent applied to the other substrate contacts and pressure-bonds, the A agent contains either a polyol compound or a polyisocyanate compound as a curing component, and the B agent is a curing component As a manufacturing method of the film for flexible packaging containing any one of the polyol compound or polyisocyanate compound different from A agent as.
  • the present invention also provides a soft food packaging material using a soft packaging film obtained by the production method described in the previous term.
  • a method for producing a film for soft packaging in which there is less entrapment of bubbles during lamination, the appearance of the laminate film is improved, the adhesive coating film after curing becomes hard, and the texture of the soft packaging is improved. can do.
  • agent A contains either a polyol compound or a polyisocyanate compound as a curing component
  • agent B as a curing component. It includes any one of different polyol compounds or polyisocyanate compounds.
  • B agent when a polyol compound is included as a hardening component of A agent, B agent contains a polyisocyanate compound.
  • the agent B when a polyisocyanate compound is included as a curing component of the agent A, the agent B includes a polyol compound.
  • the agent A or agent B does not contain both a polyol compound and a polyisocyanate compound.
  • the polyol compound used in the present invention is not particularly limited.
  • polyester polyol, polyether polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol Mention may be made of polymer polyols selected from polyhydroxyl alkanes, polyurethane polyols, castor oil or mixtures thereof.
  • polyester polyol examples include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neodymium.
  • dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neodymium.
  • Glycols such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol or the like; Ring opening of lactones such as polyester polyol or polycaprolactone, polyvalerolactone, poly ( ⁇ -methyl- ⁇ -valerolactone) obtained by reacting with these mixtures The polyester polyol obtained by superposition
  • polymerization is mentioned.
  • polyether polyol for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran is polymerized using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, and the like as a low-part polyol.
  • the polyether polyol obtained is mentioned.
  • the polyether ester polyol include a polybasic acid obtained by reacting the above polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof. Examples include ether ester polyols.
  • the polyether (polyurethane) polyol is a polyol having a urethane bond in one molecule.
  • it is a reaction product of a polyether polyol having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate, and NCO / OH is 1 It is preferably less than 0.9, more preferably 0.9 or less.
  • polyester (polyurethane) polyol examples include a reaction product of a polyester polyol, a polyether ester polyol, and the like and an organic polyisocyanate, and NCO / OH is preferably less than 1, more preferably 0.9 or less.
  • the polyesteramide polyol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine as a raw material in the esterification reaction.
  • acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyhydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.
  • polycarbonate polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane.
  • polyhydroxyalkane examples include butadiene or liquid rubber obtained by copolymerization with butadiene and acrylamide.
  • a polyether (polyurethane) polyol is particularly preferable.
  • polyisocyanate compound examples include organic compounds having at least two isocyanate groups in the molecule.
  • examples of the organic polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, Polyisocyanates such as 1,3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; adducts of these polyisocyanates, burettes of these polyisocyanates, or these polyisocyanates And polyisocyanate derivatives (modified products) such as isocyanurates.
  • the polyisocyanate compound used in the present invention acts as a curing agent and can be appropriately selected and used, but may be aromatic or aliphatic.
  • the polyisocyanate compound preferably used in the present invention include polyisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • the curing agent exhibits performance only with the polyisocyanate compound (B), it can also impart high hydrolysis resistance to the cured coating film by using the polyisocyanate compound and the epoxy resin described later.
  • reaction product of polyisocyanate and bis (hydroxyalkyl) amine having a urea bond group at the terminal can be preferably used.
  • the blending ratio of the polyol compound and the polyisocyanate compound is such that the equivalent ratio [(b) / (a)] of the solid content hydroxyl equivalent (a) of the polyol compound to the solid isocyanate equivalent (b) of the polyisocyanate compound is 0. It is designed to be 5 to 4.0, more preferably 0.9 to 3.0.
  • the amount of the polyisocyanate compound contained in the B agent is calculated from the solid content hydroxyl equivalent (a) of the polyol compound contained in the A agent. decide.
  • the agent A or agent B used in the present invention may contain a catalyst for promoting the reaction, if necessary.
  • the catalyst used in the present invention is not particularly limited as long as it is for accelerating the urethanization reaction.
  • a catalyst such as a compound / titanium chelate complex can be used.
  • the catalyst can be used in the coating step in the form of a solution or dispersion, and used in the form of a solution or dispersion with an organic solvent, a plasticizer, a polyol such as polyethylene polyol or polypropylene polyol, or the polyol compound of the present invention. be able to.
  • the polyurethane resin production catalyst used in the present invention include known and commonly used catalysts such as metal-based catalysts, amine-based catalysts, DBU-based, aliphatic cyclic amide compounds, and titanium chelate complexes.
  • the metal catalyst examples include a metal complex system, an inorganic metal system, and an organic metal system.
  • the metal complex system is selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt).
  • Metal acetylacetonate salt for example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate, etc.
  • iron acetylacetonate Acetonate (Fe (acac) 3 ) or manganese acetylacetonate (Mn (acac) 2 ) is preferred.
  • inorganic metal catalyst examples include catalysts selected from Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
  • organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.
  • the tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because of their excellent catalytic activity and industrial availability.
  • tertiary amine catalysts include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ′′, N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis Dimethyla
  • Examples of the aliphatic cyclic amide compound include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthol lactam, ⁇ -capryllactam, ⁇ -propiolactam, and the like.
  • ⁇ -caprolactam is preferable from the viewpoint of excellent curing acceleration effect.
  • the titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic or aromatic diketone as a ligand from the viewpoint of excellent curing acceleration effect. Further, in the present invention, those having an alcohol having 2 to 10 carbon atoms in addition to an aromatic or aliphatic diketone as a ligand are preferable because the effects of the present invention become more remarkable.
  • the above catalysts may be used alone or in combination.
  • the amount of the catalyst used may be converted from the amount of polyol used for the agent A or agent B. For example, when the polyol is 100 parts, it is preferably 0.001 to 10 parts, more preferably 0.00. 01 to 10 parts.
  • the catalyst in the method of the present invention, it is desirable to use the catalyst by mixing it in advance with a polyol compound or an isocyanate compound used for the agent A or agent B. Further, it can be used by dissolving in a solvent when mixing.
  • the solvent is not particularly limited.
  • alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, and butanediol
  • hydrocarbons such as toluene, xylene, and mineral terpenes
  • acetic acid Esters such as ethyl, butyl acetate, methyl glycol acetate, and cellosolve acetate
  • organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones
  • ⁇ -diketones such as acetylacetone and its fluorinated substituents
  • examples include chelatable solvents such as ketoesters such as ethyl acetate.
  • the adhesive used in the present invention may contain other additives other than those described above, if necessary.
  • the additive include additives generally used in resin compositions that form films and coating films.
  • Additives include, for example, colloidal silica; inorganic fine particles such as alumina sol; polymethyl methacrylate organic fine particles; antifoaming agents; anti-sagging agents; silane coupling agents; viscosity modifiers; Peroxide decomposer; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust preventive agent; Fluorescent whitening agent; Inorganic heat absorber; Flameproof agent; Antistatic agent; Can be mentioned.
  • an epoxy group-containing compound may be blended for the purpose of promoting adhesion and curing.
  • the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester , Glycidyl methacrylate, butyl glycidyl ether, etc., oligomers containing epoxy groups with molecular weights of hundreds to thousands, and polymers with weight average molecular weights of thousands to hundreds of thousands. Even
  • thermoplastic elastomers known and commonly used thermoplastic elastomers, tackifiers, catalysts, phosphoric acid compounds, melamine resins, or reactive elastomers can be used as other additives.
  • the content of these additives can be appropriately adjusted and used as long as the function of the adhesive of the present invention is not impaired.
  • Examples of the film used in the present invention include paper, plastic film, metal vapor deposition film or copper foil, metal foil such as aluminum foil, and the like.
  • a plastic film is a biaxially stretched film made of an organic polymer resin, stretched in the longitudinal direction and / or width direction after melt extrusion, and further heat-set and cooled, or heated without stretching after melt extrusion. Non-stretched film that has been fixed and cooled.
  • Organic polymer resins include olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, fluorine resins, poly (meta )
  • ABS resins acrylonitrile-butadiene-styrene copolymers
  • polyvinyl chloride resins fluorine resins
  • poly (meta ) There are acrylic resins, carbonate resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins, and biaxially stretched films were obtained from polyester resins such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • Synthetic resin film biaxially oriented polypropylene (OPP), plastic Vinylidene chloride-coated OPP (KOP), nylon (NY), polyvinylidene chloride-coated nylon, polyvinyl chloride, polyvinyl alcohol, biaxially oriented polystyrene (OPS), and the like.
  • Non-stretched films include LDPE (low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene), HDPE (high density polyethylene), EVA (ethylene-vinyl acetate copolymer), Examples thereof include CPP (non-axially stretched polypropylene).
  • These organic polymer resins may be copolymerized in a small amount with other organic monomers or blended with other organic polymers.
  • the film etc. which have a vapor deposition film on the said plastic film like aluminum vapor deposition PET, silica vapor deposition PET, alumina vapor deposition PET, and aluminum vapor deposition CPP are mentioned.
  • the transparency of the film is not particularly limited, but when transparency is required, a film having a light transmittance of 50% or more is preferable.
  • the plastic film before the organic layer or inorganic layer is laminated may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, flame treatment, surface roughening treatment, known anchor coating treatment, printing, decoration, etc. Good.
  • the thickness of the film is preferably in the range of 3 to 500 ⁇ m, more preferably in the range of 6 to 300 ⁇ m.
  • the polyurethane adhesive used in the present invention can be dissolved in a suitable solvent or dispersant such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, and an alicyclic hydrocarbon at an arbitrary ratio.
  • a suitable solvent or dispersant such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, and an alicyclic hydrocarbon at an arbitrary ratio.
  • a suitable solvent or dispersant such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, and an alicyclic hydrocarbon at an arbitrary ratio.
  • a suitable solvent or dispersant such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, and an alicyclic hydrocarbon at an arbitrary ratio.
  • Disperse die coat, lip coat, gravure coat, direct reverse gravure coat, kiss reverse gravure coat, non-sol coat, roll coat, reverse
  • the polyurethane adhesive used in the present invention does not contain an organic solvent having high solubility such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, or the like. It can also be used as a solvent type.
  • an organic solvent having high solubility such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, or the like. It can also be used as a solvent type.
  • the amount of the polyurethane adhesive used in the present invention applied to the film is not particularly limited, but is, for example, from 0.1 to 10 g / m 2 , and particularly from 0.1 to 5.0 g / m 2 . It is preferable to select from the viewpoint that excellent weather resistance and the like can be imparted in a small amount.
  • the coating weight is less than 0.1 g / m 2 , a problem arises in continuous uniform coating properties.
  • the coating weight exceeds 10.0 g / m 2 , the solvent detachability after coating is lowered and workability is reduced. In addition to a significant reduction, the problem of residual solvent arises.
  • the polyurethane adhesive used in the present invention is composed of the A agent and the B agent, and is applied to the A agent applied to one base material and the other base material. It is a two-component fractional coating process in which the B agent comes into contact and pressure bonding, and the A agent contains either a polyol compound or a polyisocyanate compound as a curing component, and the B agent is different from the A agent as a curing component. Or any one of a polyisocyanate compound is included.
  • the pressure bonding method is preferably a method of bonding by dry lamination (dry lamination method).
  • the temperature of the laminating roll is preferably about room temperature to 120 ° C., and the pressure is preferably about 3 to 300 kg / cm 2 . In this way, a flexible packaging film can be obtained.
  • the film for soft packaging coated with the adhesive used in the present invention is preferably subjected to aging after production.
  • the aging conditions are preferably a temperature of 25 to 80 ° C. and a time of 12 to 240 hours, during which the adhesive strength is generated.
  • the appearance of the laminate film is improved, and the production of a flexible packaging film with improved soft packaging texture is possible. It can be used as a packaging material for food. Other various packaging materials can be used industrially.
  • Example 1 A polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) is applied to an ink surface of a printed PET (polyethylene terephthalate) film 12 ⁇ m, while aluminum vapor deposited CPP (unstretched polypropylene) 30 ⁇ m.
  • a polyol compound manufactured by DIC Corporation: polyether polyol HA-220B was applied to the vapor-deposited surface, and the coated surfaces were pressure-bonded with a nip roll (nip roll temperature: 50 ° C.) to produce a plastic film laminate.
  • the processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
  • Example 2 A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) is applied to an ink surface of a printed PET (polyethylene terephthalate) film 12 ⁇ m, while a polyisocyanate is deposited on an aluminum-deposited CPP (unstretched polypropylene) 30 ⁇ m deposition surface.
  • a compound (DIC Co., Ltd .: aromatic polyether isocyanate 2K-SF-220A) was applied, and the coated surfaces were pressure-bonded with a nip roll (nip roll temperature: 50 ° C.) to produce a plastic film laminate.
  • the processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
  • Example 3 Polyisocyanate compound (DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) and catalyst (photo-latent titanium catalyst and ⁇ -caprolactam) are applied to the printed surface of 12 ⁇ m PET (polyethylene terephthalate) film. The added mixture is applied, and on the other hand, a polyol compound (DIC Co., Ltd .: polyether polyol HA-220B) is applied to a vapor-deposited surface of aluminum vapor-deposited CPP (unstretched polypropylene) 30 ⁇ m, and the nip roll (nip roll temperature: (50 ° C.) to produce a plastic film laminate. The processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
  • DIC Co., Ltd . polyether polyol HA-220B
  • Example 4 A mixture obtained by adding a polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) and a catalyst (photolatent titanium catalyst and ⁇ -caprolactam) to an ink surface of a printed PET (polyethylene terephthalate) film 12 ⁇ m is applied.
  • a polyisocyanate compound manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A
  • the processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
  • Example 5 A polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) is applied to a corona-treated surface of a PET (polyethylene terephthalate) film 50 ⁇ m, while a linear low density polyethylene (LLDPE) 60 ⁇ m is coated.
  • a polyol compound manufactured by DIC Corporation: polyether polyol HA-220B was applied to the corona-treated surface, and the coated surfaces were pressure-bonded by hand bonding without using a laminating machine to produce a plastic film laminate.
  • the adhesive application amount was 15 g / m 2 .
  • Example 6 A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) is applied to a corona-treated surface of a PET (polyethylene terephthalate) film 50 ⁇ m, while a polyisocyanate is applied to a corona-treated surface of a linear low density polyethylene (LLDPE) 60 ⁇ m.
  • a compound manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A was applied, and the coated surfaces were pressure-bonded by hand bonding without using a laminating machine to produce a plastic film laminate.
  • the adhesive application amount was 15 g / m 2 .
  • Example 7 Polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) and catalyst (photolatent titanium catalyst and ⁇ -caprolactam) were added to the corona-treated surface of 50 ⁇ m PET (polyethylene terephthalate) film.
  • a polyol compound (DIC Co., Ltd .: polyether polyol HA-220B) was applied to a corona-treated surface of linear low density polyethylene (LLDPE) 60 ⁇ m, and a laminating machine was used between the coated surfaces.
  • LLDPE linear low density polyethylene
  • a plastic film laminate was prepared by hand bonding. The adhesive application amount was 15 g / m 2 .
  • Example 8 A PET (polyethylene terephthalate) film was coated on a corona-treated surface of 50 ⁇ m with a mixture in which a polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) and a catalyst (photolatent titanium catalyst and ⁇ -caprolactam) were added, Apply a polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) to a corona-treated surface of linear low density polyethylene (LLDPE) 60 ⁇ m, and use a laminating machine between the coated surfaces.
  • a plastic film laminate was prepared by hand bonding. The adhesive application amount was 15 g / m 2 .
  • the soft wrapping film obtained by the method for producing a soft wrapping film having the two-component fractionation coating process of the present invention is excellent in appearance and texture, as apparent from the results of the above examples and comparative examples. It is clear that there is no soft packaging film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

A method for producing a film for soft packaging in which a polyurethane adhesive agent is applied to a base material, wherein: the polyurethane adhesive agent has an agent A and an agent B as reaction base materials; the method has a two-liquid separate-application step in which the agent A, which is applied to one base material, and the agent B, which is applied to another base material, come into contact and bond under pressure; the agent A contains either a polyol compound or a polyisocyanate compound as a curing component; and the agent B contains either a polyol compound or a polyisocyanate compound as a curing component different from that in the agent A.

Description

軟包装用フィルムの製造方法Method for producing flexible packaging film
　本発明は軟包装用フィルムの製造方法、特に２液分別塗布工程を有する製造方法に関する。 The present invention relates to a method for producing a flexible packaging film, and more particularly to a production method having a two-liquid fractionation coating step.
　２液硬化型ポリウレタン樹脂接着剤は、軟包装用フィルムの接着剤として広く用いられている。
　プラスチックフィルムには裏刷りの印刷が施されており、そのインキ面に接着剤を塗布しもう片方のプラスチックフィルムを貼り合わせていくため、そのインキは外観をきれいに仕上げるための妨げとなっており、外観の向上が求められている。
さらには、プラスチック積層体を用いた軟包装材は硬い風合いが好まれ、接着剤塗膜は硬い方が風合いが良好となるので、このような製品が希求されている。 Two-component curable polyurethane resin adhesives are widely used as adhesives for soft packaging films.
The plastic film is printed on the back side, and the ink is applied to the ink surface and the other plastic film is bonded together. There is a need for improved appearance.
Furthermore, since a soft packaging material using a plastic laminate is preferred to have a hard texture, and a harder adhesive coating film has a better texture, such a product is desired.
　当該接着剤を基材に塗工する際には、イソシアネート成分とポリオール成分を主原料とする２成分を混合した組成物を基材に塗工する方法が主流であるが、速硬化性であって初期接着力の発現が速く、かつ、硬化後は優れた弾性、接着強度、耐熱性、耐寒性等を発現する２液分別塗布型ウレタン系接着剤を提供する方法として、２液分別塗布工程を有する塗工方法も知られている。例えば特許文献１～３には、この方法に用いられる接着剤として、Ａ剤とＢ剤とから構成され、一方の基材に塗布されたＡ剤と他方の基材に塗布されたＢ剤とが接触した時に硬化反応を開始する２液分別塗布型接着剤であって、上記Ａ剤は、分子両末端にイソシアネート基を有する化合物を主成分としてなる常温で液状の無溶剤型Ａ剤であり、上記Ｂ剤は、分子両末端にアミノ基を有する化合物、分子内に３級アミンを有する化合物および粘着性付与樹脂を含有してなる常温で液状の無溶剤型Ｂ剤であることを特徴とする２液分別塗布型ウレタン系接着剤等が記載されている。 When the adhesive is applied to a substrate, a method of coating the substrate with a composition in which two components mainly composed of an isocyanate component and a polyol component are mixed is the mainstream, but it is fast-curing. As a method for providing a two-component fractionation-applied urethane adhesive that expresses initial adhesive force quickly and exhibits excellent elasticity, adhesive strength, heat resistance, cold resistance, etc. after curing, a two-component fractionation coating step A coating method having the following is also known. For example, in Patent Documents 1 to 3, the adhesive used in this method is composed of agent A and agent B, and agent A applied to one substrate and agent B applied to the other substrate. Is a two-component fractional coating type adhesive that starts a curing reaction when it comes into contact, and the agent A is a non-solvent agent A which is liquid at room temperature and mainly comprises a compound having an isocyanate group at both molecular ends. The B agent is a solvent-free B agent which is liquid at room temperature and contains a compound having an amino group at both molecular ends, a compound having a tertiary amine in the molecule, and a tackifying resin. A two-part fractionation-type urethane adhesive is described.
特開２００３－１７１６４１号公報JP 2003-171641 A 特開２００３－１７１６４２号公報JP 2003-171642 A 特開２００３－１７１６４３号公報Japanese Patent Laid-Open No. 2003-171643
　本発明では、従来技術には挙げられていない課題、即ち、分別塗布することにより、ラミネート時に気泡のかみこみが少なく、ラミネートフィルムの外観が向上し、硬化後の接着剤塗膜が硬くなり、軟包装の風合いが良化する軟包装用フィルムの製造方法を提供することにある。 In the present invention, problems that are not listed in the prior art, that is, by separately coating, there is less entrapment of bubbles at the time of lamination, the appearance of the laminated film is improved, the cured adhesive coating film is hardened, and softened. An object of the present invention is to provide a method for producing a flexible packaging film that improves the packaging texture.
　即ち本発明は、ポリウレタン接着剤が基材に塗布された軟包装用フィルムの製造方法において、該ポリウレタン接着剤がＡ剤とＢ剤を反応原料とし、一方の基材に塗布されたＡ剤と他方の基材に塗布されたＢ剤とが接触して圧着する２液分別塗布工程を有し、Ａ剤が硬化成分としてポリオール化合物又はポリイソシアネート化合物のいずれか一方を含み、Ｂ剤が硬化成分としてＡ剤とは異なるポリオール化合物又はポリイソシアネート化合物のいずれか一方を含む軟包装用フィルムの製造方法を提供する。 That is, the present invention relates to a method for producing a flexible packaging film in which a polyurethane adhesive is applied to a base material, wherein the polyurethane adhesive uses the A agent and the B agent as reaction raw materials, and the A agent applied to one base material It has a two-component fractionation coating process in which the B agent applied to the other substrate contacts and pressure-bonds, the A agent contains either a polyol compound or a polyisocyanate compound as a curing component, and the B agent is a curing component As a manufacturing method of the film for flexible packaging containing any one of the polyol compound or polyisocyanate compound different from A agent as.
　また本発明は、前期記載の製造方法により得られる軟包装用フィルムを用いた食品用軟包装材を提供する。 The present invention also provides a soft food packaging material using a soft packaging film obtained by the production method described in the previous term.
　本発明によれば、ラミネート時に気泡のかみこみが少なく、ラミネートフィルムの外観が向上し、硬化後の接着剤塗膜が硬くなり、軟包装の風合いが良化する軟包装用フィルムの製造方法を提供することができる。 According to the present invention, there is provided a method for producing a film for soft packaging, in which there is less entrapment of bubbles during lamination, the appearance of the laminate film is improved, the adhesive coating film after curing becomes hard, and the texture of the soft packaging is improved. can do.
（ポリウレタン接着剤）
　本発明で使用する該ポリウレタン接着剤は、Ａ剤とＢ剤を反応原料とし、Ａ剤が硬化成分としてポリオール化合物又はポリイソシアネート化合物のいずれか一方を含み、Ｂ剤が硬化成分としてＡ剤とは異なるポリオール化合物又はポリイソシアネート化合物のいずれか一方を含むことを特徴とする。
　本発明においては、Ａ剤の硬化成分としてポリオール化合物を含む場合は、Ｂ剤はポリイソシアネート化合物を含む。一方Ａ剤の硬化成分としてポリイソシアネート化合物を含む場合は、Ｂ剤はポリオール化合物を含む。なお本発明においてＡ剤またはＢ剤はポリオール化合物とポリイソシアネート化合物の両方は含まないものとする。 (Polyurethane adhesive)
The polyurethane adhesive used in the present invention uses agent A and agent B as reaction raw materials, agent A contains either a polyol compound or a polyisocyanate compound as a curing component, and agent B as a curing component. It includes any one of different polyol compounds or polyisocyanate compounds.
In this invention, when a polyol compound is included as a hardening component of A agent, B agent contains a polyisocyanate compound. On the other hand, when a polyisocyanate compound is included as a curing component of the agent A, the agent B includes a polyol compound. In the present invention, the agent A or agent B does not contain both a polyol compound and a polyisocyanate compound.
（ポリオール化合物）
　本発明に用いるポリオール化合物は、特に限定はないが、例えばポリエステルポリオール、ポリエーテルポリオール、ポリエーテルエステルポリオール、ポリエステル（ポリウレタン）ポリオール、ポリエーテル（ポリウレタン）ポリオール、ポリエステルアミドポリオール、アクリルポリオール、ポリカーボネートポリオール、ポリヒドロキシルアルカン、ポリウレタンポリオール、ひまし油又はそれらの混合物から選ばれるポリマーポリオールを挙げることができる。 (Polyol compound)
The polyol compound used in the present invention is not particularly limited. For example, polyester polyol, polyether polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, Mention may be made of polymer polyols selected from polyhydroxyl alkanes, polyurethane polyols, castor oil or mixtures thereof.
　ポリエステルポリオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等二塩基酸若しくはそれらのジアルキルエステル又はそれらの混合物と、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、３，３’－ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール等のグリコール類若しくはそれらの混合物とを反応させて得られるポリエステルポリオール或いはポリカプロラクトン、ポリバレロラクトン、ポリ（β－メチル－γ－バレロラクトン）等のラクトン類を開環重合して得られるポリエステルポリオールが挙げられる。 Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neodymium. Glycols such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol or the like; Ring opening of lactones such as polyester polyol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) obtained by reacting with these mixtures The polyester polyol obtained by superposition | polymerization is mentioned.
　ポリエーテルポリオールとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を、例えば、水、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン等の低分量ポリオールを開始剤として重合して得られるポリエーテルポリオールが挙げられる。 ポリエーテルエステルポリオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等の二塩基酸若しくはそれらのジアルキルエステル又はそれらの混合物と、上記ポリエーテルポリオールを反応させて得られるポリエーテルエステルポリオールが挙げられる。 As the polyether polyol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran is polymerized using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, and the like as a low-part polyol. The polyether polyol obtained is mentioned. Examples of the polyether ester polyol include a polybasic acid obtained by reacting the above polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof. Examples include ether ester polyols.
　ポリエーテル（ポリウレタン）ポリオールとしては、１分子中にウレタン結合を有するポリオールであり、例えば、数平均分子量２００～２０，０００のポリエーテルポリオールと有機ポリイソシアネートとの反応物で、ＮＣＯ／ＯＨが１未満が好ましく、より好ましくは０．９以下のものを挙げることができる。 The polyether (polyurethane) polyol is a polyol having a urethane bond in one molecule. For example, it is a reaction product of a polyether polyol having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate, and NCO / OH is 1 It is preferably less than 0.9, more preferably 0.9 or less.
　ポリエステル（ポリウレタン）ポリオールとしては、ポリエステルポリオール、ポリエーテルエステルポリオール等と有機ポリイソシアネートとの反応物で、ＮＣＯ／ＯＨが１未満が好ましく、より好ましくは０．９以下のものを挙げることができる。 Examples of the polyester (polyurethane) polyol include a reaction product of a polyester polyol, a polyether ester polyol, and the like and an organic polyisocyanate, and NCO / OH is preferably less than 1, more preferably 0.9 or less.
　ポリエステルアミドポリオールとしては、上記エステル化反応に際し、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等のアミノ基を有する脂肪族ジアミンを原料としてあわせて使用することによって得られる。
　アクリルポリオールの例としては、１分子中に１個以上の水酸基を含むアクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロプル、アクリルヒドロキシブチル等、或いはこれらの対応するメタクリル酸誘導体等と、例えばアクリル酸、メタクリル酸又はそのエステルとを共重合することによって得られる。 The polyesteramide polyol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine as a raw material in the esterification reaction.
Examples of acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyhydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.
　ポリカーボネートポリオールとしては、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，９－ノナンジオール、１，８－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、ビスフェノールＡ、水添ビスフェノールＡの中から選ばれた１種又は２種以上のグリコールをジメチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲン等との反応によって得られたものが挙げられる。 Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One selected from diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or The thing obtained by reaction of 2 or more types of glycol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.
　ポリヒドロキシアルカンとしては、ブタジエン、又はブタジエンとアクリルアミド等と共重合して得られる液状ゴムが挙げられる。
　中でも、ポリエーテル（ポリウレタン）ポリオールが特に好ましい。 Examples of the polyhydroxyalkane include butadiene or liquid rubber obtained by copolymerization with butadiene and acrylamide.
Among these, a polyether (polyurethane) polyol is particularly preferable.
（ポリイソシアネート化合物）
　本発明で用いられるポリイソシアネート化合物としては、イソシアネート基を分子内に少なくとも２つ有する有機化合物が挙げられる。
　有機ポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、１，３－（イソシアナートメチル）シクロヘキサン、１，５－ナフタレンジイソシアネート、トリフェニルメタントリイソシアネートなどのポリイソシアネート；これらのポリイソシアネートのアダクト体、これらのポリイソシアネートのビュレット体、または、これらのポリイソシアネートのイソシアヌレート体などのポリイソシアネートの誘導体（変性物）などが挙げられる。 (Polyisocyanate compound)
Examples of the polyisocyanate compound used in the present invention include organic compounds having at least two isocyanate groups in the molecule.
Examples of the organic polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, Polyisocyanates such as 1,3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; adducts of these polyisocyanates, burettes of these polyisocyanates, or these polyisocyanates And polyisocyanate derivatives (modified products) such as isocyanurates.
　本発明に用いるポリイソシアネート化合物は、硬化剤として作用し適宜選択して用いることができるが、芳香族系であっても脂肪族系であってもよい。本発明で好ましく用いられるポリイソシアネート化合物としては、例えばヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）等のポリイソシアネート、を挙げることができる。
　硬化剤は、ポリイソシアネート化合物（Ｂ）のみでも性能を発現するが、ポリイソシアネート化合物と後述するエポキシ樹脂とを併用することより、硬化塗膜により高度な耐加水分解性を付与することも出来る。 The polyisocyanate compound used in the present invention acts as a curing agent and can be appropriately selected and used, but may be aromatic or aliphatic. Examples of the polyisocyanate compound preferably used in the present invention include polyisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).
Although the curing agent exhibits performance only with the polyisocyanate compound (B), it can also impart high hydrolysis resistance to the cured coating film by using the polyisocyanate compound and the epoxy resin described later.
　また、ポリイソシアネートとビス（ヒドロキシアルキル）アミンの反応物であって末端にウレア結合基を有するものも好ましく用いることができる。 Also, a reaction product of polyisocyanate and bis (hydroxyalkyl) amine having a urea bond group at the terminal can be preferably used.
　前記ポリオール化合物とポリイソシアネート化合物との配合割合は、ポリオール化合物の固形分水酸基当量（ａ）とポリイソシアネート化合物の固形分イソシアネート当量（ｂ）の当量比〔（ｂ）／（ａ）〕が０．５～４．０、より好ましくは０．９～３．０となるように設計する。例えばＡ剤としてポリオール化合物を含み、一方Ｂ剤としてポリイソシアネート化合物を含む場合は、Ａ剤が含有するポリオール化合物の固形分水酸基当量（ａ）から換算しＢ剤が含有するポリイソシアネート化合物の量を決定する。 The blending ratio of the polyol compound and the polyisocyanate compound is such that the equivalent ratio [(b) / (a)] of the solid content hydroxyl equivalent (a) of the polyol compound to the solid isocyanate equivalent (b) of the polyisocyanate compound is 0. It is designed to be 5 to 4.0, more preferably 0.9 to 3.0. For example, when a polyol compound is included as the A agent and a polyisocyanate compound is included as the B agent, the amount of the polyisocyanate compound contained in the B agent is calculated from the solid content hydroxyl equivalent (a) of the polyol compound contained in the A agent. decide.
　本発明で使用するＡ剤またはＢ剤は、必要に応じて反応を促進するための触媒を含んでいてもよい。本発明で使用する触媒は、ウレタン化反応を促進するためのものであれば、特に制限はないが、例えば、金属系、アミン系、ジアザビシクロウンデセン（ＤＢＵ）系、又は脂肪族環状アミド化合物・チタンキレート錯体等の触媒を用いることができる。 The agent A or agent B used in the present invention may contain a catalyst for promoting the reaction, if necessary. The catalyst used in the present invention is not particularly limited as long as it is for accelerating the urethanization reaction. For example, metal-based, amine-based, diazabicycloundecene (DBU) -based, or aliphatic cyclic amide A catalyst such as a compound / titanium chelate complex can be used.
　触媒は、溶液状或いは分散状にして、塗布工程に用いることができ、有機溶剤、可塑剤、ポリエチレンポリオール若しくはポリプロピレンポリオール等のポリオール、又は本発明のポリオール化合物等により溶液状或いは分散状にして用いることができる。
　本発明で用いられるポリウレタン樹脂製造用触媒としては、金属系触媒、アミン系触媒、ＤＢＵ系、又は脂肪族環状アミド化合物、チタンキレート錯体等の公知慣用の触媒を挙げることができる。 The catalyst can be used in the coating step in the form of a solution or dispersion, and used in the form of a solution or dispersion with an organic solvent, a plasticizer, a polyol such as polyethylene polyol or polypropylene polyol, or the polyol compound of the present invention. be able to.
Examples of the polyurethane resin production catalyst used in the present invention include known and commonly used catalysts such as metal-based catalysts, amine-based catalysts, DBU-based, aliphatic cyclic amide compounds, and titanium chelate complexes.
　金属系触媒は、金属錯体系、無機金属系、有機金属系を挙げることができる。
金属錯体系は、Ｆｅ（鉄）、Ｍｎ（マンガン）、Ｃｕ（銅）、Ｚｒ（ジルコニウム）、Ｔｈ（トリウム）、Ｔｉ（チタン）、Ａｌ（アルミニウム）及びＣｏ（コバルト）からなる群より選ばれる金属のアセチルアセトナート塩であり、例えば、鉄アセチルアセトネート、マンガンアセチルアセトネート、銅アセチルアセトネート、ジルコニアアセチルアセトネート等が挙げられるが、これらのうち、毒性と触媒活性の点から、鉄アセチルアセトネート（Ｆｅ（ａｃａｃ）３）又はマンガンアセチルアセトネート（Ｍｎ（ａｃａｃ）２）が好ましい。 Examples of the metal catalyst include a metal complex system, an inorganic metal system, and an organic metal system.
The metal complex system is selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt). Metal acetylacetonate salt, for example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate, etc. Among these, from the viewpoint of toxicity and catalytic activity, iron acetylacetonate Acetonate (Fe (acac) 3 ) or manganese acetylacetonate (Mn (acac) 2 ) is preferred.
　無機金属系触媒としては、Ｆｅ、Ｍｎ、Ｃｕ、Ｚｒ、Ｔｈ、Ｔｉ、Ａｌ及びＣｏ等から選ばれる触媒を挙げることができる。 Examples of the inorganic metal catalyst include catalysts selected from Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
　有機金属系触媒としては、スタナスジアセテート、スタナスジオクトエート、スタナスジオレエート、スタナスジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジクロライド、ジオクチル錫ジラウレート、オクチル酸ニッケル、ナフテン酸ニッケル、オクチル酸コバルト、ナフテン酸コバルト、オクチル酸ビスマス、ナフテン酸ビスマス等が挙げられる。これらのうち好ましい化合物としては有機錫触媒であり、更に好ましくはスタナスジオクトエート、ジブチル錫ジラウレートである。 Examples of organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.
　第３級アミン触媒は、上記構造を有する化合物であれば良く特に限定されないが、例えば、トリエチレンジアミン、２－メチルトリエチレンジアミン、キヌクリジン、２－メチルキヌクリジン等が挙げられる。これらの中でも、触媒活性に優れ工業的に入手可能なことからトリエチレンジアミン、２－メチルトリエチレンジアミンが好ましい。 The tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because of their excellent catalytic activity and industrial availability.
　その他の第３級アミン触媒としては、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチル－（３－アミノプロピル）エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジプロピレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサメチレンジアミン、ビス（２－ジメチルアミノエチル）エーテル、ジメチルエタノールアミン、ジメチルイソプロパノールアミン、ジメチルアミノエトキシエタノール、Ｎ，Ｎ－ジメチル－Ｎ’－（２－ヒドロキシエチル）エチレンジアミン、Ｎ，Ｎ－ジメチル－Ｎ’－（２－ヒドロキシエチル）プロパンジアミン、ビス（ジメチルアミノプロピル）アミン、ビス（ジメチルアミノプロピル）イソプロパノールアミン、３－キヌクリジノール、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルグアニジン、１，３，５－トリス（Ｎ，Ｎ－ジメチルアミノプロピル）ヘキサヒドロ－Ｓ－トリアジン、１，８－ジアザビシクロ［５．４．０］ウンデセン－７、Ｎ－メチル－Ｎ’－（２－ジメチルアミノエチル）ピペラジン、Ｎ，Ｎ’－ジメチルピペラジン、ジメチルシクロヘキシルアミン、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、１－メチルイミダゾール、１，２－ジメチルイミダゾール、１－イソブチル－２－メチルイミダゾール、１－ジメチルアミノプロピルイミダゾール、Ｎ，Ｎ－ジメチルヘキサノールアミン、Ｎ－メチル－Ｎ’－（２－ヒドロキシエチル）ピペラジン、１－（２－ヒドロキシエチル）イミダゾール、１－（２－ヒドロキシプロピル）イミダゾール、１－（２－ヒドロキシエチル）－２－メチルイミダゾール、１－（２－ヒドロキシプロピル）－２－メチルイミダゾール等が挙げられる。 Other tertiary amine catalysts include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis Dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro -S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N -Methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl-N '-(2-hydroxyethyl) pipette Gin, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, etc. Is mentioned.
　脂肪族環状アミド化合物は、例えば、δ－バレロラクタム、ε－カプロラクタム、ω－エナントールラクタム、η－カプリルラクタム、β－プロピオラクタム等が挙げられる。これらの中でも硬化促進効果に優れる点からε－カプロラクタムが好ましい。 Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enanthol lactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is preferable from the viewpoint of excellent curing acceleration effect.
　チタンキレート錯体は、紫外線照射により触媒活性が高められる化合物であり、脂肪族又は芳香族ジケトンをリガンドとするチタンキレート錯体であることが硬化促進効果に優れる点から好ましい。また、本発明ではリガンドとして芳香族又は脂肪族ジケトンに加え、炭素原子数２～１０のアルコールを持つものがより本発明の効果が顕著なものとなる点から好ましい。
　本発明においては、上記触媒を単独でも、併用してもよい。
　本発明において触媒の使用量は、Ａ剤またはＢ剤に使用するポリオール量から換算すればよく、例えばポリオ－ルを１００部としたとき、０．００１～１０部が好ましく、より好ましくは０．０１～１０部である。 The titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic or aromatic diketone as a ligand from the viewpoint of excellent curing acceleration effect. Further, in the present invention, those having an alcohol having 2 to 10 carbon atoms in addition to an aromatic or aliphatic diketone as a ligand are preferable because the effects of the present invention become more remarkable.
In the present invention, the above catalysts may be used alone or in combination.
In the present invention, the amount of the catalyst used may be converted from the amount of polyol used for the agent A or agent B. For example, when the polyol is 100 parts, it is preferably 0.001 to 10 parts, more preferably 0.00. 01 to 10 parts.
　本発明の方法において、触媒は、予めＡ剤またはＢ剤に使用するポリオール化合物やイソシアネート化合物と混合して用いるのが望ましい。また、混合する際に溶媒に溶解して使用することも出来る。本発明の方法において、溶媒は特に限定されるものではないが、例えば、エチレングリコール、ジエチレングリコール、ジプロピレングリコール、プロピレングリコール、ブタンジオール等のアルコール類、トルエン、キシレン、ミネラルターペン等の炭化水素、酢酸エチル、酢酸ブチル、メチルグリコールアセテート、酢酸セルソルブ等のエステル類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類の有機溶媒、アセチルアセトン及びそのフッ素化置換体等のβ－ジケトン類、アセト酢酸メチル、アセト酢酸エチル等のケトエステル類等のキレート化可能な溶媒等が挙げられる。 In the method of the present invention, it is desirable to use the catalyst by mixing it in advance with a polyol compound or an isocyanate compound used for the agent A or agent B. Further, it can be used by dissolving in a solvent when mixing. In the method of the present invention, the solvent is not particularly limited. For example, alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, and butanediol, hydrocarbons such as toluene, xylene, and mineral terpenes, acetic acid Esters such as ethyl, butyl acetate, methyl glycol acetate, and cellosolve acetate, organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, β-diketones such as acetylacetone and its fluorinated substituents, methyl acetoacetate, acetoacetate Examples include chelatable solvents such as ketoesters such as ethyl acetate.
　本発明で使用する接着剤には、必要であれば、前記以外のその他の添加剤を含有させてもよい。添加剤としては、フィルムやコーティング膜などを形成する樹脂組成物に一般に使用されている添加剤などが挙げられる。添加剤としては、例えば、コロイド状シリカ；アルミナゾルなどの無機微粒子；ポリメチルメタクリレート系の有機微粒子；消泡剤；タレ性防止剤；シランカップリング剤；粘性調整剤；紫外線吸収剤；金属不活性化剤；過酸化物分解剤；難燃剤；補強剤；可塑剤；潤滑剤；防錆剤；蛍光性増白剤；無機系熱線吸収剤；防炎剤；帯電防止剤；脱水剤；などが挙げられる。 The adhesive used in the present invention may contain other additives other than those described above, if necessary. Examples of the additive include additives generally used in resin compositions that form films and coating films. Additives include, for example, colloidal silica; inorganic fine particles such as alumina sol; polymethyl methacrylate organic fine particles; antifoaming agents; anti-sagging agents; silane coupling agents; viscosity modifiers; Peroxide decomposer; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust preventive agent; Fluorescent whitening agent; Inorganic heat absorber; Flameproof agent; Antistatic agent; Can be mentioned.
　更に、接着性及び硬化を促進する目的でエポキシ基含有化合物を配合されている場合もあり、エポキシ基含有化合物としては、トリグリシジルトリス（２－ヒドロキシエチル）イソシアヌレート、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、アクリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、フェノールグリシジルエーテル、ｐ－ｔ－ブチルフェニルグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、グリシジルメタクリレート、ブチルグリシジルエーテル等の化合物や、エポキシ基を含有した分子量が数百から数千のオリゴマーや重量平均分子量が数千から数十万のポリマーを配合されているケースもある。 Further, an epoxy group-containing compound may be blended for the purpose of promoting adhesion and curing. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester , Glycidyl methacrylate, butyl glycidyl ether, etc., oligomers containing epoxy groups with molecular weights of hundreds to thousands, and polymers with weight average molecular weights of thousands to hundreds of thousands. Even if that case there.
＜その他の添加剤＞
　本発明では、その他の添加剤として、公知慣用の熱可塑性エラストマー、粘着付与剤、触媒、燐酸化合物，メラミン樹脂、又は反応性エラストマーを用いることができる。これらの添加剤の含有量は、本発明の接着剤の機能を損なわない範囲内で適宜調整して用いることができる。 <Other additives>
In the present invention, known and commonly used thermoplastic elastomers, tackifiers, catalysts, phosphoric acid compounds, melamine resins, or reactive elastomers can be used as other additives. The content of these additives can be appropriately adjusted and used as long as the function of the adhesive of the present invention is not impaired.
＜フィルム＞
　本発明に用いられるフィルムとしては、例えば、紙、プラスチックフィルム、金属蒸着フィルム又は銅箔、アルミニウム箔の様な金属箔等を挙げることができる。プラスチックフィルムとは、有機高分子樹脂からなり、溶融押出し後、長手方向および／または幅方向に延伸され、さらに熱固定、冷却を施された二軸延伸フィルム、または溶融押出し後、延伸無しで熱固定、冷却を施された無延伸フィルムであり、有機高分子樹脂としては、オレフィン系樹脂、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、ポリ塩化ビニル系樹脂、フッ素系樹脂、ポリ（メタ）アクリル系樹脂、カーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド系樹脂があり、二軸延伸フィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル系樹脂から得られた合成樹脂フィルム、二軸延伸ポリプロピレン（ＯＰＰ）、ポリ塩化ビニリデンコートＯＰＰ（ＫＯＰ）、ナイロン（ＮＹ）、ポリ塩化ビニリデンコートナイロン、ポリ塩化ビニル、ポリビニルアルコール、二軸延伸ポリスチレン（ＯＰＳ）等が挙げられる。また、無延伸フィルムとしては、ＬＤＰＥ（低密度ポリエチレン）、ＬＬＤＰＥ（直鎖状低密度ポリエチレン）、ＭＤＰＥ（中密度ポリエチレン）、ＨＤＰＥ（高密度ポリエチレン）、ＥＶＡ（エチレン－酢酸ビニル共重合体）、ＣＰＰ（無軸延伸ポリプロピレン）等が挙げられる。これらの有機高分子樹脂は、他の有機単量体を少量共重合したり、他の有機重合体をブレンドしたりしてもよい。
　またアルミ蒸着ＰＥＴ、シリカ蒸着ＰＥＴ、アルミナ蒸着ＰＥＴ、アルミ蒸着ＣＰＰのように、前記プラスチックフィルムに蒸着膜を有するフィルム等も挙げられる。 <Film>
Examples of the film used in the present invention include paper, plastic film, metal vapor deposition film or copper foil, metal foil such as aluminum foil, and the like. A plastic film is a biaxially stretched film made of an organic polymer resin, stretched in the longitudinal direction and / or width direction after melt extrusion, and further heat-set and cooled, or heated without stretching after melt extrusion. Non-stretched film that has been fixed and cooled. Organic polymer resins include olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, fluorine resins, poly (meta ) There are acrylic resins, carbonate resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins, and biaxially stretched films were obtained from polyester resins such as polyethylene terephthalate (PET). Synthetic resin film, biaxially oriented polypropylene (OPP), plastic Vinylidene chloride-coated OPP (KOP), nylon (NY), polyvinylidene chloride-coated nylon, polyvinyl chloride, polyvinyl alcohol, biaxially oriented polystyrene (OPS), and the like. Non-stretched films include LDPE (low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene), HDPE (high density polyethylene), EVA (ethylene-vinyl acetate copolymer), Examples thereof include CPP (non-axially stretched polypropylene). These organic polymer resins may be copolymerized in a small amount with other organic monomers or blended with other organic polymers.
Moreover, the film etc. which have a vapor deposition film on the said plastic film like aluminum vapor deposition PET, silica vapor deposition PET, alumina vapor deposition PET, and aluminum vapor deposition CPP are mentioned.
　前記フィルムとしての透明度は特に限定するものではないが、透明性を要求される場合には、５０％以上の光線透過率をもつものが好ましい。また有機層や無機層を積層する前のプラスチックフィルムに、コロナ放電処理、プラズマ放電処理、火炎処理、表面粗面化処理などの表面処理、公知のアンカーコート処理、印刷、装飾などを施してもよい。 The transparency of the film is not particularly limited, but when transparency is required, a film having a light transmittance of 50% or more is preferable. The plastic film before the organic layer or inorganic layer is laminated may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, flame treatment, surface roughening treatment, known anchor coating treatment, printing, decoration, etc. Good.
　また、前記フィルムの厚みは、３～５００μｍの範囲が好ましく、６～３００μｍの範囲がより好ましい。   The thickness of the film is preferably in the range of 3 to 500 μm, more preferably in the range of 6 to 300 μm.
　本発明で使用するポリウレタン接着剤は、例えば、エステル系溶剤、ケトン系溶剤、芳香族系炭化水素、脂肪族炭化水素、脂環族炭化水素等の適当な溶剤または分散剤に任意の割合で溶解／分散させて、ダイコート、リップコート、グラビアコート、ダイレクトリバースグラビアコート、キスリバースグラビアコート、ノンソルコート、ロールコート、リバースコート、ナイフコート、ドクターコート、エクストルージョンコート、スライドコート、ワイヤーバーコート、押出コート等の公知の塗布方式を用いて接着層を形成することができる。
　また、本発明で使用するポリウレタン接着剤は、エステル系溶剤、ケトン系溶剤、芳香族系炭化水素、脂肪族炭化水素、脂環族炭化水素等の溶解性の高い有機溶剤を含まない、いわゆる無溶剤型としても用いることができる。 The polyurethane adhesive used in the present invention can be dissolved in a suitable solvent or dispersant such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, and an alicyclic hydrocarbon at an arbitrary ratio. / Disperse, die coat, lip coat, gravure coat, direct reverse gravure coat, kiss reverse gravure coat, non-sol coat, roll coat, reverse coat, knife coat, doctor coat, extrusion coat, slide coat, wire bar coat, The adhesive layer can be formed using a known coating method such as extrusion coating.
The polyurethane adhesive used in the present invention does not contain an organic solvent having high solubility such as an ester solvent, a ketone solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, or the like. It can also be used as a solvent type.
　本発明で使用するポリウレタン接着剤のフィルムへの塗布量は、特に制限されるものではないが、例えば、０．１～１０ｇ／ｍ２、中でも０．１～５．０ｇ／ｍ２の範囲から選択することが、少量で優れた耐候性等が付与できる点で好ましい。
　本発明では、塗布重量が、０．１ｇ／ｍ２を下回ると連続均一塗布性に難点が生じ、一方、１０．０ｇ／ｍ２を越えると塗布後における溶剤離脱性も低下し、作業性が著しく低下する上に残留溶剤の問題が生じる。 The amount of the polyurethane adhesive used in the present invention applied to the film is not particularly limited, but is, for example, from 0.1 to 10 g / m 2 , and particularly from 0.1 to 5.0 g / m 2 . It is preferable to select from the viewpoint that excellent weather resistance and the like can be imparted in a small amount.
In the present invention, when the coating weight is less than 0.1 g / m 2 , a problem arises in continuous uniform coating properties. On the other hand, when the coating weight exceeds 10.0 g / m 2 , the solvent detachability after coating is lowered and workability is reduced. In addition to a significant reduction, the problem of residual solvent arises.
＜２液分別塗布工程＞
　本発明における分別塗布工程は、前述の通り、本発明に用いられるポリウレタン接着剤がＡ剤とＢ剤とから構成され、一方の基材に塗布されたＡ剤と他方の基材に塗布されたＢ剤とが接触して圧着する２液分別塗布工程であって、Ａ剤が硬化成分としてポリオール化合物又はポリイソシアネート化合物のいずれか一方を含み、Ｂ剤が硬化成分としてＡ剤とは異なるポリオール化合物又はポリイソシアネート化合物のいずれか一方を含む。一方の基材にＡ剤を塗布し、他方の基材にＢ剤を塗布して、両基材を貼り合わせることにより、Ａ剤とＢ剤とが接触し、圧着させ反応が開始することにより、速やかに硬化が進行するものであるとともに、通常の２液混合型接着剤のような２液の混合が不要であり、従って２液混合後の可使時間（ポットライフ）を懸念する必要がなく、溶剤の乾燥も不要であるので、作業性にも優れるものである。圧着方法はドライラミネーション（乾式積層法）により貼り合わせる方法が好ましく、ラミネートロールの温度は室温～１２０℃程度、圧力は、３～３００ｋｇ／ｃｍ２程度が好ましい。このようにして軟包装フィルムを得ることができる。 <2-liquid fraction application process>
As described above, in the fractional application step in the present invention, the polyurethane adhesive used in the present invention is composed of the A agent and the B agent, and is applied to the A agent applied to one base material and the other base material. It is a two-component fractional coating process in which the B agent comes into contact and pressure bonding, and the A agent contains either a polyol compound or a polyisocyanate compound as a curing component, and the B agent is different from the A agent as a curing component. Or any one of a polyisocyanate compound is included. By applying the agent A to one base material, applying the agent B to the other base material, and bonding both base materials, the agent A and the agent B are brought into contact with each other, pressure-bonded, and the reaction starts. In addition to the rapid progress of curing, it is not necessary to mix two liquids as in a normal two-liquid mixed adhesive, and therefore there is a need to worry about the pot life after mixing the two liquids. In addition, since the solvent does not need to be dried, the workability is excellent. The pressure bonding method is preferably a method of bonding by dry lamination (dry lamination method). The temperature of the laminating roll is preferably about room temperature to 120 ° C., and the pressure is preferably about 3 to 300 kg / cm 2 . In this way, a flexible packaging film can be obtained.
　本発明で使用する接着剤を塗布した軟包装用フィルムは、作製後エージングを行うことが好ましい。エージング条件は、好ましい温度は２５～８０℃、時間は１２～２４０時間であり、この間に接着強度が生じる。 The film for soft packaging coated with the adhesive used in the present invention is preferably subjected to aging after production. The aging conditions are preferably a temperature of 25 to 80 ° C. and a time of 12 to 240 hours, during which the adhesive strength is generated.
　本発明の軟包装用フィルムの製造方法によれば、ラミネートフィルムの外観が向上し、軟包装の風合いが良化する軟包装用フィルムの製造が可能となるので、得られる軟包装用フィルムは、食品用包装材としての利用が可能である。その他各種包装材料として工業的に使用することができる。 According to the method for producing a flexible packaging film of the present invention, the appearance of the laminate film is improved, and the production of a flexible packaging film with improved soft packaging texture is possible. It can be used as a packaging material for food. Other various packaging materials can be used industrially.
　以下、実施例により、具体的に本発明を説明する。
（実施例１）
　印刷済みのＰＥＴ（ポリエチレンテレフタレート）フィルム１２μｍのインキ面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、一方アルミ蒸着ＣＰＰ（無延伸ポリプロピレン）３０μｍの蒸着面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、塗布面同士をニップロール（ニップロール温度：５０℃）で圧着しプラスチックフィルム積層体を作製した。加工速度は２００ｍ／ｍｉｎ、接着剤塗布量は１．８ｇ／ｍ２であった。 Hereinafter, the present invention will be specifically described by way of examples.
(Example 1)
A polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) is applied to an ink surface of a printed PET (polyethylene terephthalate) film 12 μm, while aluminum vapor deposited CPP (unstretched polypropylene) 30 μm. A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) was applied to the vapor-deposited surface, and the coated surfaces were pressure-bonded with a nip roll (nip roll temperature: 50 ° C.) to produce a plastic film laminate. The processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
（実施例２）
　印刷済みのＰＥＴ（ポリエチレンテレフタレート）フィルム１２μｍのインキ面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、一方アルミ蒸着ＣＰＰ（無延伸ポリプロピレン）３０μｍの蒸着面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、塗布面同士をニップロール（ニップロール温度：５０℃）で圧着しプラスチックフィルム積層体を作製した。加工速度は２００ｍ／ｍｉｎ、接着剤塗布量は１．８ｇ／ｍ２であった。 (Example 2)
A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) is applied to an ink surface of a printed PET (polyethylene terephthalate) film 12 μm, while a polyisocyanate is deposited on an aluminum-deposited CPP (unstretched polypropylene) 30 μm deposition surface. A compound (DIC Co., Ltd .: aromatic polyether isocyanate 2K-SF-220A) was applied, and the coated surfaces were pressure-bonded with a nip roll (nip roll temperature: 50 ° C.) to produce a plastic film laminate. The processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
（実施例３）
　印刷済みのＰＥＴ（ポリエチレンテレフタレート）フィルム１２μｍのインキ面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）と触媒（光潜在性チタン触媒とε－カプロラクタム）を添加した混合物を塗布し、一方アルミ蒸着ＣＰＰ（無延伸ポリプロピレン）３０μｍの蒸着面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、塗布面同士をニップロール（ニップロール温度：５０℃）で圧着しプラスチックフィルム積層体を作製した。加工速度は２００ｍ／ｍｉｎ、接着剤塗布量は１．８ｇ／ｍ２であった。 (Example 3)
Polyisocyanate compound (DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) and catalyst (photo-latent titanium catalyst and ε-caprolactam) are applied to the printed surface of 12 μm PET (polyethylene terephthalate) film. The added mixture is applied, and on the other hand, a polyol compound (DIC Co., Ltd .: polyether polyol HA-220B) is applied to a vapor-deposited surface of aluminum vapor-deposited CPP (unstretched polypropylene) 30 μm, and the nip roll (nip roll temperature: (50 ° C.) to produce a plastic film laminate. The processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
（実施例４）
　印刷済みのＰＥＴ（ポリエチレンテレフタレート）フィルム１２μｍのインキ面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）と触媒（光潜在性チタン触媒とε－カプロラクタム）を添加した混合物を塗布し、一方アルミ蒸着ＣＰＰ（無延伸ポリプロピレン）３０μｍの蒸着面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、塗布面同士をニップロール（ニップロール温度：５０℃）で圧着しプラスチックフィルム積層体を作製した。加工速度は２００ｍ／ｍｉｎ、接着剤塗布量は１．８ｇ／ｍ２であった。 Example 4
A mixture obtained by adding a polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) and a catalyst (photolatent titanium catalyst and ε-caprolactam) to an ink surface of a printed PET (polyethylene terephthalate) film 12 μm is applied. On the other hand, a polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) is applied to a vapor-deposited surface of aluminum vapor-deposited CPP (unstretched polypropylene) 30 μm, and the coated surfaces are nip-rolled (nip roll temperature: (50 ° C.) to produce a plastic film laminate. The processing speed was 200 m / min, and the adhesive coating amount was 1.8 g / m 2 .
（比較例１）
　実施例１、２、３、４の分別塗布を行う代わりに、印刷済みのＰＥＴフィルムのインキ面に接着剤（ＤＩＣ（株）製：２Ｋ－ＳＦ－２２０ＡとＨＡ－２２０Ｂの混合液）を塗布した後、アルミ蒸着ＣＰＰの蒸着面をニップロールで圧着した。
　なお、実施例１、２、３、４、比較例１共にフィルム貼り合わせ面は、印刷済みのＰＥＴフィルムのインキ面とアルミ蒸着ＣＰＰの蒸着面とした。 (Comparative Example 1)
Instead of performing fractional application in Examples 1, 2, 3, and 4, an adhesive (made by DIC Corporation: mixed solution of 2K-SF-220A and HA-220B) was applied to the ink surface of the printed PET film. After that, the vapor deposition surface of the aluminum vapor deposition CPP was pressure-bonded with a nip roll.
In Examples 1, 2, 3, 4, and Comparative Example 1, the film bonding surfaces were the ink surface of a printed PET film and the vapor deposition surface of aluminum vapor deposition CPP.
（外観の判定方法）
　圧着後のプラスチックフィルム積層体は４０℃雰囲気下で４８時間の養生後、外観を目視評価した。作製したラミネートフィルムをＰＥＴフィルム側から観察した時に、気泡状外観不良がなく均一な塗工面であるかを評価した。
　・評価
　　〇：気泡無（外観良好）　　　　×：気泡有（外観不良） (Appearance judgment method)
The external appearance of the plastic film laminated body after press bonding was visually evaluated after curing for 48 hours in an atmosphere of 40 ° C. When the produced laminate film was observed from the PET film side, it was evaluated whether it was a uniform coated surface with no bubble-like appearance defect.
・ Evaluation ○: No bubbles (good appearance) ×: Bubbles (good appearance)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例５）
　ＰＥＴ（ポリエチレンテレフタレート）フィルム５０μｍのコロナ処理面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、一方直鎖状低密度ポリエチレン（ＬＬＤＰＥ）６０μｍのコロナ処理面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、塗布面同士をラミネート機は使用せず手貼りで圧着しプラスチックフィルム積層体を作製した。接着剤塗布量は１５ｇ／ｍ２で行った。 (Example 5)
A polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) is applied to a corona-treated surface of a PET (polyethylene terephthalate) film 50 μm, while a linear low density polyethylene (LLDPE) 60 μm is coated. A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) was applied to the corona-treated surface, and the coated surfaces were pressure-bonded by hand bonding without using a laminating machine to produce a plastic film laminate. The adhesive application amount was 15 g / m 2 .
（実施例６）
　ＰＥＴ（ポリエチレンテレフタレート）フィルム５０μｍのコロナ処理面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、一方直鎖状低密度ポリエチレン（ＬＬＤＰＥ）６０μｍのコロナ処理面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、塗布面同士をラミネート機は使用せず手貼りで圧着しプラスチックフィルム積層体を作製した。接着剤塗布量は１５ｇ／ｍ２で行った。 (Example 6)
A polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) is applied to a corona-treated surface of a PET (polyethylene terephthalate) film 50 μm, while a polyisocyanate is applied to a corona-treated surface of a linear low density polyethylene (LLDPE) 60 μm. A compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) was applied, and the coated surfaces were pressure-bonded by hand bonding without using a laminating machine to produce a plastic film laminate. The adhesive application amount was 15 g / m 2 .
（実施例７）
　ＰＥＴ（ポリエチレンテレフタレート）フィルム５０μｍのコロナ処理面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）と触媒（光潜在性チタン触媒とε－カプロラクタム）を添加した混合物を塗布し、一方直鎖状低密度ポリエチレン（ＬＬＤＰＥ）６０μｍのコロナ処理面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）を塗布し、塗布面同士をラミネート機は使用せず手貼りで圧着しプラスチックフィルム積層体を作製した。接着剤塗布量は１５ｇ／ｍ２で行った。 (Example 7)
Polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) and catalyst (photolatent titanium catalyst and ε-caprolactam) were added to the corona-treated surface of 50 μm PET (polyethylene terephthalate) film. On the other hand, a polyol compound (DIC Co., Ltd .: polyether polyol HA-220B) was applied to a corona-treated surface of linear low density polyethylene (LLDPE) 60 μm, and a laminating machine was used between the coated surfaces. A plastic film laminate was prepared by hand bonding. The adhesive application amount was 15 g / m 2 .
（実施例８）
　ＰＥＴ（ポリエチレンテレフタレート）フィルム５０μｍのコロナ処理面にポリオール化合物（ＤＩＣ（株）製：ポリエーテルポリオールＨＡ－２２０Ｂ）と触媒（光潜在性チタン触媒とε－カプロラクタム）を添加した混合物を塗布し、一方直鎖状低密度ポリエチレン（ＬＬＤＰＥ）６０μｍのコロナ処理面にポリイソシアネート化合物（ＤＩＣ（株）製：芳香族系ポリエーテルイソシアネート２Ｋ－ＳＦ－２２０Ａ）を塗布し、塗布面同士をラミネート機は使用せず手貼りで圧着しプラスチックフィルム積層体を作製した。接着剤塗布量は１５ｇ／ｍ２で行った。 (Example 8)
A PET (polyethylene terephthalate) film was coated on a corona-treated surface of 50 μm with a mixture in which a polyol compound (manufactured by DIC Corporation: polyether polyol HA-220B) and a catalyst (photolatent titanium catalyst and ε-caprolactam) were added, Apply a polyisocyanate compound (manufactured by DIC Corporation: aromatic polyether isocyanate 2K-SF-220A) to a corona-treated surface of linear low density polyethylene (LLDPE) 60 μm, and use a laminating machine between the coated surfaces. A plastic film laminate was prepared by hand bonding. The adhesive application amount was 15 g / m 2 .
（比較例２）
　実施例５、６、７、８の分別塗布を行う代わりに、ＰＥＴフィルムのコロナ処理面に接着剤（ＤＩＣ（株）製：２Ｋ－ＳＦ－２２０ＡとＨＡ－２２０Ｂの混合液）塗布した後、ＬＬＤＰＥフィルムのコロナ処理面を手貼りで圧着した。
　なお、実施例５、６、７、８及び比較例２共にフィルム貼り合わせ面は、ＰＥＴフィルムのコロナ処理面とＬＬＤＰＥフィルムのコロナ処理面とした。 (Comparative Example 2)
Instead of performing the separate application of Examples 5, 6, 7, and 8, after applying the adhesive (DIC Co., Ltd .: mixed solution of 2K-SF-220A and HA-220B) to the corona-treated surface of the PET film, The corona-treated surface of the LLDPE film was pressure bonded by hand.
In Examples 5, 6, 7, 8 and Comparative Example 2, the film bonding surfaces were the corona-treated surface of the PET film and the corona-treated surface of the LLDPE film.
（風合いの判定方法）
　圧着後のプラスチックフィルム積層体は４０℃雰囲気下で４８時間の養生後、３０℃雰囲気下でプラスチックフィルム積層体の接着剤層の押し込み硬度（ヤング率）を測定し、接着剤層の風合いの評価を行った。
　　〇：風合い良好　　　　　　　　×：風合い不良 (Texture judgment method)
The pressed plastic film laminate is cured for 48 hours in an atmosphere of 40 ° C., and then the indentation hardness (Young's modulus) of the adhesive layer of the plastic film laminate is measured in an atmosphere of 30 ° C. to evaluate the texture of the adhesive layer. Went.
◯: Good texture ×: Bad texture
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の２液分別塗布工程を有する軟包装用フィルムの製造方法により得られる軟包装用フィルムは、以上の実施例、比較例の結果から明らかなように、外観及び風合いに優れ、これまでにない軟包装用フィルムであることが明らかである。 The soft wrapping film obtained by the method for producing a soft wrapping film having the two-component fractionation coating process of the present invention is excellent in appearance and texture, as apparent from the results of the above examples and comparative examples. It is clear that there is no soft packaging film.

Claims (5)

  1. ポリウレタン接着剤が基材に塗布された軟包装用フィルムの製造方法において、該ポリウレタン接着剤がＡ剤とＢ剤を反応原料とし、一方の基材に塗布されたＡ剤と他方の基材に塗布されたＢ剤とが接触して圧着する２液分別塗布工程を有し、Ａ剤が硬化成分としてポリオール化合物又はポリイソシアネート化合物のいずれか一方を含み、Ｂ剤が硬化成分としてＡ剤とは異なるポリオール化合物又はポリイソシアネート化合物のいずれか一方を含むことを特徴とする軟包装用フィルムの製造方法。 In a method for producing a film for flexible packaging in which a polyurethane adhesive is applied to a base material, the polyurethane adhesive uses A agent and B agent as reaction raw materials, and the A agent applied to one base material and the other base material It has a two-component fractionation coating process in which the applied B agent comes into contact and pressure-bonded, the A agent contains either a polyol compound or a polyisocyanate compound as a curing component, and the B agent is an A agent as a curing component The manufacturing method of the film for soft packaging characterized by including any one of a different polyol compound or polyisocyanate compound.
  2. ポリオール化合物が、ポリエーテルポリオール、又はポリエステルポリオールを必須成分とするポリマーポリオールである請求項１に記載の軟包装用フィルムの製造方法。 The method for producing a film for flexible packaging according to claim 1, wherein the polyol compound is a polymer polyol having a polyether polyol or a polyester polyol as an essential component.
  3. ポリイソシアネート化合物が、イソシアネート基を分子内に少なくとも２つ有するイソシアネート化合物である請求項１又は２に記載の軟包装用フィルムの製造方法。 The method for producing a flexible packaging film according to claim 1 or 2, wherein the polyisocyanate compound is an isocyanate compound having at least two isocyanate groups in the molecule.
  4. 前記Ａ剤またはＢ剤が、金属系触媒、アミン系触媒、ジアザビシクロウンデセン系、又は脂肪族環状アミド化合物、チタンキレート錯体から選ばれる少なくとも１つの触媒を有する請求項１～３の何れかに記載の軟包装用フィルムの製造方法。 The agent A or B has at least one catalyst selected from a metal catalyst, an amine catalyst, a diazabicycloundecene, an aliphatic cyclic amide compound, and a titanium chelate complex. The manufacturing method of the film for soft packaging as described in 2.
  5. 前記基材が、プラスチックフィルム、金属蒸着フィルム又は金属箔である請求項１～４の何れかに記載の軟包装用フィルムの製造方法。 The method for producing a flexible packaging film according to any one of claims 1 to 4, wherein the substrate is a plastic film, a metal-deposited film, or a metal foil.
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CN108559435A (en) * 2018-04-27 2018-09-21 上海回天新材料有限公司 A kind of and excellent no-solvent type polyurethane laminating adhesive and its preparation method and application of polyurethane ink matching
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WO2021256270A1 (en) * 2020-06-18 2021-12-23 Dic株式会社 Adhesive agent, laminate, method for manufacturing laminate, and packaging material
WO2022172436A1 (en) * 2021-02-15 2022-08-18 Dic株式会社 Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film
WO2022172448A1 (en) * 2021-02-15 2022-08-18 Dic株式会社 Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film
WO2022239667A1 (en) * 2021-05-11 2022-11-17 Dic株式会社 Method for producing laminate
WO2023032690A1 (en) * 2021-08-31 2023-03-09 Dic株式会社 Adhesive, laminate, method for manufacturing laminate, and packaging material

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CN108559440A (en) * 2018-04-27 2018-09-21 上海回天新材料有限公司 A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging
CN108559435A (en) * 2018-04-27 2018-09-21 上海回天新材料有限公司 A kind of and excellent no-solvent type polyurethane laminating adhesive and its preparation method and application of polyurethane ink matching
CN115461424A (en) * 2020-06-18 2022-12-09 Dic株式会社 Adhesive, laminate, method for producing laminate, and packaging material
WO2021256270A1 (en) * 2020-06-18 2021-12-23 Dic株式会社 Adhesive agent, laminate, method for manufacturing laminate, and packaging material
JPWO2021256270A1 (en) * 2020-06-18 2021-12-23
JP2023024587A (en) * 2020-06-18 2023-02-16 Dic株式会社 Adhesive agent, laminate, method for manufacturing laminate, and packaging material
JP7207609B2 (en) 2020-06-18 2023-01-18 Dic株式会社 Adhesive, laminate, method for producing laminate, packaging material
CN115551965A (en) * 2021-02-15 2022-12-30 Dic株式会社 Two-component curable adhesive, laminated film, apparatus for producing laminated film, and method for producing laminated film
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JP7136364B1 (en) * 2021-02-15 2022-09-13 Dic株式会社 Two-component curing adhesive, laminated film, laminated film manufacturing apparatus, laminated film manufacturing method
US11525074B2 (en) 2021-02-15 2022-12-13 Dic Corporation Two-component curing adhesive, laminated film, laminated film-manufacturing apparatus, and method for manufacturing laminated film
JP7136363B1 (en) * 2021-02-15 2022-09-13 Dic株式会社 Two-component curing adhesive, laminated film, laminated film manufacturing apparatus, laminated film manufacturing method
WO2022172448A1 (en) * 2021-02-15 2022-08-18 Dic株式会社 Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film
EP4071222A4 (en) * 2021-02-15 2023-01-25 DIC Corporation Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film
TWI792909B (en) * 2021-02-15 2023-02-11 日商Ｄｉｃ股份有限公司 Two-component hardening adhesive, laminated film, laminated film manufacturing device, and laminated film manufacturing method
WO2022172436A1 (en) * 2021-02-15 2022-08-18 Dic株式会社 Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film
WO2022239667A1 (en) * 2021-05-11 2022-11-17 Dic株式会社 Method for producing laminate
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JP7306597B1 (en) 2021-08-31 2023-07-11 Dic株式会社 Adhesive, laminate, method for producing laminate, packaging material

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