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
  • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • 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 an adhesive, a laminate obtained using the adhesive, and a packaging material.
• Laminates used for various packaging materials, labels, etc. are given design, functionality, storage stability, convenience, transportation resistance, etc. by laminating a wide variety of base materials such as plastic films, metal foils, and paper. be done.
• a packaging material formed by molding the laminate into a bag shape is used as a packaging material for foods, medicines, detergents, and the like.
• laminates used for packaging materials are produced by applying an adhesive dissolved in a volatile organic solvent (sometimes referred to as a solvent-based lamination adhesive) to the base material, and then passing through an oven.
• a volatile organic solvent sometimes referred to as a solvent-based lamination adhesive
• reaction lamination methods that do not contain volatile organic solvents have been used.
• Demand for a two-liquid type lamination adhesive (hereinafter referred to as a non-solvent adhesive) is increasing (Patent Document 1).
• Solvent-free adhesives do not require a drying process and do not emit solvents. They are energy-saving and have low running costs. It has many merits, such as the fact that there is no concern that the solvent will remain in the laminate after being combined. On the other hand, it is necessary to design the component used in the solventless adhesive to have a low molecular weight so that the viscosity can be applied when heated to about 40°C to 100°C, and the boiling resistance of the laminate is satisfactory. There was a problem that it was not at a certain level.
• a printed layer is generally provided with printing ink on the back side of the base material that is the outermost layer (viewed from the content), and the printed layer and other base materials are connected via an adhesive. are pasted together.
• low-molecular-weight polyols used in non-solvent adhesives tend to re-dissolve the printed layer.
• the present invention has been made in view of such circumstances, and uses a two-component curing adhesive that is excellent in boiling resistance and re-dissolution resistance of the printed layer even when the molecular weight is low.
• An object of the present invention is to provide a laminate and a packaging material to be obtained.
• the present invention includes a polyol composition (X) and a polyisocyanate composition (Y), and the polyol composition (X) is a composition containing a polyhydric alcohol (a) and a polyhydric carboxylic acid (b).
• the polyisocyanate composition (Y) is a polyester polyol (C'1) which is a reaction product of a polyhydric alcohol (c) and a polycarboxylic acid (d)
• a urethane prepolymer (C) that is a reaction product of a polyol composition (y) containing an isocyanate compound (C'2)
• a polyhydric alcohol (a) is a glycol having only one alkyl side chain (a1 )
• the polyhydric alcohol (c) comprises a glycol (c1) having only one alkyl side chain, and the glycol (a1) and the glycol occupying the total amount of the polyol composition (X) and the polyis
• the adhesive of the present invention it is possible to provide laminates and packaging materials with excellent boiling resistance and good appearance.
• the adhesive of the present invention is a two-liquid curing adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y).
• X polyol composition
• Y polyisocyanate composition
• polyester polyol (A) (Polyester polyol (A))
• the polyol composition (X) used in the adhesive of the present invention contains polyester polyol (A) which is a reaction product of a composition containing polyhydric alcohol (a) and polycarboxylic acid (b).
• Polyhydric alcohols (a) also include glycols (a1) having only one alkyl side chain. As a result, the adhesive can have excellent boiling resistance.
• the glycol (a1) includes 1,2-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and the like.
• polyhydric alcohols (a) that can be used in combination with glycol (a1) are not particularly limited.
• bifunctional alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, and butylethyl.
• Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; Modified poly(s) obtained by ring-opening polymerization of aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
• ether diol
• Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactanoids and ⁇ -caprolactone; Bisphenols such as bisphenol A and bisphenol F; Alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F can be mentioned.
• Tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol; Modified polyols obtained by ring-opening polymerization of aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
• ether polyols examples include lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols with various lactones such as ⁇ -caprolactone.
• the polyhydric alcohol (a) contains diethylene glycol, since it has an excellent effect of suppressing re-dissolution for printing when the adhesive is applied onto the printed layer.
• the proportion of diethylene glycol in the polyhydric alcohol (a) excluding the glycol (a1) is preferably 50% by mass or more, more preferably 60% by mass or more.
• Polycarboxylic acids (b) include orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3 - naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, aromatic polybasic acids such as benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; methyl esters of aromatic polybasic acids
• Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; Aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate Alkyl ester of;
• the polycarboxylic acid (b) preferably contains adipic acid.
• adipic acid preferably contains adipic acid.
• the amount of adipic acid to be blended can be appropriately adjusted depending on the coating conditions and the like. As an example, it is preferably 40% by mass or more, more preferably 60% by mass or more, of the polyvalent carboxylic acid (b).
• the total amount of polycarboxylic acid (b) may be adipic acid.
• the adhesive of the present invention has sufficient boiling resistance even when the amount of aromatic polycarboxylic acid used is small or not used at all.
• the content of the acid is preferably 15% by mass or less, more preferably 10% by mass or less.
• the number average molecular weight of the polyester polyol (A) is not particularly limited, it is preferably 350 or more and 5,000 or less.
• the number average molecular weight in this specification is a value calculated according to the following formula from the number of design functional groups and the actually measured hydroxyl value (mgKOH/g).
• the hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070.
• the number of design functional groups is the number of moles of carboxyl groups (O), the number of moles of polycarboxylic acid (P), the number of moles of hydroxyl groups (Q), and the It is calculated by (Q+O)/(R+P) from the number of moles (R) of the alcohol.
• the blending amount of the polyester polyol (A) is preferably 60% by mass or more of the solid content of the polyol composition (X).
• the adhesive can be excellent in boiling resistance and resistance to re-dissolution of the printed layer.
• the polyol composition (X) may contain a polyol (B) other than the polyester polyol (A).
• a polyol (B) include difunctional, trifunctional or higher alcohols similar to those exemplified as the polyhydric alcohol (a), polyurethane polyol, polyester polyol, polyether polyol, polyester polyurethane polyol, polyether polyurethane.
• the blending amount of the polyol (B) is not particularly limited, but it is preferable to limit it to 40% by mass or less of the total amount with the polyester polyol (A).
• the viscosity of the polyol composition (X) is adjusted within a range suitable for the non-solvent lamination method.
• the viscosity at 40° C. is adjusted to be in the range of 100-5000 mPas, more preferably 100-3000 mPas.
• the viscosity of the polyol composition (X) can be adjusted, for example, by the skeleton of the polyester polyol (A) and the plasticizer described later.
• the isocyanate composition (Y) is obtained by reacting the polyol composition (y) containing the polyester polyol (C'1) and the isocyanate compound (C'2) having a plurality of isocyanate groups under conditions where the isocyanate groups are excessive.
• urethane prepolymer (C) obtained by Further, the polyester polyol (C'1) is a reaction product of a composition containing a polyhydric alcohol (c) and a polyhydric carboxylic acid (d), and the polyhydric alcohol (c) has only one alkyl side chain. Glycol (c1) with As a result, the adhesive can have excellent boiling resistance.
• the glycol (c1) the same glycol (a1) can be used.
• the polyhydric alcohol (c) may contain polyhydric alcohols other than the glycol (c1).
• the polyhydric alcohol that can be used in combination with the glycol (c1) the same ones as exemplified for the polyhydric alcohol (a) can be used.
• polyvalent carboxylic acid (d) the same one as exemplified for the polyvalent carboxylic acid (b) can be used.
• Polyvalent carboxylic acid (d) preferably contains adipic acid. This can be expected to reduce the viscosity of the polyester polyol (C'1) and, in turn, the urethane prepolymer (C), thereby improving pot life and coatability at low temperatures. In addition, it can be expected that the wettability of the adhesive to the substrate is improved and the appearance of the laminate is improved.
• the amount of adipic acid to be blended can be appropriately adjusted depending on the coating conditions and the like. As an example, it is preferably 40% by mass or more, more preferably 60% by mass or more, of the polyvalent carboxylic acid (d).
• the total amount of polycarboxylic acid (d) may be adipic acid.
• the adhesive of the present invention has sufficient boiling resistance even when the amount of aromatic polycarboxylic acid used is small or not used at all.
• the acid content is preferably 15% by mass or less, more preferably 10% by mass or less.
• the number average molecular weight of the polyester polyol (C'1) is not particularly limited, it is, for example, 400 or more and 10,000 or less, more preferably 500 or more and 2,000 or less.
• the isocyanate compound (C'2) is not particularly limited, and aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and burettes, nurates, adducts, allophanates, and carbodiimide modifications of these diisocyanates. and uretdione-modified forms, etc., and these can be used singly or in combination.
• aromatic diisocyanates examples include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI).
• Araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, m- or p-xylylene diisocyanate (also known as XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetra Methyl xylylene diisocyanate (another name: TMXDI) and the like can be mentioned, but not limited to these.
• Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples include, but are not limited to, diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
• Alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, etc., and these is not limited to
• aromatic diisocyanate and/or its derivatives From the viewpoint of initial cohesion and shortening of aging time, it is preferable to use aromatic diisocyanate and/or its derivatives.
• the polyol composition (y) may contain a polyether polyol (C'3).
• C'3 polyether polyol
• the wettability of the adhesive to the substrate is improved, and a laminate with a better appearance can be provided.
• the polyisocyanate composition (Y) may become turbid during long-term storage, but this can be suppressed.
• the polyether polyol (C'3) is not particularly limited, and includes oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and low-molecular-weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin.
• the initiator include those obtained by polymerization, and can be used alone or in combination of two or more.
• the number of functional groups of the polyether polyol (b2) is not particularly limited, and in addition to bifunctional ones, trifunctional or higher functional groups can also be used. It is preferred to use bifunctional or trifunctional polypropylene glycol.
• the number average molecular weight of the polyether polyol (C'3) is not particularly limited, it is, for example, 200 or more and 10,000 or less, more preferably 400 or more and 2,000 or less.
• the blending amount is preferably 5% by mass or more and 50% by mass or less of the total amount of the polyester polyol (C'1) and the polyether polyol (C'3). From the viewpoint of balance with boiling resistance, it is more preferably 5% by mass or more and 35% by mass or less.
• the urethane prepolymer (C) is obtained by reacting the above-described polyol composition (y) and the isocyanate compound (C'2) under conditions of excess isocyanate groups.
• the ratio [NCO]/[OH] between the number of moles [NCO] of isocyanate groups and the number of moles [OH] of hydroxyl groups used for the reaction is preferably 1.0 or more and 3.0 or less. It is more preferably 1.5 to 2.0.
• the polyisocyanate composition (Y) may contain a polyisocyanate compound (D) other than the urethane prepolymer (C).
• a polyisocyanate compound (D) other than the urethane prepolymer (C).
• examples of the polyisocyanate compound (D) include compounds exemplified as the isocyanate compound (C'2), urethane prepolymers that are reaction products of these isocyanate compounds and polyols, and the like. They can be used in combination.
• the viscosity of the polyisocyanate composition (Y) is adjusted within a range suitable for the non-solvent lamination method.
• the viscosity at 40° C. is adjusted to be in the range of 500-5000 mPas, more preferably 500-3000 mPas.
• the viscosity of the polyisocyanate composition (Y) can be adjusted, for example, by the amount of the low-molecular-weight isocyanate compound contained in the polyisocyanate composition (Y).
• the ratio of the total amount of glycols (a1) and (c1) used in preparing the adhesive to the solid content of the adhesive is 5% by mass or more and 20% by mass or less.
• the adhesive of the present invention may contain components other than those mentioned above. Other components may be contained in either or both of the polyol composition (X) and the polyisocyanate composition (Y), or may be prepared separately from these and added to the polyol immediately before coating the adhesive. It may be used by mixing with the composition (X) and the polyisocyanate composition (Y). Each component will be described below.
• catalysts examples include metal-based catalysts, amine-based catalysts, and aliphatic cyclic amide compounds.
• Metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts.
• the metal complex catalyst a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt)
• acetylacetonate salts of metals selected from the above such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like.
• inorganic metal-based catalysts examples include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
• Organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; , dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride and other organic tin compounds, nickel octylate, nickel naphthenate and other organic nickel compounds, cobalt octylate, cobalt naphthenate and other organic cobalt compounds, bismuth octylate, neodecanoic acid At least one of organic bismuth compounds such as bismuth and bismuth naphthenate, tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and alcohols having 2 to 10 carbon atoms.
• Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, 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-hydroxyethyl)ethylenediamine, N,N-dimethyl
• Aliphatic cyclic amide compounds include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthollactam, ⁇ -capryllactam, ⁇ -propiolactam and the like. Among these, ⁇ -caprolactam is more effective in accelerating hardening.
• the acid anhydrides include cycloaliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, and the like, and may be used alone or in combination of two or more. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid Anhydride, poly(ethyloctadecanedioic anhydride), poly(phenylhexadecanedioic anhydride), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , methylhimic acid anhydride, trialkyltetrahydrophthalic anhydride
• glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Furthermore, two or more of these glycols and/or copolymerized polyether glycols of polyether glycols can also be used.
• coupling agent examples include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.
• Silane coupling agents include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -amino Aminosilanes such as propyltrimethyldimethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxy epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyl
• Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. are mentioned.
• aluminum-based coupling agents examples include acetoalkoxyaluminum diisopropylate.
• Pigments are not particularly limited, and include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, and pigments described in the 1970 edition of Handbook of Paint Raw Materials (edited by the Japan Paint Manufacturers Association). Examples include organic pigments such as metal powder pigments, luminescent pigments, and pearlescent pigments, inorganic pigments, and plastic pigments.
• Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
• organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
• insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
• soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
• various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
• Phthalocyanine pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments vat dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
• inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange; various ferrocyanic compounds such as Prussian blue; Various metal oxides such as zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of silicon such as calcium silicate and ultramarine blue.
• chromates such as yellow lead, zinc chromate, molybdate orange
• ferrocyanic compounds such as Prussian blue
• metal oxides such as zirconium oxide
• various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide
• various sulfates such as barium sulfate and lead sulfate
• silicon such as calcium silicate and ultramarine blue.
• various acid salts such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; These metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica-like iron oxide pigments and mica-like iron oxide pigments coated with metal oxides; graphite, carbon black and the like.
• plastic pigments examples include "Grandol PP-1000" and “PP-2000S” manufactured by DIC Corporation.
• the pigment to be used may be appropriately selected according to the purpose.
• inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they are excellent in durability, weather resistance, and design.
• Carbon black is preferably used as the pigment.
• the amount of the pigment compounded is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y), thereby improving adhesion and blocking resistance. It is more preferable to use 10 to 300 parts by mass in order to obtain the desired content.
• plasticizers examples include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers. plasticizers, and the like.
• phthalic plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, Phthalic ester plasticizers such as di-(2-ethylhexyl) isophthalate and diisooc
• fatty acid-based plasticizers include adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
• adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
• azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, diisooctyl azelate, di-n-butyl sebacate, di-(2- ethylhexyl) sebacate, diisononyl sebacate and other sebacic acid plasticizers, e.g.
• di-n-butyl fumarate, di-(2-ethylhexyl) fumarate and other fumaric acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Itaconic acid plasticizers such as di-(2-ethylhexyl) itaconate, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, butyl oleate, glyceryl monooleate, Oleic acid plasticizers such as diethylene glycol monooleate, citric acid such as triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltributyl citrate, acetyl tri-(2-ethylhexyl) citrate ric acid
• aromatic polycarboxylic acid-based plasticizers include tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, and triisononyl. trimellitate, tridecyl trimellitate, triisodecyl trimellitate and other trimellitic acid plasticizers, e.g., tetra-(2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate and other pyromellitic acid plasticizers plasticizers, and the like.
• Phosphate plasticizers include, for example, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, trichlé Zyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(isopropylphenyl) phosphate and the like.
• polyol plasticizers examples include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate ), glycol-based plasticizers such as dibutylmethylene bisthioglycolate, and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• glycol-based plasticizers such as dibutylmethylene bisthioglycolate
• glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate. etc.
• polyester-based plasticizers examples include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.
• Propylene carbonate and ethylene carbonate are examples of carbonate-based plasticizers.
• plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, polymerizable plasticizers such as acrylic monomers and oligomers, and the like. These plasticizers can be used alone or in combination of two or more.
• Phosphoric acid compounds include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.
• the adhesive of the present invention may be either a solvent type or a non-solvent type, but is particularly suitable for the non-solvent type where the boiling resistance tends to be insufficient and re-dissolution of the printed layer tends to be a problem.
• solvent-based adhesive means that after the adhesive is applied to the base material, it is heated in an oven or the like to volatilize the organic solvent in the coating film, and then bonded to another base material. It refers to a form used in a method, a so-called dry lamination method.
• Either one or both of the polyol composition (X) and the polyisocyanate composition (Y) dissolve (dilute) the components of the polyol composition (X) and the polyisocyanate composition (Y) used in the present invention.
• organic solvents examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene. , methylene chloride, halogenated hydrocarbons such as ethylene chloride, dimethylsulfoxide, dimethylsulfamide and the like.
• the organic solvent used as a reaction medium during the production of the constituents of the polyol composition (X) or the polyisocyanate composition (Y) may also be used as a diluent during coating.
• solvent-free adhesive means that the polyol composition (X) and the polyisocyanate composition (Y) are esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, Highly soluble ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethylsulfoxide and dimethylsulfamide.
• esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, Highly soluble ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic
• a method in which an adhesive that does not substantially contain an organic solvent, particularly ethyl acetate or methyl ethyl ketone, is applied to a substrate, and then bonded to another substrate without a step of heating in an oven or the like to volatilize the solvent It refers to the form of adhesive used in the so-called non-solvent lamination method.
• the constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyol composition (X) or the polyisocyanate composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained.
• the polyol composition (X) contains a low-molecular-weight alcohol
• the low-molecular-weight alcohol reacts with the polyisocyanate composition (Y) and becomes part of the coating film, so it is not necessary to volatilize after coating.
• Such forms are therefore also treated as solventless adhesives and low molecular weight alcohols are not considered organic solvents.
• the adhesive of the present invention has a ratio [NCO]/[ OH] is preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.
• the laminate of the present invention is obtained by laminating a plurality of substrates (films or papers) using the adhesive of the present invention by a dry lamination method or a non-solvent lamination method.
• the film to be used is not particularly limited, and a suitable film can be selected according to the application.
• PET polyethylene terephthalate
• polystyrene film polyamide film
• polyacrylonitrile film polyethylene film
• LLDPE low density polyethylene film
• HDPE high density polyethylene film
• CPP unstretched Polyolefin films such as polypropylene film, OPP (biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like.
• the film may be stretched.
• a stretching treatment method it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching.
• sequential biaxial stretching it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
• Various surface treatments such as flame treatment and corona discharge treatment may be applied to the film surface as necessary so that an adhesive layer without defects such as film breakage and repellency is formed.
• a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used. good.
• a laminate having barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic substances (aroma), and the like can be obtained.
• a known paper base material can be used without any particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified.
• natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps.
• the types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acid/neutral/alkaline sulfite cooking, soda salt cooking, and the like.
• various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, paperboard, etc. can also be used.
• More specific and preferable configurations of the laminate in which the properties of the adhesive of the present invention are exhibited include OPP film/adhesive layer/CPP film, OPP film/adhesive layer/LLDPE film, and OPP/adhesive layer/aluminum vapor deposition.
• the adhesive layer is a cured coating film of the adhesive of the present invention.
• the adhesive layer' may be a cured coating film of the adhesive of the present invention, or may be a cured coating film of another adhesive.
• a printed layer may be provided between the adhesive layer and the substrate (usually the substrate that is the outermost layer for the content).
• the printing layer is formed by a general printing method conventionally used for printing on films using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
• the adhesive of the present invention is a solvent type
• the adhesive of the present invention is applied to one base material using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like.
• the laminate of the present invention is obtained by laminating the substrates. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 80° C.
• the aging time is preferably 12 to 240 hours.
• the adhesive of the present invention When the adhesive of the present invention is solvent-free, the adhesive of the present invention preheated to about 40° C. to 100° C. is applied to one substrate using a roll such as a coat roll, and then immediately.
• the laminate of the present invention is obtained by laminating the other base material. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.
• the amount of adhesive to be applied is appropriately adjusted.
• the solid content is adjusted to 1 g/m 2 or more and 10 g/m 2 or less, preferably 2 g/m 2 or more and 5 g/m 2 or less.
• the coating amount of the adhesive is, for example, 1 g/m 2 or more and 5 g/m 2 or less, preferably 1 g/m 2 or more and 3 g/m 2 or less.
• the laminate of the present invention is obtained by bonding two base materials together with the adhesive of the present invention, but may contain other base materials as necessary.
• known methods such as dry lamination, non-solvent lamination, heat lamination, heat sealing, and extrusion lamination may be used.
• the adhesive used at this time may or may not be that of the present invention.
• another base material the same base material as described above can be used.
• the packaging material of the present invention is formed by molding the laminate into a bag shape and heat-sealing the bag.
• Packaging materials include three-side seal bags, four-side seal bags, gusset packaging bags, pillow packaging bags, gobel-top type bottomed containers, tetraclassics, Bruck types, tube containers, paper cups, lids, and the like.
• the packaging material of the present invention may be appropriately provided with an easy-opening treatment or resealing means.
• the packaging material of the present invention can be used industrially as a packaging material mainly filled with foods, detergents, and medicines. Specific uses include detergents and chemicals such as liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and pharmaceutical tablets. It can also be used as a secondary packaging material for packaging the container described above.
• a polyester polyol (A-1) was obtained by performing a condensation reaction until the acid value was reached.
• Table 1 shows the acid value (mgKOH/g), the hydroxyl value (mgKOH/g), the number of designed functional groups, and the number average molecular weight calculated from the number of designed functional groups of the polyester polyol (A-1).
• Polyester polyol (A-1) was used as polyol composition (X-1).
• Polyester polyols (A-2) to (A-7) were obtained in the same manner as in (Synthesis Example 1), except that the raw materials shown in Table 1 were used. They were used as polyol compositions (X-2) to (X-7), respectively.
• DEG is diethylene glycol
• 2MPD is 2-methyl-1,3-propanediol
• AA is adipic acid.
• a polyester polyol (C'1-1) was obtained by conducting a condensation reaction until the acid value was reached.
• Table 2 shows the acid value (mgKOH/g), the hydroxyl value (mgKOH/g), the number of designed functional groups, and the number average molecular weight calculated from the number of designed functional groups of the polyester polyol (C'1-1).
• Polyester polyols (C'1-2) to (C'1-5) were obtained in the same manner as in (Synthesis Example 8) except that the raw materials shown in Table 2 were used.
• EG is ethylene glycol
• 2MPD is 2-methyl-1,3-propanediol
• 3MPD is 3-methyl-1,5-pentanediol
• AA is adipic acid.
• Urethane-based lamination ink (Finart R794 White G3; manufactured by DIC Corporation) was adjusted to 15 seconds (25°C) with Zahn Cup #3 manufactured by Rigosha, and corona treatment was performed using a gravure printing machine equipped with a 43 ⁇ m plate depth gravure plate. It was printed on a PET (polyethylene terephthalate) film (Toyobo Ester Film E5102#12) and passed through an oven at 70° C. to dry or harden to form a printed layer on the PET film.
• PET polyethylene terephthalate
• Toyobo Ester Film E5102#12 Toyobo Ester Film E5102#12

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• 2022
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