Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated

Definitions

• the present invention relates to two-component curing adhesives, laminates, and packaging materials.
• 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 laminating adhesive (hereinafter referred to as solventless adhesive) is also increasing (Patent Document 1).
• the isocyanate monomer remaining in the adhesive layer may pose a problem.
• the aromatic isocyanate monomer reacts with the surrounding water to form a primary aromatic amine (PAA).
• PAA primary aromatic amine
• the resulting PAA may migrate through the film and be eluted into the contents (food).
• various regulations have been established, such as the European Commission's regulation on plastic materials and products for food contact, which stipulates its detection limit.
• the PAA generated by the reaction between the aromatic isocyanate and water further reacts with water, so even if the aromatic isocyanate remains in the adhesive layer, the concentration of PAA will gradually decrease and eventually fall below the detection limit.
• the PAA concentration decreases at a faster rate. From this point of view, it is preferable to use 4,4'-diphenylmethane diisocyanate, which has relatively excellent reactivity, as the raw material for the isocyanate component of the adhesive.
• 4,4'-diphenylmethane diisocyanate has high crystallinity, and urethane prepolymers with a high content of 4,4'-diphenylmethane diisocyanate have poor storage stability, such as crystallization or turbidity during storage even at room temperature. Inferior.
• the present invention has been made in view of such circumstances, and an object of the present invention is to provide a two-component curing adhesive that has a high reduction rate of PAA and excellent storage stability.
• the content of 4,4′-diphenylmethane diisocyanate is 75.0% by mass or more, the content of 2,2′-diphenylmethane diisocyanate is 0.5% by mass or less, and 2,4′-diphenylmethane
• a urea derivative of 4,4′-diphenylmethane diisocyanate wherein the content of the biuret derivative is 0.4% by mass or more and 20.0% by mass or less, and the content of the biuret derivative is 1 of the content of the urea derivative. It relates to a two-part curable adhesive containing an isocyanate composition (X) having a ratio of 0.0 or more and a polyol composition (Y) containing a polyol compound.
• the adhesive of the present invention it is possible to provide a two-liquid curing adhesive that has a high reduction rate of PAA and excellent storage stability.
• the adhesive of the present invention is a two-component curing adhesive containing the polyisocyanate composition (X) and the polyol composition (Y).
• the adhesive of the present invention will be described in detail below.
• the polyisocyanate composition (X) used in the adhesive of the present invention has a 4,4′-diphenylmethane diisocyanate (hereinafter referred to as 4,4′-MDI) content of 75.0% by mass or more, and 2,2′ -The content of diphenylmethane diisocyanate (hereinafter referred to as 2,2'-MDI) is 0.5% by mass or less, and the content of 2,4'-diphenylmethane diisocyanate (hereinafter referred to as 2,4'-MDI) is 5.0% by mass.
• 4,4′-MDI 4,4′-diphenylmethane diisocyanate
• 2,2'-MDI diphenylmethane diisocyanate
• 2,4'-MDI 2,4'-diphenylmethane diisocyanate
• Such urethane prepolymers are synthesized with 4,4'-MDI, which has excellent reactivity, as the main component, so the rate of reduction of PAA is high, and they are particularly suitable for producing laminates for food packaging. More preferably, the amount of 4,4'-MDI in the isocyanate composition (i) is 80% by mass or more. Note that 2,2'-MDI and 2,4'-MDI have lower reactivity than 4,4'-MDI, and the rate of PAA decrease is relatively slow, so it is preferable that the content is small. ,4'-MDI may be mixed as an impurity during the synthesis and isolation of 4'-MDI. The above-mentioned content does not significantly affect the reduction rate of PAA.
• the urethane prepolymer is excellent in storage stability, in which the occurrence of crystallization and cloudiness is suppressed. If the content of the biuret derivative is less than 0.4% by mass, the effect of suppressing the crystallization and cloudiness of the urethane prepolymer is weak, and if it exceeds 20.0% by mass, the viscosity of the urethane prepolymer increases, resulting in poor coating suitability. . Also, if the content of the biuret derivative is less than 1.0 times the content of the urea derivative, the effect of suppressing white turbidity is weakened. Although the upper limit of the ratio of the amount of the biuret derivative and the urea derivative is not particularly limited, it is, for example, 10 times or less that of the urea derivative.
• a method of introducing a urea derivative and a biuret derivative into the isocyanate composition (X) includes a method of using a urea derivative and a biuret derivative as the isocyanate composition (i), and a method of using water or an amine compound as the polyol composition (ii).
• a urea derivative can be synthesized, for example, by reacting 4,4'-MDI with water and/or an amine compound at about 65-85°C.
• a biuret derivative can be synthesized, for example, by reacting a urea derivative with 4,4'-MDI at about 95 to 110°C.
• Amine compounds suitably used for synthesizing urea derivatives and biuret derivatives include primary or secondary monoamine compounds described later.
• the isocyanate composition (i) used for synthesizing the urethane prepolymer may contain isocyanate compounds other than 4,4'-MDI, 2,2'-MDI and 2,4'-MDI.
• Isocyanate compounds used in combination with these isocyanates are non-aromatic isocyanate compounds such as araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and their derivatives (biuret, nurate, adduct, allophanate). preferable.
• 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
• the blending amount is preferably 20% by mass or less of the total amount of the isocyanate composition (i) from the viewpoint of the reaction speed of the adhesive and the like.
• the polyol composition (ii) used for synthesizing the urethane prepolymer contains a polyol compound.
• the polyol compound is not particularly limited, and those commonly used for synthesizing urethane prepolymers can be appropriately used.
• ethylene glycol 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4- Glycols such as cyclohexanediol, 1,4-cyclohexanedimethanol;
• trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol; Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of polymerization initiators such as glycols and trifunctional or tetrafunctional aliphatic alcohols. ; Polyether urethane polyol obtained by further increasing the molecular weight of polyether polyol with an isocyanate compound;
• Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and the aforementioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.
• polyester polyol (1) which is a reaction product with a polyhydric alcohol
• Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
• Polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid
• a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
• polyester polyols (5) which are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acids;
• Polyvalent carboxylic acids used in the synthesis of polyester polyols (2) to (4) 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 ) aromatic polybasic acids such as ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride
• 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;
• isocyanate compounds used in the synthesis of polyurethane polyols the same non-aromatic isocyanates as those usable in the isocyanate composition (i) can be used.
• aromatic isocyanates 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).
• the polyol compound preferably contains at least one polyether polyol or polyester polyol.
• the number average molecular weight of the polyol compound is not particularly limited, it is preferably 300 or more and 4000 or less as an example.
• the number average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
• HLC-8320GPC manufactured by Tosoh Corporation Column
• TSKgel 4000HXL TSKgel 3000HXL
• TSKgel 2000HXL TSKgel 1000HXL manufactured by Tosoh Corporation Detector
• RI differential refractometer
• Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions
• Monodisperse polystyrene Sample 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
• the water content of the polyol composition (ii) is 0.01% by mass or more and 0.5% by mass or less. is preferably As a result, even when synthesized using 4,4'-MDI as a main component, it is possible to obtain a urethane prepolymer that is free from crystallization and cloudiness and has excellent storage stability. If the water content of the polyol composition is low, water may be added. If the polyol has a high water content, it may be heated to 80 to 100° C. and dehydrated under reduced pressure.
• the amine compound used when introducing a urea derivative or a biuret derivative into the urethane prepolymer by using an amine compound in the polyol composition (ii) preferably contains a primary or secondary monoamine compound.
• Primary monoamine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tri Aliphatic unsaturated primary amines such as dodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, hardened beef tallow alkylamine, allylamine, aniline, benzylamine etc.
• Secondary monoamine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl Amine, di-cured beef tallow alkylamine, distearylamine and the like.
• the amount of the monoamine compound compounded is preferably 40% by mass or less of the total amount of the polyol composition (ii).
• the urethane prepolymer is obtained by combining the isocyanate composition (i) and the polyol composition (ii) so that the isocyanate groups contained in the isocyanate group (i) are excessive with respect to the active hydrogen groups contained in the polyol composition (ii). It is obtained by reacting under the following conditions.
• the equivalent ratio [NCO]/[active hydrogen group] of the isocyanate group to the active hydrogen group contained in the polyol composition (ii) can be appropriately adjusted depending on the purpose. be.
• the synthesized urethane prepolymer may be used as it is, or an isocyanate compound may be added to adjust the viscosity.
• isocyanate compounds include non-aromatic isocyanates and their derivatives, urethane prepolymers obtained from non-aromatic isocyanates and polyols, carbodiimide-modified diphenylmethane diisocyanates, allophanate-modified diphenylmethane diisocyanates, and polymeric diphenylmethane diisocyanates.
• non-aromatic isocyanate and derivatives thereof the same ones as exemplified as those that can be used in combination with the isocyanate composition (i) can be used.
• the same polyol compounds as exemplified for the polyol composition (ii) can be used.
• Carbodiimide-modified diphenylmethane diisocyanate, allophanate-modified diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate usually contain monomeric diphenylmethane diisocyanate.
• the content of 2,2'-MDI is 2.0% by mass or less and the content of 2,4'-MDI is 5.0% by mass or less.
• the viscosity of the polyisocyanate composition (X) is adjusted within a range suitable for the non-solvent lamination method.
• the viscosity at 25° C. is adjusted to be in the range of 1000-10000 mPas, more preferably 1000-5000 mPas.
• the viscosity of the polyisocyanate composition (X) can be adjusted, for example, by adjusting the amount of the urethane prepolymer and the isocyanate monomer.
• Polyol composition (Y) contains a polyol compound having a plurality of hydroxyl groups.
• the polyol compound those exemplified as the polyol compound that can be used in the polyol composition (ii) can be used. It preferably contains at least one of polyester polyol, polyether polyol, and castor oil-based polyol.
• the viscosity of the polyol 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 100-5000 mPas, more preferably 100-3000 mPas.
• the viscosity of the polyol composition (Y) can be adjusted by the skeleton of the polyol compound, the plasticizer described below, and the like.
• the viscosity can be lowered by using, for example, polypropylene glycol or a polyester polyol obtained by reacting an aliphatic carboxylic acid and a polyol.
• the viscosity can be increased by using a polyester polyol obtained by reacting an aromatic carboxylic acid and a polyol.
• 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 polyisocyanate composition (X) and the polyol composition (Y), or may be prepared separately from these and added to the polyisocyanate composition (X) immediately before coating the adhesive. It may be used by mixing with the isocyanate composition (X) and the polyol 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 non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y). 10 to 300 parts by mass is more preferable.
• 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 (C6) 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, and isododecyl acid.
• the adhesive of the present invention may be in the form of either a solvent type or a non-solvent type. It is suitable for solvent-free types that tend to have insufficient stability.
• 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 polyisocyanate composition (X) and the polyol composition (Y) dissolve (dilute) the components of the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention. Contains organic solvents that can
• 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 the reaction medium during the production of the constituent components of the polyisocyanate composition (X) and the polyol composition (Y) may also be used as a diluent during coating.
• solvent-free adhesive means that the polyisocyanate composition (X) and the polyol 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 polyisocyanate composition (X) or the polyol 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 polyisocyanate composition (X) and the polyol 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 (Y) contains a low-molecular-weight alcohol
• the low-molecular-weight alcohol reacts with the polyisocyanate composition (X) 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 adhesive of the present invention can be suitably used for producing laminates, particularly laminates for food packaging.
• a laminate can be obtained by laminating a plurality of substrates (films or papers) using the above-described adhesive 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.
• Biomass films are sold by various companies, and for example, sheets listed in the list of certified biomass products described by the Japan Organic Resources Association can be used.
• biomass films include those made from biomass-derived ethylene glycol.
• Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol).
• biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method.
• commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.
• films containing biomass polyester, biomass polyethylene terephthalate, etc. having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It has been known.
• the dicarboxylic acid unit of biomass polyester uses the dicarboxylic acid derived from a fossil fuel.
• dicarboxylic acids aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
• a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride in addition to the above diol component and dicarboxylic acid component, a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride.
• a copolymerization component such as at least one polyfunctional compound selected from the group consisting of polycarboxylic acids and tri- or more functional oxycarboxylic acids.
• biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol, biomass polyethylene-polypropylene films, etc. Films are also known.
• the polyethylene-based resin is not particularly limited except that the biomass-derived ethylene glycol is used as a part of the raw material.
• ethylene- ⁇ -olefin copolymer containing 90% by mass or more of units can be used alone or in combination of two or more.
• the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and may be 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or the like having 4 to 10 carbon atoms. 8 ⁇ -olefins.
• Known polyethylene resins such as low density polyethylene resins, medium density polyethylene resins and linear low density polyethylene resins can be used.
• linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or ethylene and 1 - octene) are preferred, and linear low density polyethylene resins with densities between 0.910 and 0.925 g/cm 3 are more preferred.
• Radiocarbon 14C exists in the atmosphere at a rate of 1 in 1012, and this rate does not change even with carbon dioxide in the atmosphere. Therefore, the carbon of the plant-derived resin contains radioactive carbon 14C. In contrast, the carbon of the fossil fuel-derived resin contains almost no radioactive carbon 14C. Therefore, by measuring the concentration of radioactive carbon 14C in the resin with an accelerator mass spectrometer, the content ratio of the plant-derived resin in the resin, that is, the degree of biomass plasticity can be obtained.
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866 include, for example, Braskem's product names "SBC818" and "SPB608". "SBF0323HC”, “STN7006”, “SEB853", “SPB681” and the like can be mentioned, and films using these as raw materials can be preferably used.
• Films and sheets containing starch which is a biomass raw material, and polylactic acid are also known. These can be appropriately selected and used depending on the application.
• the biomass film may be a laminate obtained by laminating a plurality of biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film. Moreover, these biomass films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited.
• 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 gas, volatile organic matter (fragrance) 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 preferred configurations of the laminate exhibiting the properties of the present invention include, for example, PET film/adhesive layer'/aluminum foil/adhesive layer/CPP film, PET film/adhesive layer'/Ny film/adhesive layer"/aluminum foil/adhesive layer/CPP film, PET film/adhesive layer'/aluminum foil/adhesive layer/Ny film/adhesive layer/CPP film, etc.
• These laminates are often subjected to boiling treatment or retorting treatment.
• the adhesive of the present invention satisfies such requirements.It is preferable to use the adhesive of the present invention in the adhesive layer disposed between the aluminum foil and the sealant film.Adhesive layer', The "adhesive layer" may or may not be formed using the adhesive of the present invention.
• 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
• the laminate may have a printed layer 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 is a solvent type
• the adhesive of the present invention is applied to one of the substrates using a roll such as a gravure roll, the organic solvent is volatilized by heating in an oven or the like, and then the other substrate is applied.
• the laminate of the present invention is obtained. 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 preheated to about 40° C. to 100° C. is applied to one substrate using a roll such as a coat roll, and then immediately applied to the other substrate.
• the laminate of the present invention is obtained by bonding the materials together. 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 may be obtained by bonding two base materials together with the adhesive of the present invention, or 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 the one described above.
• another base material the same base material as described above can be used.
• the laminate described above can be suitably used as a packaging material, particularly as a packaging material for food packaging.
• the packaging material is formed by molding the laminate into a bag and heat-sealing it.
• 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 may be appropriately provided with an easy-open treatment or a resealing means.
• the packaging material of the present invention can be suitably used not only for food applications, but also as a packaging material for filling 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.
• polyester polyol A 11.9 parts of polypropylene glycol having a number average molecular weight of 2000 (hereinafter referred to as PPG2000), 0.00264 parts of phosphoric acid, and a polyol composition having a water content of 0.042% by mass ( ii-1) was added dropwise in several portions, and the mixture was further heated and maintained at an internal temperature of 80° C. for 3 hours to carry out a urethanization reaction. After further heating to 100° C. over 1 hour, the mixture was held for 3 hours for reaction to obtain a urethane prepolymer.
• PPG2000 polypropylene glycol having a number average molecular weight of 2000
• ii-1 polypropylene glycol having a number average molecular weight of 2000
• the urethane prepolymer in the reaction vessel was cooled to 50° C., and 13.1 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Lupranate MM103, manufactured by BASF) was added thereto and stirred until uniform, resulting in an NCO% of 16.7. %, a urea derivative content of 0.3% by weight, a biuret derivative content of 0.6% by weight, and a viscosity at 25° C. of 2380 mPa.s.
• a polyisocyanate composition (X-1) of Synthesis Example 1 of s was obtained.
• Synthesis Example 2 to Synthesis Example 5 were prepared in the same manner as in Synthesis Example 1 except that the amount of the isocyanate compound added to the isocyanate composition (i), polyol composition (ii), and urethane prepolymer used was changed as shown in Table 1. of polyisocyanate compositions (X-2) to (X-5) were obtained.
• Synthesis Example 7 The polyisocyanate composition of Synthesis Example 7 was prepared in the same manner as in Synthesis Example 1 except that the amount of the isocyanate compound added to the isocyanate composition (i), polyol composition (ii), and urethane prepolymer used was changed as shown in Table 2.
• Product (X-7) was prepared.
• the urea compound used in the isocyanate composition (i) was a 4,4′-MDI urea compound synthesized from 4,4′-MDI and water, and the biuret compound was synthesized from 4,4′-MDI and water. It is a biuret form of 4,4'-MDI.
• Synthesis Example 8 The polyisocyanate composition of Synthesis Example 8 was prepared in the same manner as in Synthesis Example 1, except that the amount of the isocyanate compound added to the isocyanate composition (i), polyol composition (ii), and urethane prepolymer used was changed as shown in Table 2.
• Product (X-8) was prepared.
• the urea compound added to the synthesized urethane prepolymer was the urea compound of 4,4′-MDI synthesized from 4,4′-MDI and water, and the biuret compound was synthesized from 4,4′-MDI and water. , 4′-MDI.
• Synthesis Example 9 A polyisocyanate composition (X-9) of Synthesis Example 9 was prepared in the same manner as in Synthesis Example 1 except that no carbodiimide-modified diphenylmethane diisocyanate was added.
• polyisocyanate composition (X-10) The amount of the isocyanate compound added to the isocyanate composition (i), the polyol composition (ii), and the urethane prepolymer used was changed as shown in Table 3, and the urethane prepolymer was kept at 100°C for 8 hours. synthesized the polyisocyanate composition (X-10) of Synthesis Example 10 in the same manner as in Synthesis Example 1.
• PPG1000 in the table is a polypropylene glycol having a number average molecular weight of 1,000.
• Synthesis Example 11 The polyisocyanate composition of Synthesis Example 11 was prepared in the same manner as in Synthesis Example 1 except that the amount of the isocyanate compound added to the isocyanate composition (i), polyol composition (ii), and urethane prepolymer used was changed as shown in Table 3. (X-11) was synthesized.
• PPG400 in the table is a polypropylene glycol having a number average molecular weight of 400.
• polyester polyol A 11.9 parts of PPG2000, 0.00264 parts of phosphoric acid, and a polyol composition (ii-9) having a water content of 0.042% by mass were added dropwise in several portions. Then, the mixture was further heated and held at an internal temperature of 80°C for 3 hours for a urethanization reaction to obtain a urethane prepolymer having a urea derivative content of 0.6% by mass and a biuret derivative content of 0.1% by mass. rice field.
• the urethane prepolymer in the reaction vessel was cooled to 50° C., and 13.1 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Lupranate MM103, manufactured by BASF) was added thereto and stirred until uniform, resulting in an NCO% of 16.7. % of the polyisocyanate composition (X-12) of Synthesis Example 9 was obtained.
• carbodiimide-modified diphenylmethane diisocyanate product name: Lupranate MM103, manufactured by BASF
• polyester polyol A 11.9 parts of PPG2000, 0.00264 parts of phosphoric acid, and a polyol composition (ii-13) having a water content of 0.042% by mass were added dropwise in several portions. Then, the mixture was further heated and held at an internal temperature of 80°C for 3 hours for a urethanization reaction to obtain a urethane prepolymer having a urea derivative content of 0.6% by mass and a biuret derivative content of 0.1% by mass. rice field.
• the urethane prepolymer in the reaction vessel was cooled to 50° C., and 13.1 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Lupranate MM103, manufactured by BASF) was added thereto and stirred until uniform, resulting in an NCO% of 16.7. % of the polyisocyanate composition (X-13) of Synthesis Example 13 was obtained.
• carbodiimide-modified diphenylmethane diisocyanate product name: Lupranate MM103, manufactured by BASF
• the content of the urea derivative and biuret derivative in the polyisocyanate composition (X) was measured using a liquid chromatograph quadrupole time-of-flight mass spectrometer (LC-QTOF-MS) under the following conditions.
• Measuring device Waters ACQUITY UPLC H-Class, Synapt G2-S MS Column: Waters ACQUITY UPLC HSS-T3 C18 Column Flow rate: 0.3mL/min Mobile phase A: acetonitrile/THF (80/20 weight ratio) Mobile phase B: 10 mM ammonium acetate aqueous solution Mass measurement range (m / z): 50-1800
• the polyol composition (Y) When the acid value becomes 5.0 mgKOH/g or less, the pressure inside the reaction vessel is gradually reduced, and the reaction is performed at 40 Torr or less to obtain a polyester polyol having an acid value of 1.0 mgKOH/g and a hydroxyl value of 200 mgKOH/g and having hydroxyl groups at both ends. got This was used as the polyol composition (Y).
• PAA elution amount The two-component adhesive blended in the combination of Examples or Comparative Examples was applied to a PET film so that the coating amount was 3.0 g/m 2 of solid content, and the coated surface of this film and the CPP film were separated by a laminator. They were laminated to produce a laminated film.
• This laminated film was stored in a constant temperature bath at 40°C for 3 days.
• This laminated film was cut to 120 mm ⁇ 220 mm, folded so that the CPP film was on the inside, and heat-sealed in three directions with a width of 10 mm at 1 atm at 190 ° C. for 1 second to produce a pouch in which the contents contacted 2 dm 2 . bottom.
• a pouch filled with a 3% acetic acid/acetic acid solution was retort-sterilized at 121°C for 0.5 hours, and then PAA was measured by LC/MS/MS.
• the evaluation was as follows. ⁇ : Less than 10 ppb ⁇ : 10 ppb or more
• Laminate strength A two-part adhesive compounded in a combination of Examples or Comparative Examples is applied to a Ny film on which a design is gravure-printed with printing ink Univia NT (manufactured by DIC) so that the coating amount is 3.0 g/m 2 in solid content. bottom. Then, the coated surface of the film and the LLDPE film were laminated with a laminator to prepare a laminated film. This laminate film was stored in a constant temperature bath at 40° C. for 3 days to prepare a laminate film for a laminate strength test.
• a test piece having a width of 15 mm was cut from the laminated film, and the adhesive strength (N/15 mm) was measured by 180 degree peeling at a peeling speed of 300 mm/min using a tensile tester.
• the evaluation was as follows. ⁇ : 5 N / 15 mm or more ⁇ : less than 5 N / 15 mm

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