WO2019188334A1 - Reactive adhesive, laminated film, and packaging body - Google Patents

Abstract

Provided are: a reactive adhesive that contains a polyisocyanate composition (X), a polyol composition (Y), and a pyromellitic anhydride and in which the pyromellitic anhydride content is 0.2-2.0 wt% relative to the total solids of the reactive adhesive; and a laminated film that is obtained by layering an adhesive layer between a first plastic film and a second plastic film, said adhesive layer being a layer of the aforementioned reactive adhesive. The reactive adhesive preferably additionally includes 3a,4,5,7a-tetrahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-1,3-iso-benzofurandione or gallic acid.

Description

Reactive adhesive, laminated film, and package

The present invention relates to a reactive adhesive, a laminated film using the same, and a package.

Laminate films (sometimes referred to as laminate films) used for various packaging materials, labels, etc. are designed, functional, storable, and convenient by laminating various types of plastic films, metal foil, paper, etc. A package that is provided with transportability and is formed by forming the laminated film into a bag shape is used as a package for foods, pharmaceuticals, detergents, and the like. As an adhesive used when laminating these films, a reactive adhesive (also referred to as a two-component adhesive) in which a polyisocyanate composition and a polyol composition are combined is known.

Laminate film adhesives for food packaging may affect the appearance of the packaging film even after a certain period of time after the contents (for example, food) are placed in a food packaging bag made from food packaging film and sterilized. It is required not to be affected, that is, to have excellent content resistance. As these evaluations, acid resistance and oil resistance are usually evaluated. For example, Patent Document 1 includes an organic polyisocyanate, a polyol, a phosphorus oxygen acid or a derivative thereof, a carboxylic acid compound or an anhydride thereof, and an epoxy resin. It is disclosed that the polyurethane adhesive composition thus formed exhibits high hot water resistance and acid resistance even for highly acidic foods. Patent Document 2 contains a urethane resin obtained by blending (A) a polyol component, (B) an isocyanate component, and (C) an aromatic compound having both a phenolic hydroxyl group and a carboxyl group or an ester group. It has been disclosed that an adhesive for food packaging film has excellent peel strength and is excellent in resistance after pressure hot water sterilization with respect to the contents of 1/1/1 / weight ratio of grain vinegar / salad oil / tomato ketchup. Yes.

However, there are various types of food additives. For example, ethyl maltol added to food as a flavoring agent reduces the strength of the adhesive after retort sterilization. However, the adhesive having ethyl maltol resistance has not been evaluated so far.

Japanese Patent Laid-Open No. 2-84482 Japanese Patent Laid-Open No. 2015-113411

An object of the present invention is to provide a reactive adhesive with improved reduction in adhesive strength after retort sterilization with ethyl maltol.

The present inventors provide a reactive adhesive containing a polyisocyanate composition (X), a polyol composition (Y), and pyromellitic acid anhydride, wherein the pyromellitic acid anhydride is used as a reactive adhesive. By containing 0.2 to 2.0% by weight with respect to the solid content, the above-mentioned problems were solved.

That is, the present invention is a reactive adhesive containing a polyisocyanate composition (X), a polyol composition (Y), and pyromellitic acid anhydride, and the pyromellitic acid anhydride is used as a reactive adhesive all solid. A reactive adhesive containing 0.2 to 2.0% by weight based on the content is provided.

The present invention also provides a laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive described above. Provide film.

Moreover, this invention is a package formed by shape | molding the laminated film formed by laminating | stacking an adhesive bond layer between a 1st plastic film and a 2nd plastic film in a bag shape, Comprising: The said adhesive bond layer is the said description. A package is provided which is a layer of a reactive adhesive.

The reactive adhesive of the present invention has improved adhesive strength reduction after retort sterilization with ethyl maltol, and therefore can be suitably used as a food packaging bag to which ethyl maltol is added as a fragrance.

(Reactive adhesive)
The reactive adhesive of the present invention is a reactive adhesive containing a polyisocyanate composition (X), a polyol composition (Y), and pyromellitic acid anhydride, and the pyromellitic acid anhydride is reactive. It is characterized by containing 0.2 to 2.0% by weight based on the total solid content of the adhesive.
Above all, the pyromellitic anhydride is preferably contained in an amount of 0.2 to 1.5% by weight, and most preferably 0.3 to 0.8% by weight, based on the total solid content of the reactive adhesive.

(Pyromellitic anhydride)
The pyromellitic anhydride used in the present invention is a compound having the following structure.

In the present invention, in addition to the pyromellitic anhydride, 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso- It is preferable to use benzosoflange on or gallic acid in combination.
When used in combination, 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofuranfion is a reactive adhesive all solid The content is preferably 0.2 to 2.0% by weight, and most preferably 0.3 to 1.0% by weight.
The gallic acid is preferably contained in an amount of 0.2 to 2.0% by weight, most preferably 0.3 to 1.0% by weight, based on the total solid content of the reactive adhesive.

In the present invention, there is no particular limitation except that a specific amount of the pyromellitic anhydride is added, and a known polyisocyanate composition (X) and a polyol composition (Y) used as a reactive adhesive are used. Can be used in combination.

(Polyisocyanate composition (X))
The polyisocyanate composition (X) used in the present invention is a composition containing a polyisocyanate compound as a main component. As the polyisocyanate compound used in the present invention, known compounds can be used without any particular limitation, and they can be used alone or in combination.
For example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, NCO groups of these polyisocyanates Compounds partially modified with carbodiimide; alphanate compounds derived from these polyisocyanates; molecular structures such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane Polyisocyanate having an alicyclic structure: 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethyle Linear aliphatic polyisocyanates such as diisocyanates, and the alphanate compounds; isocyanurates of these polyisocyanates; allophanates derived from these polyisocyanates; biurets derived from these polyisocyanates; trimethylolpropane Modified adduct bodies; and polyisocyanates that are reaction products of the various polyisocyanates and polyol components described above.

Moreover, it is preferable from the point that a linear aliphatic polyisocyanate is reacted with a polyol compound together with a polyisocyanate having an aromatic structure in the molecular structure to give flexibility to the laminate and increase the actual packaging property. . In this case, the linear aliphatic polyisocyanate can be introduced into the polyisocyanate compound while forming a urethane bond or an allophanate bond when reacting with a hydroxyl group in the polyol compound. When the polyisocyanate having an aromatic structure and the linear aliphatic polyisocyanate are used in combination, the use ratio thereof is [polyisocyanate having an aromatic structure / linear aliphatic polyisocyanate] of 99 on a mass basis. A ratio of 1 to 70/30 is preferable from the viewpoint of reducing the viscosity.

Here, the reaction ratio between the polyisocyanate compound and the polyol compound is such that the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group and the hydroxyl group is in the range of 1.0 to 5.0. From the viewpoint of the balance between cohesive strength and flexibility.

Specific examples of the polyol compound to be reacted with a polyisocyanate having an alicyclic structure or an aromatic structure in the molecular structure include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene Chain aliphatic glycols such as glycol, dipropylene glycol, tripropylene glycol and bishydroxyethoxybenzene; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; Serine, trimethylolpropane, aliphatic trifunctional or tetrafunctional pentaerythritol alcohol;
Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F;

Dimer diol; addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene in the presence of a polymerization initiator such as glycol, trifunctional or tetrafunctional aliphatic alcohol. Polyether polyols;
A polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the above-mentioned glycol or trifunctional or tetrafunctional aliphatic Polyester polyol (1) which is a reaction product with alcohol;
A polyester polyol (2) obtained by reacting a polyol such as the chain aliphatic glycol, alicyclic glycol, dimer diol, bisphenol or the polyether polyol with a polyvalent carboxylic acid;
A polyester polyol (3) obtained by reacting the 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 polyol (5), which is a polymer of hydroxyl acid such as dimethylolpropionic acid and castor oil fatty acid;
A mixture of the polyester polyol (1), (2), (3), (4), (5) and a polyether polyol;
Castor oil, dehydrated castor oil, castor oil that is a hydrogenated product of castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and the like.

Here, examples of the polyvalent carboxylic acid used in the production of the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and maleic anhydride. Acyclic aliphatic dicarboxylic acids such as fumaric acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid An anhydride or ester-forming derivative of these aliphatic or aromatic dicarboxylic acids; p-hydroxy Ikikosan, p-(2-hydroxyethoxy) benzoic acid and ester forming derivatives of these dihydroxy carboxylic acids include polybasic acids such as dimer acid.

Among these, a polyisocyanate compound obtained by reacting the polyether polyol with the polyisocyanate compound is preferable from the viewpoint of wettability with respect to the substrate.

The polyisocyanate compound preferably has a weight average molecular weight (Mw) in the range of 3,000 to 10,000 from the viewpoint of ensuring proper packaging while shortening the aging time. Those having an isocyanate content of 5 to 20% by mass (using -n-butylamine) are preferable from the viewpoint of having an appropriate resin viscosity and excellent coating properties.

(Polyol composition (Y))
The polyol composition (Y) used in the present invention is a composition containing a polyol compound as a main component. Polyol compounds can be used alone or in combination.
Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol , Neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1, Glycols such as 4-cyclohexanedimethanol and triethylene glycol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; Dimer diol; Lumpur A, bisphenol F, hydrogenated bisphenol A, bisphenol such as hydrogenated bisphenol F;

Polyether polyol obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene in the presence of a polymerization initiator such as glycol, trifunctional or tetrafunctional aliphatic alcohol. A polyether urethane polyol obtained by further increasing the molecular weight of the polyether polyol with the aromatic or aliphatic polyisocyanate;

Polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the above-mentioned glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Polyester polyol (1) which is a reaction product of a polyhydric alcohol of the above; Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol or bisphenol with a polycarboxylic acid; Polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic Polyester obtained by reacting with acid Ether polyol (4); dimethylolpropionic acid, a polymer of hydroxyl acids such as castor oil fatty acid, a polyester polyol (5);

Polyester polyether polyol obtained by reacting the polyester polyols (1) to (5) with the polyether polyol and an aromatic or aliphatic polyisocyanate. The polyester polyols (1) to (5) are aromatic or aliphatic. Polyester polyurethane polyol obtained by increasing the molecular weight with polyisocyanate; mixture of polyester polyols (1) to (5) and polyether polyol; castor oil, dehydrated castor oil, castor oil hydrogenated castor oil, castor And castor oil-based polyols such as 5 to 50 mol adducts of alkylene oxide of oil. The weight average molecular weight (Mw) of the polyol used is preferably 400 to 5000.

Examples of the polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as acids; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis Aromatic dicarboxylic acids such as (phenoxy) ethane-p, p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid Acids and ester-forming derivatives of these dihydroxycarboxylic acids, dyes It includes polybasic acids such as over acid.

(solvent)
The reactive adhesive used in the present invention is an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent-type or solvent-free type adhesive. The "solvent" of the solvent-type adhesive referred to in the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound and polyol compound used in the present invention, and "no solvent" Means that these highly soluble organic solvents are not included. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, n-hexane, and cyclohexane. Can be mentioned. Of these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.

In the reactive adhesive used in the present invention, the blending ratio of the polyisocyanate composition (X) and the polyol composition (Y) is in the polyisocyanate compound contained in the polyisocyanate composition (X). The equivalence ratio [isocyanate group / hydroxyl group] of the isocyanate group and the hydroxyl group in the polyol compound contained in the polyol composition (Y) is in the range of 0.6 to 5.0. From the viewpoint of excellent heat resistance at the time, the range of 1.0 to 3.5 is particularly preferable because these performances become remarkable.

(Aliphatic cyclic amide compound)
As described in detail, the reactive adhesive of the present invention comprises the polyol component A and the isocyanate component B as essential components. Further, the aliphatic cyclic amide compound is further combined with the polyol component A and the isocyanate component B. Elution into the contents of harmful low-molecular-weight chemicals typified by aromatic amines in the laminate package is effective by mixing with either component or by blending at the time of coating as the third component Can be suppressed.

Examples of the aliphatic cyclic amide compound used here include δ-valerolactam, ε-caprolactam, ω-enanthol lactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is preferable because it is excellent in reducing the amount of low-molecular chemical substances eluted. The blending amount is preferably such that the aliphatic cyclic amide compound is mixed in the range of 0.1 to 5 parts by mass per 100 parts by mass of the polyol component A.

(catalyst)
In the present invention, by using a catalyst, elution of harmful low molecular chemical substances typified by aromatic amines into the contents of the laminate package can be effectively suppressed.
The catalyst used in the present invention is not particularly limited as long as it is for accelerating the urethanation reaction. For example, metal catalysts, amine catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds A catalyst such as a titanium chelate complex can be used.

Examples of metal catalysts include metal complex systems, inorganic metal systems, and organic metal systems. Specific examples of metal complex systems include Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt) metal acetylacetonate salts, such as iron acetylacetonate, manganese acetylacetonate, copper acetyl Acetonate, zirconia acetylacetonate and the like can be mentioned. Among these, iron acetylacetonate (Fe (acac) ₃ ) or manganese acetylacetonate (Mn (acac) ₂ ) is preferable from the viewpoint of toxicity and catalytic activity. .

Examples of the inorganic metal catalyst include catalysts selected from Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.

Examples of organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.

The tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because of their excellent catalytic activity and industrial availability.

Other tertiary amine catalysts include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis Dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro -S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N -Methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl-N '-(2-hydroxyethyl) pipette Gin, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, etc. Is mentioned.

Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enanthol lactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is more effective for promoting curing.

The titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic or aromatic diketone as a ligand from the viewpoint of excellent curing acceleration effect. In the present invention, those having an alcohol having 2 to 10 carbon atoms in addition to an aromatic or aliphatic diketone as a ligand are preferred from the viewpoint that the effects of the present invention become more remarkable.
In the present invention, the catalysts may be used alone or in combination.

.
The mass ratio of the catalyst is preferably in the range of 0.001 to 80 parts, preferably in the range of 0.01 to 70 parts, when the mixed liquid of the polyisocyanate composition (X) and the polyol composition (Y) is 100 parts. More preferred.

The reactive adhesive of the present invention may be used in combination with a pigment, if necessary. In this case, usable pigments are not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments described in the Paint Material Handbook 1970 edition (edited by the Japan Paint Industry Association) Examples thereof include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. Specific examples of these colorants include various types, and examples of organic pigments include various insoluble azo pigments such as Bench Gin Yellow, Hansa Yellow, and Raked 4R; soluble properties such as Raked C, Carmine 6B, Bordeaux 10 and the like. Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Various vat dyes such as pigments, thioindigo pigments and perinone pigments; various quinacridone pigments such as Cincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azos such as chromoftal Pigment; aniline black, etc. And the like.

Examples of inorganic pigments include various chromates such as chrome lead, zinc chromate, and molybdate orange; various ferrocyan compounds such as bitumen; titanium oxide, zinc white, mapico yellow, iron oxide, bengara, chrome oxide Various metal oxides such as green and zirconium oxides; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue Silicates; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder Pigments; flake pigments of these metals, mica flake pigments; mica flakes coated with metal oxides Click pigments, micaceous iron oxide pigments such as metallic pigment and pearl pigment; graphite, carbon black and the like.

Examples of extender pigments include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, cryolite, alumina white, silica, hydrous finely divided silica (white carbon), ultrafine anhydrous silica (Aerosil), and silica sand (silica). Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, ocher and the like.

Furthermore, examples of the plastic pigment include “Grandall PP-1000” and “PP-2000S” manufactured by DIC Corporation.

As the pigment used in the present invention, since it is excellent in durability, weather resistance and design, inorganic oxides such as titanium oxide and zinc white as a white pigment, and carbon black as a black pigment are more preferable.

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to a total of 100 parts by mass of the isocyanate component B and the polyol component A. More preferable.

(Adhesion promoter)
Moreover, an adhesion promoter can also be used together with the reactive adhesive used in the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Me Mercaptopropyl trimethoxysilane and the like.

Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.

Also, examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

As epoxy resins, there are generally commercially available Epbis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, many Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcin type, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, - phthalic acid diglycidyl ester, glycidyl methacrylate, compounds such as butyl glycidyl ether.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives other than those described above. Examples of additives include leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate organic fine particles, antifoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, metals Deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant, rust preventive, fluorescent brightener, inorganic heat absorber, flame retardant, antistatic agent, dehydrating agent, Known and commonly used thermoplastic elastomers, tackifiers, phosphoric acid compounds, melamine resins, or reactive elastomers can be used. The content of these additives can be appropriately adjusted and used within a range that does not impair the function of the reactive adhesive used in the present invention.

These adhesion promoters and additives may be mixed with either one of the polyisocyanate composition (X) or the polyol composition (Y), or may be used as a third component by blending at the time of application. it can. Usually, a premix in which components other than the polyisocyanate composition (X) are blended in advance with the polyol composition (Y) is prepared, and the premix and the polyisocyanate composition (X) are added immediately before construction. Prepare by mixing.

(Laminated film)
The laminated film of the present invention is formed by laminating an adhesive layer made of the reactive adhesive between a first plastic film and a second plastic film. Specifically, the reactive adhesive is applied to a first plastic film, then a second plastic film is laminated on the coated surface, and the adhesive layer is cured. Although it may be applied by any method as long as it is publicly known, it is generally applied by a gravure roll coating method. The application amount of the adhesive is 1.0 to 5.0 g / m ² , preferably 1.5 to 4.0 g / m ² in terms of solid content.

Further, a gravure, flexo, ink jet or offset print of printing ink may be used on the first plastic film, and even in this case, a good laminate appearance can be exhibited. As the above-mentioned printing ink, a solvent type, aqueous type or active energy ray curable ink can be used.

When the reactive adhesive used in the present invention is used, the adhesive is cured in 12 to 72 hours at room temperature or under heating after laminating, and expresses practical physical properties.

The first plastic film used here is a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K-coated film such as polyvinylidene chloride, a base film such as various deposited films, and an aluminum foil. Examples of the second plastic film include CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), LLDPE (linear low density polyethylene), and LDPE. Examples thereof include sealant films such as (low density polyethylene), HDPE (high density polyethylene), and VMLDPE (aluminum vapor-deposited low density polyethylene film) films.

(Packaging body)
The package of the present invention is formed by forming the laminated film into a bag shape. Specifically, the package is formed by heat-sealing the laminated film. In addition, when considering the use as a package, required performance (easy tearability and hand cutability), rigidity and durability required for the package (for example, impact resistance, pinhole resistance, etc.) Other layers can be laminated as required. Usually, it is used with a base material layer, a paper layer, a second sealant layer, a non-work cloth layer and the like. As a method of laminating other layers, a known method can be used. For example, an adhesive layer may be provided between other layers and laminated by a dry laminate method, a heat laminate method, a heat seal method, an extrusion laminate method, or the like. As the adhesive, the reactive adhesive may be used, or other one-component type urethane adhesive, epoxy adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.

As a specific laminate structure, the first plastic film layer / adhesive layer / second plastic layer, first plastic layer, which can be suitably used for general packaging bodies, lid materials, refill containers, etc. A second plastic layer / paper that can be suitably used for a base layer / adhesive layer / first plastic film layer / adhesive layer / second plastic layer, paper container, paper cup, etc. Layer / adhesive layer / first plastic film layer / adhesive layer / second plastic, second plastic layer / paper layer / polyolefin resin layer / substrate layer / first plastic layer / adhesive layer / second plastic Layer, paper layer / first plastic film layer / adhesive layer / sealant layer, second plastic layer / adhesive layer / first plastic that can be suitably used for tube containers, etc. Click layer / adhesive layer / etc. second plastic layer. These laminates may have a print layer, a top coat layer, or the like as necessary.

The first plastic film layer includes, for example, a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); a polyolefin resin film such as polypropylene; a polystyrene resin film; a nylon 6, a poly- Polyamide resin film such as p-xylylene adipamide (MXD6 nylon); Polycarbonate resin film; Polyacrylonitrile resin film; Polyimide resin film; Multilayers thereof (for example, nylon 6 / MXD6 / nylon 6, nylon 6 / An ethylene-vinyl alcohol copolymer / nylon 6) or a mixture is used. Among them, those having mechanical strength and dimensional stability are preferable. Of these, a film arbitrarily stretched in the biaxial direction is preferably used.

Further, the first plastic film layer is made of a soft metal foil such as an aluminum foil to provide a barrier function, as well as a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition; vinylidene chloride resin An organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon or the like can be used. *

As the second plastic film layer, a conventionally known sealant resin can be used. For example, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate Examples thereof include polyolefin resins such as copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene- (meth) acrylic acid copolymers, and ionomers. Of these, polyethylene resins are preferred from the viewpoint of low temperature sealing properties, and polyethylene is particularly preferred because of its low cost. The thickness of the sealant layer is not particularly limited, but is preferably in the range of 10 to 60 μm and more preferably in the range of 15 to 40 μm in consideration of processability to packaging materials and heat sealability. Further, by providing the sealant layer with irregularities with a height difference of 5 to 20 μm, it is possible to impart slipperiness and tearability of the packaging material to the sealant layer. *

Examples of paper layers include natural paper and synthetic paper. The first and second sealant layers can be formed of the same material as the above-described sealant layer. You may provide a printing layer in the outer surface or inner surface side of a base material layer and a paper layer as needed. *

The “other layer” may contain a known additive or stabilizer, for example, an antistatic agent, an easy adhesion coating agent, a plasticizer, a lubricant, an antioxidant, or the like. In addition, “other layers” are those in which the surface of the film has been subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve adhesion when laminated with other materials. May be. *

As an aspect of the package of the present invention, a three-sided seal bag, a four-sided seal bag, a gusset packaging bag, a pillow packaging bag, a gobeltop-type bottomed container, a tetra classic, a backpack type, a tube container, a paper cup, a lid, There are various types. In addition, an easy-opening treatment or resealability means may be provided as appropriate in the package of the present invention.

The package of the present invention can be industrially used not only as a food package subjected to retort sterilization but also as a package filled with general foods, detergents and drugs. Specific applications include food packaging, detergents, and drugs such as laundry liquid detergent, kitchen liquid detergent, bath liquid detergent, bath liquid soap, liquid shampoo, liquid conditioner, and pharmaceutical tablet. . Moreover, it can be used also for the secondary package which packages said container.

Hereinafter, the contents and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the examples, “parts” means “parts by weight”.

(Polyisocyanate composition (X))
(Adjustment Example 1 Polyisocyanate composition (X1))
In a flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube, 100 parts of Desmodur L-75 (TMP-3TDI adduct, manufactured by Sumika Covestrourethane Co., Ltd.), pyromellitic acid anhydride (Daicel Corporation) 1.5 parts of the mixture was diluted with ethyl acetate to obtain a polyisocyanate composition (X1) of NV45% solution.

(Adjustment Example 2 Polyisocyanate Composition (X2))
Desmodur L-75 (TMP-3TDI adduct, manufactured by Sumika Covestro Urethane Co., Ltd.) was used.

(Adjustment Example 3 Polyisocyanate Composition (X3))
Rupranate MP102 (diphenylmethane diisocyanate prepolymer BASF INOAC Polyurethane Co., Ltd.) was used.

(Polyol composition (Y))
(Synthesis Example 1)
145 parts of terephthalic acid, 350 parts of isophthalic acid, 225 parts of adipic acid, 15 parts of sebacic acid, 85 parts of ethylene glycol in a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, rectification tube, moisture separator, etc. Then, 310 parts of diethylene glycol and 45 parts of neopentyl glycol were charged, and an esterification reaction was performed at an internal temperature of 250 ° C. After the dehydration reaction, a polyester polyol A1 having a number average molecular weight of about 9000 was obtained.

(Synthesis Example 2)
A polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, moisture separator, etc. is charged with 375 parts of isophthalic acid, 250 parts of adipic acid and 545 parts of diethylene glycol, and esterified at an internal temperature of 240 ° C. Reaction was performed. After the dehydration reaction, a polyester polyol having a number average molecular weight of about 1500 was obtained. Cosmonate T-80 in which 100 parts of this polyester polyol and 78 parts of ethyl acetate were previously charged in a reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, cooling tube, etc. By reacting with 18 parts, a polyester polyurethane polyol B1 having a number average molecular weight of about 4000 was obtained.

(Adjustment Example 4 Polyol Composition (Y1))
Polyester polyol A1 obtained in Synthesis Example 1 was dissolved and diluted with ethyl acetate to obtain a polyol composition (Y1) having a solid content (hereinafter abbreviated as NV) 70% solution.

(Adjustment Example 5 Polyol Composition (Y2))
Pyromellitic acid anhydride (Daicel product) 1.0% by weight in terms of solid content was added to the polyester polyol A1 obtained in Synthesis Example 1, and further dissolved and diluted with ethyl acetate to obtain a polyol composition (N2) in an NV 70% solution. Got.

(Adjustment Example 6 Polyol Composition (Y3))
Polyester polyol A1 obtained in Synthesis Example 1 was added to EPICLON B-4500 (3a, 4, 5, 7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3- 1% by weight in terms of solid content was added and further dissolved and diluted with ethyl acetate to obtain a polyol composition (Y3) of NV 70% solution.

(Example of adjustment 7 polyol composition (Y4))
To polyester polyol A1 obtained in Synthesis Example 1, purified gallic acid (DSP Gokyo Food & Chemical Co., Ltd.) is added at 1.0% by weight in terms of solid content, and further dissolved and diluted with ethyl acetate to obtain a polyol composition of an NV 70% solution. A product (Y4) was obtained.

(Adjustment Example 8 Polyol Composition (Y5)
A pyromellitic anhydride (Daicel product) 0.7% by weight in terms of solid content was added to the polyester polyurethane polyol B1 obtained in Synthesis Example 2, and further dissolved and diluted with ethyl acetate to prepare a polyol composition (Y5 )

(Comparative Adjustment Example 1 Polyol Composition (YH1))
To polyester polyol A1 obtained in Synthesis Example 1, purified gallic acid (DSP Gokyo Food & Chemical Co., Ltd.) is added at 1.0 weight percent in terms of solid content, and further dissolved and diluted with ethyl acetate to obtain a polyol composition of NV70% solution. A product (YH1) was obtained.

(Comparative Adjustment Example 2 Polyol Composition (YH2))
Polyester polyol A1 obtained in Synthesis Example 1 was added to EPICLON B-4500 (3a, 4, 5, 7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3- 1% by weight in terms of solid content was added, and further dissolved and diluted with ethyl acetate to obtain a polyol composition (YH2) of NV 70%.

(Mixing ratio)
Tables 1 and 2 show the blending ratio of each adhesive. In Example 1, 1 part by weight of the isocyanate composition was added to 3 parts by weight of the polyol composition, and the mixture was adjusted to have an NV of 30% with ethyl acetate. In Examples 2, 3, and 4, the polyol composition and the isocyanate composition shown in Table 1 were blended in their respective parts by weight, and adjusted to 30% NV with ethyl acetate.
In Comparative Example, as shown in Table 2, 1 part by weight of the isocyanate composition was added to 5 parts by weight of the polyol composition, and the mixture was adjusted to have an NV of 30% with ethyl acetate.

(Evaluation method of peel strength test after retort test and storage stability test)
(Method for creating laminated film for evaluation)
Using a DL-600DX dry laminator (manufactured by Orient Sogyo Co., Ltd.), it was applied to a PET film printed with transparent or indigo ink so that the solid content weight of the adhesive was 4.0 g / m ^2, and a dryer ( After evaporating the solvent at 60 ° C./70° C./80° C., it was bonded to the surface of the aluminum foil. Next, the adhesive is applied to the surface opposite to the surface already bonded to the PET film with the adhesive so that the solid weight of the adhesive is 4.0 g / m ² . After drying the solvent, it was laminated with a CPP film to produce a laminated film. Next, this laminated film was aged at 50 ° C. for 3 days to cure the adhesive coating film, and a laminated film of PET film / adhesive composition / aluminum foil / adhesive composition / CPP film was obtained.
The following films and inks were used.
PET film: Toyobo STC Co., Ltd. E5102 12 μm
Aluminum foil film: Toyo Aluminum Co., Ltd. aluminum foil O material 9μm
CPP film: Toray Industries, Inc. Trefan NO ZK-207 70μm
Ink: XS-853 R507 Genshoukui K1 made by DIC

1. Peel strength test after aging From a laminated film for evaluation prepared by the above method, a test piece of 200 mm × 15 mm was cut out and using a tensile strength tester (manufactured by Shimadzu Corporation) in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The peel rate was 300 mm / min, a T-type peel test was performed, and the peel strength (N / 15 mm) of the aluminum foil / CPP film was measured. The peel strength is acceptable if it is 1 N / 15 mm or more.

2-1. Ethyl maltol solution resistance test (peel strength immediately after retort sterilization)
A pouch having a size of 120 mm × 120 mm was prepared from the laminated film for evaluation prepared by the above method, and an ethyl maltol 0.3% aqueous solution (pseudo food) was prepared as a content and filled with 50 g. About the produced pouch, the retort sterilization process for 30 minutes was performed at 121 degreeC. Then, the packaging bag was chosen at random, it was opened, and the test piece of 100 mm x 15 mm was cut out.

2-2. Ethyl maltol solution resistance test (appearance immediately after retort sterilization)
A pouch having a size of 120 mm × 120 mm was prepared from the laminated film for evaluation prepared by the above method, and an ethyl maltol 0.3% aqueous solution (pseudo food) was prepared as a content and filled with 50 g. About the produced pouch, the retort sterilization process for 30 minutes was performed at 121 degreeC. Then, the packaging bag was chosen at random and the external appearance was evaluated visually.

2-3. Commercial food resistance test with ethyl maltol (appearance immediately after retort sterilization)
The peel strength (N / 15 mm) between the aluminum foil / CPP film of the test piece was measured by the same method as the peel strength test, and the film appearance immediately after sterilization was visually evaluated.
Moreover, the commercially available food containing ethyl maltol was refilled into a pouch having the above size, and the film appearance after retort sterilization was visually evaluated.

3-1. Ethyl maltol solution resistance test (peel strength after sterilization at 80 ° C after 1 day)
A pouch having a size of 120 mm × 120 mm was prepared from the laminated film for evaluation prepared by the above method, and an ethyl maltol 0.3% aqueous solution (pseudo food) was prepared as a content and filled with 50 g. About the produced pouch, the retort sterilization process for 30 minutes was performed at 121 degreeC. Thereafter, the packaging bag was stored in a thermostatic bath at 80 ° C., and the peel strength (N / 15 mm) between the aluminum foil / CPP film of the test piece was measured by the same method as the peel strength test one day later.

3-2. Ethyl maltol solution resistance test (appearance after 1 day at 80 ° C after sterilization)
A pouch having a size of 120 mm × 120 mm was prepared from the laminated film for evaluation prepared by the above method, and an ethyl maltol 0.3% aqueous solution (pseudo food) was prepared as a content and filled with 50 g. About the produced pouch, the retort sterilization process for 30 minutes was performed at 121 degreeC. Thereafter, the packaging bag was stored in a constant temperature bath at 80 ° C., and the film appearance after 1 day was visually evaluated.

3-3. Commercial food containing ethyl maltol (resistance test after 1 week at 80 ° C)
From the laminated film for evaluation prepared by the above method, a pouch having a size of 120 mm × 120 mm is prepared, and as a content, a commercially available food containing ethyl maltol is refilled with a pouch having the above size, and after retort sterilization. The packaging bag was stored in a constant temperature bath at 80 ° C., and the appearance of the film was visually evaluated after one week.

3-4. Commercial food containing ethyl maltol (resistance test after 3 weeks at 80 ° C)
From the laminated film for evaluation prepared by the above method, a pouch having a size of 120 mm × 120 mm is prepared, and as a content, a commercially available food containing ethyl maltol is refilled with a pouch having the above size, and after retort sterilization. The packaging bag was stored in a constant temperature bath at 80 ° C., and the film appearance was visually evaluated after 3 weeks.

3-5. Commercial food containing ethyl maltol (Appearance after 4 weeks resistance test at 80 ° C)
From the laminated film for evaluation prepared by the above method, a pouch having a size of 120 mm × 120 mm is prepared, and as a content, a commercially available food containing ethyl maltol is refilled with a pouch having the above size, and after retort sterilization. The packaging bag was stored in a constant temperature bath at 80 ° C., and the film appearance was visually evaluated after 4 weeks.

In any case, the visual evaluation is based on the following criteria.
○: No change in appearance Δ: Partial delamination between aluminum foil / CPP film
X: Delamination between aluminum foil / CPP film.

As a result, the laminated film using the reactive adhesive obtained in the examples satisfies all the evaluation physical properties. In particular, using pyromellitic anhydride and 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofuranone In Example 3, or Example 4 in which pyromellitic anhydride and gallic acid were used in combination, the ethyl maltol solution resistance test was good even after 4 weeks. On the other hand, although a comparative example is an example which does not contain a pyromellitic acid anhydride, it could not satisfy | fill all the evaluation physical properties.

Claims (5)

1. A reactive adhesive comprising a polyisocyanate composition (X), a polyol composition (Y), and pyromellitic anhydride, wherein the pyromellitic anhydride is added to the total solid content of the reactive adhesive in an amount of 0.001. A reactive adhesive comprising 2 to 2.0% by weight.
2. 3. 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzosofuranone, or gallic acid The reactive adhesive as described.
3. The reactive adhesion according to claim 1 or 2, wherein the polyol composition (Y) is at least one polyol selected from polyester polyols, polyurethane polyols, polyether polyols, polyester polyurethane polyols, and polyether polyurethane polyols. Agent.
4. The reactive adhesive layer according to any one of claims 1 to 3, wherein the adhesive layer is formed by laminating an adhesive layer between a first plastic film and a second plastic film. A laminated film characterized by the above.
5. A packaging body formed by forming a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film into a bag shape, wherein the adhesive layer is any one of claims 1 to 3. A package comprising the reactive adhesive layer according to claim 1.