WO2022220151A1

WO2022220151A1 - Two-pack curable adhesive composition, anchor coating material, adhesive, laminate, and packaging material

Info

Publication number: WO2022220151A1
Application number: PCT/JP2022/016451
Authority: WO
Inventors: 千勇徳永; 常行手島; 正光新居
Original assignee: Dic株式会社
Priority date: 2021-04-13
Filing date: 2022-03-31
Publication date: 2022-10-20
Also published as: JPWO2022220151A1; JP7207617B1

Abstract

Provided are an adhesive having excellent gas-barrier properties, a laminate, and a packaging material.　Also provided is a two-pack solvent-free adhesive composition which comprises a polyol composition (X) comprising a polyester polyol (A1) and a polyol (A2) and a polyisocyanate composition (Y) including a polyisocyanate compound (C), wherein the polyester polyol (A1), when reacted with a trimethylolpropane adduct of xylylene diisocyanate under the conditions of NCO/OH of 2±0.2, gives a cured coating film which has an oxygen permeability at 23°C and 0% RH of 300 cc/m²/day/atm or less in terms of 3 g/m², and the polyol (A2) has two or more hydroxyl groups, a density of 1.2 g/cm³ or higher, and a melting point of 20°C or greater. The adhesive, anchor coating material, laminate, and packaging material each comprise or are obtained using the adhesive composition.

Description

Two-component curable adhesive composition, anchor coating agent, adhesive, laminate, packaging material

The present invention relates to a two-part curable adhesive composition, an anchor coating agent, an adhesive, a laminate, and a packaging material.

Packaging materials for food and beverages protect the contents from various distributions, preservation such as refrigeration, and heat sterilization. A wide variety of functions are required, such as excellent transparency so that the contents can be confirmed.
On the other hand, when a bag is sealed by heat sealing, a non-stretched polyolefin film with excellent heat processability is essential, but the unstretched polyolefin film has many functions lacking as a packaging material.

For this reason, composite flexible films made by combining different types of polymer materials are widely used as the packaging material. In general, a composite flexible film consists of a thermoplastic film layer, etc., which serves as an outer layer for product protection and various functions, and a thermoplastic film layer, etc., which serves as a sealant layer. , a method in which three layers of an adhesive and a thermoplastic for a sealant layer are melt-extruded to form an unstretched laminated sheet and then stretched (Patent Document 1); A dry lamination method (Patent Document 2) and the like are known for producing a multilayer film. Furthermore, from the viewpoint of reducing the environmental burden and improving the working environment, the demand for reactive two-liquid type lamination adhesives (hereinafter referred to as solvent-free adhesives) that do not contain volatile organic solvents is increasing ( Patent document 3).

In addition, in recent years, there has been a demand for even higher functionality in multilayer films, and in order to suppress oxidation, oxygen barrier properties that prevent the intrusion of oxygen from the outside, carbon dioxide barrier properties, and barrier properties against various aroma components, etc. are also required. ing. In addition, as one of the methods to extend the expiration date and expiration date of food, in order to prevent the propagation of microorganisms and molds that cause deterioration and spoilage of food, inert gas, ethyl alcohol transpiration material and ethyl alcohol It is widely practiced to enclose steam, together with food, in packages. Such packages are required to have a barrier function to prevent leakage of inert gas and ethyl alcohol in order to maintain the state of the food.

JP 2006-341423 A JP-A-2003-13032 JP 2014-159548 A

On the other hand, in recent years, along with the growing demand for building a recycling-oriented society, attempts have been made to recycle and use packaging materials. However, it is difficult to separate the resins by type in the above-described laminated body in which different types of resin films are bonded together, and thus it is not suitable for recycling. As a laminate of films of the same type, a laminate of stretched polyethylene film or stretched polypropylene film and unstretched polyethylene or unstretched polypropylene film has been proposed. has insufficient oxygen barrier properties.

The present invention has been made in view of such circumstances, and an object thereof is to provide a solventless adhesive composition having excellent gas barrier properties. Furthermore, by using a solvent-free adhesive composition with excellent gas barrier properties, it is a transparent film that can be used as a packaging material mainly for food and as a transparent barrier film for electronic materials such as solar cells and display elements. To provide a gas-barrier laminate excellent in gas barrier function and resistant to bending, or a laminate and a packaging material excellent in recyclability.

A polyol composition (X) containing a polyester polyol (A1) and a polyol (A2), and a polyisocyanate composition (Y) containing a polyisocyanate compound (C), wherein the polyester polyol (A1) is a polyester Polyol (A1) and trimethylolpropane adduct of xylene diisocyanate are reacted at NCO/OH of 2 ± 0.2. Oxygen permeability of the cured coating film at 23 ° C. 0% RH converted to 3 g / m ² value is 300 cc/m ² /day/atm or less, the polyol (A2) has two or more hydroxyl groups, a density of 1.2 g/cm ³ or more, and a melting point of 20° C. or more. The present invention relates to a solvent-type adhesive composition, an adhesive, an anchor coating agent, a laminate, and a packaging material using the same.

According to the present invention, it is possible to provide an adhesive composition with excellent gas barrier properties without fear of solvent discharge, and an adhesive and an anchor coating agent using the same. In addition, by using the gas barrier adhesive composition of the present invention, a transparent film that can be used as a packaging material mainly for food and a transparent barrier film for electronic materials such as solar cells and display elements has a gas barrier function. It is possible to provide a gas-barrier multilayer film that is excellent and resistant to bending, a laminate, and a packaging material that are excellent in recyclability.

<Two-liquid curable adhesive composition>
The two-component curable adhesive composition of the present invention is a polyol composition (X) containing a polyester polyol (A1) and a polyol (A2), and a polyisocyanate composition (Y) containing a polyisocyanate compound (C). Consists of The two-pack curable adhesive composition of the present invention is described in detail below.

(Polyol composition (X))
The polyol composition of the present invention contains polyester polyol (A1) and polyol (A2) as essential components. The polyol composition (X) of the present invention will be described in detail below.

(Polyester polyol (A1))
The polyester polyol (A1) is obtained by reacting the polyester polyol (A1) and the trimethylolpropane adduct of xylene diisocyanate at a [NCO]/[OH] ratio of 2 ± 0.2. The 3 g/m ² conversion value of the oxygen permeability at % RH is 300 cc/m ² /day/atm or less. [NCO] is the number of moles of isocyanate groups possessed by the XDI-TMP adduct, and [OH] is the number of moles of hydroxyl groups possessed by the polyester polyol (A1). The oxygen permeability is measured according to JIS-K7126 (isobaric method). In the following, the trimethylolpropane adduct of xylene diisocyanate is also referred to as the XDI-TMP adduct, and the oxygen transmission rate of polyester polyol (A1) measured under the above conditions, converted to 3 g/ ^m2 , is the oxygen transmission rate of polyester polyol (A1). Also called rate.

It is known that the oxygen permeability of the laminate is calculated by the following formula.

In the above formula, A is the oxygen permeability of the laminate, and F1 and F2 are the oxygen permeability of each layer constituting the laminate. Therefore, for example, a mixture of the polyester polyol (A1) and the XDI-TMP adduct is coated on a plastic film, cured, and then the oxygen transmission rate A is measured. Calculate the oxygen permeability F2 of the cured coating film from the oxygen permeability A of the laminate and the oxygen permeability F1 of the plastic film, and set F2 to ((coating amount of mixture of polyester polyol (A1) and XDI-TMP adduct body (g /m ² ))/3 (g/m ² )) to obtain the oxygen permeability of the polyester polyol (A1).

The polyester polyol (A1) used in the present invention reacts with a general polyisocyanate compound to cure, and the coating exhibits good oxygen barrier properties, but is liquid under room temperature and normal pressure. Therefore, since the oxygen transmission rate of the polyester polyol (A1) alone at 23°C and 0% RH cannot be measured, the above evaluation method is substituted.

A polyester polyol (A1) is a reaction product of a composition (A1') containing a polyhydric carboxylic acid, a polyhydric alcohol, and an optionally used compound having reactivity with a carboxyl group or a hydroxyl group. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid; unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid and fumaric acid; Carboxylic acid; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2- Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, 2,3-anthracenecarboxylic acid, anthraquinone-2 ,3-dicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and acid anhydrides or ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p-( 2-Hydroxyethoxy)benzoic acid and aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dihydroxycarboxylic acids, and the like can be used alone or in combination of two or more.

The use of the ortho-oriented aromatic polycarboxylic acid (a1) as the polycarboxylic acid is preferable because the gas barrier properties are improved (the oxygen permeability of the polyester polyol (A1) is reduced). Since the ortho-oriented aromatic polycarboxylic acid (a1) has an asymmetric skeleton, it is presumed that rotation suppression occurs in the molecular chain of the polyester polyol (A1), thereby improving gas barrier properties.

The ortho-oriented aromatic polycarboxylic acid (a1) includes orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, naphthalene 1,2-dicarboxylic acid or its acid anhydride, and anthraquinone. 2,3-dicarboxylic acid or its acid anhydride, 2,3-anthracenecarboxylic acid or its acid anhydride, and the like. These compounds may have a substituent at any carbon atom of the aromatic ring. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

From the viewpoint of gas barrier properties, the amount of the ortho-oriented aromatic polycarboxylic acid (a1) in the composition (A1′) is preferably 20% by mass or more, more preferably 30% by mass or more. . From the viewpoint of coatability, the amount of the ortho-oriented aromatic polycarboxylic acid (a1) in the composition (A1') is preferably 50% by mass or less.

Polyhydric alcohols include methylene glycol, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol. , methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and other aliphatic diols; glycerin, trimethylolpropane, trimethylolethane, tris (2 -Hydroxyethyl) isocyanurate, trihydric or higher polyhydric alcohols such as 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extensions thereof, aromatic polyhydric phenols such as hydrogenated alicyclics, etc. can be mentioned, and one or more of them can be used in combination.

Since the oxygen permeability of the polyester polyol (A1) can be lowered by using one having a short methylene chain between hydroxyl groups, the polyhydric alcohol has 1 to 3 carbon atoms between hydroxyl groups. (a2) is preferably used. Examples of the aliphatic polyol (a2) include methylene glycol, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol.

In order to improve the gas barrier properties of the polyester polyol (A1), the composition (A1') preferably contains a compound (a3) having an isocyanuric ring. The compound (a3) preferably has two or more functional groups capable of reacting with at least one of a carboxyl group and a hydroxyl group, and preferably has 4 or less carbon atoms in the shortest methylene chain connecting the isocyanuric ring and the functional group. . When the number of carbon atoms in the methylene chain exceeds 4, gas barrier properties tend to deteriorate. The functional groups possessed by the compound (a3) may be independently bonded to the isocyanuric ring via a methylene chain, or may be such that a plurality of functional groups are bonded to one methylene chain bonded to the isocyanuric ring. good. Of the multiple functional groups bonded to one methylene chain, the number of carbon atoms in the methylene chain between the functional group closest to the isocyanuric ring and the isocyanuric ring should be 4 or less. The number of carbon atoms in the methylene chain is preferably 1 or more and 4 or less.

Examples of such compounds (a3) include 1,3,5-tris(aminomethyl)isocyanuric acid, 1,3,5-tris(2-aminoethyl)isocyanuric acid, 1,3-bis(2-amino ethyl)-5-methyl-isocyanuric acid, 1,3-bis(2-aminoethyl)-5-ethyl-isocyanuric acid, 1,3-bis(2-aminoethyl)-5-propyl-isocyanuric acid, 1, 3-bis(2-aminoethyl)-5-butyl-isocyanuric acid, 1,3,5-tris(3-aminopropyl)isocyanuric acid, 1,3-bis(3-aminopropyl)-5-methyl-isocyanuric acid isocyanuric acid having an amino group such as acid,

1,3,5-tris(hydroxymethyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5-methyl-isocyanuric acid, 1,3-bis(hydroxymethyl)-5-ethyl-isocyanuric acid, 1, 3-bis(hydroxymethyl)-5-butyl-isocyanuric acid, 1,3-bis(hydroxymethyl)-5-phenyl-isocyanuric acid, 1-(hydroxyethyl)-3,5-bis(hydroxymethyl)-isocyanuric acid acid, 1,3,5-tris(1-hydroxyethyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5-(2-hydroxypropyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5 -(2-hydroxy-1-methylpropyl)isocyanuric acid, 1,3-bis(hydroxymethyl)-5-(2-hydroxy-2-methylpropyl)isocyanuric acid, 1,3,5-tris(2-hydroxy ethyl)isocyanuric acid, 1,3-bis(2-hydroxyethyl)-5-methyl-isocyanuric acid, 1,3-bis(2-hydroxyethyl)-5-ethyl-isocyanuric acid, 1,3-bis(2 -hydroxyethyl)-5-(1-hydroxy-1-methylethyl)isocyanuric acid, 1,3,5-tris(3-hydroxypropyl)isocyanuric acid, 1,3,5-tris(2-hydroxypropyl)isocyanuric acid acid, 1,3,5-tris(4-hydroxybutyl)isocyanuric acid, 1,3,5-tris(3-hydroxybutyl)isocyanuric acid, 1,3,5-tris(1,2-hydroxyethyl)isocyanuric acid acid, isocyanuric acid having a hydroxyl group such as 1,3,5-tris(2,3-hydroxypropyl)isocyanuric acid, 1,3-bis(2,4-hydroxybutyl)-5-(hydroxymethyl)isocyanuric acid ,

1,3,5-tris(2,3-epoxypropyl)isocyanuric acid, 1,3-bis(2,3-epoxypropyl)-5-methyl-isocyanuric acid, 1,3-bis(2,3-epoxy propyl)-5-ethyl-isocyanuric acid, 1,3-bis(2,3-epoxypropyl)-5-propyl-isocyanuric acid, 1,3,5-tris(3,4-epoxybutyl)isocyanuric acid, etc. isocyanuric acid having a glycidyl group,

1,3,5-tris(carboxy)isocyanuric acid, 1,3,5-tris(carboxymethyl)isocyanuric acid, 1,3-bis(carboxymethyl)-5-methyl-isocyanuric acid, 1,3-bis( carboxymethyl)-5-ethyl-isocyanuric acid, 1,3-bis(carboxymethyl)-5-butyl-isocyanuric acid, 1,3-bis(carboxymethyl)-5-phenyl-isocyanuric acid, 1,3-bis (Carboxyethyl)-5-methyl-isocyanuric acid, 1,3-bis(carboxyethyl)-5-ethyl-isocyanuric acid, 1,3-bis(carboxypropyl)-5-methyl-isocyanuric acid, 1,3- Isocyanuric acid having a carboxyl group such as bis(carboxyethyl)-5-butyl-isocyanuric acid, 1,3,5-tris(carboxypropyl)isocyanuric acid, 1,3-bis(carboxypropyl)-5-methyl-isocyanuric acid acids, and the like, but are not limited to these. Any one of these compounds may be used, or two or more thereof may be used in combination.

By having the structure derived from the compound (a3) in the polyester polyol (A1), the polyol composition (X) of the present invention has excellent gas barrier properties. From the viewpoint of gas barrier properties, the compounding amount of compound (a3) in composition (A1') is preferably 5% by mass or more, more preferably 10% by mass or more. From the viewpoint of coatability, the compounding amount of the compound (a3) in the composition (A1') is preferably 60% by mass or less, more preferably 50% by mass or less.

The higher the molar concentration of the isocyanuric rings in the polyester polyol (A1), the lower the oxygen permeability of the polyester polyol (A1), and the adhesive composition of the present invention has excellent gas barrier properties. The molecular weight of the compound (a3) is preferably 350 or less because the smaller the molecular weight of the compound (a3), the higher the molar concentration of the isocyanuric ring.

Alternatively, it is also preferable to use a linear dicarboxylic acid as the polyhydric carboxylic acid (a1) and a linear diol as the polyhydric alcohol (a2) to make the polyester polyol (A1) crystalline. This can also reduce the oxygen permeability of the polyester polyol (A1).

From the viewpoint of gas barrier properties, the polyester polyol (A1) preferably has a number average molecular weight of 300 or more. From the viewpoint of coatability, the polyester polyol (A1) preferably has a number average molecular weight of 800 or less. In the present invention, the number average molecular weight (Mn) is a value calculated according to the following formula from the number of design functional groups and the actually measured hydroxyl value (mgKOH/g). The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070.

The number of designed functional groups is the number of moles of carboxyl groups (O), the number of moles of polyvalent carboxylic acid (P), the number of moles of functional groups capable of reacting with carboxyl groups (Q), which are contained in the composition (A1′). It is calculated by (QO)/(RP) from the number of moles (R) of the compound having a functional group capable of reacting with a carboxyl group.

(Polyol (A2))
The polyol (A2) used in the present invention is a compound having two or more hydroxyl groups, a density of 1.2 g/cm ³ or more, and a melting point of 20° C. or more. The density of polyol (A2) is a value at 20° C. and 1 atm. By using the polyester polyol (A1) and the polyol (A2) together, it is possible to obtain a non-solvent adhesive having gas barrier properties superior to those of conventional adhesives. Although the upper limit of the density of the polyol (A2) is not particularly limited, it is about 1.6 g/cm ³ as an example. Although the upper limit of the melting point of the polyol (A2) is not particularly limited, it is 120°C as an example. From the viewpoint of coatability, the temperature is preferably 80° C. or lower, more preferably 70° C. or lower.

The polyol (A2) is not particularly limited as long as it satisfies the above requirements. Examples include isosorbide, isoidide, isomannide, furandimethanol, trans-tetrahydrofuran-3,4-diol, sorbitol, erythritol and the like.

　Polyester polyol (A1) has excellent gas barrier properties, but has high viscosity at room temperature, so it must be heated in order to be applied to the base material without being diluted with an organic solvent such as ethyl acetate. By using a polyol (A2) having a relatively low melting point, the viscosity suitable for coating can be obtained without diluting with an organic solvent without impairing the gas barrier properties derived from the polyester polyol (A1). can. From the viewpoint of pot life, it is preferable to use a polyol (A2) having a secondary hydroxyl group.

From the viewpoint of coatability, the blending amount of the polyol (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, of the total amount of the polyester polyol (A1) and the polyol (A2). From the viewpoint of gas barrier properties, the blending amount of the polyol (A2) is preferably 90% by mass or less, more preferably 80% by mass or less, of the total amount of the polyester polyol (A1) and the polyol (A2). , 70% by mass or less.

(Other components (B))
The polyol composition (X) may contain a component (B) other than the polyester polyol (A1) and the polyol (A2) within a range that does not impair the gas barrier properties. Component (B) includes inorganic filler (B1), coupling agent (B2), acid anhydride (B3), oxygen scavenger (B4), phosphoric acid (B5), tackifier (B6), urethane Examples include, but are not limited to, catalyst (B7). Stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, coloring agents, crystal nucleating agents, antifoaming agents, leveling agents, etc. may be included. .

Examples of the inorganic filler (B1) include silica, alumina, aluminum flakes and glass flakes. In particular, it is preferable to use a plate-like inorganic compound as the inorganic filler (B1) because the adhesive strength, gas barrier properties, light shielding properties, etc. are improved. Plate-like inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite Light-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or Mica group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, sudoite, clinochlore, chamosite, nimite, etc.), hydrotalcite, platy sulfuric acid barium, boehmite, aluminum polyphosphate, and the like. These minerals may be natural clay minerals or synthetic clay minerals. Plate-like inorganic compounds can be used singly or in combination of two or more.

The plate-like inorganic compound may be an ionic compound having an electric charge between layers, or may be a nonionic compound having no electric charge. The presence or absence of charge between layers does not directly affect the gas barrier property of the adhesive layer. However, ionic plate-like inorganic compounds and inorganic compounds that swell with water have poor dispersibility in solvent-based adhesives, and when the amount added increases, the adhesive becomes thicker and thixotropic. As a result, the coating suitability may deteriorate. For this reason, it is preferable that the plate-like inorganic compound is non-ionic with no interlayer electrification.

Although the average particle diameter of the plate-like inorganic compound is not particularly limited, it is preferably 0.1 μm or more, more preferably 1 μm or more, as an example. If it is smaller than 0.1 μm, the detour path of oxygen molecules will not be long, and a sufficient improvement in gas barrier properties cannot be expected. The upper limit of the average particle size is not particularly limited, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle diameter is preferably 100 μm or less, and preferably 20 μm or less. In this specification, the average particle size of the plate-like inorganic compound means the particle size with the highest appearance frequency when the particle size distribution of the plate-like inorganic compound is measured with a light scattering type measuring device.

It is preferable that the aspect ratio of the plate-like inorganic compound is high in order to improve gas barrier properties due to the labyrinth effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

When the polyol composition (X) contains the inorganic filler (B1), the blending amount is preferably 50% by mass or less of the total amount of the polyol composition (X). This makes it possible to obtain an adhesive with an excellent balance of gas barrier properties and coatability.

Examples of the coupling agent (B2) include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like. Coupling agents are expected to have the effect of improving the adhesiveness to various film materials, especially metal and metal oxide deposited layers.
When the polyol composition (X) contains the coupling agent (B2), the amount thereof is preferably 5% by mass or less of the total amount of the polyol composition (X), and is 2% by mass or more and 3% by mass or less. is preferred.

Examples of the acid anhydride (B3) include phthalic anhydride, succinic anhydride, het acid anhydride, hymic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, tetra promphthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5 -(2,5-oxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.

When the polyol composition (X) contains the acid anhydride (B3), the amount thereof is preferably 5% by mass or less of the total amount of the polyol composition (X).

Examples of the oxygen scavenger (B4) include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol and other low-molecular-weight organic compounds that react with oxygen, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

Phosphoric acids (B5) 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 phosphate. , butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.

When the polyol composition (X) contains phosphoric acids (B5), the amount thereof is preferably 200 ppm or less based on the total amount of the polyol composition.

The tackifier (B6) includes xylene resin, terpene resin, phenol resin, rosin resin, and the like. By blending the tackifier (B6), it can be expected that the adhesion to the substrate will be improved.

Examples of the urethanization catalyst (B7) include metal-based catalysts (B7-1) and aliphatic cyclic amide compounds (B7-2). The urethanization catalyst (B7) can be used alone or in combination of two or more.

Metal-based catalysts (B7-1) include metal complex-based, inorganic metal-based, and organic metal-based catalysts. As the metal complex catalyst, a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt) Examples include acetylacetonate salts of metals selected from the above, such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like. From the point of view of toxicity and catalytic activity, iron acetylacetonate (Fe(acac) ₃ ) or manganese acetylacetonate (Mn(acac) ₂ ) are preferred.

Examples of inorganic metal-based catalysts 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. Examples include titanium-based compounds such as titanium chelate complexes used as ligands.

Examples of the aliphatic cyclic amide compound (B7-2) include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam and the like. Among these, ε-caprolactam is more effective in accelerating hardening.

When the polyol composition (X) contains the urethanization catalyst (B7), the amount thereof is preferably 5% by mass or less of the total amount of the polyol composition (X), and is 2% by mass or more and 3% by mass or less. is preferred.

(Polyisocyanate composition (Y))
The polyisocyanate composition (Y) contains an isocyanate compound (C). As the isocyanate compound (C), conventionally known ones can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Isophorone diisocyanate or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, Low-molecular-weight active hydrogen compounds such as trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine and their alkylene oxide adducts, polyester polyols, polyether polyols and adducts obtained by reacting with high-molecular-weight active hydrogen compounds such as polyamides.

A blocked isocyanate may also be used as the isocyanate compound (C). Examples of isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; oximes thereof such as acetoxime, methylethylketoxime and cyclohexanone oxime; alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Lactams such as caprolactam, δ-valerolactam, γ-butyrolactam and β-propyrolactam, and active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetate and ethyl malonate. , mercaptans, imines, ureas, diaryl compounds, sodium bisulfite, and the like. The blocked isocyanate can be obtained by addition reaction of the above isocyanate compound and an isocyanate blocking agent by a known and commonly used appropriate method.

An isocyanate having an aromatic ring or a derivative thereof (C1) is preferably used as the isocyanate compound (C) because good gas barrier properties can be obtained. Specific examples of the isocyanate compound (C1) include xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and isocyanate compounds having a skeleton derived from diphenylmethane diisocyanate.

As the isocyanate compound (C), it is also preferable to use a urethane prepolymer (C2) which is a reaction product of the polyester polyol (c1) and the isocyanate compound (c2). The polyester polyol (c1) is a cured coating film when the polyester polyol (c1) and the XDI-TMP adduct are reacted at a [NCO]/[OH] of 2 ± 0.2. Oxygen permeation at 23 ° C. 0% RH It is preferable that the 3 g/m ² conversion value of the rate is 300 cc/m ² /day/atm or less. By using such a urethane prepolymer (C2), gas barrier properties can be further improved.

The oxygen permeability of the polyester polyol (c1) is measured in the same manner as the polyester polyol (A1). Hereinafter, the oxygen permeability measured as described above is also simply referred to as the oxygen permeability of the polyester polyol (c1).

A polyester polyol (c1) is a reaction product of a composition (c1') containing a polyhydric carboxylic acid, a polyhydric alcohol, and optionally a compound having reactivity with a carboxyl group or a hydroxyl group. As these compounds, the same compounds as those exemplified as the raw materials of the polyester polyol (A1) can be used.

The polyester polyol (c1) preferably contains a skeleton derived from an ortho-oriented aromatic polycarboxylic acid, since gas barrier properties are improved. From the viewpoint of gas barrier properties, the content of the ortho-oriented aromatic polycarboxylic acid in the composition (c1') is preferably 20% by mass or more, more preferably 30% by mass or more. From the viewpoint of coatability, the amount of the ortho-oriented aromatic polycarboxylic acid in the composition (c1') is preferably 50% by mass or less.

Alternatively, the polyester polyol (c1) preferably has an isocyanuric ring. From the viewpoint of gas barrier properties, the amount of the compound having an isocyanuric ring in the composition (c1') is preferably 5% by mass or more, more preferably 10% by mass or more. From the viewpoint of coatability, the compounding amount of the compound having an isocyanuric ring in the composition (c1') is preferably 40% by mass or less, more preferably 30% by mass or less.

Although the number average molecular weight of the polyester polyol (c1) is not particularly limited, it is preferably 300 or more and 800 or less as an example.

As the isocyanate compound (c2), those exemplified above as the isocyanate compound (C) can be used. From the viewpoint of improving gas barrier properties, it is preferable to use the same isocyanate compound (C1) as exemplified.

(Other components (D))
The polyisocyanate composition (Y) may contain a component (D) other than the isocyanate compound (C) as long as the gas barrier properties are not impaired. As the component (D), those similar to the component (B) can be used. Moreover, the polyol composition (X) and the polyisocyanate composition (Y) may each contain the same component. For example, both the polyol composition (X) and the polyisocyanate composition (Y) may contain phosphoric acids.

The two-liquid curable composition of the present invention is used in a solventless form. In the present specification, the term "solvent-free type" refers to one that is used without undergoing a step of volatilizing the solvent by heating in an oven or the like after coating the two-component curable composition of the present invention. Both polyol composition (X) and polyisocyanate composition (Y) are toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK). , cyclohexanone, toluol, xylol, n-hexane, cyclohexane and other organic solvents. The constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyol composition (X) or the polyisocyanate composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained. Further, when the polyol composition (X) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (Y) and becomes part of the coating film, so it is not necessary to volatilize after coating. Therefore, such a form is also treated as a non-solvent type.

The two-component curable composition of the present invention has excellent gas barrier properties and coating suitability, and can be applied to applications such as two-component curable gas barrier adhesives and anchor coating agents with no concerns about solvent emissions.

<Two-liquid curing adhesive, laminate 1>
(Two liquid curing adhesive)
The two-pack curable adhesive of the present invention contains the above-described polyol composition (X) and polyisocyanate composition (Y), and is suitable for lamination applications. The adhesive of the present invention is excellent in gas barrier properties and coatability, and since it does not contain an organic solvent, there is no fear of solvent emission. By using the adhesive of the present invention, it is possible to provide a laminate having excellent gas barrier properties even if it does not contain a vapor deposited layer of metal or metal oxide, or a barrier layer such as a metal foil.

The adhesive of the present invention is used by mixing the polyol composition (X) and the polyisocyanate composition (Y) immediately before coating on the substrate. The polyol composition (X) and the polyisocyanate composition (Y) are equivalent ratios [NCO]/[ OH] is preferably 0.5-4. If [NCO]/[OH] exceeds 4, excess isocyanate groups may bleed out from the cured coating film of the adhesive, and if it is less than 0.5, adhesive strength may be insufficient.

In the two-component curable adhesive of the present invention, when the viscosity of the polyol composition (X) at 70°C is [X] and the viscosity of the polyisocyanate composition (Y) at 70°C is [Y], the viscosity ratio [X]/[Y] is preferably 0.1 or more and 10 or less. This makes it possible to obtain an adhesive with excellent coatability. When the viscosity of one of the polyol composition (X) and the polyisocyanate composition (Y) exceeds 10 times the viscosity of the other, the polyol composition (X) and the polyisocyanate composition (Y) are uniformly mixed. difficult to do

(Laminate 1)
The laminate of the present invention is obtained by laminating a plurality of substrates (film, paper, etc.) with the adhesive of the present invention by a non-solvent lamination method. The laminated laminate has excellent gas barrier properties and can be used as a gas barrier laminate. The base material to be used is not particularly limited, and can be appropriately selected according to the application. For example, for food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched Polyolefin films such as polypropylene film, OPP (biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like.

The film may be stretched. As 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. In the case of 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 lateral 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.

As the paper, 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. Examples of 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. Moreover, various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, paperboard, etc. can also be used.

Since the adhesive of the present invention has extremely high gas barrier properties, the base material is a metal such as aluminum, an inorganic oxide such as silica, a deposited layer of a metal oxide such as alumina, polyvinyl alcohol, or an ethylene-vinyl alcohol copolymer. Even if it does not contain a gas barrier layer such as vinylidene chloride, it is possible to provide a laminate having excellent gas barrier properties. However, as the base material, the film or paper described above may be laminated with a metal, inorganic oxide, or metal oxide deposited layer, or may contain a gas barrier layer. By using such a base material, it is possible to obtain a laminate having even better barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic substances (fragrance), and the like.

As a more specific structure of the laminate,
(1) Base material 1/adhesive layer 1/sealant film (2) Base material 1/adhesive layer 1/metal vapor deposition unstretched film (3) Base material 1/adhesive layer 1/metal vapor deposition stretched film (4) Transparent vapor deposition stretching Film/adhesive layer 1/sealant film (5) Substrate 1/adhesive layer 1/substrate 2/adhesive layer 2/sealant film (6) Substrate 1/adhesive layer 1/stretched metal deposition film/adhesive layer 2/sealant Film (7) Substrate 1/adhesive layer 1/transparent evaporated stretched film/adhesive layer 2/sealant film (8) Substrate 1/adhesive layer 1/metal layer/adhesive layer 2/sealant film (9) Substrate 1/ Adhesive layer 1/substrate 2/adhesive layer 2/metal layer/adhesive layer 3/sealant film (10) substrate 1/adhesive layer 1/metal layer/adhesive layer 2/substrate 2/adhesive layer 3/sealant film, etc. but not limited to.

Examples of the base material 1 used in configuration (1) include OPP film, PET film, nylon film, paper, and the like. Further, as the base material 1, a material coated for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer, which will be described later, may be used. Commercial products of the coated base film 1 include K-OPP film and K-PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films include CPP films and LLDPE films. On the surface of the substrate 1 on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coated substrate film 1 is used) or the surface opposite to the adhesive layer 1, A printing layer may be provided. The printing layer is formed by general printing methods conventionally used for printing on polymer films and paper using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.

Examples of the base material 1 used in configurations (2) and (3) include OPP film, PET film, paper, and the like. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. A VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film may be used as the unstretched metal vapor-deposited film, and a VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film may be used as the stretched metal-deposited film. can be done. A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on OPP films, PET films, nylon films, or the like. For the purpose of protecting the inorganic deposition layer of silica or alumina, etc., a film obtained by coating the deposition layer may be used. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).

Examples of the base material 1 used in configuration (5) include PET film, paper, and the like. Examples of the base material 2 include a nylon film and the like. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

As the base material 1 of configuration (6), the same ones as those of configurations (2) and (3) can be mentioned. Examples of the metal-deposited oriented film include VM-OPP film and VM-PET film obtained by subjecting an OPP film or PET film to metal deposition such as aluminum. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

Examples of the base material 1 of configuration (7) include PET film, paper, and the like. Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

Examples of the base material 1 of configuration (8) include PET film, paper, and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

Examples of the substrate 1 of configurations (9) and (10) include PET film, paper, and the like. Examples of the base material 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1, 2 and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).

When the laminate of the present invention includes at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer, the metal vapor deposition layer, the transparent vapor deposition layer, and the adhesive layer in contact with the metal layer are cured coating films of the adhesive of the present invention. is preferably

In the laminate of the present invention, 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 the other substrate is immediately attached. Together, 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 70° C., and the aging time is preferably 6 to 240 hours.

The amount of adhesive to be applied is appropriately adjusted. For example, it is 1 g/m ² or more and 10 g/m ² or less, preferably 1 g/m ² or more and 5 g/m ² or less.

The laminate of the present invention may further contain other films and substrates in addition to the above-described configurations (1) to (10). As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather can also be used. The adhesive used when bonding other substrates may or may not be the adhesive of the present invention.

<Anchor coating agent, laminate 2>
(Anchor coating agent)
The anchor coating agent of the present invention contains the above-described polyol composition (X) and polyisocyanate composition (Y), and is suitable as an adhesion aid for extrusion lamination. The anchor coating agent of the present invention is excellent in gas barrier properties and coatability, and since it does not contain an organic solvent, there is no fear of solvent emission. By using the anchor coating agent of the present invention, a substrate having excellent gas barrier properties can be provided.

The anchor coating agent of the present invention is used by mixing the polyol composition (X) and the polyisocyanate composition (Y) immediately before coating on the substrate. The polyol composition (X) and the polyisocyanate composition (Y) are equivalent ratios [NCO]/[ OH] is preferably 0.5-4. If [NCO]/[OH] exceeds 4, excessive isocyanate groups may bleed out from the cured coating film of the coating agent, and if it is less than 0.5, adhesive strength may be insufficient.

In the anchor coating agent of the present invention, when the viscosity of the polyol composition (X) at 70°C is [X] and the viscosity of the polyisocyanate composition (Y) at 70°C is [Y], the viscosity ratio [X] /[Y] is preferably 0.1 or more and 10 or less. As a result, an anchor coating agent having excellent coatability can be obtained. When the viscosity of one of the polyol composition (X) and the polyisocyanate composition (Y) exceeds 10 times the viscosity of the other, the polyol composition (X) and the polyisocyanate composition (Y) are uniformly mixed. difficult to do

(Laminate 2)
The laminate of the present invention is prepared by applying the anchor coating agent of the present invention preheated to about 40° C. to 100° C. on a film using a laminator, aging the film, and then melting the polymer material using an extruder. Obtained by lamination (extrusion lamination method). As the film, the same film as used for the laminate 1 can be used. Polyolefin-based resins such as low-density polyethylene resin, linear low-density polyethylene resin, and ethylene-vinyl acetate copolymer resin are preferable as the polymer material to be melted.

The aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours. The amount of the anchor coating agent to be applied is appropriately adjusted, but as an example, it is 0.03 g/m ² or more and 0.09 g/m ² or less (solid content).

The laminate of the present invention may be used alone, or may be used by laminating with another base material. Other substrates include the stretched film, unstretched film, transparent deposition film, paper, wood, leather and the like exemplified for the laminate 1 . The adhesive used when bonding other substrates may or may not be the adhesive of the present invention.

<Packaging material>
The laminates 1 and 2 of the present invention can be used as multi-layer packaging materials for the purpose of protecting foods, medicines, and the like. When used as a multilayer packaging material, the layer structure may vary depending on the contents, usage environment, and usage pattern.

The packaging material of the present invention is obtained by using the laminate of the present invention, superimposing the sealant film surfaces of the laminate on each other, and then heat-sealing the peripheral edges. As a bag-making method, the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-side seal type, four-side seal type, envelope seal type, palm-joint seal type, pleated seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-sealing methods. be done. The packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use. A self-supporting packaging material (standing pouch) or the like is also possible. As a heat sealing method, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.

After the packaging material of the present invention is filled with contents through its opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. Contents to be filled include rice crackers, bean confections, nuts, biscuits, cookies, wafer confections, marshmallows, pies, half-baked cakes, candies, snacks, bread, snack noodles, instant noodles, dried noodles, and pasta. , aseptic packaged rice, rice porridge, rice porridge, packaged mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, mushrooms, konjac, processed wild plants, jams, peanut cream, salads, frozen Vegetables, processed agricultural products such as processed potatoes, processed hams, bacon, sausages, processed chicken products, processed livestock products such as corned beef, fish hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, bonito flakes, salted fish, Processed marine products such as smoked salmon and cod roe, fruits such as peaches, mandarin oranges, pineapples, apples, pears and cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes, hamburgers, and meat. Frozen and chilled prepared foods such as bowls, fried seafood, gyoza, and croquettes, prepared foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as infant formula powder, liquid seasonings, and retort pouches Examples include foods such as curry and pet food. The packaging material of the present invention can also be used as a packaging material for cigarettes, disposable body warmers, medicines such as infusion packs, cosmetics, and vacuum insulation materials.

The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these. Compositions and other numerical values are based on mass unless otherwise specified.

<Adhesive adjustment>
<Synthesis of polyester polyol (A1)>
(Polyester polyol (A1-1))
79.10 parts of ethylene glycol, 74.06 parts of phthalic anhydride, 73.07 parts of adipic acid and 0.01 part of titanium tetraisopropoxide were placed in a polyester reaction vessel equipped with an agitator, nitrogen gas inlet tube, Snyder tube and condenser. was charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain (A1-1) having a number average molecular weight of 800. The hydroxyl value was 143.2 mgKOH/g, and the oxygen permeability was 148.7 cc/m ² /day/atm or less.

(Polyester polyol (A1-2))
27.02 parts of ethylene glycol, 110.4 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and 62 parts of phthalic anhydride were placed in a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. .60 parts were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (A1-2) having a number average molecular weight of 450. The hydroxyl value was 371.2 mgKOH/g, and the oxygen permeability was 102.3 cc/m ² /day/atm or less.

(Polyester polyol (A1-3))
33.88 parts of ethylene glycol, 98.86 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and 67 parts of phthalic anhydride were added to a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. .26 parts were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (A1-3) having a number average molecular weight of 420. The hydroxyl value was 378.3 mgKOH/g, and the oxygen permeability was 103.7 cc/m ² /day/atm or less.

(Polyol (AH1))
73.98 parts of castor oil and 51.02 parts of polypropylene glycol (molecular weight: about 4000) are placed in a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, and the mixture is stirred while heating to 70°C. 2.55 parts of Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was added dropwise using a dropping funnel, and the mixture was further stirred for 4 hours to obtain polyol (AH1). The hydroxyl value was 115.0 mgKOH/g, and the oxygen permeability exceeded 300 cc/m ² /day/atm.

<Synthesis of urethane prepolymer (C2)>
(Urethane prepolymer (C2-1))
92.00 parts of ethylene glycol, 118.50 parts of phthalic anhydride, 29.23 parts of adipic acid and 0.01 part of titanium tetraisopropoxide were placed in a polyester reaction vessel equipped with an agitator, nitrogen gas inlet tube, Snyder tube and condenser. was charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (c1-1) having a number average molecular weight of 500. The polyester polyol (c1-1) had an oxygen permeability of 131.8 cc/m ² /day/atm or less.

71.45 parts of xylylene diisocyanate, Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was placed in a reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, cooling condenser, and dropping funnel. ) was added and stirred while heating to 70° C., 92.28 parts of the polyester polyol (c1-1) was added dropwise using a dropping funnel over 2 hours, and further stirred for 4 hours to obtain a urethane press. A polymer (C2-1) was obtained. The NCO% measured according to JIS-K1603 was 15.1%.

(Urethane prepolymer (C2-2))
100.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 parts of titanium tetraisopropoxide were charged into a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. The inner temperature was maintained at 220°C by gradually heating so that the upper temperature did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (c1-2) having a number average molecular weight of 400. The polyester polyol (c1-2) had an oxygen permeability of 104.6 cc/m ² /day/atm or less.

75.55 parts of xylylene diisocyanate, Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was placed in a reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, cooling condenser, and dropping funnel. ) was added and stirred while heating to 70° C., 76.37 parts of the polyester polyol (c1-2) was added dropwise over 2 hours using a dropping funnel, and the mixture was further stirred for 4 hours to give a urethane press. A polymer (C2-2) was obtained. The NCO% measured according to JIS-K1603 was 16.6%.

(Urethane prepolymer (C2-3))
114.91 parts of xylylene diisocyanate was put into a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, and stirred while heating to 70° C., and polyester polyol (c1-2) was added to 92.5 parts. 93 parts were added dropwise over 2 hours using a dropping funnel, and further stirred for 4 hours to obtain a urethane prepolymer (C2-3). The NCO% measured according to JIS-K1603 was 15.3%.

(Urethane prepolymer (C2-4))
58.84 parts of ethylene glycol, 57.88 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and 83 parts of phthalic anhydride were added to a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. .30 parts were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (c1-3) having a number average molecular weight of 380. The oxygen permeability of polyester polyol (c1-3) was 103.8 cc/m ² /day/atm or less.

120.96 parts of xylylene diisocyanate was added to a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, and stirred while heating to 70° C. to give polyester polyol (c1-3) 79.04. Using a dropping funnel, the mixture was added dropwise over 2 hours and stirred for 4 hours to obtain a urethane prepolymer (C2-4). The NCO% measured according to JIS-K1603 was 16.5%.

(Urethane prepolymer (C2-5))
73.60 parts of ethylene glycol, 25.06 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and 101 parts of phthalic anhydride were added to a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. .36 parts were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol (c1-4) having a number average molecular weight of 360. The polyester polyol (c1-4) had an oxygen permeability of 105.5 cc/m ² /day/atm or less.

136.47 parts of xylylene diisocyanate was added to a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, and stirred while heating to 70°C to obtain 83.24 parts of polyester polyol (c1-4). Using a dropping funnel, the mixture was added dropwise over 2 hours and stirred for 4 hours to obtain a urethane prepolymer (C2-5). The NCO% measured according to JIS-K1603 was 16.7%.

(Urethane prepolymer (CH2))
114.00 parts of Millionate MN (mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was placed in a reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, cooling condenser and dropping funnel. While stirring while heating to 70° C., 28.16 parts of polypropylene glycol (molecular weight: about 400) and 58.44 parts of polypropylene glycol (molecular weight: about 1000) were added dropwise using a dropping funnel over 2 hours, followed by further stirring for 4 hours. to obtain a urethane prepolymer (CH2). The NCO% measured according to JIS-K1603 was 13.5%. All the polypropylene glycols used in synthesizing the urethane prepolymer (CH2) had an oxygen permeability exceeding 300 cc/m ² /day/atm.

<Preparation of adhesive>
Synthesized polyester polyol (A1) and polyol (A2) are blended in the ratio shown in Table 1-4, phosphoric acid is added so that the total amount of polyester polyol (A1) and polyol (A2) is 100 ppm, and polyol A composition (X) was prepared. Also, the isocyanate compound (C1) and the urethane prepolymer (C2) were blended at the ratio shown in Table 1-4 to prepare a polyisocyanate composition (Y). Polyol composition (X) and polyol composition (Y) were blended at the ratio shown in Table 1-4 to obtain adhesives of Examples and Comparative Examples. In the table, polyol (A2) is isosorbide, XDI is xylylene diisocyanate, and MDI is Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate).

<Production of laminate 1>
The adhesives of Examples and Comparative Examples were heated to about 70 ° C., and a 20 μm thick OPP film (“ ^P2161 ” manufactured by Toyobo Co., Ltd.) was coated using a solventless test coater. Then, a CPP film (“P1128” manufactured by Toyobo Co., Ltd.) having a film thickness of 30 μm was laminated to the coated surface of the adhesive. Aging was performed at 50° C. for 4 days to obtain laminates of Examples and Comparative Examples.

<Evaluation>
(adhesion strength)
The adhesive strength (N/15 mm) between the OPP film and the CPP film was measured by a 180° peeling method using a tensile tester under an atmosphere of 25°C, setting the peeling speed to 300 mm/min. The results are summarized in Tables 1-4.

(Oxygen permeability)
The obtained laminate was adjusted to a size of 10 cm × 10 cm, and was subjected to JIS-K7126 (isobaric method) using OX-TRAN2/21 (manufactured by Mocon Co., Ltd.: oxygen permeability measuring device) at 23 ° C. 0% RH. Oxygen permeability was measured under ambient conditions. Note that RH represents humidity. Since the coating amount of the adhesive actually applied is not uniform, the measured oxygen permeability (cc/m ² /day/atm) is calculated when the adhesive coating amount is 3 g/m ² . After conversion, the results are summarized in Table 1-4.

Claims

A polyol composition (X) containing a polyester polyol (A1) and a polyol (A2), and a polyisocyanate composition (Y) containing a polyisocyanate compound (C),
The polyester polyol (A1) is a cured coating film obtained by reacting the polyester polyol (A1) and a trimethylolpropane adduct of xylene diisocyanate at an NCO/OH ratio of 2 ± 0.2 at 23 ° C. and 0% RH. 3 g/m 2 conversion value of oxygen permeability in is 300 cc/m 2 /day/atm or less,
The polyol (A2) is a two-component solventless adhesive composition having two or more hydroxyl groups, a density of 1.2 g/cm 3 or more, and a melting point of 20° C. or more.
The polyisocyanate compound (C) contains a urethane prepolymer (C2) which is a reaction product of a polyester polyol (c1) and a polyisocyanate,
The polyester polyol (c1) is obtained by reacting the polyester polyol (c1) and a trimethylolpropane adduct of xylene diisocyanate at an NCO/OH ratio of 2 ± 0.2 to obtain a cured coating film at 23 ° C. and 0% RH. 2. The two-liquid solvent-free adhesive composition according to claim 1, wherein the 3 g/m 2 equivalent oxygen permeability at 300 cc/m 2 /day/atm or less.
3. The two-liquid liquid according to claim 1 or 2, wherein the blending amount of the polyol (A2) is 5% by mass or more and 90% by mass or less of the total amount of the polyester polyol (A1) and the polyol (A2). A solventless adhesive composition.
The polyol composition (X) according to any one of claims 1 to 3;
A two-part curable adhesive comprising a polyisocyanate composition (Y).
The polyol composition (X) according to any one of claims 1 to 3;
An anchor coating agent having a polyisocyanate composition (Y).
A laminate comprising a substrate and a cured coating film of the two-component solventless adhesive composition according to any one of claims 1 to 3.
A packaging material containing the laminate according to claim 6.