JP7323082B2 - Adhesives, laminates, packaging materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive, a laminate obtained using the adhesive, and a packaging material.

Laminates used for various packaging materials, labels, etc. are given design, functionality, preservability, convenience, transportation resistance, etc. by laminating a wide variety of base materials such as plastic films, metal foils, and paper. be done. A packaging material formed by molding the laminate into a bag shape is used as a packaging material for foods, medicines, detergents, and the like.

Conventionally, laminates used for packaging materials are produced by applying an adhesive dissolved in a volatile organic solvent (sometimes referred to as a solvent-based lamination adhesive) to the base material, and then passing through an oven. In recent years, from the viewpoint of reducing the environmental load and improving the working environment, reaction lamination methods that do not contain volatile organic solvents have been used. Demand for a two-liquid type lamination adhesive (hereinafter referred to as a non-solvent adhesive) is increasing (Patent Document 1).

JP 2014-159548 A

Solvent-free adhesives do not require a drying process and do not emit solvents. They are energy-saving and have low running costs. It has many merits, such as the fact that there is no concern that the solvent will remain in the laminate after being combined. On the other hand, it is necessary to design the component used in the solventless adhesive to have a low molecular weight so that the viscosity can be applied when heated to about 40°C to 100°C, and the boiling resistance of the laminate is satisfactory. There was a problem that it was not at a certain level.

The present invention has been made in view of such circumstances, and provides a two-component curable adhesive that is excellent in boiling resistance even when the molecular weight is low, and a laminate and packaging material obtained using the adhesive. intended to

The present invention includes a polyol composition (X) containing a polyester polyol (A1) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B1), wherein the polyester polyol (A1) is a polyhydric alcohol (a1) and a polyhydric carboxylic acid (a2), wherein the polyhydric alcohol (a1) contains glycerin, and the content of glycerin in the polyhydric alcohol (a1) is 1% by mass or more and 50% by mass. It relates to the following two-part curable adhesive.

Furthermore, the present invention includes a first base material, a second base material, and an adhesive layer for bonding the first base material and the second base material, and the adhesive layer is the above-described two-liquid curing type The present invention relates to a laminate that is a cured coating film of an adhesive, and a packaging material comprising the laminate.

According to the adhesive of the present invention, it is possible to provide laminates and packaging materials with excellent resistance to boiling.

<Adhesive>
The adhesive of the present invention is a two-liquid curing adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y). The adhesive of the present invention will be described in detail below.

(Polyol composition (X))
(Polyester polyol (A1))
The polyol composition (X) used in the adhesive of the present invention is a polyester polyol (A1) which is a reaction product of a composition (A1') containing a polyhydric alcohol (a1) and a polycarboxylic acid (a2). including. Moreover, the polyhydric alcohol (a1) contains 1% by mass or more and 50% by mass or less of glycerin. Thereby, the adhesive of the present invention can be made excellent in boiling resistance.

Although the reason why the adhesive of the present invention is excellent in boiling resistance is not clear, it is presumed as follows. Since glycerin has a secondary hydroxyl group, it is difficult to gel during the production of the polyester polyol (A1), and the reaction proceeds smoothly when the polyol composition (X) and the polyisocyanate composition (Y) are reacted. , a large number of crosslinked structures can be introduced into the adhesive cured coating while maintaining a sufficient pot life. For this reason, it is considered that the adhesion strength does not easily decrease even during the boiling treatment, and good resistance to boiling is exhibited. If the amount of glycerin is too large, it tends to gel during the production of the polyester polyol (A1), which increases the difficulty of production and shortens the pot life during coating. It is more preferable to make it mass % or less.

The polyhydric alcohol (a1) that can be used in combination with glycerin is not particularly limited. Examples of difunctional alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3 -methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxy Aliphatic diols such as ethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;

Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;
Modified poly(s) obtained by ring-opening polymerization of aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. ether diol;

Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactanoids and ε-caprolactone;
Bisphenols such as bisphenol A and bisphenol F;
Alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F can be mentioned.

Tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, hexanetriol and pentaerythritol;
Modified polyols obtained by ring-opening polymerization of aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. ether polyols;
Examples include lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols with various lactones such as ε-caprolactone.

Fine air bubbles are involved in the adhesive when it is applied to the base material. If the trapped air bubbles come out of the adhesive layer (cured adhesive film) or remain trapped, they will not be visible to the human eye and will not cause an appearance defect, but they will gradually coalesce during the aging process. , and when the size becomes visible, the appearance becomes defective. In general, poor appearance due to air bubbles is less likely to occur when the compound contained in the polyol composition (X) or the polyisocyanate composition (Y) has a polyester skeleton, and tends to occur when it has a polyether skeleton. This is presumably because the adhesive itself has a high cohesive force when it has a polyester skeleton, preventing the cohesion of air bubbles.

In addition, in laminates for packaging materials, a printed layer is generally provided with printing ink on the back side (content side) of the base material that is the outermost layer (viewed from the content), and the printed layer and other base materials are separated. are pasted together with an adhesive. At this time, the printed layer may be dissolved by the component of the adhesive applied on the printed layer, resulting in poor appearance. When the printed layer is redissolved, the printed layer has a densely filled portion and a relatively sparse portion, and unevenness in print density and a pattern resembling the rind of a citron are visible. . Such problems are less likely to occur when the compounds contained in the polyol composition (X) and the polyisocyanate composition (Y) have a polyether skeleton, and tend to occur when they have a polyester skeleton.

In order to suppress such problems, the polyhydric alcohol (a1) preferably contains diethylene glycol. It is not clear why this can suppress poor appearance due to air bubbles and re-dissolution of the printed layer, but the structure derived from diethylene glycol prevents re-dissolution of the printed layer, while maintaining the cohesive force of the adhesive derived from the polyester skeleton. It is considered that aggregation of air bubbles can be suppressed. The content of diethylene glycol in the polyhydric alcohol (a1) excluding glycerin is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more. The total amount of polyhydric alcohol (a1) used in combination with glycerin may be diethylene glycol.

Problems due to air bubbles and dissolution of the printed layer are likely to occur when the adhesive is solvent-free. Therefore, the use of diethylene glycol is more effective when using the adhesives of the present invention in solventless form.

In addition, such poor appearance occurs when substrates with high gas barrier properties, such as nylon films, polyester films, metals such as aluminum, and films with inorganic deposition layers such as metal oxides such as silica and alumina, are bonded together. prone to occur. Therefore, the use of diethylene glycol is also effective when obtaining such laminates. Specific examples of bonding substrates with high gas barrier properties are PET film/adhesive layer/aluminum-deposited OPP film, PET film/adhesive layer/aluminum-deposited CP film, PET film/adhesive layer/aluminum-deposited PET film. , PET film/adhesive layer/aluminum foil, Ny film/adhesive layer/aluminum deposited PET film, PET film/adhesive layer/transparent deposited PET film, and the like. Here, the adhesive layer is a cured coating film of the adhesive of the present invention.

Examples of the polycarboxylic acid (a2) include orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3 - naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, aromatic polybasic acids such as benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride;
methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;

Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid;
Aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate Alkyl ester of;

1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, hymic anhydride, hetic anhydride, etc. group polybasic acid; and the like, and can be used alone or in combination of two or more.

It is preferred that the polycarboxylic acid (a2) contains adipic acid. As a result, the effect of reducing the viscosity of the polyester polyol (A1) and improving the pot life and coatability at low temperatures can be expected. In addition, it can be expected that the wettability to the substrate is improved and the appearance of the laminate is improved. The amount of adipic acid to be blended can be appropriately adjusted depending on the coating conditions and the like. As an example, it is preferably 40% by mass or more, more preferably 60% by mass or more, of the polyvalent carboxylic acid (a2). Adipic acid may be sufficient as the whole amount of polyhydric carboxylic acid (a2).

When an aromatic polycarboxylic acid is used as the polycarboxylic acid (a2), the boiling resistance is improved, but the wettability to the substrate is lowered, and the pot life tends to be shortened. The adhesive of the present invention has sufficient boiling resistance even when the amount of aromatic polycarboxylic acid used is small or not used at all. The content of the acid is preferably 15% by mass or less, more preferably 10% by mass or less.

Although the number average molecular weight of the polyester polyol (A1) is not particularly limited, it is preferably 350 or more and 5,000 or less as an example. The number average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate 0.35 ml/min Standard; monodisperse polystyrene Sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

The blending amount of the polyester polyol (A1) is preferably 60 mass % or more of the solid content of the polyol composition (X). The polyester polyol (A1) may be the total amount of the polyol composition (X). This makes it possible to obtain an adhesive with excellent boiling resistance.

(Polyol (A2))
The polyol composition (X) may contain a polyol (A2) other than the polyester polyol (A1). As such a polyol (A2),
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol , 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, and the like;

trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol;
bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol;
Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of polymerization initiators such as glycols and trifunctional or tetrafunctional aliphatic alcohols. ;
A polyether urethane polyol obtained by further increasing the molecular weight of a polyether polyol with the aromatic or aliphatic polyisocyanate;

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

Polyester polyether polyols obtained by reacting polyester polyols (1) to (5) with the above polyether polyols and aromatic or aliphatic polyisocyanates;
Polyester polyurethane polyols obtained by polymerizing polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates;
Castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof. Examples of the polyvalent carboxylic acid used for preparing the polyester polyol (2) include those exemplified as the raw material for the polyester polyol (A1).

The blending amount of the polyol (A2) is not particularly limited, but it is preferably kept to 40% by mass or less of the total amount with the polyester polyol (A1).

When the adhesive of the present invention is used as a non-solvent type, the viscosity of the polyol composition (X) is adjusted within a range suitable for the non-solvent lamination method. As an example, the viscosity at 40° C. is adjusted to be in the range of 100-5000 mPas, more preferably 100-3000 mPas. The viscosity of the polyol composition (X) can be adjusted, for example, by the skeleton of the polyester polyol (A1) and the plasticizer (C5) described below.

(Polyisocyanate composition (Y))
(Polyisocyanate compound (B1))
The polyisocyanate composition (Y) contains a polyisocyanate compound (B1) having multiple isocyanate groups. The polyisocyanate compound (B1) is not particularly limited, and includes aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and burettes, nurates, adducts, allophanates, and carbodiimide modifications of these diisocyanates. , uretdione-modified products, urethane prepolymers obtained by reacting these polyisocyanates with polyols, and the like, and these can be used alone or in combination.

Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI). , 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4 ,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′,4″-triphenylmethane triisocyanate and the like. It is not limited to these.

The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, m- or p-xylylene diisocyanate (also known as XDI), α, α, α', α'-tetra Methyl xylylene diisocyanate (another name: TMXDI) and the like can be mentioned, but not limited to these.

Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples include, but are not limited to, diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, etc., and these is not limited to

Polyols used for synthesis of urethane prepolymers include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Alkylene glycols such as 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;

Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F;
dimer diall;
bishydroxyethoxybenzene;
Polyalkylene glycols such as diethylene glycol, triethylene glycol, other polyethylene glycols, polypropylene glycol, polybutylene glycol;
Urethane bond-containing polyether polyol obtained by further polymerizing polyalkylene glycol with aromatic or aliphatic polyisocyanate;

Alkylene glycol or polyalkylene glycol and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, etc. Obtained by reacting with at least one aromatic polyvalent carboxylic acid such as aliphatic dicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid having a carbon atom number in the range of 2 to 13 a polyester polyol;
Polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, glycol, glycerin, trimethylolpropane, pentaerythritol, etc. and a polyester polyol which is a reaction product with a polyhydric alcohol.

Since it becomes an adhesive with excellent boiling resistance, the polyisocyanate compound (B1) includes at least one polyol selected from the group consisting of polyester polyol (b1) and polyether polyol (b2), and polyisocyanate compound (b3). It is preferably a reaction product with Among them, a urethane prepolymer which is a reaction product of a polyester polyol (b1), a polyether polyol (b2), and a polyisocyanate compound (b3) can effectively suppress air bubbles and poor appearance due to redissolution of ink. It preferably contains (B1′).

Polyester polyol (b1) is a reaction product of a composition containing polyhydric alcohol (b1-1) and polyhydric carboxylic acid (b1-2). As the polyhydric alcohol (b1-1), those exemplified for the polyhydric alcohol (a1) can be used. The polyhydric alcohol (b1-1) preferably contains diethylene glycol because the ink is difficult to re-dissolve when the adhesive is applied onto the printed layer. The proportion of diethylene glycol in the polyhydric alcohol (b1-1) is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass or more. All of the polyhydric alcohol (b1-1) may be diethylene glycol.

As the polycarboxylic acid (b1-2), the same ones as exemplified for the polycarboxylic acid (a2) can be used. It is preferable that the polycarboxylic acid (b1-2) contains adipic acid because it is effective in reducing the viscosity of the urethane prepolymer (B1') and improving the coatability at low temperatures. The blending amount of adipic acid can be appropriately adjusted according to the temperature at the time of coating, etc., but it is preferably 80% by mass or more of the polycarboxylic acid (b1-2), more preferably 90% by mass or more. preferable. The total amount of the polycarboxylic acid (b1-1) may be adipic acid.

Although the number average molecular weight of the polyester polyol (b1) is not particularly limited, it is, for example, 400 or more and 10,000 or less, more preferably 500 or more and 2,000 or less.

As the polyether polyol (b2), an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran is polymerized using a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin as an initiator. Those obtained can be mentioned, and one type or two or more types can be used in combination. The number of functional groups of the polyether polyol (b2) is not particularly limited, and in addition to bifunctional ones, trifunctional or higher functional groups can also be used. It is preferred to use bifunctional or trifunctional polypropylene glycol.

Although the number average molecular weight of the polyether polyol (b2) is not particularly limited, it is, for example, 200 or more and 10,000 or less, more preferably 400 or more and 2,000 or less.

The polyester polyol (b1) content in the total amount of the polyester polyol (b1) and the polyether polyol (b2) is 50% by mass or more and 95% by mass because of its excellent effect of suppressing appearance defects due to dissolution of air bubbles or ink. The following are preferable.

The polyisocyanate compound (b3) is not particularly limited, and those exemplified as the polyisocyanate compound (B1) can be used. From the viewpoint of initial cohesive strength and shortening of aging time, it is preferable to use aromatic diisocyanate and/or its derivative.

The urethane prepolymer (B1') is obtained by reacting the polyester polyol (b1), the polyether polyol (b2), and the polyisocyanate compound (b3) described above under conditions of excessive isocyanate groups. The ratio [NCO]/[OH] between the number of moles [NCO] of isocyanate groups and the number of moles [OH] of hydroxyl groups used for the reaction is preferably 1.0 or more and 3.0 or less. It is more preferably 1.5 to 2.0.

When the adhesive of the present invention is used as a non-solvent type, the viscosity of the polyisocyanate composition (Y) is adjusted within a range suitable for the non-solvent lamination method. As an example, the viscosity at 40° C. is adjusted to be in the range of 500-5000 mPas, more preferably 500-3000 mPas. The viscosity of the polyisocyanate composition (Y) can be adjusted, for example, by adjusting the amounts of the polyisocyanate compound (B1) and the urethane prepolymer (B1').

(Other components (C) of the adhesive)
The adhesive of the present invention may contain components other than those mentioned above. The other component (C) may be contained in either or both of the polyol composition (X) and the polyisocyanate composition (Y), or may be prepared separately from these before coating the adhesive. It may be mixed with the polyol composition (X) and the polyisocyanate composition (Y) immediately before use. Each component will be described below.

(Catalyst (C1))
Examples of the catalyst (C1) include metal-based catalysts, amine-based catalysts, and aliphatic cyclic amide compounds.

Examples of the metal-based catalyst (C1) 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.

Examples of inorganic metal 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.

Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N', N″,N″-pentamethyldipropylenetriamine, N,N,N′,N′-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol , N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-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-methyl imidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1- (2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole and the like.

Aliphatic cyclic amide compounds include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam and the like. Among these, ε-caprolactam is more effective in accelerating hardening.

(Acid anhydride (C2))
The acid anhydride (C2) includes cyclic aliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, and the like, and can be used alone or in combination of two or more. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid Anhydride, poly(ethyloctadecanedioic anhydride), poly(phenylhexadecanedioic anhydride), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , methylhimic acid anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, het acid anhydride, nadic acid anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2, 3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride and the like.

Moreover, what modified|denatured the compound mentioned above with glycol may be used as an acid anhydride (C). Glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Furthermore, two or more of these glycols and/or copolymerized polyether glycols of polyether glycols can also be used.

(Coupling agent (C3))
Examples of the coupling agent (C3) include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like.

Silane coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-amino Aminosilanes such as propyltrimethyldimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercaptopropyltrisilane; methoxysilane and the like.

Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. are mentioned.

Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

(Pigment (C4))
The pigment (C4) is not particularly limited, and includes extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, and pigments described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association). Organic pigments and inorganic pigments such as blue pigments, metal powder pigments, luminescent pigments and pearlescent pigments, and plastic pigments can be used.

Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.

Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) pigments such as phthalocyanine blue and phthalocyanine green. Phthalocyanine pigments; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments vat dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;

Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange; various ferrocyanic compounds such as Prussian blue; Various metal oxides such as zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of silicon such as calcium silicate and ultramarine blue. acid salts; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; These metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica-like iron oxide pigments and mica-like iron oxide pigments coated with metal oxides; graphite, carbon black and the like.

Examples of plastic pigments include "Glandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

The pigment (C4) to be used may be appropriately selected depending on the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide may be used as white pigments because they are excellent in durability, weather resistance, and design. Carbon black is preferably used as the black pigment.

The amount of the pigment (C4) is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (A) and the polyol composition (B). It is more preferable to use 10 to 300 parts by mass for better results.

(Plasticizer (C5))
Examples of plasticizers include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers. plasticizers, and the like.

Examples of phthalic plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, Phthalic ester plasticizers such as di-(2-ethylhexyl) isophthalate and diisooctyl isophthalate, tetrahydro phthalates such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate and diisodecyltetrahydrophthalate Examples include phthalate plasticizers.

Examples of fatty acid-based plasticizers include adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate. azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, diisooctyl azelate, di-n-butyl sebacate, di-(2- ethylhexyl) sebacate, diisononyl sebacate and other sebacic acid plasticizers, e.g. , di-n-butyl fumarate, di-(2-ethylhexyl) fumarate and other fumaric acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Itaconic acid plasticizers such as di-(2-ethylhexyl) itaconate, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, butyl oleate, glyceryl monooleate, Oleic acid plasticizers such as diethylene glycol monooleate, citric acid such as triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltributyl citrate, acetyl tri-(2-ethylhexyl) citrate ricinoleic acid plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate, and diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid esters, etc. and other fatty acid-based plasticizers.

Examples of aromatic polycarboxylic acid-based plasticizers include tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, and triisononyl. trimellitate, tridecyl trimellitate, triisodecyl trimellitate and other trimellitic acid plasticizers, e.g., tetra-(2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate and other pyromellitic acid plasticizers plasticizers, and the like.

Phosphate plasticizers include, for example, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, trichlé Zyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(isopropylphenyl) phosphate and the like.

Examples of polyol plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate ), glycol-based plasticizers such as dibutylmethylene bisthioglycolate, and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

Examples of epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate. etc.

Examples of polyester plasticizers include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.

Carbonate-based plasticizers include propylene carbonate and ethylene carbonate.

Other plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, and polymerizable plasticizers such as acrylic monomers and oligomers. These plasticizers can be used alone or in combination of two or more.

(Phosphate compound (C6))
Phosphoric acid compounds (C6) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, and isododecyl acid. phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.

(form of adhesive)
The adhesive of the present invention may be either a solvent type or a non-solvent type, but is particularly suitable for the non-solvent type, which tends to have insufficient resistance to boiling. In this specification, the term "solvent-based" adhesive means that after the adhesive is applied to the base material, it is heated in an oven or the like to evaporate the organic solvent in the coating film, and then bonded to another base material. It refers to a form used in a method, a so-called dry lamination method. Either one or both of the polyol composition (X) and the polyisocyanate composition (Y) dissolve (dilute) the components of the polyol composition (X) and the polyisocyanate composition (Y) used in the present invention. Contains organic solvents that can

Examples of organic solvents include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene. , methylene chloride, halogenated hydrocarbons such as ethylene chloride, dimethylsulfoxide, dimethylsulfamide and the like. The organic solvent used as a reaction medium during the production of the constituents of the polyol composition (X) or the polyisocyanate composition (Y) may also be used as a diluent during coating.

As used herein, the term "solvent-free" adhesive means that the polyol composition (X) and the polyisocyanate composition (Y) are esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, Highly soluble ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethylsulfoxide and dimethylsulfamide. A method in which an adhesive that does not substantially contain an organic solvent, particularly ethyl acetate or methyl ethyl ketone, is applied to a substrate, and then bonded to another substrate without a step of heating in an oven or the like to volatilize the solvent, It refers to the form of adhesive used in the so-called non-solvent lamination method. The constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyol composition (X) or the polyisocyanate composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained. 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. Such forms are therefore also treated as solventless adhesives and low molecular weight alcohols are not considered organic solvents.

The adhesive of the present invention has a ratio [NCO]/[ OH] is preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.

<Laminate>
The laminate of the present invention is obtained by laminating a plurality of substrates (films or papers) using the adhesive of the present invention by a dry lamination method or a non-solvent lamination method. The film to be used is not particularly limited, and a suitable film can be selected according to the application. 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 stretched 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 transverse stretching using a tenter is often used.

Various surface treatments such as flame treatment and corona discharge treatment may be applied to the surface of the film, if necessary, so that an adhesive layer free from defects such as film tearing and repelling is formed.

Alternatively, a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used. good. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic matter (fragrance) and the like can be obtained.

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, acidic/neutral/alkaline sulfite cooking, soda salt cooking, and the like. Various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, and paperboard can also be used.

More specific and preferable configurations of the laminate in which the properties of the adhesive of the present invention are exhibited include OPP film/adhesive layer/CPP film, OPP film/adhesive layer/LLDPE film, OPP/adhesive layer/aluminum vapor deposition. CPP film, PET film/adhesive layer/LLDPE film, PET film/adhesive layer/aluminized CPP film, Ny film/adhesive layer/LLDPE film, OPP film/adhesive layer/aluminized PET film/adhesive layer'/LLDPE film, PET film/adhesive layer/aluminum-deposited PET film/adhesive layer'/LLDPE film, Ny film/adhesive layer/aluminum-deposited PET film/adhesive layer'/LLDPE film, etc., but not limited thereto. In the above construction, the adhesive layer is a cured coating film of the adhesive of the present invention. The adhesive layer' may be a cured coating film of the adhesive of the present invention, or may be a cured coating film of another adhesive.

The laminate of the present invention may have a printed layer between the adhesive layer and the substrate (usually the substrate which is the outermost layer for the contents). The printing layer is formed by a general printing method conventionally used for printing on films using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.

When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to one base material using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. The laminate of the present invention is obtained by laminating the substrates. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 80° C., and the aging time is preferably 12 to 240 hours.

When the adhesive of the present invention is solvent-free, the adhesive of the present invention preheated to about 40° C. to 100° C. is applied to one substrate using a roll such as a coat roll, and then immediately. The laminate of the present invention is obtained by laminating the other base material. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.

The amount of adhesive to be applied is appropriately adjusted. In the case of a solvent-based adhesive, for example, the solid content is adjusted to 1 g/m ² or more and 10 g/m ² or less, preferably 2 g/m 2 ^or more and 5 g/m ² or less. In the case of a solventless adhesive, the coating amount of the adhesive is, for example, 1 g/m ² or more and 5 g/m ² or less, preferably 1 g/m ² or more and 3 g/m ² or less.

The laminate of the present invention is obtained by bonding two substrates together with the adhesive of the present invention, but may contain other substrates as necessary. As a method for laminating other substrates, known methods such as dry lamination, non-solvent lamination, heat lamination, heat sealing, and extrusion lamination may be used. The adhesive used at this time may or may not be that of the present invention. As another base material, the same base material as described above can be used.

<Packaging material>
The packaging material of the present invention is formed by molding the laminate into a bag shape and heat-sealing the bag. Packaging materials include three-side seal bags, four-side seal bags, gusset packaging bags, pillow packaging bags, gobel-top type bottomed containers, tetraclassics, Bruck types, tube containers, paper cups, lids, and the like. Moreover, the packaging material of the present invention may be appropriately provided with an easy-opening treatment or resealing means.

The packaging material of the present invention can be industrially used as a packaging material mainly filled with foods, detergents and medicines. Specific uses include detergents and chemicals such as liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and pharmaceutical tablets. It can also be used as a secondary packaging material for packaging the container described above.

Hereinafter, the present invention will be described in more detail with specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "mass parts" and "mass%", respectively, unless otherwise specified.

<Polyol composition (X)>
(Synthesis Example 1) Synthesis of polyester polyol (A1-1) Into a 2-liter four-neck glass flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectifying column, 47.1 parts by mass of diethylene glycol and glycerin were added. 2.8 parts by mass and 50.1 parts by mass of adipic acid were charged. The temperature was gradually raised to 220°C while performing dehydration reaction under normal pressure nitrogen stream, and the reaction was continued at 220°C. After confirming that the top temperature of the rectifying column became 80° C. or lower, the rectifying column was removed, the condenser was switched to a glass condenser, and a vacuum pump was connected from the nitrogen gas introduction pipe to a predetermined temperature under reduced pressure of 50 Torr. A condensation reaction was carried out until the acid value was reached to obtain a polyester polyol (A1-1). Polyester polyol (A1-1) acid value (mgKOH/g), hydroxyl value (mgKOH/g), average functional group number, number average molecular weight, amount of glycerin in polyhydric alcohol (a1) (% by mass), Table 1 shows the blending amount (% by mass) of the aromatic polycarboxylic acid in the alcohol (a2).

(Synthesis Example 2) to (Synthesis Example 8)
Polyester polyols (A1-2) to (A1-6), (AH-1) and (AH-2) were obtained in the same manner as in (Synthesis Example 1) except that the starting materials shown in Tables 1 and 2 were used. rice field. Polyester polyols (A1-2) to (A1-6), (AH-1), (AH-2) acid value (mgKOH/g), hydroxyl value (mgKOH/g), average functional group number, number average molecular weight, Tables 1 and 2 show the amount (% by mass) of glycerin in the polyhydric alcohol (a1) and the amount (% by mass) of the aromatic polycarboxylic acid in the polyhydric alcohol (a2). Polyester polyols (A1-1) to (A1-6), (AH-1) and (AH-2) were used as polyol compositions (X-1) to (X-8), respectively.

The details of the compounds in Table 1 are as follows.
DEG: diethylene glycol GLY: glycerin AA: adipic acid IPA: isophthalic acid

<Polyisocyanate composition (Y)>
(Synthesis Example 9) Synthesis of polyester polyol 46 parts of diethylene glycol was charged into a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc., and stirred under a nitrogen gas stream. Heat to 80°C. Further, 54 parts of adipic acid was charged into the reaction vessel while stirring, and the mixture was gradually heated so that the temperature at the top of the rectifying tube did not exceed 100°C, and the internal temperature was maintained at 250°C to carry out an esterification reaction. When the acid value became 12.0 mgKOH/g or less, the temperature was raised to 240°C, the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 40 Torr or less. A polyester polyol having hydroxyl groups was obtained.

(Synthesis Example 10) Synthesis of urethane prepolymer A mixture of 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate ( Hereinafter, abbreviated as "MDI-50".) was charged and heated to 60° C. while stirring under a nitrogen gas stream. 38 parts of the polyester polyol obtained in Synthesis Example 9 and 9 parts of polypropylene glycol having a number average molecular weight of 1000 were added dropwise in several portions, and further heated and held at an internal temperature of 70°C for 4 hours to carry out a urethanization reaction. , a urethane prepolymer having isocyanate groups at both ends and having an NCO group content of 14.6% was obtained. This urethane prepolymer was used as the polyisocyanate composition (Y).

<Preparation of adhesive>
Polyol composition (X) heated to 40° C. and polyisocyanate composition (Y) were blended according to Tables 3 and 4 to prepare solvent-free adhesives of Examples 1 to 6 and Comparative Examples 1 and 2. .

<Production of evaluation sample>
(Manufacture of evaluation sample 1)
An adhesive was applied to a Ny film (thickness: 15 μm, width: 600 mm) on which a design was gravure-printed with printing ink (Finert manufactured by DIC Corporation) so that the coating amount was 1.5 g/m ² , and the adhesive was applied to the surface. and the corona-treated surface of an LLDPE film (thickness: 60 μm, width: 600 mm) were laminated together and aged at 40° C. for 3 days to obtain a laminate of Ny/adhesive layer/LLDPE. This was used as sample 1 for evaluation.

(Manufacture of evaluation sample 2)
The prepared adhesive was applied to the printed surface of an OPP film (thickness: 20 μm, width: 600 mm) on which a pattern was gravure-printed with printing ink (Finert manufactured by DIC Corporation) at a coating speed of 200 m/min and a coating amount of 1.8 g/m. ² , and then this coated surface and the aluminum-deposited surface of a VMCPP film (thickness: 25 μm, width: 600 mm) were laminated to obtain a laminate of OPP/adhesive layer/VMCPP. This was used as sample 2 for evaluation.

<Evaluation>
(Boil resistance)
A sample 1 for evaluation was cut into a size of 150 mm×300 mm, folded so that the LLDPE film was on the inside, and two sides were heat-sealed at 1 atm and 180° C. for 1 second to prepare a pouch. After the pouch was filled with 1/1/1 sauce (meat sauce: vegetable oil: vinegar = 1:1:1), the remaining one side was heat-sealed under the same conditions to seal the pouch. The pouch filled with the content was immersed in hot water at 98° C. and boiled for 1 hour. After the contents were removed, the appearance of the pouch was observed and evaluated on a two-grade basis depending on the presence or absence of delamination.
〇: No float ×: With float

(Laminated appearance)
The deposition surface of the evaluation sample 2 was visually observed through the printed layer and the adhesive layer from the OPP film side, and evaluated according to the following criteria.
◎: No air bubbles, unevenness, or citron skin-like pattern 〇: Air bubbles, unevenness, or yuzu skin-like pattern can be observed very slightly ×: Bubbles, unevenness, or yuzu skin-like pattern can be clearly confirmed

(pot life)
Immediately after preparation, 0.8 ± 0.2 g of the adhesives of Examples and Comparative Examples were placed on the measurement site of the rheometer, and the viscosity immediately after blending was measured at a temperature of 1,000 ± 100 mPa s for 30 minutes. . Based on the measured values of viscosity at the start of measurement and after 30 minutes, evaluation was made according to the following criteria.
◎: The viscosity after 30 minutes is 1 to 2 times the viscosity at the start
○: The viscosity after 30 minutes is 2 times or more and less than 3 times the viscosity at the start
×: The viscosity after 30 minutes is 3 times or more the viscosity at the start

Claims (12)

A polyol composition (X) containing a polyester polyol (A1) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B1),
The polyester polyol (A1) consists of a reaction product of a polyhydric alcohol (a1) that is diethylene glycol and/or glycerin and a polycarboxylic acid (a2) that is adipic acid and/or isophthalic acid,
The content of glycerin in the polyhydric alcohol (a1) is 1% by mass or more and 50% by mass or less,
A solvent-free two-component curing adhesive characterized in that the polyol composition (X) has a viscosity of 100 to 5000 mPas at 40°C . 2. The two-component curing adhesive according to claim 1, wherein the content of said glycerin in said polyhydric alcohol (a1) is 1% by mass or more and 30% by mass or less. 2. The two-component curing adhesive according to claim 1, wherein the content of said isophthalic acid in said polyvalent carboxylic acid (a2) is 15% by mass or less. 2. The two-component curable adhesive according to claim 1, wherein the polyester polyol (A1) has a number average molecular weight of 350 or more and 5,000 or less. The two-pack curable adhesive according to claim 1, wherein the polyester polyol (A1) has a number average molecular weight of 350 or more and 650 or less. 2. The two-component curable adhesive according to claim 1, wherein the polyester polyol (A1) content in the polyol composition (X) is 60% by mass or more. 2. According to claim 1, wherein the polyisocyanate compound (B1) is a reaction product of at least one polyol selected from the group consisting of polyester polyol (b1) or polyether polyol (b2) and polyisocyanate compound (b3). A two-part curable adhesive as described. 2. The two-component curing adhesive according to claim 1, which is solventless. A first base material, a second base material, and an adhesive layer for bonding the first base material and the second base material, wherein the adhesive layer is any one of claims 1 to 8 A laminate which is a cured coating film of the two-component curing adhesive according to item 1. The first base material is a polyester film,
10. The laminate according to claim 9 , wherein the second base material has an inorganic deposition layer on the adhesive layer side surface. 10. The laminate according to claim 9 , wherein the first base material has a printed layer on the adhesive layer side surface. A packaging material comprising the laminate according to claim 9 .