JPH08269428A - Adhesive composition for laminate and production of laminated film - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition useful in the production of a laminated film by adding a specified catalyst to a polyurethane component obtained by reacting a specified isocyanate compound with an active hydrogen compound. CONSTITUTION: This composition is prepared by adding 0.05-10.0 pts.wt. uretidinedione group dissociation catalyst to 100 pts.wt. polyurethane component having a uretidinedione group/active hydrogen group equivalent ratio of at least 0.25-1.0 and obtained by reacting a polyisocyanate component (A) comprising a polyisocyanate compound containing at least a uretidinedione group and an isocyanurate group with an active hydrogen compound component (B) having a molecular weight of 18-20000 and containing at least two active hydrogen groups in the molecule under conditions in which the equivalent ratio of the isocyanate groups of component A to the active hydrogen groups of component B is above 1.0.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive composition for laminating, which is capable of laminating a plastic film and a metal foil, and a method for producing a laminated film. More specifically, the adhesive composition for lamination has a polyurethane-based component containing a uretdione group and an active hydrogen group in a predetermined ratio and an uretdione group dissociation catalyst as essential components, and can be chain-extended in a short time even at room temperature. The present invention relates to a laminating adhesive composition that does not contain a free polyisocyanate monomer and an isocyanate group-terminated compound that can be crosslinked and cured.

[0002]

2. Description of the Related Art Recently, as a packaging method, composite flexible packaging is used because of its strength, product protection, workability at the time of packaging, advertising effect of packaging, large amount of plastic materials, and reduction of packaging cost due to inexpensive supply. Is developing significantly. As a typical laminating method of the film used here, there is a dry lamination method suitable for a field requiring adhesive strength, heat resistance and retort resistance. As an adhesive for dry lamination, it generally has an active hydrogen group such as a hydroxyl group because of its excellent adhesive performance, cold resistance, heat resistance, wide range of application to various plastics, base materials such as metal foils, etc. Two-component polyurethane adhesives composed of a main agent and a curing agent having an isocyanate group (hereinafter abbreviated as NCO group) have become the mainstream.

[0003]

However, current two-component polyurethane-based adhesives for laminates require a curing accelerating process called so-called aging because the curing reaction of the adhesives after bonding is very slow. Specifically, the laminated film laminated is 35 ° C. to 60 ° C.
It becomes necessary to cure the adhesive by storing it in the greenhouse for 1 to 4 days and aging it. At this time, the degree of curing of the adhesive changes depending on the aging conditions, which may affect the adhesive strength of the laminated film, but if the aging is insufficient, it causes delamination due to insufficient curing of the adhesive. Sometimes. Particularly in the case of an aliphatic polyurethane adhesive, this curing reaction requires a long time. Therefore,
Such an aging step is an indispensable step in the dry lamination process, and it requires a capital investment for installing a greenhouse for aging and a utility cost for heat retention thereafter. Furthermore, since the conventional two-component polyurethane-based laminate adhesive is generally one in which a curing agent having an NCO group at the molecular chain end is added to the main agent, it does not contain a free isocyanate monomer and an NCO group end compound. Therefore, it cannot be said that there are no safety and health problems. As described above, there is no need for aging under heating, which is usually used for two-component polyurethane adhesives, there is no scattering of substances such as blocked isocyanate blocking agents, and, if possible, free isocyanate monomer and NCO The development of an adhesive composition for laminating, which does not contain a terminal compound at all in the system, is revolutionary.The development of such an adhesive requires capital investment for installing a greenhouse for aging and subsequent heat retention. There is no need for utility costs, etc., and it also brings the advantages of improving productivity and shortening the delivery time of products. INDUSTRIAL APPLICABILITY The present invention is capable of completing a curing reaction at room temperature in a short time, and does not include a free isocyanate monomer and an NCO group terminal compound at all.
It is an object of the present invention to provide an adhesive composition for lamination excellent in workability and safety.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned conventional problems, the present inventors have found that the uretdione group and the active hydrogen group are contained in a predetermined ratio, and further the isocyanurate group is added. An adhesive composition containing a polyurethane-based component and a uretdione group dissociation catalyst that can complete a curing reaction at room temperature in a short time, and is for a laminate that does not contain a free polyisocyanate monomer and an NCO group terminal compound. They have found that they can be an essential component of an adhesive composition, and have completed the present invention.

That is, the present invention provides a polyisocyanate component (A) comprising a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group, and a molecular weight of 18 to 20,000 and two or more molecules in the molecule. And the active hydrogen compound component (B) containing the active hydrogen group (1), the equivalent ratio of the active hydrogen group of the active hydrogen compound component (B) to the NCO group of the polyisocyanate component (A) exceeds 1.0. With respect to 100 parts by weight of a polyurethane-based component containing at least an uretdione group and an active hydrogen group in an equivalent ratio of uretdione group / active hydrogen group = 0.25 to 1.0 An adhesive composition for laminating comprising 0.05 to 10.00 parts by weight of a uretdione group dissociation catalyst.

The polyisocyanate component (A) of the present invention comprises a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group and a polyisocyanate compound (a2) having two or more NCO groups in the molecule. And an active hydrogen compound component (B) having a molecular weight of 18 to 20,000 and containing two or more active hydrogen groups in the molecule, an active hydrogen compound component for the NCO group of the polyisocyanate component (A). The equivalent ratio of at least a uretdione group and an active hydrogen group obtained by reacting (B) under the condition that the equivalent ratio of the active hydrogen group exceeds 1.0, is an equivalent ratio of uretdione group / active hydrogen group = 0.25 to 1.0. Polyurethane-based component contained in 1 and the polyurethane-based component 1
An adhesive composition for laminating characterized in that it comprises 0.05 to 10.00 parts by weight of a uretdione group dissociation catalyst with respect to 00 parts by weight.

In the present invention, the polyisocyanate compound (a1) contains a uretdione group and an isocyanurate group in an NCO group-terminated prepolymer obtained by reacting a polyisocyanate monomer and a bifunctional or higher functional polyol having a side chain. An adhesive composition for laminating characterized by the above.

According to the present invention, the adhesive composition for lamination is applied to the first plastic film or metal foil, dried, and then the second plastic film or metal foil is adhered to the first plastic film or metal foil. A method for producing a laminated film, which is at 10 to 35 ° C. for 24 hours.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Of the polyisocyanate component (A) of the present invention, the polyisocyanate compound (a1) is
It contains at least a uretdione group and an isocyanurate group. As long as it contains at least a uretdione group and an isocyanurate group, it may be one kind or a mixture of two or more kinds. For example, a mixture of a uretdione group-containing polyisocyanate compound (dimer and polyuretdione body), an isocyanurate group-containing polyisocyanate compound (trimer and polyisocyanurate body), and a uretdione group- and isocyanurate group-containing polyisocyanate compound It may be. The uretdione group content of the polyisocyanate compound (a1) is preferably 7 to 25% by weight, more preferably 10 to 23% by weight. The isocyanurate group content is preferably 1 to 24% by weight. Furthermore 3
-20% by weight is preferred. In addition, as the polyisocyanate monomer constituting the polyisocyanate compound (a1), 1,6-hexamethylene diisocyanate is particularly suitable from the viewpoint that the produced polyisocyanate compound becomes liquid and does not undergo yellowing modification. .

In the polyisocyanate component (A) of the present invention, the polyisocyanate compound (a1) is
If desired, it is possible to contain groups other than uretdione groups and isocyanurate groups derived from isocyanate groups. As the groups other than the uretdione group and the isocyanurate group derived from the NCO group, a urethane group,
Examples thereof include a urea group, a carbodiimide group, a uretonimine group, an oxazolidone group, and a hydantoin group, and they may be one kind or a mixture of two or more kinds.

Of the polyisocyanate component (A), the polyisocyanate compound (a2) is a polyisocyanate compound having two or more isocyanate groups in the molecule, and contains a free polyisocyanate monomer and a polymer thereof. May be. The polyisocyanate compound (a2) can be used alone or as a mixture of two or more kinds.

The polyisocyanate compound (a of the present invention
Examples of the polyisocyanate compound or polyisocyanate compound (a2) for forming 1) include a polyisocyanate compound containing one or more polyisocyanate monomers and a polymer thereof. For example, 2,4-tolylene diisocyanate,
2,6-Tolylene diisocyanate, xylene-1,4
-Diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-
4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-
1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl-4,
Aromatic diisocyanates such as 4'-diisocyanate,
Aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene diisocyanate and other alicyclic compounds Suitable are diisocyanates such as diisocyanates, and polyisocyanates obtained by reacting the above-mentioned diisocyanate polymers or difunctional or higher-functional polyols with the above-mentioned diisocyanates or their polymeric products.
That is, any of the polymer of polyisocyanate and the polyol adduct of polyisocyanate can be used in the present invention.

The polyisocyanate compound (a1) is generally formed by a dimerization reaction (uretdione formation reaction), a trimerization reaction (isocyanurate formation reaction) or the like of a polyisocyanate monomer. For example, it is produced as follows. You can

From the corresponding polyisocyanate monomer and / or polymer, known uretdione-forming catalysts such as triethylphosphine, dibutylethylphosphine, tributylphosphine, tri-n-propylphosphine, triamylphosphine, tribenzylphosphine, etc. In the presence of trialkylphosphines, pyridine, etc., usually at a reaction temperature of 0 to 90 ° C., without solvent, or with an inert solvent commonly used in the polyurethane industry, for example, toluene, xylene and other aromatic solvents, methyl ethyl ketone, methyl. Ketone solvents such as isobutyl ketone, ethyl acetate, ester solvents such as butyl acetate, propylene glycol methyl ether acetate, ethyl-
It can be produced in the presence of a glycol ether ester solvent such as 3-ethoxypropionate, and optionally in a liquid polyol at the reaction temperature or a plasticizer such as DOP.

The reaction solution has an NCO group content of 20 to 5
When 0 mol% of NCO groups have reacted, for example, a solution of phosphoric acid, methyl paratoluenesulfonate, sulfur or the like is added to inactivate the uretdione-forming catalyst to stop the reaction. Depending on the type of polyisocyanate used, some may be crystallized and precipitated during this reaction process. In particular, aromatic polyisocyanates generally crystallize and separate from the reaction system.

By such a method, a polyisocyanate compound containing a uretdione group (that is, a dimer and a poly-uretdione body), a polyisocyanate compound containing an isocyanurate group (that is, a trimer and a polyisocyanurate body), and a uretdione group. And a mixture of the isocyanurate group-containing polyisocyanate compound and the raw material polyisocyanate monomer. By removing the raw material polyisocyanate monomer from this mixture by thin film distillation or the like, a desired mixture of the uretdione group-containing polyisocyanate compound, the uretdione group- and isocyanurate group-containing polyisocyanate compound and the like can be obtained. The higher the temperature of the reaction during the production, and the lower the content of the polyisocyanate monomer at the time of stopping the reaction, the higher the production ratio of isocyanurate groups.
In addition, the larger the amount of catalyst such as triethylphosphine, the higher the uretdione group formation rate. By controlling these reaction conditions, a polyisocyanate compound containing a specific ratio of uretdione groups and isocyanurate groups can be obtained.

When not only the uretdione group but also the isocyanurate group is positively introduced as in the present invention, excellent heat resistance and durability can be exhibited. When the polyisocyanate compound molecule contains a certain proportion of isocyanurate group and / or other isocyanate polymer in addition to the uretdione group, the resulting polyurethane-based component has a branching point which does not reach gelation. Can be introduced.
Therefore, in the curing step when actually used as an adhesive, by a dissociation reaction of the uretdione group of the adhesive composition for lamination and a subsequent reaction with an active hydrogen group, it is compared with that obtained from a conventionally known uretdione group-containing polyurethane compound. Then, excellent physical properties are developed in a short time and with a low reaction rate.

Furthermore, when the polyisocyanate compound (a1) used in the present invention is partially reacted in advance with a difunctional polyol having a side chain structure before forming a uretdione group and an isocyanurate group, active hydrogen can be obtained. It may be preferable in some cases because it may improve the compatibility with the compound (B), the solvent and the like and the adhesiveness with various substrate films. The bifunctional polyol having a side chain structure, as used herein, means that two hydroxyl groups are branched in the molecule.
A dihydric alcohol having one or more hydrocarbon groups, one or more branched hydrocarbon groups having a total carbon number of 1 to 33, and a total carbon number of 4 to 35, such as neo. Pentyl glycol, 3-methyl-1,5-pentanedio-
1,3-butanediol, 2,2-diethyl-1,
3-propanediol, 2-n-butyl-2-ethyl-
1,3-propanediol, 2,2,4-trimethyl-
1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eicosane-1,2-ethylene glycol, 2,2-Dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropione-
And hydrogenated bisphenol A. Moreover, these dihydric alcohols can also be used in combination of 2 or more types.

The uretdione group- and isocyanurate group-containing polyisocyanate compound (a1) excluding the unreacted polyisocyanate monomer is mixed with the polyisocyanate monomer to reduce the number of functional groups to form the active hydrogen compound component (B). It may be preferable to react with the above because it does not cause problems such as gelation during the production of the polyurethane-based component, and it may be effective in controlling the reactivity and the physical properties of development. The NCO group equivalent ratio of the polyisocyanate compound (a1) excluding the unreacted polyisocyanate monomer and the polyisocyanate compound (a2) is selected from polyisocyanate compound (a2) / polyisocyanate compound (a1) = 0 to 5.70. 0.10-4.
00 is preferable, and 0.15 to 3.00 is more preferable.

Active hydrogen compound component (B) in the present invention
Has a molecular weight of 18 to 20,000 and contains two or more active hydrogen groups in the molecule. Specifically, in addition to water, polyol, polyamine containing amino groups, urea resin, melamine resin, epoxy resin, polyester resin,
Those containing one kind or two or more kinds selected from acrylic resin, polyvinyl alcohol and the like are preferable. As this polyol, known polyols in the polyurethane industry can be used, and since the polyisocyanate component (A) has an NCO group of two or more functional groups,
In order to prevent gelation during the production of the polyurethane-based component, polyols having a low functional group number such as bifunctionality are suitable.

Examples of polyols include polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols and polycarbonate polyols. Specifically, for example, known succinic acid, adipic acid (hereinafter abbreviated as AA), sebacic acid, azelaic acid, terephthalic acid (hereinafter abbreviated as TP), isophthalic acid (hereinafter abbreviated as IP), hexahydroterephthalic acid, hexa Dicarboxylic acids such as hydroisophthalic acid, their acid esters, acid anhydrides, etc., ethylene glycol, 1,3-propylene glycol,
1,2-propylene glycol (hereinafter abbreviated as 1,2-PG), 1,4-butylene glycol (hereinafter 1,4-BG)
Abbreviated), 1,5-pentane glycol, 1,6-hexane glycol (hereinafter abbreviated as 1,6-HG), 3-methyl-1,5-pentane glycol, 2-butyl-2-ethyl-1,3- Propanediol, neopentyl glycol, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol, cyclohexane-1,4
-Diol, cyclohexane-1,4-dimethanol,
Dimer acid diol, trimethylolpropane (hereinafter T
Abbreviated as MP), glycerin, hexanetriol, N,
N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, glycol such as ethylene oxide or propylene oxide adduct of bisphenol A, hexamethylenediamine, xylenediamine, isophoronediamine, monoethanolamine, isopropanoltriamine, etc. Examples of the polyester polyols and polyester amide polyols obtained by dehydration condensation reaction with diamine, triamine, amino alcohol and the like, or with a mixture thereof. Further, there are polyester polyols such as lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (ie, lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone.

As the polyether polyol, for example,
Examples thereof include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol and the like. Examples of the polyether / ester polyol include polyester polyols produced from the above polyether polyol and the above-mentioned dicarboxylic acid or acid anhydride. Polycarbonate polyols are obtained, for example, from the reaction of hexane glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol and the like with diethyl carbonate and diphenyl carbonate. Specific products include Nippon Polyurethane Industry Nippon Polan 980, Nippon Polan 981 and the like.

Further, the monomolecular diols and triols listed as the raw materials for the polyester polyols, that is, ethylene glycol, 1,3-propylene glycol, 1,
2-PG, 1,4-BG, 1,5-pentane glycol, 1,6-HG, 3-methyl-1,5-pentane glycol, neopentyl glycol, 1,8-octane glycol, 1,9-nonane Diol, diethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, T
MP, glycerin, hexanetriol, quadrol, ethylene oxide or propylene oxide adduct of bisphenol A and the like can also be used in the present invention as the polyol.

Examples of polyamines containing amino groups and the like include short molecule diamines, triamines, aromatic diamines, and polyether polyamines in which the end of the polyether is an amino group. In addition, urea resin, melamine resin, epoxy resin, polyester resin, acrylic resin, polyvinyl alcohol and the like are generally known in the polyurethane industry, and if they contain two or more active hydrogen groups, the active hydrogen compound component (B ) Can be used in whole or in part.

The molecular weight of these active hydrogen compound components (B) is 18 to 20,000, and especially water and 62 to 1
Those of 10,000 are preferable. If the molecular weight is too high,
The amount of uretdione group, isocyanurate group, urethane group, etc. introduced is decreased, and the toughness and strong cohesive force of the polyurethane resin are decreased, which is not preferable. If the molecular weight is too small, the polyurethane resin tends to become brittle, which is not preferable. This molecular weight needs to be appropriately selected depending on the application, and it is preferable to use a low molecular weight one in order to enhance heat resistance and cohesive energy. Further, in consideration of the adhesive performance, an aromatic polyester polyol using terephthalic acid, isophthalic acid or the like and a polyester polyol using adipic acid are particularly preferable.

Next, the production of the polyurethane component which is an essential component of the adhesive composition for lamination of the present invention will be described in detail. The polyurethane component comprises the polyisocyanate component (A) and the active hydrogen compound component (B) in an equivalent amount of the active hydrogen group in the active hydrogen compound component (B) to the NCO group in the polyisocyanate component (A). The ratio is 1.
Obtained by reacting under an excess of active hydrogen groups exceeding 0,
At least an uretdione group and an active hydrogen group are contained at an equivalent ratio of uretdione group / active hydrogen group = 0.25 to 1.0.

This active hydrogen group excess condition is a condition necessary for the produced polyurethane precursor to contain an active hydrogen group without leaving an NCO group, and when the adhesive performance is taken into consideration, the polyisocyanate component (A The equivalent ratio of the active hydrogen group in the active hydrogen compound component (B) to the NCO group in () is preferably 1.0 to 2.0. Actually, polyisocyanate component (A) due to isocyanurate group content, etc.
The average number of functional groups of (1) and the average number of functional groups of the active hydrogen compound component (B) due to the introduction of triol, etc. determine the conditions under which no gelation occurs during the production of the polyurethane precursor. It is important to keep the reaction temperature below the ring-opening temperature for the reaction. The mixing ratio is J. P. According to the gelation theory theoretically calculated by Flory, Khun, etc., in reality, the reaction is carried out at a blending ratio taking into account the reactivity ratio of the reactive groups contained in the molecules of the components (A) and (B). Thereby, the polyurethane precursor can be produced without gelation and does not contain free isocyanate monomer and NCO group terminated compound.

The polyurethane component may be in a molten state, a bulk state, or, if necessary, an inert solvent commonly used in the polyurethane industry, for example, an aromatic hydrocarbon solvent such as toluene or xylene, an ester such as ethyl acetate or butyl acetate. Type solvent, ketone type solvent such as methyl ethyl ketone, cyclohexanone, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, glycol ether ester type solvent such as ethyl-3-ethoxypropionate, tetrahydrofuran, ether type solvent such as dioxane, dimethyl Using one or more polar solvents such as formamide, dimethylacetone, N-methylpyrrolidone, and furfural, the temperature conditions at which the uretdione group does not ring-open, preferably 100 ° C. or less, and the above formulation conditions are used. Uniformly mixed by reacting the components in a range can be produced. As the reaction device, any device may be used as long as the above-mentioned homogeneous reaction can be achieved, and examples thereof include a reaction kneader equipped with a stirring device, a kneader, and a mixing and kneading device such as a uniaxial or multiaxial extrusion reactor. In order to accelerate the reaction, a metal catalyst such as dibutyltin dilaurate or a tertiary amine catalyst such as triethylamine, which is commonly used in the production of polyurethane, can be used as a catalyst.

The polyurethane component produced in this manner is a polyisocyanate compound (a1) to be used, and in addition to the uretdione group and the active hydrogen group, isocyanurate group, urethane group, carbodiimide group, uretonimine group, oxazolidone group, hydantoin group. Although it may contain a group derived from an NCO group such as, but does not substantially contain an NCO group, uretdione group and active hydrogen group uretdione group / active hydrogen group = 0.25-1.0, It is necessary to contain it in a ratio of preferably 0.35 to 0.75.

This is a regulation of the equivalence ratio when the uretdione group is opened by heating or the like. When the ratio of the uretdione group to the active hydrogen group is set to a ratio at which the concentration of the uretdione group becomes excessive, the present invention can be used. The adhesive composition is a cross-linking / chain extension or urethane bond by a reaction with moisture in the environment, a reaction to become an allophanate or burette by a reaction with a urea bond, and a polymerization reaction with an NCO group alone, for example, carbodiimidization, The chain can be extended and / or crosslinked by isocyanurate formation or the like, or can be a thermoplastic polymer resin when the active hydrogen groups are excessive. Further, in consideration of workability and adhesive performance, the molecular weight of the polyurethane component is preferably 3,000 to 60,000, and particularly preferably 5,000 to 30,000.

Next, the composition of the adhesive composition for lamination of the present invention will be described. In the adhesive composition for laminating containing the polyurethane-based component as a main component, the uretdione group of the polyurethane-based component, the active hydrogen group of the system-based component, and the active hydrogen group of the active hydrogen compound mixed when the adhesive composition is mixed are included. Active hydrogen compounds, such as the above-mentioned polyols, so that the equivalent ratio to the total active hydrogen groups is uretdione groups / total active hydrogen groups = 0.25 to 1.0, preferably 0.35 to 0.75. An active hydrogen compound containing one or more selected from polyamines containing amino groups, urea resins, melamine resins, epoxy resins, polyester resins, acrylic resins, polyvinyl alcohols, etc. may be blended.

The equivalent ratio of the uretdione groups to the total active hydrogen groups in the adhesive composition for laminating containing the active hydrogen compound of the present invention is in the range of uretdione groups / total active hydrogen groups = 0.5 to 1.0. When the concentration of uretdione groups is excessive, crosslinking / chain extension or urethane bond due to reaction with moisture in the environment, reaction to allophanate or burette due to reaction with urea bond, and polymerization reaction with isocyanate alone, for example, carbodiimide Chain extension and / or cross-linking can be carried out by cationization, isocyanurate formation or the like, or conversely, when the active hydrogen group excess condition is set in the range of uretdione group / total active hydrogen group = 0.25 to 0.5 It may be a thermoplastic polymer resin.

Finally, in the adhesive composition of the present invention, the uretdione groups contained therein are dissociated, and a polyurethane resin is formed by chain extension and / or cross-linking curing reaction with active hydrogen groups to give excellent adhesive properties. With excellent coatability,
Workability is also demonstrated. In the adhesive composition of the present invention, the uretdione group may not be completely dissociated in the case where the uretdione group remains to give a constantly excellent adhesive property even if the uretdione group remains. The polyurethane-based component described above may be liquid, solid, or powdery in a normal state, and in order to improve the function as an adhesive, the polyurethane-based component as an essential component may be added with a silane cup, if necessary. Ring agents, isocyanate-based curing agents, gelation inhibitors such as ester / urethane exchange reaction inhibitors to prevent gelation during storage, antioxidants, UV absorbers, hydrolysis inhibitors, dyes, pigments, leveling agents A flame retardant, a viscosity modifier, a flow improver, a plasticizer, a thixotropic agent, a filler and the like can be added to complete the adhesive. The adhesive composition of the present invention prepared here may be in a liquid state, a solid state, a powder state or the like in a normal state.

Here, the uretdione group dissociation catalyst will be particularly described. It is the uretdione group dissociation catalyst that imparts a practical curing rate at low temperature to the laminating adhesive composition of the present invention. Since the uretdione group dissociation catalyst can lower the dissociation temperature of the uretdione group of the polyurethane-based component, the curing of the resin proceeds more quickly at a lower temperature than when the catalyst is not added. The degree of decrease in the dissociation temperature of the uretdione group and the subsequent curing rate largely depend on the type and amount of the catalyst to be added, but by appropriately selecting these, it is practical even in the temperature range near room temperature. It is possible to obtain a high curing rate.

However, for example, when the amount of the catalyst added is less than 0.05% by weight with respect to the resin solid content of the polyurethane component, the curing reaction accelerating effect due to the addition of the catalyst is less likely to appear, and the addition amount of 10.00% by weight. If it exceeds%,
It is not preferable because there are adverse effects such that the curing speed is too fast, coating becomes difficult, and hydrolysis of the adhesive composition after curing may be accelerated. Therefore, the amount of the uretdione group dissociation catalyst added to the resin solid content of the polyurethane-based component is 0.05 to 10.00% by weight, preferably 0.1 to 10% by weight.
It is preferably set to 2.00% by weight.

The uretdione group dissociation catalyst described here is
Transesterification catalysts, urethanization catalysts, blocked isocyanate dissociation catalysts, included in what is generally known as isocyanurate formation catalysts, specifically dibutyltin dilaurate, stannous octoate and other tin-based catalysts,
Triethylenediamine, triethylamine, N, N,
N ', N'-tetramethylpropylenediamine, N,
N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2
-Dimethylimidazole, 1,5-diaza-bicyclo (4,3,0) nonene-5,1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter referred to as DBU), of these amine-based catalysts Various amine salt catalysts such as borane salt, DBU phenol salt, DBU octylate salt, DBU carbonate salt, magnesium naphthenate, lead naphthenate,
Carboxylates such as CH ₃ COOK ⁺ , trialkylphosphines such as triethylphosphine and tribenzylphosphine, alkoxides such as CH ₃ ONa,
Examples include zinc-based organometallic catalysts. Of these, DBU and various acid salts of DBU can be preferably used in view of the catalytic effect and the stability of the adhesive composition after addition.

As the plastic film used for laminating in the present invention, oriented polypropylene (OP
P), unstretched polypropylene (CPP), polyester (PET), nylon (NY), low density polyethylene (PE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), polypinyl alcohol ( P
VA), ethylene vinyl alcohol copolymer (EVO
H), polystyrene (PS), polycarbonate (P
C), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), Al, Cu, paper and the like, and films coated with these. It is preferable that these plastic films be subjected to an appropriate surface treatment such as corona discharge treatment before being laminated in order to improve the adhesive force. In addition, since the polymer-coated film may cause problems such as bubble generation and decrease in adhesive strength,
It is necessary to consider in advance the type of polymer to be coated, the coating amount, the surface characteristics, etc.

Next, a method of laminating films will be described.
The laminating adhesive of the present invention can be used by known laminating methods such as dry lamination, hot melt lamination, and extrusion lamination. The laminated films can complete the curing reaction by aging at room temperature for about 1 day.

[0039]

EXAMPLES Next, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited to these examples. Unless otherwise specified, parts and% in the examples mean "parts by weight" and "% by weight", respectively.
The uretdione group content and isocyanurate group content in the examples are obtained by converting the respective functional groups into NCO group content.

Synthesis of Polyisocyanate Component (a1) Synthesis Example 1 3000 parts of HDI (Nippon Polyurethane Industry Co., Ltd., NCO group content 49.9%) was added to a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser. As a catalyst, 6.0 parts of trioctylphosphine was charged, heated to 65 to 70 ° C. with stirring and reacted at the same temperature for 6 hours, and then 3.5 parts of phosphoric acid was added to stop the reaction. A pale yellow reaction product liquid having an NCO group content of 30.3% was obtained. Unreacted HDI was removed from this reaction product solution by thin film distillation at 120 ° C. and 0.01 Torr. The NCO group content of the product is 21.1%,
From FT-IR and ¹³ C-NMR, the product was NC
It was confirmed that O group, uretdione group and isocyanurate group were present. NCO group content determined by reacting with dibutylamine (hereinafter abbreviated as DBA) at the boiling point of propylene glycol methyl ether acetate (hereinafter abbreviated as PGM-Ac), which is a high boiling point solvent, and by back titration with an aqueous hydrochloric acid solution 3
It was 7.5%, and thus the NCO group content generated by dissociation of the uretdione group was 16.4%. The isocyanurate group content was 12.5%. This uretdione group- and isocyanurate group-containing polyisocyanate compound is designated as polyisocyanate A.

Synthesis Example 2 3000 parts of HDI (Nippon Polyurethane Industry Co., Ltd., NCO group content 49.9%) and trioctylphosphine 6.5 as a catalyst were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser. A portion was charged and reacted at 50 to 55 ° C. for 8 hours with stirring, and then 1.9 parts of phosphoric acid was added to stop the reaction. The NCO group content of the product is 37.3%,
From FT-IR and ¹³ C-NMR, the product was NC
It was confirmed that O group, uretdione group and isocyanurate group were present. NCO group content determined by reacting with DBA at the boiling point of PGM-Ac and back titrating with an aqueous solution of hydrochloric acid 44.
5%, and therefore N produced by dissociation of the uretdione group
The CO group content was 7.2%. The isocyanurate group content was 5.5%. This uretdione group- and isocyanurate group-containing polyisocyanate compound is designated as polyisocyanate B.

Synthesis Example 3 In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, 3000 parts of HDI (Nippon Polyurethane Industry Co., Ltd., NCO group content 49.9%) and 2-n-butyl-2- 23 parts of ethyl-1,3-propanediol was added, the atmosphere in the reactor was replaced with nitrogen, and the mixture was heated to a reaction temperature of 60 to 70 ° C. with stirring and reacted at the same temperature for 3 hours. At this time, the NCO content of the reaction solution was 49.1%. Next, 6.0 parts of trioctylphosphine was charged as a catalyst, heated to 65 to 70 ° C. with stirring and reacted at the same temperature for 6 hours, then 3.5 parts of phosphoric acid was added to stop the reaction, and NCO content was increased. A 30.3% pale yellow reaction product solution was obtained. From this reaction product solution, unreacted HDI was added at 120 ° C. and 0.01 Tor.
Removed by thin film distillation at r. NCO content of product 2
1.1%, and from FT-IR and ¹³ C-NMR, this product had a urethane group, an NCO group, a uretdione group,
It was confirmed that an isocyanurate group was present. PG
The NCO group content was 37.5%, which was determined by reacting with DBA at the boiling point of M-Ac and back titrating with an aqueous solution of hydrochloric acid. Therefore, the amount of NCO group generated by dissociation of the uretdione group was 16.4%. The isocyanurate group content was 12.5%. This urethane group, uretdione group, and isocyanurate group-containing polyisocyanate compound is referred to as polyisocyanate C.

Example 1, Comparative Example 1 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate A and MDI of Synthesis Example 1 and molecular weight 20
Aromatic Polyesterdiol of 00 and NPG / HG / EG
= 2/1/2 molar ratio of polyester and molecular weight 2,
A composition of the present invention was obtained by adding a uretdione group dissociation catalyst to a polyurethane-based component consisting of 000 hexamethylene adipate diols. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, the polyisocyanate A of Synthesis Example 1 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate group) was used. 12.5%) 100 parts, MDI 189 parts and molecular weight 2000 aromatic polyester diol (IP
/ TP / AA = 5/5/1 molar ratio and NPG / HG / EG
= 2/1/2 mole ratio polyester, hereinafter PES
(Referred to as —A) 1552 parts, 681 parts of hexamethylene adipate diol having a molecular weight of 2000, 3026 parts of toluene and 4540 parts of ethyl acetate were added and reacted at 70 ° C.
After 3 hours, the absorption peaks of isocyanurate group and uretdione group by FT-IR did not change from those at the start of the reaction, and
It was confirmed that the absorption peak of only the CO group had disappeared, the urethanization was completed, and a polyurethane component (PU-1) was obtained. A composition in which 0.5 wt% of uretdione group dissociation catalyst (DBU phenol salt, hereinafter abbreviated as DBU-PH) was added to this PU-1 with respect to the resin solid content was used as an example, and a composition not added was used as a comparative example. The curability of the film is shown in Table 1.
Table 3 shows the physical properties of the laminated film, and Table 7 shows a comparative example.

Example 2, Comparative Example 2 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate B and MDI of Synthesis Example 2 and molecular weight 20
Aromatic polyester diol of 00 and 3 of molecular weight 2000
A composition of the present invention was obtained by adding a uretdione group dissociation catalyst to a polyurethane component composed of -methyl-1,5-pentane adipate diol. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, the polyisocyanate B of Synthesis Example 2 (NCO group content 37.3%, uretdione group content 7.2%, isocyanurate group) was used. Content 5.5%) P of 100 parts and molecular weight 2000
ES-A489 parts and 3-methyl-1, having a molecular weight of 2000,
500 parts of 5-pentane adipate diol and 1089 parts of ethyl acetate were added and reacted at 70 ° C. 5 hours later, F
In T-IR, the absorption of isocyanurate group and uretdione group does not change from that at the start of the reaction, the absorption of only NCO group disappears and the urethanization ends, and the polyurethane component (PU-2)
I got The composition in which 0.5% by weight of DBU-PH was added to this PU-2 with respect to the resin solid content was taken as an example, and the composition without addition was taken as a comparative example. The film curability is shown in Table 1. Table 4 shows the physical properties of the laminated film, and Table 8 shows a comparative example.

Example 3, Comparative Example 3 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate A of Synthesis Example 1, isophorone diisocyanate, PES-A, aromatic polyester diol of 0 and NPG / HG / EG = A uretdione group dissociation catalyst was added to a polyurethane component composed of a polyester having a 2/1/2 molar ratio and 3-methyl-1,5-penta5-pentaneadipatediol having a molecular weight of 6000 to obtain a composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, the polyisocyanate A of Synthesis Example 1 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate group) was used. 12.5%), 100 parts of isophorone diisocyanate, 167 parts of PES-A, 1360 parts of 3-methyl-1,5-penta5-pentane adipate diol having a molecular weight of 6000 and 3200 parts of ethyl acetate,
The reaction was carried out at ° C. After 5 hours, absorption of isocyanurate group and uretdione group by FT-IR did not change from that at the start of the reaction, absorption of only NCO group disappeared and urethanization was completed, and polyurethane component (PU-3) was obtained. A composition in which 0.5% by weight of DBU-PH was added to PU-3 was used as an example, and a composition in which DBU-PH was not added was used as a comparative example. The film curability is shown in Table 3. The physical properties of the laminated film are shown in Tables 5 and 9.

Example 4, Comparative Example 4 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate C of Synthesis Example 3, isophorone diisocyanate, PES-A, aromatic polyester diol of 0 and NPG / HG / EG = A uretdione group dissociation catalyst was added to a polyurethane component composed of a polyester having a molar ratio of 2/1/2, hexamethylene adipate diol having a molecular weight of 2000, and ethylene glycol to obtain a composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, polyisocyanate C of Synthesis Example 3 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate group) was used. 12.5%) 100 parts, 130 parts isophorone diisocyanate and 2000 molecular weight PES-A1
000 parts and 700 parts of hexamethylene adipate diol having a molecular weight of 2000, 7 parts of ethylene glycol and 2130 parts of ethyl acetate were added and reacted at 70 ° C. 5 hours later
In FT-IR, the absorption of isocyanurate group and uretdione group did not change from that at the start of the reaction, the absorption of only NCO group disappeared, and the urethanization was completed to obtain a urethane component (PU-4). The composition in which 0.5 wt% of DBU-PH was added to this PU-4 with respect to the resin solid content was taken as an example, and the one not added was taken as a comparative example. The film curability is shown in Table 2. The physical properties of the laminated film are shown in Tables 6 and 10.

[Evaluation of Curability of Film Using Adhesive Composition] After being formed into a film under the following conditions, the softening point and gel fraction of each film were measured. Table 1,
As shown in 2, it was found that the softening point and the gel fraction were improved by the reaction of the uretdione group with the addition of the catalyst, and the curing reaction was completed at 25 ° C. for about 1 day. Film curing conditions: room temperature x 2 hours + 80 ° C x 20 seconds +
25 ° C. × number of days elapsed (1) Softening point The softening point of the film was measured under the following conditions. The results are shown in Table 1.
~ 2. Definition of softening point: The softening point was defined as the temperature at which the film suddenly stretched or was cut when the film was hung in a hot-air circulation dryer with a constant load applied and the temperature was raised under constant conditions. Test piece shape: punched out with JIS No. 2 type dumbbell, load on the test piece: 500 g / cm ² heating rate: 10 ° C / min (starting heating from room temperature) (2) gel fraction gel fraction under the following conditions The rate was measured. The results are shown in Tables 1-2. Definition of gel fraction: About 1 g of the film in the cylindrical filter paper was extracted with a solvent, and the weight residual ratio of the film after extraction was taken as the gel fraction. Test piece shape: thickness about 80 μm, length x width = 5 mm x 8
0mm Extractor: SOXTEC SYSTEM HT
1043 (manufactured by tecaor) Extraction solvent: methyl ethyl ketone Extraction conditions: 5 hours of boiling + 1 hour of washing with a reflux solvent

[Evaluation of Adhesive Strength] (1) Time-dependent Change in Peeling Adhesive Strength As described above, addition of the catalyst improved the softening point and gel fraction, and the progress of the curing reaction was confirmed. It was also confirmed from the results in Table 1 that this curing reaction was almost completed at 25 ° C for 1 day. Then, next, the peeling adhesive strength with various adherends was measured for the catalyst-added system in which the curing reaction proceeds even at 25 ° C. under the following adhesive conditions. The results are shown in Tables 3-10. Added catalyst: DBU-PH added amount of catalyst: 0.2 parts based on solid content of polyurethane component resin Solid content of adhesive: 25% (diluted with ethyl acetate) Application amount: 4.0 g / m ² Drying temperature : 80 ° C. Drying time: 30 seconds Aging condition: 25 ° C. × 1 day, 3 days, 7 days Peeling adhesion strength: According to JIS K 6854.
(T-type peeling, pulling speed 200 mm / min, unit of adhesive strength g / 15 mm) (2) Retort test Among the laminated films prepared in the above adhesion test, those whose aging condition is 25 ° C x 1 day are as follows. The retort treatment was performed under the conditions shown in, and the peel adhesion strength was measured. The results are shown in Tables 3-10. Retort treatment conditions: 120 ° C x 30 min

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

[Table 8]

[0057]

[Table 9]

[0058]

[Table 10]

[0059]

As described above, in the adhesive composition for laminating of the present invention, the curing reaction is almost completed when the aging condition is 25 ° C. × 1 day, and the softening point and the gel fraction are improved, It was found that the resin has excellent heat resistance and solvent resistance. In addition, the adhesive composition for lamination of the present invention,
It has been found that it has a good peel adhesion strength to various adherends, and that it has a practical adhesion strength even after aging. Further, it was confirmed that no abnormality such as delamination was observed in the appearance of the laminated film even after the retort treatment, and the adhesive strength was maintained. Further, the laminating adhesive composition of the present invention enables the above points in a system containing no free polyisocyanate monomer. Therefore,
According to the present invention, it is possible to cure at a low temperature for a short time, productivity,
It has become possible to provide a laminating adhesive composition having excellent work environment safety and the like.

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[Procedure amendment]

[Submission date] December 1, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Of the polyisocyanate component (A) of the present invention, the polyisocyanate compound (al) is
It contains at least a uretdione group and an isocyanurate group. As long as it contains at least a uretdione group and an isocyanurate group, it may be one kind or a mixture of two or more kinds. For example, a mixture of a uretdione group-containing polyisocyanate compound (dimer and polyuretdione body), an isocyanurate group-containing polyisocyanate compound (trimer and polyisocyanurate body), and a uretdione group- and isocyanurate group-containing polyisocyanate compound It may be. The uretdione group content of the polyisocyanate compound (al) is preferably 7 to 25% by weight , more preferably 10 to 23% by weight. The isocyanurate group content is preferably 1 to 24% by weight , and further 3
-20% by weight is preferred. In addition, as the polyisocyanate monomer constituting the polyisocyanate compound (al), 1,6-hexamethylene diisocyanate is particularly suitable from the viewpoint that the produced polyisocyanate compound becomes liquid and does not undergo yellowing modification. .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Example 1, Comparative Example 1 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate A and MDI of Synthesis Example 1 and molecular weight 20
00 aromatic polyester Le diol having a molecular weight of 2,000
A uretdione group dissociation catalyst was added to the polyurethane-based component consisting of hexamethylene adipate diol, to obtain the composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, the polyisocyanate A of Synthesis Example 1 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate group) was used. 12.5%) 100 parts, MDI 189 parts and molecular weight 2000 aromatic polyester diol (IP
/ TP / AA = 5/5/1 molar ratio and NPG / HG / EG
= 2/1/2 mole ratio polyester, hereinafter PES
(Referred to as —A) 1552 parts, 681 parts of hexamethylene adipate diol having a molecular weight of 2000, 3026 parts of toluene and 4540 parts of ethyl acetate were added and reacted at 70 ° C.
After 3 hours, the absorption peaks of isocyanurate group and uretdione group by FT-IR did not change from those at the start of the reaction, and
It was confirmed that the absorption peak of only the CO group had disappeared, the urethanization was completed, and a polyurethane component (PU-1) was obtained. A composition in which 0.5 wt% of uretdione group dissociation catalyst (DBU phenol salt, hereinafter abbreviated as DBU-PH) was added to this PU-1 with respect to the resin solid content was used as an example, and a composition not added was used as a comparative example. The curability of the film is shown in Table 1.
Table 3 shows the physical properties of the laminated film, and Table 7 shows a comparative example.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

Example 2, Comparative Example 2 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate B and MDI of Synthesis Example 2 and molecular weight 20
The polyurethane-based component consisting 00 aromatic polyester Le diol and 3-methyl-1,5-pentanediol adipate diol having a molecular weight of 2000 was added uretdione groups dissociation catalyst to give a composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, the polyisocyanate B of Synthesis Example 2 (NCO group content 37.3%, uretdione group content 7.2%, isocyanurate group) was used. Content 5.5%) P of 100 parts and molecular weight 2000
ES-A 489 parts and 3-methyl-1, having a molecular weight of 2000
500 parts of 5-pentane adipate diol and 1089 parts of ethyl acetate were added and reacted at 70 ° C. 5 hours later, F
In T-IR, the absorption of isocyanurate group and uretdione group does not change from that at the start of the reaction, the absorption of only NCO group disappears and the urethanization ends, and the polyurethane component (PU-2)
I got The composition in which 0.5% by weight of DBU-PH was added to this PU-2 with respect to the resin solid content was taken as an example, and the composition without addition was taken as a comparative example. The film curability is shown in Table 1. Table 4 shows the physical properties of the laminated film, and Table 8 shows a comparative example.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Example 3, Comparative Example 3 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate A of Synthesis Example 1, isophorone diisocyanate, PES-A, and 3-methyl-1,5-penta5- having a molecular weight of 6000. A uretdione group dissociation catalyst was added to a polyurethane-based component composed of pentane adipate diol to obtain a composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, polyisocyanate A of Synthesis Example 1 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate) was used. 100 parts of group content 12.5%), 167 parts of isophorone diisocyanate, PES-A, 1360 parts of 3-methyl-1,5-penta5-pentane adipate diol having a molecular weight of 6000 and 3200 parts of ethyl acetate,
The reaction was carried out at ° C. After 5 hours, absorption of isocyanurate group and uretdione group by FT-IR did not change from that at the start of the reaction, absorption of only NCO group disappeared and urethanization was completed, and polyurethane component (PU-3) was obtained. A composition in which 0.5% by weight of DBU-PH was added to PU-3 was used as an example, and a composition in which DBU-PH was not added was used as a comparative example. The film curability is shown in Table 3. The physical properties of the laminated film are shown in Tables 5 and 9.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Example 4, Comparative Example 4 Method for Producing Laminating Adhesive Composition and Laminated Film Polyisocyanate C of Synthesis Example 3, isophorone diisocyanate, PES-A, hexamethylene adipate diol having a molecular weight of 2000, and polyurethane made of ethylene glycol. A uretdione group dissociation catalyst was added to the system components to obtain a composition of the present invention. Method for producing laminated film In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, polyisocyanate C of Synthesis Example 3 (NCO group content 21.1%, uretdione group content 16.4%, isocyanurate group) was used. 12.5%) 100 parts, 130 parts isophorone diisocyanate and 2000 molecular weight PES-A1
000 parts and 700 parts of hexamethylene adipate diol having a molecular weight of 2000, 7 parts of ethylene glycol and 2130 parts of ethyl acetate were added and reacted at 70 ° C. 5 hours later
In FT-IR, the absorption of isocyanurate group and uretdione group did not change from that at the start of the reaction, the absorption of only NCO group disappeared, and the urethanization was completed to obtain a urethane component (PU-4). The composition in which 0.5 wt% of DBU-PH was added to this PU-4 with respect to the resin solid content was taken as an example, and the one not added was taken as a comparative example. The film curability is shown in Table 2. The physical properties of the laminated film are shown in Tables 6 and 10.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[Evaluation of Adhesive Strength] (1) Change with Time of Peel Adhesive Strength Next, the peel adhesive strength with various adherends was measured under the following adhesive conditions. The results are shown in Tables 3-10. Addition catalyst: DBU-PH catalyst addition amount: 0.2 part with respect to polyurethane component resin solid content Adhesive solid content: 25% (dilution with ethyl acetate) Application amount: 4.0 g / m ² Drying temperature : 80 ° C. Drying time: 30 seconds Aging condition: 25 ° C. × 1 day, 3 days, 7 days Peeling adhesion strength: According to JIS K 6854.
(T-type peeling, pulling speed 200 mm / min, unit of adhesive strength g / 15 mm) (2) Retort test Among the laminated films prepared in the above adhesion test, those whose aging condition is 25 ° C x 1 day are as follows. The retort treatment was performed under the conditions shown in, and the peel adhesion strength was measured. The results are shown in Tables 3-10. Retort treatment conditions: 120 ° C x 30 min

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Claims (4)

[Claims] 1. A polyisocyanate compound (a) containing at least a uretdione group and an isocyanurate group.
1) a polyisocyanate component (A) and an active hydrogen compound component (B) having a molecular weight of 18 to 20,000 and containing two or more active hydrogen groups in the molecule, a polyisocyanate component (A) The equivalent ratio of the active hydrogen group of the active hydrogen compound component (B) to the isocyanate group of 1. is 1.
100 parts by weight of a polyurethane-based component containing at least a uretdione group and an active hydrogen group at an equivalent ratio of uretdione group / active hydrogen group = 0.25 to 1.0, which is obtained by reacting under a condition of more than 0. An adhesive composition for laminating, which comprises 0.05 to 10.00 parts by weight of a uretdione group dissociation catalyst with respect to 1 part by weight. 2. A polyisocyanate compound (a) containing at least a uretdione group and an isocyanurate group.
1) and a polyisocyanate component (A) comprising a polyisocyanate compound (a2) having two or more isocyanate groups in the molecule, and a molecular weight of 18 to 20,000 and two or more active hydrogen groups in the molecule. Obtained by reacting the contained active hydrogen compound component (B) under the condition that the equivalent ratio of the active hydrogen group of the active hydrogen compound component (B) to the isocyanate group of the polyisocyanate component (A) exceeds 1.0. And a polyurethane component containing at least an uretdione group and an active hydrogen group in an equivalent ratio of uretdione group / active hydrogen group = 0.25 to 1.0 and 0.05 to 10 parts by weight based on 100 parts by weight of the polyurethane component. An adhesive composition for lamination, which comprises 0.000 part by weight of a uretdione group dissociation catalyst. 3. The polyisocyanate compound (a1)
The urethdione group and the isocyanurate group are contained in an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate monomer and a bifunctional or higher functional polyol having a side chain. Adhesive composition. 4. The adhesive composition for laminating according to claim 1, 2, or 3 is applied to a first plastic film or metal foil and dried, and then a second plastic film or metal foil is applied thereto. The curing condition after pasting is 10
A method for producing a laminated film, which is at 35 ° C. for 24 hours.