JPH09316423A - Adhesive composition for laminating and method for producing laminated film using the same - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide an adhesive composition for laminating, which can be cured at room temperature in a short time and is excellent in productivity and workability, and a method for producing a laminated film using the same. SOLUTION: An isocyanurate group-, uretdione group- and isocyanate-reactive group-containing organic compound (A),
An adhesive composition for lamination comprising an organic isocyanate compound (B), a catalyst (C), and optionally a coupling agent (D). The organic compound (A) is a polyisocyanate component (a) composed of a polyisocyanate compound (a1) containing a uretdione group and an isocyanurate group and optionally a polyisocyanate compound (a2) having two or more isocyanate groups, and a molecular weight. 18-2
It is obtained by reacting with a component (b) having two or more isocyanate-reactive groups at 10,000. Further, it is a method for producing a laminate film using this adhesive composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive composition suitable for laminating films, and a method for producing a laminated film using the same.

[0002]

2. Description of the Related Art Recently, a composite flexible package has been used as a packaging method because of its strength, product protection, workability at the time of packaging, advertising effect by packaging, large amount of plastic material, and reduction of packaging cost by inexpensive supply. Has developed significantly. As an adhesive used for laminating such a film, a hydroxyl group is generally used 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 having an active hydrogen group and a curing agent having an isocyanate 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, it becomes necessary to cure the adhesive by storing the laminated film in a greenhouse at 35 to 60 ° C. for about 3 to 5 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 laminate film.If the aging is insufficient, delamination (layer May cause peeling). Especially in the case of an aliphatic polyurethane adhesive, this curing reaction requires a considerably long time. Therefore, such an aging step is an indispensable step in the dry lamination process, and a capital investment for installing a greenhouse for aging and a utility for heating after that are required. The present invention provides an adhesive composition for laminating, which is capable of completing a curing reaction at room temperature in a short time and is excellent in productivity and workability, and a laminated film using the adhesive composition for laminating. It is intended to provide a manufacturing method.

[0004]

Means for Solving the Problems As a result of intensive studies to solve such conventional problems, the present inventors have found that an organic compound containing at least an isocyanurate group, a uretdione group and an isocyanate-reactive group ( An adhesive composition comprising A), an organic isocyanate compound (B), a catalyst (C), and optionally a coupling agent (D), completes a curing reaction at room temperature in a short time in bonding films to each other. The present invention has been completed and the present invention has been completed.

That is, according to the present invention, at least an isocyanurate group and an uretdione group and an isocyanate-reactive group are added, and the uretdione group / isocyanate-reactive group = 0.
Organic compound (A) contained in an equivalent ratio of 25 to 1.0
A polyisocyanate compound (a1) in which the organic compound (A) contains at least a uretdione group and an isocyanurate group, the adhesive composition for laminating comprising: an organic isocyanate compound (B); and a catalyst (C). And a component (b) having a molecular weight of 18 to 20,000 and having two or more isocyanate-reactive groups in the molecule, based on the isocyanate group of the polyisocyanate component (a). The equivalent ratio of the isocyanate-reactive group of component (b) is 1.0
The above-mentioned adhesive composition for lamination is an organic compound obtained by reacting under a condition of exceeding the above.

In the present invention, the uretdione group and the isocyanate-reactive group, together with at least the isocyanurate group, are uretdione group / isocyanate-reactive group = 0.25.
An adhesive composition for lamination comprising an organic compound (A) contained in an equivalent ratio of 1.0, an organic isocyanate compound (B), and a catalyst (C), wherein the organic compound (A) is at least Polyisocyanate compound (a1) containing uretdione group and isocyanurate group
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 isocyanate-reactive groups in the molecule. An organic compound obtained by reacting the component (b) with a condition that the equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) exceeds 1.0. The adhesive composition for laminating.

In the present invention, the uretdione group and the isocyanate-reactive group, together with at least the isocyanurate group, are uretdione group / isocyanate-reactive group = 0.25 to
An adhesive composition for lamination comprising an organic compound (A) contained in an equivalent ratio of 1.0, an organic isocyanate compound (B), a catalyst (C), and a coupling agent (D), The organic compound (A) is a polyisocyanate component (a) composed of a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group, and a isocyanate having a molecular weight of 18 to 20,000 and two or more isocyanates in the molecule. An organic compound obtained by reacting a component (b) having a reactive group under the condition that the equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) exceeds 1.0. The adhesive composition for lamination is characterized in that

In the present invention, at least an isocyanurate group and an uretdione group and an isocyanate-reactive group are added together, and the uretdione group / isocyanate-reactive group = 0.25.
An adhesive composition for lamination comprising an organic compound (A) contained in an equivalent ratio of 1.0, an organic isocyanate compound (B), a catalyst (C), and a coupling agent (D), A polyisocyanate component (a) comprising an organic compound (A) containing at least a uretdione group and an isocyanurate group (a1) and a polyisocyanate compound (a2) having two or more isocyanate groups in the molecule; , Molecular weight 18 ~
The component (b) having a molecular weight of 20,000 and having two or more isocyanate-reactive groups in the molecule has an equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) of 1 The above-mentioned adhesive composition for lamination, which is an organic compound obtained by reacting under conditions exceeding 0.0.

The present invention is the above adhesive composition for laminating, wherein the component (b) contains a rosin polyol (b1).

Further, the present invention is characterized in that each of the above-mentioned adhesive compositions for laminating is applied to a first film and dried, and then a second film is laminated thereon and aged at room temperature. It is a method of manufacturing a laminated film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION First, an organic compound (A) containing at least an isocyanurate group, a uretdione group and an isocyanate-reactive group, which is an essential component in the present invention, will be described. The organic compound (A) is a polyisocyanate component composed of a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group, and a polyisocyanate compound (a2) having two or more isocyanate groups in the molecule as necessary. (A) and a component (b) having a molecular weight of 18 to 20,000 and having two or more isocyanate-reactive groups in the molecule.
And (2) are reacted under the condition that the equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) exceeds 1.0.

The reaction condition that the isocyanate-reactive group is in excess is a condition necessary for making the isocyanate-reactive group terminal without leaving the isocyanate group in the produced organic compound (A), and the adhesive performance is taken into consideration. In this case, the equivalent ratio of the isocyanate-reactive group in the component (b) to the isocyanate group in the polyisocyanate component (a) is preferably 1.0 to 2.0. Actually, the conditions for preventing gelation during these reactions are determined by the average number of functional groups of the polyisocyanate component (a) due to the isocyanurate group content and the like and the average number of functional groups of the component (b) due to the introduction of triol and the like. It is important that the compounding is performed so as to satisfy the conditions, and that the reaction is performed under the temperature condition where the uretdione group is opened.

The organic compound (A) 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, ethyl acetate, butyl acetate or the like. Ester solvent, methyl ethyl ketone, ketone solvent such as cyclohexanone, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, glycol ether ester solvent such as ethyl-3-ethoxypropionate, tetrahydrofuran, ether solvent such as dioxane , One or more polar solvents such as dimethylformamide, dimethylacetone, N-methylpyrrolidone, and furfural are used, and temperature conditions at which the uretdione group does not ring-open, preferably 100 ° C. or less, and 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 organic compound (A) thus produced is the polyisocyanate compound (a1) used.
Derived from a urethane group, a urea group, a carbodiimide group, a uretonimine group, an oxazolidone group, a hydantoin group, etc., in addition to a functional group capable of reacting with an uretdione group, an isocyanurate group and an isocyanate group (isocyanate-reactive group). Group can be contained, but the isocyanate group is not substantially contained, and the uretdione group and the isocyanate-reactive group are contained in the uretdione group / isocyanate-reactive group = 0.25.
It should be contained in an equivalent ratio of 1.0, preferably 0.35 to 0.75.

When workability and adhesive performance are taken into consideration,
The molecular weight of the organic compound (A) is 3,000 to 60,000.
0, especially 5,000-40,000 is suitable.

The polyisocyanate compound (al) in the polyisocyanate component (a) contains at least a uretdione group and an isocyanurate group. The polyisocyanate compound (al) may be one kind or a mixture of two or more kinds as long as it contains at least a uretdione group and an isocyanurate group. For example, it may be a mixture of a uretdione group-containing polyisocyanate compound, an isocyanurate group-containing polyisocyanate compound, and a uretdione group- and isocyanurate group-containing polyisocyanate compound. The uretdione group content of the polyisocyanate compound (a1) is preferably 3 to 25% by weight, and more preferably 5 to 23% by weight. The isocyanurate group content is preferably 1 to 24% by weight,
Further, 3 to 20% by weight is suitable.

The polyisocyanate compound (a1) may optionally contain a group other than an uretdione group and an isocyanurate group derived from an isocyanate group. Examples of the groups other than the uretdione group and the isocyanurate group derived from the isocyanate group include a urethane group, a urea group, a carbodiimide group, a uretonimine group, an oxazolidone group, and a hydantoin group. You may mix and contain 1 or more types.

Of the polyisocyanate component (a), a polyisocyanate compound (a2) is optionally used in combination.
Is a polyisocyanate compound having two or more isocyanate groups in the molecule.

The polyisocyanate compound (a of the present invention
Examples of the polyisocyanate compound or the polyisocyanate compound (a2) for forming 1) include a polyisocyanate compound containing a polyisocyanate monomer in addition to a polyisocyanate monomer, and one or more of them may be mixed. Can be used. Specifically, for example, 2,4-tolylene diisocyanate, 2,
6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate,
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,
Aromatic diisocyanates such as 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), aliphatic diisocyanates such as lysine diisocyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI) ), Hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, diisocyanates such as alicyclic diisocyanates such as tetramethyl xylene diisocyanate, and a polymer of the diisocyanate or a bifunctional or higher functional polyol. The polyisocyanate compound obtained by the reaction with the above-mentioned diisocyanate or its polymer is suitable. As the polyisocyanate monomer for forming the polyisocyanate compound (a1), 1,6-hexamethylene diisocyanate is particularly suitable from the viewpoint that the polyisocyanate compound to be produced becomes liquid and does not undergo yellowing modification. .

The polyisocyanate compound (a1) is generally formed by a dimerization reaction (uretdione formation reaction) or a trimerization reaction (isocyanurate formation reaction) of a polyisocyanate monomer. Specifically, for example, Can be manufactured.

From the corresponding polyisocyanate compound,
In the presence of a known uretdione-forming catalyst, for example, triethylphosphine, dibutylethylphosphine, tributylphosphine, tri-n-propylphosphine, triamylphosphine, tribenzylphosphine, or another trialkylphosphine, or pyridine, etc. ℃
At a reaction temperature, without a solvent, or in an inert solvent commonly used in the polyurethane industry, for example, toluene, xylene and other aromatic solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. Production in the presence of a system solvent, a glycol ether ester system solvent such as propylene glycol methyl ether acetate, ethyl-3-ethoxypropionate, etc., and in some cases, in a liquid polyol or a plasticizer such as DOP at the reaction temperature. be able to.

When 20 to 50 mol% of isocyanate groups in the reaction solution have reacted with the reaction solution, for example, phosphoric acid, methyl paratoluenesulfonate,
A solution such as sulfur is added to inactivate the uretdione-forming catalyst and stop the reaction. Depending on the type of polyisocyanate compound used, some may become crystals and precipitate during this reaction process. In particular, aromatic polyisocyanates generally crystallize and separate from the reaction system.

By such a method, a uretdione group-containing polyisocyanate compound (that is, a dimer or poly-uretdione body), an isocyanurate group-containing polyisocyanate compound (that is, a trimer or polyisocyanurate body), a uretdione group and an isocyanate group. A mixture of a polyisocyanate compound containing a nurate group and a polyisocyanate monomer as a raw material is produced. By removing the raw material polyisocyanate monomer from this mixture by thin film distillation or the like, the desired uretdione group-containing polyisocyanate compound, isocyanurate group-containing polyisocyanate compound, and a mixture of uretdione group and isocyanurate group-containing polyisocyanate compound, etc. are obtained. To be The higher the temperature of the reaction during the production, and the lower the content of the polyisocyanate compound at the time of stopping the reaction, the higher the production ratio of isocyanurate groups. Then, the larger the amount of catalyst such as triethylphosphine, the higher the production ratio of uretdione groups. By controlling these reaction conditions, a polyisocyanate compound (al) 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. Further, when the polyisocyanate compound molecule contains a fixed ratio of isocyanurate groups in addition to the uretdione group, a branch point which does not reach gelation can be introduced into the product compound molecule. Due to this branched structure, excellent physical properties are exhibited in a short time and at a low reaction rate in comparison with those obtained from the conventionally known uretdione group-containing polyurethane compound in the curing process when used as an adhesive for lamination. To do.

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, the component ( In some cases, it may be preferable because it may improve the compatibility with b), a solvent, or the like, and may improve the adhesiveness with the film. The bifunctional polyol having this side chain structure is 2
It is a compound having one hydroxyl group and a hydrocarbon group (that is, a branched hydrocarbon group) bonded to the dihydric alcohol molecular skeleton in which one or more hydrocarbon groups are linearly connected between them. A dihydric alcohol having two or more branched structures or a long branched hydrocarbon group is preferable. Especially, molecular weight 1
A dihydric alcohol of 00 to 1000 is preferred. For example,
Neopentyl glycol (hereinafter abbreviated as NPG), 3
-Methyl-1,5-pentanediol, 1,3-butanediol, 2,2-diethyl-1,3-propanedio-
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-hydroxypropionate, hydrogenated bisphenol A and the like can be mentioned. 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 and the polyisocyanate compound (a2) are mixed to form the component (b) in a form having a reduced number of functional groups. The reaction with is preferable in some cases because problems such as gelation do not occur during the reaction, and may be effective in controlling reactivity and expression physical properties. The isocyanate group equivalent ratio of the polyisocyanate compound (a1) excluding the unreacted polyisocyanate monomer and the polyisocyanate compound (a2) is the isocyanate group equivalent of the polyisocyanate compound (a2) / the isocyanate group equivalent of the polyisocyanate compound (a1). = 0 to 5.70
0.10 to 4.00 is preferable, and 0.15 to 3.00 is more preferable.

The component (b) has a molecular weight of 18 to 20,0.
And a compound containing two or more isocyanate-reactive groups, preferably active hydrogen groups, in the molecule. Specifically, in addition to water, one or more selected from polyols, amino group-containing polyamines, urea resins, melamine resins, polyester resins, rosin resins, acrylic resins, polyvinyl alcohols, etc. Is preferred.

Examples of this polyol include polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, rosin polyols (b1) and other polyols known in the polyurethane industry. Specifically, for example, dicarboxylic acids such as known succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, their acid esters, acid anhydrides, etc. , Ethylene glycol (hereinafter EG
Abbreviated), 1,3-propylene glycol, 1,2
-Propylene glycol, 1,4-butylene glycol, 1,5-pentane glycol, 1,6-hexane glycol, 3-methyl-1,5-pentane glycol,
2-butyl-2-ethyl-1,3-propanediol,
NPG, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol, cyclohexane-
1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, trimethylolpropane,
Glycerin, hexanetriol, glycol or triol such as ethylene oxide or propylene oxide adduct of bisphenol A, or
Hexamethylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, xylenediamine, isophoronediamine, monoethanolamine, isopropanoltriamine and other diamines, triamine or aminoalcohol alone or a mixture thereof. Examples thereof include polyester polyols and polyester amide polyols obtained by a dehydration condensation reaction with.
Further, there are 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.

Examples of the polyether polyol include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol and the like. Examples of the polyether / ester polyol include those produced from these polyether polyols and the above-mentioned dicarboxylic acids, acid anhydrides and the like. Polycarbonate polyols include, for example, hexane glycol, 3-methyl-1,5-pentanediol,
It is obtained from the reaction of 1,4-cyclohexanedimethanol and the like with diethyl carbonate, diphenyl carbonate and the like, and specific products include Nippon Polyurethane Industry Co., Ltd.'s Nipolan 980, Nipolan 981 and the like.

The monomolecular glycols or triols mentioned as the raw materials for the polyester polyols, that is, EG, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol,
1,5-pentane glycol, 1,6-hexane glycol, 3-methyl-1,5-pentane glycol, NP
G, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol, cyclohexane-1,4
-Diol, cyclohexane-1,4-dimethanol,
Dimer acid diol, trimethylolpropane, glycerin, hexanetriol, quadrol or ethylene oxide or propylene oxide adduct of bisphenol A can also be used as the polyol.

The amino group-containing polyamine includes
Examples include monomolecular diamines such as hexamethylenediamine, ethylenediamine, and isophoronediamine, 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 resins, polyvinyl alcohols, etc. are generally known in the polyurethane industry, and as long as they contain two or more isocyanate-reactive groups such as active hydrogen groups, they should be used as all or part of component (b). You can

The molecular weight of this component (b) is 18-20,0.
00, especially water and a molecular weight of 400 to 10,000
Are preferred. If the molecular weight is too large, the introduction amount of urethane groups and the like decreases, and the toughness and strong cohesive force of the organic compound (A) decrease, which is not preferable. If the molecular weight is too small, the organic compound (A) 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.

Considering the adhesive performance with the base film, aromatic polyester polyols using terephthalic acid, isophthalic acid, etc. and polyester polyols using adipic acid are preferred.

In view of the adhesive performance, it is more preferable to use the rosin polyol (b1) as a part or all of the component (b). Rosin polyol (b
1) has a functional group capable of reacting with an isocyanate group, and is a rosin ester obtained from rosin and a polyhydric alcohol (see JP-A-2-155978) or a rosin ester obtained from an epoxy compound and rosin (special Kaihei 5-155972). Further, a polyether having a rosin skeleton is also preferable. Among these, in particular, a rosin ester consisting of one molecule of a diepoxy compound and two molecules of hydrogenated, disproportionated and purified rosins (see JP-A-5-263059) is easily introduced into the molecule of the organic compound (A). It is preferable because the molecular weight of the produced organic compound can be easily controlled. Specific examples of the rosin polyol (b1) include KE-601, KE-615-3, and K manufactured by Arakawa Chemical Industry Co., Ltd.
E-622, KE-623, KE-624, etc. are mentioned.

As the organic isocyanate compound (B) which is an essential component in the present invention, the compounds mentioned above as the polyisocyanate component (a) can be used, but specifically, they are manufactured by Nippon Polyurethane Industry Co., Ltd. Coronate L, Coronate 3041, Coronate HL,
Coronate HX and the like can be mentioned. The compounding amount of the organic isocyanate compound (B) is preferably 1 to 30 parts by weight, particularly 3 to 15 parts by weight in terms of solid content, relative to 100 parts by weight of the solid content of the organic compound (A).

Next, the catalyst (C) which is an essential component in the present invention will be described. The catalyst (C) includes those generally known as transesterification catalysts, urethanization catalysts, blocked isocyanate dissociation catalysts, isocyanurate formation catalysts, and the like, and specifically, dibutyltin dilaurate, stannas octoate, etc. Tin catalyst, 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 abbreviated as DBU), borane salts of these amine-based catalysts, DBU phenol salts, DBU octylates, various amine salt-based catalysts such as DBU carbonates, magnesium naphthenate, lead naphthenate, CH. Carboxylates such as ₃ COOK, trialkylphosphines such as triethylphosphine and tribenzylphosphine, CH ₃ O
Examples thereof include alkoxides such as Na and 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. The curing rate largely depends on the type and amount of the catalyst to be added, but by appropriately selecting these, a practical curing rate can be obtained even in a temperature range near room temperature, preferably 15 to 35 ° C. It becomes possible. However, for example, when the amount of the catalyst added is less than 0.01% by weight with respect to the solid content of the organic compound (A), the effect of promoting the curing reaction due to the addition of the catalyst is difficult to appear, and
If it exceeds 5.00% by weight, the curing speed is too fast, which makes coating difficult, and there is a possibility that hydrolysis of the adhesive after curing may be accelerated, which is not preferable. Therefore, the amount of the uretdione group dissociation catalyst added to the solid content of the organic compound (A) is preferably 0.01 to 5.00% by weight, and particularly preferably 0.05% to 2.00% by weight.

Examples of the coupling agent (D) that can be used in the present invention include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like. The amount of the coupling agent added is 0.05 to 1 with respect to 100 parts by weight of the solid content of the organic compound (A).
0.00 parts by weight is preferred. More preferred is 0.
1 to 5.00 parts by weight. The addition amount shown here is
It is calculated after taking into consideration the coating area of the base film of the coupling agent, the coating efficiency, the adhesive performance and the like.

Examples of the silane coupling agent include vinylsilane compounds such as γ-methacryloxypropyltrimethoxysilane and vinyltriethoxysilane, and β- (3,3.
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and other epoxysilane compounds, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane and the like Aminosilane compounds and mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane are preferably used.

Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). Phyto) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl Titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiac Ruchitaneto, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N
-Amidoethylaminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and the like. Specifically, Aplanator KR TTS, KR 46 manufactured by Ajinomoto Co., Inc.
B, KR 55, KR41B, KR 38S, KR 1
38S, KR 238S, KR 338X, KR 1
2, KR 44, KR 9SA, KR 34S and the like can be preferably used.

As the aluminum-based coupling agent,
Examples thereof include acetoalkoxyaluminum diisopropylate, and as a commercial product, Planeact AL-M manufactured by Ajinomoto Co., Inc. can be preferably used.

Of the above coupling agents, epoxy silane compounds, aminosilane compounds, phosphoric acid titanates, etc. are considered in view of improving the adhesive strength to widely used polyethylene terephthalate film, aluminum film, nylon film, polyolefin film and the like. It is suitable. Of these, particularly preferred is a case where an epoxysilane compound is used as the coupling agent (D) and DBU and various acid salts of DBU are used in combination as the catalyst (C). Since DBU and various acid salts of DBU are not only ordinary urethane-forming catalysts but also isocyanurate-forming catalysts that pass through uretdione groups, they accelerate the curing rate of the organic compound (A) containing uretdione groups. Guessed. In addition, DBU and various acid salts of DBU are
Since it is also a catalyst for promoting the reaction between the epoxy group and the isocyanate group of the epoxysilane compound, it is presumed that it has a favorable effect on the adhesive strength.

The film used for laminating in the present invention includes stretched polypropylene, unstretched polypropylene (hereinafter abbreviated as CPP), polyester (hereinafter abbreviated as PET), nylon (hereinafter abbreviated as NY), low density polyethylene. , High-density polyethylene, ethylene-vinyl acetate copolymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH), polystyrene, polycarbonate, polyvinylidene chloride, polyvinyl chloride and other plastic films, Al, Cu Examples thereof include metal foils, papers, and the like, and films obtained by applying a polymer coating to these. These films are preferably subjected to an appropriate surface treatment such as corona discharge treatment before laminating in order to improve the adhesive force. In addition, the polymer coated film is
Since problems such as bubble generation and adhesive strength reduction may occur, it is necessary to consider in advance the type of coated polymer, the coating amount, the surface characteristics, and the like.

Next, a film laminating method will be described. The adhesive composition for lamination of the present invention can be used by known lamination methods such as dry lamination, hot melt lamination, and extrusion lamination. The laminated film can complete the curing reaction by aging at room temperature (preferably 15 to 35 ° C.) for a fixed time (preferably within 24 hours). By such a method of the present invention, not only a film in which two films are laminated but also a film in which three or more films are laminated can be manufactured.

[0044]

EXAMPLES Next, examples of the present invention will be described in detail, but the present invention is not construed as being limited to these examples. Unless otherwise specified, parts and% in Synthesis Examples, Examples and Comparative Examples mean "parts by weight" and "% by weight", respectively. In addition, the uretdione group content and isocyanurate group content in the synthesis examples are obtained by converting each functional group into an isocyanate group content.

Synthesis of Polyisocyanate Compound (a1) Synthesis Example 1 HDI (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate group content = 49.9% ) was placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser. , Solid content = 100%)
3,000 parts and trioctylphosphine as a catalyst 6.
5 parts were charged and reacted with stirring at 50 to 55 ° C. for 8 hours, and then 1.9 parts of phosphoric acid was added to stop the reaction. The isocyanate group content of the product was 37.3%, and FT-IR and ¹³ C-NMR confirmed that the product had an isocyanate group, a uretdione group and an isocyanurate group. Isocyanate group content = 44.5 obtained 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. %, And thus the content of isocyanate groups produced by the dissociation of uretdione groups was 7.2%. Further, the isocyanurate group content was 5.5%. This uretdione group- and isocyanurate group-containing polyisocyanate compound is designated as polyisocyanate A.

Synthesis Example 2 HDI (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate group content = 49.9%, solid content = 100%) was placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser.
3,000 parts and 2-n-butyl-2-ethyl-1,3-
Twenty-three parts of 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 isocyanate group content of the reaction liquid 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, and then 3.5 parts of phosphoric acid was added to stop the reaction. A pale yellow reaction product liquid having an isocyanate group content of 30.3% was obtained. Unreacted HDI from this reaction product solution at 120 ° C,
Removed by thin film distillation at 0.01 Torr. Isocyanate group content of the product = 21.1%, FT-IR
And ¹³ C-NMR confirmed the presence of isocyanate groups, uretdione groups and isocyanurate groups in this product. The isocyanate group content obtained by reacting with DBA at the boiling point of PMG-Ac and by back titration with an aqueous hydrochloric acid solution was 37.5%, and therefore the isocyanate 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 B.

Synthesis of Organic Compound (A) Synthesis Example 3 100 parts of polyisocyanate A and dimethyl terephthalate / sebacic acid = 1/1 (molar ratio) were placed in a reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser. And E
987 parts of a polyester polyol having a number average molecular weight of 2000, synthesized from G / NPG = 3/7 (molar ratio), and 1087 parts of ethyl acetate were added and reacted at 75 ° C. After 4 hours, it was confirmed by FT-IR that the absorption peak of the isocyanate group had disappeared, and the reaction was terminated to obtain a polyurethane resin containing a uretdione group, an isocyanurate group and an active hydrogen group. This is designated as PU-1.

Synthesis Example 4 100 parts of polyisocyanate B and IPDI 1 were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser.
2058 parts of a polyester polyol (hereinafter abbreviated as polyol A) having a number average molecular weight of 2000 synthesized from 50 parts of isophthalic acid / azelaic acid = 1/1 (molar ratio) and EG / NPG = 3/7 (molar ratio), 2308 parts of ethyl acetate was added and reacted at 75 ° C. 4 hours later, F
It was confirmed by T-IR that the absorption peak of the isocyanate group had disappeared, the reaction was terminated, and a polyurethane resin containing a uretdione group, an isocyanurate group and an active hydrogen group was obtained. This is designated as PU-2.

Synthesis Example 5 100 parts of polyisocyanate B and IPDI1 were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser.
50 parts, polyol A1646 parts, and rosin-containing polyol KE-601 (manufactured by Arakawa Chemical Industry Co., Ltd., hydroxyl value 111.2 KOHmg / g, acid value 1.8 KOHmg /
g, number average molecular weight 1010) 205 parts and ethyl acetate 2
100 parts was added and it was made to react at 75 degreeC. 4 hours later, FT
After confirming that the absorption peak of the isocyanate group disappeared by -IR, the reaction was terminated to obtain a polyurethane resin containing a uretdione group, an isocyanurate group and an active hydrogen group. This is designated as PU-3.

Synthesis Example 6 100 parts of polyisocyanate B and IPDI1 were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser.
50 parts, polyol A1646 parts, and rosin-containing polyol KE-615-3 (manufactured by Arakawa Chemical Industry Co., Ltd., hydroxyl value 58.5 KOHmg / g, acid value 1.5 KOHmg /
g, number average molecular weight 2000) 385 parts and ethyl acetate 2
281 parts were added and the mixture was reacted at 75 ° C. 4 hours later, FT
After confirming that the absorption peak of the isocyanate group disappeared by -IR, the reaction was terminated to obtain a polyurethane resin containing a uretdione group, an isocyanurate group and an active hydrogen group. This is designated as PU-4.

Examples 1 to 5 and Comparative Examples 1 to 4 Preparation of Adhesive Composition for Laminating Formulation A polyurethane resin containing an uretdione group, an isocyanurate group and an active hydrogen group, an organic isocyanate compound, a catalyst, and a coupling agent are blended. Then, an adhesive composition for lamination was prepared. These are shown in Table 1.

Manufacture of Laminated Film Under the conditions shown below, the adhesive compositions of Examples 1-5 or Comparative Examples 1-4 were applied to the first plastic film and dried, and then the second plastic film was applied thereto. Alternatively, a metal foil was laminated with a nip roll, the adhesive composition was further applied thereto and dried, and then a third plastic film was laminated with a nip roll and aged to produce a laminated film. Solid content of adhesive composition: 25% (diluted with ethyl acetate) Composition of laminate film: 25 μNY / 15 μEVO
H / 50 μCPP 12 μPET / 7 μAl / 70 μCPP Coating amount of adhesive composition: 3.5 g / m ² (after drying) Drying condition: 80 ° C. × 15 seconds Aging condition: 25 ° C. × 24 hours

Evaluation of Laminated Film The laminated film was evaluated under the following conditions.
The results are shown in Tables 2-6. Peeling adhesive strength: T-type peeling test (based on JIS K 6854) Tensile speed: 300 mm / min Boiling treatment: A laminated film made of NY / EVOH / CPP is heat-sealed to form a pouch, and water is filled at 95 ° C. And boiled for 30 minutes. Retort treatment: A laminated film made of PET / Al / CPP was heat-sealed to form a pouch, which was filled with water and then retort-treated at 120 ° C. for 30 minutes.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

(Uretedione Group and Isocyanurate
Synthesis of Polyurethane Resin (Containing No Group) Synthesis Example 7 100 parts of IPDI, 720 parts of polyol A, and rosin-containing polyol KE-615-3 (Arakawa Chemical Co., Ltd.) were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser. Kogyo Co., Ltd., hydroxyl value 58.5 KOHmg / g, acid value 1.5 KOHmg / g, number average molecular weight 2000) 168
And 988 parts of ethyl acetate were added and reacted at 75 ° C. After 4 hours, it was confirmed by FT-IR that the absorption peak of the isocyanate group had disappeared, and the reaction was terminated (containing no uretdione group and isocyanurate group).
A polyurethane resin was obtained. This is called PU-RF.

Comparative Example 5 Preparation of Adhesive Composition for Laminating (Uretedione Group and Isocyanurate Group-Free) Polyurethane Resin PU-RF 100 parts, Coronate HL 5 parts, DBU phenol salt 0.05 parts, γ-
An adhesive composition was prepared using 0.5 part of glycidoxypropyltrimethoxysilane. This is compared with Example 3 and shown in Table 7.

Manufacture of Laminated Film Under the conditions shown below, the adhesive compositions of Example 3 and Comparative Example 5 were applied to a first plastic film, dried, and then a second plastic film was placed on a nip roll. After laminating, the adhesive composition was further applied thereto and dried, and then a third plastic film was laminated with a nip roll and aged to produce a laminated film. Solid content of adhesive composition: 25% (diluted with ethyl acetate) Composition of laminate film: 25 μNY / 15 μEVO
H / 50 μCPP Adhesive composition coating amount: 3.5 g / m ² (after drying) Drying conditions: 80 ° C. × 15 seconds Aging conditions: 25 ° C. × each time (12 hours, 16 hours, or 24 hours)

Evaluation of Laminated Film The laminated film was evaluated under the following conditions.
Table 8 shows the results. Peel adhesion strength: T-type peel test (based on JIS K 6854) Peeling speed: 300 mm / min

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

EFFECT OF THE INVENTION A laminate film such as a plastic film or a metal foil produced by using the adhesive composition for lamination of the present invention exhibits good adhesive strength at room temperature in a short time, and has a conventionally known adhesive composition. It has become possible to shorten the aging period and lower the aging temperature compared to the products. In addition, it was confirmed that after the boiling process or the retort process, no abnormality such as delamination was observed in the appearance of the laminate film, and that the film had a practically high adhesive strength. Therefore, according to the present invention, the productivity and workability of the laminated film are significantly improved, and the cost and the delivery time can be shortened.

Claims (6)

[Claims] 1. An organic compound (A) containing an uretdione group and an isocyanate-reactive group together with at least an isocyanurate group in an equivalent ratio of uretdione group / isocyanate-reactive group = 0.25 to 1.0, and an organic isocyanate compound. An adhesive composition for lamination comprising (B) and a catalyst (C), wherein the organic compound (A) is a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group. Ingredient (a)
And a component (b) having a molecular weight of 18 to 20,000 and having two or more isocyanate-reactive groups in the molecule,
An adhesive for a laminate, which is an organic compound obtained by reacting a polyisocyanate component (a) under an equivalence ratio of the isocyanate-reactive group of the component (b) to more than 1.0. Composition. 2. An organic compound (A) containing an uretdione group and an isocyanate-reactive group together with at least an isocyanurate group in an equivalent ratio of uretdione group / isocyanate-reactive group = 0.25 to 1.0, and an organic isocyanate compound. An adhesive composition for lamination comprising (B) and a catalyst (C), wherein the organic compound (A) and a polyisocyanate compound (a1) containing at least a uretdione group and an isocyanurate group are in the molecule. A polyisocyanate component (a) comprising a polyisocyanate compound (a2) having two or more isocyanate groups, and a molecular weight of 18 to 20,0
00 and a component (b) having two or more isocyanate-reactive groups in the molecule, the equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) is 1.0. The adhesive composition for laminating, wherein the adhesive composition is an organic compound obtained by reacting under a condition of exceeding. 3. An organic compound (A) containing an uretdione group and an isocyanate-reactive group together with at least an isocyanurate group in an equivalent ratio of uretdione group / isocyanate-reactive group = 0.25 to 1.0, and an organic isocyanate compound. An adhesive composition for laminating comprising (B), a catalyst (C) and a coupling agent (D), wherein the organic compound (A) contains at least a uretdione group and an isocyanurate group. Polyisocyanate component (a) consisting of compound (a1)
And a component (b) having a molecular weight of 18 to 20,000 and having two or more isocyanate-reactive groups in the molecule,
An adhesive for a laminate, which is an organic compound obtained by reacting a polyisocyanate component (a) under an equivalence ratio of the isocyanate-reactive group of the component (b) to more than 1.0. Composition. 4. An organic compound (A) containing an uretdione group and an isocyanate-reactive group together with at least an isocyanurate group in an equivalent ratio of uretdione group / isocyanate-reactive group = 0.25 to 1.0, and an organic isocyanate compound. An adhesive composition for laminating comprising (B), a catalyst (C) and a coupling agent (D), wherein the organic compound (A) contains at least a uretdione group and an isocyanurate group. A polyisocyanate component (a) comprising the compound (a1) and a polyisocyanate compound (a2) having two or more isocyanate groups in the molecule, and a molecular weight of 18 to 20,0.
00 and a component (b) having two or more isocyanate-reactive groups in the molecule, the equivalent ratio of the isocyanate-reactive group of the component (b) to the isocyanate group of the polyisocyanate component (a) is 1.0. The adhesive composition for laminating, wherein the adhesive composition is an organic compound obtained by reacting under a condition of exceeding. 5. The rosin polyol (b) is used as the component (b).
The adhesive composition for laminating according to any one of claims 1 to 4, which contains 1). 6. The adhesive composition for laminating according to claim 1, which is applied to a first film and dried, and then a second film is laminated thereon at room temperature. A method for producing a laminated film, which comprises aging.