JPH0860131A - Two-component curing type adhesive composition for laminating and laminating method - Google Patents

Abstract

(57) [Summary] [Structure] A polyol comprising an organic polymer polyol compound and optionally an organic polymer polyol compound in which at least one of the molecular terminals is a carboxyl group obtained by reacting the organic polymer polyol compound with a carboxylic acid anhydride. Adhesive composition for solvent-free two-component curable laminate containing component (1) and organic polyisocyanate component (2) comprising a bifunctional polyisocyanate compound and a polyfunctional polyisocyanate compound having a functionality of 3 or more Laminating method using. [Effect] It is possible to manufacture various composite packaging materials without peeling because of excellent adhesiveness, particularly adhesiveness to a metal vapor deposition film and a metal foil.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solventless two-component curable adhesive composition having excellent adhesiveness and a laminating method using the same. Specifically, when laminating various plastic films and metal vapor deposition films and metal foils to produce a composite film, laminate them,
The present invention relates to a solventless two-component curable composite adhesive composition having excellent adhesive strength after aging and a method for laminating the same.

[0002]

2. Description of the Related Art Adhesives for laminating various plastic films, metal-deposited films and metal foils are polyester resin / polyisocyanate system using hydroxyl group / isocyanate curing system, polyether polyurethane resin / isocyanate system and polyester resin. / A two-component curable organic solvent adhesive such as isocyanate is used. In recent years, there has been a strong tendency toward organic solvent removal of adhesives due to demands for improving the work environment, strengthening the Fire Service Law, and controlling VOC emissions into the atmosphere. is there. However, the solvent-free laminating adhesive is difficult to raise the molecular weight of the resin from the viewpoint of workability, and the adhesiveness is inferior as compared with the organic solvent-based adhesive, particularly for metal-deposited films and metal foils. Poor adhesion.

[0003]

In recent years, attempts have been made to add epoxy, silane coupling agent, etc. in order to solve the above drawbacks, but they are still satisfactory for metal vapor-deposited films and metal foils. At present, the adhesive strength is not obtained.

[0004]

In view of the above situation, the present inventors have studied to develop an adhesive composition for solventless laminating that exhibits good adhesiveness and a laminating method using the same. As a result, the organic polymer polyol selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol, and polyurethane polyol is reacted with the organic polymer polyol compound and carboxylic acid anhydride, if necessary. A polyol component (1) obtained by adding an organic polymer polyol compound in which at least one of the obtained molecular terminals is a carboxyl group, and an organic polyisocyanate component comprising a bifunctional polyisocyanate compound and a trifunctional or more polyfunctional polyisocyanate compound ( 2) None containing Two-component curable laminating adhesive composition in the type and lamination method found to be able to achieve this objective using the same, in which the present invention has been completed.

The polyol component (1) used in the present invention is an organic polymer polyol selected from the group consisting of polyester polyols, polyether polyols, polyether ester polyols and polyurethane polyols.

Examples of polyester polyols include polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, adipic acid, azelaic acid, sebacic acid, etc. or dialkyl esters thereof or mixtures thereof, and, for example, ethylene glycol, propylene glycol, diethylene glycol. Polyester polyols obtained by transesterification with glycols such as butylene glycol, neopentyl glycol, 1,6-hexanediol, and mixtures thereof.

Examples of polyether polyols include oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, and low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin as an initiator. The polyether polyol obtained by superposition | polymerization is mentioned.

Examples of the polyether ester polyol include isophthalic acid, terephthalic acid, adipic acid,
Azelaic acid, polyvalent carboxylic acids such as sebacic acid or their dialkyl esters or mixtures thereof,
Examples thereof include polyether ester polyols obtained by reacting the above polyether polyols.

As the polyurethane polyol, for example, the above-mentioned polyester polyol, polyether polyol, polyether ester polyol and the like and an organic polyisocyanate or a monomer thereof described below are used in an NCO / OH ratio of less than 1, preferably 0.8 or less. Obtained by reaction. These organic polymer polyol compounds are 300 to 500
It is preferred to have a number average molecular weight of zero.

In the polyol component (1) used in the present invention, in addition to the above-mentioned organic polymer polyol, at least one of the molecular terminals obtained by reacting the organic polymer polyol compound with a carboxylic acid anhydride is a carboxyl group. Certain organic polymer polyol compounds can be used in addition.

Examples of the carboxylic acid anhydride to be reacted with the organic polymer polyol compound in order to obtain the organic polymer polyol compound having at least one of the molecular terminals being a carboxyl group include, for example, phthalic acid anhydride and succinic acid anhydride. Het acid anhydride, hymic acid anhydride,
Maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, tetrapromphthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride Compounds, 2,3,6,7 naphthalenetetracarboxylic acid dianhydride, 5- (2,5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and the like. .

The usage ratio of the organic polymer polyol compound having a carboxyl group introduced is 20 in the polyol component.
The amount is preferably not more than wt%, preferably 0.5 to 20 wt%. When an organic polymer polyol compound having a carboxyl group introduced at its molecular end is used in combination, not only the adhesive property is further improved, but also one having excellent hot water resistance and acid resistance can be provided.

It is essential that the organic polyisocyanate component (2) used in the present invention comprises a bifunctional polyisocyanate compound and a trifunctional or higher polyfunctional polyisocyanate compound. Organic polyisocyanate component (2)
The content of the bifunctional polyisocyanate compound therein is 10 to 90% by weight, preferably 50 to 80% by weight.

As the organic polyisocyanate component (2), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-
4,4'-biphenylene diisocyanate, 3,3'-
Dichloro-4,4'-biphenylene diisocyanate,
1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene Diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Bifunctional or trifunctional or higher functional polyisocyanate compounds such as isocyanurate, burette, and allophanate derived from polyisocyanate monomers such as dicyclohexylmethane diisocyanate, or PP
A terminal isocyanate group-containing difunctional polyisocyanate compound obtained by reaction with a bifunctional polyol compound such as G or a terminal isocyanate group-containing polyfunctional compound obtained by reaction with a trifunctional or higher functional polyol compound such as trimethylolpropane and glycerin. A functional polyisocyanate compound etc. can be mentioned.

Specific examples of the bifunctional polyisocyanate compound include Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd.) and Vernock D-955S (manufactured by Dainippon Ink and Chemicals, Inc.). Specific examples of the trifunctional polyisocyanate compound include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) and Takenate D-170N.
(Manufactured by Takeda Pharmaceutical Co., Ltd.), Barnock D-980-S
(Manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

The solventless two-component curing type laminating adhesive according to the present invention contains the above-mentioned polyol component (1) and organic polyisocyanate component (2) as essential components. , Fillers other than the above components, softeners, antioxidants, stabilizers, adhesion promoters, leveling agents, defoamers, plasticizers, inorganic fillers,
It is of course possible to use tackifying resins, fibers, colorants such as pigments, and usable time extenders.

Furthermore, a solventless type 2 according to the present invention
An adhesion promoter may be used in the liquid curable laminating adhesive. Examples of the adhesion promoter include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and an epoxy resin. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane and γ-aminopropyl. Trimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethyldimethoxysilane, N-
Aminosilane such as phenyl-γ-aminopropyltrimethoxysilane; epoxy such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane Silane; vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and other vinylsilanes; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and the like. I can.

Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate,
Examples thereof include titanium lactate and tetrastearoxytitanium.

Examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate.

As the epoxy resin, there are generally commercially available EP bis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester. Examples thereof include various epoxy resins such as epoxy resins, polycarboxylic acid ester resins, aminoglycidyl resins, and resorcin resins.

The two-component curable solventless composite laminating adhesive composition of the present invention contains the above polyol component (1) and the organic polyisocyanate component (2) NCO immediately before use.
It is selected from various base materials such as various plastic films, various metal vapor deposition films, metal foils, papers, synthetic papers, etc., which are blended so that the equivalent ratio of / active hydrogen is in the range of 1 to 10, preferably 1 to 5. And at least one substrate selected from various substrates such as various plastic films, various metal vapor deposition films, metal foils, papers, synthetic papers, etc. and its adhesion. It is applied to a method of laminating a base material on which an agent layer is formed. In the conventional laminating apparatus, a dryer is required to volatilize the solvent of the adhesive, but the laminating apparatus used in the present laminating method does not need a dryer facility.

In the laminating method of the present invention, a solvent-free two-component curable adhesive composition prepared by blending the above polyol component (1) and the organic polyisocyanate component (2) is used.
It is heated to 0 to 120 ° C. to have fluidity, and the coating film thickness is 0.1.
1 to 10 μm, and coating amount 0.1 to 5 g / m ² -dry
Is applied to a flexible base material so that the adhesive coating surface and another flexible base material are laminated with a nip roll. The solventless coating method can be widely used if known. For example, a film split system using a rubber roll or a metal roll may be used. In this method, the amount of adhesive applied is adjusted by the nip pressure of the coating roll and the peripheral speed difference. Laminate is 30 to accelerate cross-linking
Aging at ~ 50 ° C is desirable.

In order to blend the above-mentioned polyol component (1) and organic polyisocyanate component (2), it is preferable to use a known two-liquid quantitative automatic blending and supplying device.

As the flexible substrate used in the present invention,
For example, vinyl chloride, polyethylene terephthalate, biaxially oriented polypropylene, non-oriented polypropylene, polyethylene, nylon, polyvinyl alcohol, vinylidene chloride biaxially oriented polypropylene, polystyrene, Eval, polycarbonate, various plastic films such as cellophane, various metal vapor deposition film, Metal foil or the like can be used.

Thus, the solvent-free two-component curable adhesive composition according to the present invention and the laminate produced by the laminating method using the same have improved adhesiveness, but particularly to metal vapor-deposited films, metal foils and the like. Adhesiveness has improved dramatically.

[0026]

EXAMPLES The present invention will be described below based on examples.
In the examples, “part” means “part by weight”. (Comparative Example 1) 163 parts of ethylene glycol and 273 parts of neopentyl glycol were charged into a reaction vessel, and heated to 80 ° C with stirring under a nitrogen gas stream to dissolve. With further stirring, 505 parts of isophthalic acid, sebacic acid
205 parts were charged into a reaction vessel and heated to 150 ° C to 240 ° C to carry out an esterification reaction. When the acid value became 5 or less, the pressure in the reaction vessel was gradually reduced to 1 mmHg or less, 20
The reaction was carried out at 0 to 240 ° C. for 1 hour to obtain a polyester polyol resin having an acid value of 0.8, a hydroxyl value of 130 and a molecular weight of about 800 and having hydroxyl groups at both ends. Hereinafter, this resin is referred to as a polyol resin I. Further, polyol resin I 100
Coronate HX which is a trifunctional polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., solid content: 10 parts)
100% of 0%) was heated and mixed at about 80 ° C. to obtain a composition for comparison. Table 1 shows the results of a physical property test conducted on this adhesive composition.

(Comparative Example 2) Takenate D-190N which is a bifunctional polyisocyanate compound (manufactured by Takeda Pharmaceutical Co., Ltd., solid content: 1) based on 100 parts of polyol resin I
(100%) was heated and mixed at about 80 ° C. to obtain a composition for comparison. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Example 1 Coronate HX which is a trifunctional polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., solid content: 100) based on 100 parts of polyol resin I
%) And 50 parts of a bifunctional polyisocyanate compound, Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd., solid content: 100%), were heated and mixed at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Example 2 Coronate HX which is a trifunctional polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., solid content: 100) based on 100 parts of polyol resin I
%) And 80 parts of a bifunctional polyisocyanate compound, Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd., solid content: 100%), were heated and mixed at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Comparative Example 3 Polyol Resin I 500
Parts and 2.5 parts of trimellitic anhydride were charged into a reaction vessel, heated to 200 ° C. with stirring under a nitrogen gas stream and reacted for about 2 hours to introduce a carboxyl group into one end of the organic polymer polyol compound. Mixture II having an acid value of 2.4 containing 2% by weight of an organic polymer polyol compound II
I got Furthermore, 100 parts of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., solid content 100%), which is a trifunctional polyisocyanate compound, is added to about 8 parts of 100 parts of the mixture II.
The mixture was heated and mixed at 0 ° C. to obtain a composition for comparison. Table 1 shows the results of a physical property test conducted on this adhesive composition.

(Example 3) Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., solid content 100%) 5 which is a trifunctional polyisocyanate compound, relative to 100 parts of the mixture II.
Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100) which is 0 part and a bifunctional polyisocyanate compound
%) 50 parts by heating at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Example 4 Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., solid content: 100%) 2 which is a trifunctional polyisocyanate compound based on 100 parts of the mixture II 2
Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100) which is 0 part and a bifunctional polyisocyanate compound
%) 80 parts by heating at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Comparative Example 4 Polyol Resin I 500
Parts and 70 parts of isophorone diisocyanate were charged into a reaction vessel, heated to 75 ° C. with stirring under a nitrogen gas stream and reacted for about 10 hours to obtain a polyester polyurethane polyol resin III having a molecular weight of about 1600. Further, with respect to 100 parts of the polyester polyurethane polyol resin III, Coronate HX which is a trifunctional polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., solid content 100).
%) 100 parts by heating at about 80 ° C. to obtain a composition for comparison. Table 1 shows the results of a physical property test conducted on this composition.

(Example 5) Polyester polyurethane polyol resin III 50 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., solid content 100%) which is a trifunctional polyisocyanate compound and 100 parts of a bifunctional polyisocyanate compound. Certain Takenate D-190N
50 parts (manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100%) were heated and mixed at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

Example 6 Polyester Polyurethane Polyol Resin III 20 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., solid content 100%) which is a trifunctional polyisocyanate compound and 100 parts of a bifunctional polyisocyanate compound are used. Certain Takenate D-190N
80 parts (manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100%) were heated and mixed at about 80 ° C. to obtain a composition of the present invention. Table 1 shows the results of a physical property test conducted on this adhesive composition.

(Comparative Example 5) Ethylene glycol 144
And 242 parts of neopentyl glycol were charged into a reaction vessel, and heated to 80 ° C. with stirring under a nitrogen gas stream to dissolve. With further stirring, 549 parts of isophthalic acid,
Charge 223 parts of sebacic acid to a reaction vessel at 150 ° C to 2
The esterification reaction was performed by heating to 40 ° C. When the acid value became 5 or less, the reaction vessel was gradually depressurized to 1 mmH.
g or less and reacted at 200 to 240 ° C. for 1 hour to give an acid value of 0.
8, a polyester polyol resin having a hydroxyl value of 27 and a molecular weight of about 4000 and having hydroxyl groups at both ends was obtained. Hereinafter, this resin is referred to as polyol resin IV. Further, 100 parts of Polyol resin IV, 100 parts of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., solid content: 100%), which is a trifunctional polyisocyanate compound, are heated and mixed at about 110 ° C. to prepare a composition for comparison. Got Table 1 shows the results of a physical property test conducted on this composition.

Example 7 Polyol Resin IV 100
Coronate HX which is a trifunctional polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., solid content: 10 parts)
0%) 50 parts and 50 parts of the bifunctional polyisocyanate compound Takenate D-190N (manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100%) are heated and mixed at about 110 ° C. to obtain a composition of the present invention. . Table 1 shows the results of a physical property test conducted on this adhesive composition.

Method for producing composite film Composite film structure: Polyethylene terephthalate-Al foil (9 μ) / unstretched polypropylene (70 μ) Composite film structure: Al vapor-deposited nylon (15 μ) / Polyethylene (60 μm)
μ) The above composite film was prepared by the method described below. That is,
The above adhesive composition was heated and mixed at about 80 ° C., and first applied on an Al surface or an Al vapor deposition surface to a coating amount of 1.5 g / m ² (dry) with a solventless test coater, and then the applied surface was left uncoated. A composite film was manufactured by laminating with a stretched polypropylene film (CPP film) or a polyethylene film.

Adhesive force test method The composite film produced by the above method was stored in a constant temperature bath at 50 ° C. for 3 days, and the adhesive strength and peeling state between Al surface / CPP and AL vapor deposition surface / polyethylene were measured. The adhesiveness was evaluated. Test piece is 30 from composite film
It was cut and made into 0 mm × 15 mm. The strength (g / 15 mm, five-point average) of this test piece was measured at 180 mm peeling and T-shaped peeling at a peeling speed of 300 mm / min using an Instron type tensile tester.

[0040]

[Table 1]

Composition: PET-Al foil (9μ) / CPP (70μ) Composition: Al vapor deposition nylon (15μ) / polyethylene (60μ)

From the above experimental results, it can be seen that the adhesive composition according to the present invention has excellent adhesiveness to a metal vapor deposition film such as Al or a metal foil.

[0043]

EFFECTS OF THE INVENTION According to the present invention, it is possible to produce various composite packaging materials that are free from peeling because they have excellent adhesiveness, particularly to metal vapor-deposited films and metal foils.

Claims (6)

[Claims] 1. A polyol component (1) which is an organic polymer polyol selected from the group consisting of polyester polyols, polyether polyols, polyether ester polyols and polyurethane polyols, a bifunctional polyisocyanate compound and a trifunctional or higher polyfunctional polyfunctional polyisocyanate compound. A solventless type 2 characterized by containing an organic polyisocyanate component (2) comprising an isocyanate compound
Liquid-curable adhesive composition for laminating. 2. An organic polymer polyol compound selected from the group consisting of polyester polyols, polyether polyols, polyether ester polyols and polyurethane polyols, and a molecular terminal obtained by reacting the organic polymer polyol compound with a carboxylic acid anhydride. A polyol component (1) comprising an organic polymer polyol compound in which at least one of them is a carboxyl group;
A solventless two-component curable adhesive composition for laminating, comprising a functional polyisocyanate compound and a polyisocyanate component (2) comprising a polyfunctional polyisocyanate compound having three or more functional groups. 3. The adhesive composition according to claim 1, wherein the organic polymer polyol compound selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol and polyurethane polyol has a number average molecular weight of 300 to 5,000. Stuff. 4. The adhesive composition according to claim 1, wherein the polyisocyanate component is in the range of 10 to 90% by weight of a bifunctional polyisocyanate compound and 90 to 10% by weight of a polyfunctional polyisocyanate compound having 3 or more functional groups. . 5. The adhesive composition according to claim 1, 2, 3 or 4 is applied to a flexible base material to form an adhesive layer, and then the adhesive coated surface and another flexible base material. A laminating method characterized by bonding and. 6. The laminating method according to claim 5, wherein the adhesive composition heated at 60 to 120 ° C. is applied to the flexible substrate.