JPH07278320A - Method for binding gas impermeable material and reaction type hot-melt adhesive used therefor - Google Patents

Abstract

PURPOSE:To simply stick gas impermeable materials by using a specific reaction type hot-melt adhesive so as to obtain a laminar composite material useful for a top board of a desk, etc., having excellent qualities such as appearance and heat resistance without causing environmental pollution. CONSTITUTION:Both gas impermeable materials (e.g. a decorative sheet made of a resin and a metal plate) are mutually stuck by using (A) an alkoxysilyl group-containing reaction type hot-melt adhesive such as a reaction type hot-melt agent containing a urethane prepolymer obtained by reacting an NCO group- containing urethane prepolymer with an amino group-containing silane coupling agent) such as a compound of the formula (Ar is a 6-10C aryl; R<1> is a 1-10C bifunctional organic group; R<2> and R<3> each is 1-5C alkyl; (n) is 0-3).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for laminating gas-impermeable materials and a reactive hot melt adhesive used therein.

[0002]

2. Description of the Related Art Conventionally, a plate-shaped composite material used for a top plate such as a desk or a table is manufactured by bonding a melamine decorative plate and a metal plate with an adhesive, and as an adhesive for the plate. Solvent type rubber adhesives are generally used.
However, if you use a solvent-based rubber adhesive,
There are problems as listed in.

The solvent-type rubber-based adhesive needs to be applied to both substrates to be bonded. After the solvent type rubber adhesive is applied to the base material, it is necessary to separately provide a drying step before the bonding. An organic solvent is used for the solvent-type rubber-based adhesive, and the organic solvent is vaporized and released into the atmosphere during the drying, which adversely affects the human body and the global environment.

When a solvent-type rubber-based adhesive is applied using a spray, it takes time and effort to remove the solvent-based rubber-based adhesive that has been oversprayed on a portion that does not need to be applied, resulting in work efficiency. descend. When a solvent type thermoplastic rubber adhesive is used, the heat resistance is not sufficient. In order to solve such a problem, it has been studied to use a reactive hot melt adhesive instead of the solvent type rubber adhesive. The advantages of reactive hot-melt adhesives are that they have excellent heat resistance after curing, they easily melt when heated and have high coatability, the initial strength of the adhesive is high, and they can be bonded by single-sided coating. And so on.

When such a reactive hot-melt adhesive is used, the reactive hot-melt adhesive can be applied to only one of the substrates to be bonded in a molten state and then bonded. it can. Since the cross-linked structure is formed by the progress of the curing reaction after coating, the heat resistance becomes good. Further, since the reactive hot melt adhesive does not contain an organic solvent, the solvent does not adversely affect the environment and the workability is good.

[0006]

When the adhesive is a urethane-based reactive hot melt adhesive, the above-mentioned curing reaction is caused by the isocyanate contained in the urethane prepolymer in the air and the water contained in the substrate and the adhesive. By the reaction with the group, the molecular weight is increased with the generation of carbon dioxide, and the reaction further proceeds to crosslink and cure.

When a usual urethane reactive hot melt adhesive is applied to a base material and bonded together, carbon dioxide is unavoidable due to the above reaction. At that time, if both the base materials are gas impermeable, the generated carbon dioxide does not escape to the outside, so that the carbon dioxide is concentrated and collected in a part of the adhesive layer between the bonding surfaces. Therefore, there is a problem that blisters occur on the bonded product, and the appearance and quality are deteriorated.

The present invention solves the above-mentioned problems, and a method for laminating a gas-impermeable material that does not cause blister even when laminating materials having no gas permeability, and a reactive hot melt adhesive used therefor. It is an object to provide an agent.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors have found that the cause of blisters is the production of carbon dioxide, and the reaction type of crosslinking and hardening without the production of carbon dioxide. Focusing on hot melt adhesives, research has been advanced to complete the present invention. The present invention is the first
In the method of laminating both the gas impermeable first material and the second material with a reactive hot melt adhesive, a reactive hot melt adhesive having an alkoxysilyl group is used as the reactive hot melt adhesive. A method for laminating a gas impermeable material, which is characterized by being used.

Secondly, the present invention provides the above gas-impermeable material containing a urethane prepolymer having an alkoxysilyl group obtained by reacting a urethane prepolymer having an isocyanate group at the terminal with an amino group-containing silane coupling agent. Provided is a reactive hot melt adhesive used in a method for laminating materials. The gas impermeable material of the present invention is a material having no gas permeability such as plastic, metal, glass, or the like which has no or very low ability to permeate or absorb gas. The shape is not particularly limited, but is sheet-like or plate-like, for example.

The combination of the first material and the second material is
Although not particularly limited, for example, it is a combination of a resin decorative plate and a metal plate used for manufacturing a top plate such as a desk or a table. The first material is a resin decorative board, the second is
A combination in which the material is a metal plate is preferable, and among them, a melamine decorative plate is preferable as the resin decorative plate. The reactive hot melt adhesive used in the method for adhering a gas impermeable material of the present invention is not limited as long as it is a reactive hot melt adhesive having an alkoxysilyl group. Of these, a reactive hot melt adhesive containing a urethane prepolymer having an alkoxysilyl group is particularly preferable. As the urethane prepolymer having an alkoxysilyl group,
For example, there are the following items.

Urethane prepolymer having alkoxysilyl group obtained by reaction of urethane prepolymer having isocyanate group and arylamino group-containing silane coupling agent Urethane prepolymer having isocyanate group and silane coupling agent containing alkylamino group The urethane prepolymer having an alkoxysilyl group obtained by the reaction of a urethane prepolymer having an alkoxysilyl group obtained by the reaction of a urethane prepolymer having an isocyanate group and a mercapto group-containing silane coupling agent with a urethane prepolymer having an isocyanate group Urethane prepolymer having alkoxysilyl group obtained by reaction with epoxy group-containing silane coupling agent Urethane prepolymer having hydroxyl group and isocyanate group-containing sila Urethane Prepolymer Having Alkoxysilyl Group Obtained by Reaction With Coupling Agent Urethane prepolymer having isocyanate group or urethane prepolymer having hydroxyl group used in the above (hereinafter, referred to as “urethane prepolymer having isocyanate group or The "urethane prepolymer having a hydroxyl group" may be referred to as "isocyanate group / urethane prepolymer having a hydroxyl group") is preferably obtained by reacting an organic isocyanate compound with a polyol.

Here, when the equivalent ratio (NCO / OH) represented by the ratio of the number of hydroxyl groups in the polyol to the number of isocyanate groups in the organic isocyanate compound is larger than 1, the urethane prepolymer has isocyanate groups. On the contrary, when the equivalent ratio (NCO / OH) is smaller than 1, the urethane prepolymer has a hydroxyl group. In the urethane prepolymer having an isocyanate group, the equivalent ratio (N
If the value of (CO / OH) is larger than 1, there is no particular limitation, but the equivalent ratio (NCO / OH) is used because the coating becomes easy when finished as a reactive hot melt adhesive.
Is preferably 1.2 to 2.2. For urethane prepolymers having hydroxyl groups, the equivalent ratio (NCO / OH)
If it is a value smaller than 1, there is no particular limitation, but for the same reason as above, the equivalent ratio (NCO / OH) is 0.86 to
It is preferably 0.40.

In the above case, the hydroxyl group-containing
Instead of the retan prepolymer, leave the polyol as it is
It can also be used. The above organic isocyanate compound
Has two or more isocyanate groups in the molecule
There is no particular limitation as long as it is
Diisocyanate (TDI), 4,4'-diphenylme
Tandiisocyanate (MDI), polymethylene polyph
Phenyl polyisocyanate (Polymeric MDI),
1,4'-phenylene diisocyanate (PPDI),
Tetramethyl xylene diisocyanate (TMXD
I), 4,4'-dicyclohexylmethane diisocyanate
Heart (H ₁₂MDI), cyclohexane diisocyanate
(CHDI), 1,6-hexamethylene diisocyanate
(HMDI), isophorone diisocyanate (IPD
I) and the like.

The above-mentioned polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule. As the polyol, crystalline polyester polyol, non-crystalline polyester polyol, polyether polyol, olefin-based polyol and the like are preferable. Examples of the crystalline polyester polyol include dicarboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and ethylene glycol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,9
-It is obtained by reacting with a glycol such as nonanediol. Among these, for example, those having a long carbon chain in the skeleton, such as polyester polyols obtained by reacting 1,6-hexanediol with sebacic acid and 1,9-nonanediol with adipic acid (specifically, Is preferably 13 or more) because the crystallization of the reactive hot melt adhesive is quick and a good initial cohesive force can be obtained.

Examples of the above-mentioned non-crystalline polyester polyols include dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and propylene glycol, 1,3.
-Butanediol, neopentyl glycol, diethylene glycol, 3-methyl-1,5-pentanediol, bis (hydroxyethyl) benzene and the like. At this time, as the dicarboxylic acid component, a polymerized rosin which is a resin dimer obtained by dimerizing a resin acid monomer containing an abietic acid monomer as a main component can also be used. Of these, it is particularly preferable to use one having a rosin component in the skeleton because the reactive hot melt adhesive has a low viscosity and a high initial cohesive force.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Examples of the olefin polyol include polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene polyol and the like. The urethane prepolymer having an isocyanate group / a hydroxyl group can be obtained, for example, by reacting the above organic isocyanate compound with a polyol. Any one of the above crystalline polyester polyol, non-crystalline polyester polyol, polyether polyol or olefinic polyol is reacted to obtain a crystalline urethane prepolymer or non-crystalline urethane prepolymer,
They may be used alone or in combination in each of the reactions. Further, the above crystalline polyester polyol, non-crystalline polyester polyol, polyether polyol, and olefinic polyol may be mixed in advance and reacted. The urethane prepolymer obtained thereby can also be used in the reaction of. The urethane prepolymer preferably contains at least one selected from a crystalline urethane prepolymer and an amorphous urethane prepolymer.

The urethane prepolymer having an isocyanate group / a hydroxyl group may be further combined with a thermoplastic polymer. As the thermoplastic polymer, ethylene-vinyl acetate copolymer (EVA), styrene-butadiene-
Styrene copolymer (SBS), styrene-isoprene-
Styrene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS),
Examples include α-olefin-based copolymers, atactic polypropylene (APP), polyethylene, saturated polyester resins, polyurethane resins and the like. The molecular weight of these thermoplastic polymers is preferably 10,000 to 400,000.

There is no limitation on the blending ratio of the crystalline urethane prepolymer and the amorphous urethane prepolymer in the urethane prepolymer having an isocyanate group / hydroxyl group, and any blending ratio can be used. For example, in the case of comprising a crystalline urethane prepolymer, a non-crystalline urethane prepolymer and a thermoplastic polymer, the crystalline urethane prepolymer 5 to 6 is contained in 100 parts by weight of the above three components.
Those composed of 0 parts by weight, 30 to 85 parts by weight of the non-crystalline urethane prepolymer and 10 to 30 parts by weight of the thermoplastic polymer can be preferably used.

The arylamino group-containing silane coupling agent used in the above is not particularly limited as long as it has at least one arylamino group in the molecule of the silane coupling agent. There is an arylamino group-containing silane coupling agent represented by 1.

[0021]

[Chemical 2]

(Wherein Ar is an aryl group having 6 to 10 carbon atoms, R ¹ is a divalent organic group having 1 to 10 carbon atoms, and R ^{2 is}
And R ³ are alkyl groups having 1 to 5 carbon atoms, and n is an integer of 0 to 3. As the amino group-containing silane coupling agent represented by the formula 1, for example, γ- (N-phenylamino) propyltrimethoxysilane, γ- (N-phenylamino) propyltriethoxysilane, γ- (N-phenyl amino)
Propylmethyldimethoxysilane, γ- (N-phenylamino) propylmethyldiethoxysilane, γ- (N-
Phenylamino) propylethyldimethoxysilane, γ
-(N-phenylamino) propylethyldiethoxysilane, γ- (N-phenylamino) ethyltrimethoxysilane, γ- (N-phenylamino) ethyltriethoxysilane, γ- (N-phenylamino) ethylmethyldimethoxy Examples thereof include silane, γ- (N-phenylamino) ethylmethyldiethoxysilane, γ- (N-phenylamino) ethylethyldimethoxysilane and γ- (N-phenylamino) ethylethyldiethoxysilane.

The alkylamino group-containing silane coupling agent used above is not particularly limited as long as it has one or more alkylamino groups in the molecule of the silane coupling agent, and for example, γ-amino. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, N-aminoethylaminopropyltrimethoxysilane, N-aminoethylaminopropylmethyldimethoxysilane, 1,3- Diaminoisopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, β-aminoethylmethyldimethoxysilane, β- Aminoethylmethyldiethoxysilane, β-aminoethylethyldimethoxysilane, β-aminoethylethyldiethoxysilane,
δ-aminobutyltrimethoxysilane, δ-aminobutylmethyldimethoxysilane, bis (trimethoxysilylpropyl) amine and the like can be mentioned.

The mercapto group-containing silane coupling agent used above is not particularly limited as long as it has at least one mercapto group in the molecule of the silane coupling agent, and for example, γ-mercaptopropyltriene. Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
γ-mercaptopropylethyldimethoxysilane, γ-
Mercaptopropylethyldiethoxysilane, β-mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, β-mercaptoethylmethyldimethoxysilane, β-mercaptoethylmethyldiethoxysilane, β-mercaptoethylethyldimethoxysilane, β- Mercaptoethylethyldiethoxysilane, δ
-Mercaptobutyltrimethoxysilane, δ-mercaptobutylmethyldimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane and the like. .

The epoxy group-containing silane coupling agent used in the above is not particularly limited as long as it has one or more epoxy groups in the molecule of the silane coupling agent. For example, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid Examples include xypropylethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

The isocyanate group-containing silane coupling agent used in the above is not particularly limited as long as it has at least one isocyanate group in the molecule of the silane coupling agent. Examples thereof include methoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, and γ-isocyanatopropylethyldiethoxysilane.

The reactive hot-melt adhesive used in the method for laminating a gas-impermeable material of the present invention includes the ease of reaction between a urethane prepolymer having an isocyanate group / hydroxyl group and a silane coupling agent, and a silane cup. A reactive hot melt adhesive containing the above-mentioned urethane prepolymer having an alkoxysilyl group is preferable from the viewpoint of easy handling of the ring agent. Among them, the use of the arylamino group-containing silane coupling agent having the structure represented by the above formula 1 is more preferable because it has the following advantages (1) to (5).

(1) Due to the steric hindrance and electron withdrawing effect of the aryl group bonded to the amino group, the amino group and the isocyanate group can react under mild conditions without causing gelation. (2) The heat resistance is excellent because the aryl group is bonded to the amino group. (3) The storage stability of the silane coupling agent is also good.

(4) When reacted with a urethane prepolymer having an isocyanate group, there is no problem with odor when applied as an adhesive. (5) Good compatibility with polyols containing aromatics, urethane prepolymers, and thermoplastic elastomers. The reactive hot melt adhesive used in the laminating method of the present invention is not particularly limited as to the kind and content of components other than the urethane prepolymer having the alkoxysilyl group as the main component, but various Copolymers, thermoplastic elastomers, inorganic or organic fillers, color pigments, plasticizers, tackifiers, waxes, curing catalysts, antioxidants,
Antioxidants, ultraviolet absorbers, flame retardants, fungicides, silane compounds and the like can be added as appropriate.

If the reactive hot-melt adhesive used in the present invention contains an isocyanate group, it causes blisters when laminating the gas-impermeable material, so that the content thereof should be lowered. good. For example, the isocyanate group content is preferably less than 0.5% by weight, and more preferably the isocyanate group content is not contained. The application amount of the reactive hot melt adhesive used in the present invention may be appropriately set in consideration of ensuring the adhesive strength. Generally, from the viewpoint of economy, it is desired that the coating amount be as small as possible,
Due to the unevenness of the material and the accuracy of the applicator, a small coating amount causes problems during coating. In order to avoid the above-mentioned problems, and from the balance of securing strength and economic efficiency,
The coating amount of the reactive hot melt adhesive is 50 to 300 g
/ M ² is preferable.

In the method for laminating a gas impermeable material of the present invention, the reactive hot melt adhesive may be applied to either the gas impermeable first material or the second material. Also, there is no need to separately provide a drying step after coating,
Workability is also good because the other material can be pasted and pressed immediately after application.

[0032]

In the present invention, both the gas-impermeable first material and the second material are used.
In a method of laminating a material with a reactive hot melt adhesive, a reactive hot melt adhesive having an alkoxysilyl group is used as the reactive hot melt adhesive. We offer a method. Since the urethane prepolymer in a normal reactive hot melt adhesive has an isocyanate group,
When this reacts with water in the air or the water contained in the material, it becomes a polymer with the formation of carbon dioxide, and the reaction further progresses to crosslink and harden. Also, stop the production of carbon dioxide from the reaction mechanism. Was impossible. On the other hand, in the method for laminating a gas impermeable material of the present invention, as described above, when a reaction type hot melt adhesive containing a urethane prepolymer having an alkoxysilyl group is used, a siloxane bond is introduced. Since the polymer is polymerized and the reaction progresses to crosslink and cure, carbon dioxide is not generated in the crosslink and cure reaction.

The present invention also relates to the reaction used in the above-mentioned laminating method containing a urethane prepolymer having an alkoxysilyl group obtained by reacting a urethane prepolymer having an isocyanate group with an amino group-containing silane coupling agent. Type hot melt adhesive. In particular,
When the compound represented by the formula 1 is used as the amino group-containing silane coupling agent, the amino group can be treated under mild conditions without causing gelation due to the effect of steric hindrance and electron withdrawing property by the aryl group bonded to the amino group. And an isocyanate group can react with each other, and the aryl group is bonded to the amino group, resulting in excellent heat resistance.

[0034]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. (Example 1) 15 parts by weight of a crystalline polyester diol (molecular weight: 3500, hydroxyl value: 30.5) obtained by reacting 1,6-hexanediol and sebacic acid, and Niprolane as an amorphous polyester polyol. 4032
(Nippon Polyurethane Co., molecular weight: 2500, hydroxyl value:
60.8) 60 parts by weight and 25 parts by weight of Hardec A-3200 (thermoplastic polyester polymer manufactured by Asahi Kasei Corporation) as a thermoplastic elastomer, a stirrer,
The mixture was placed in a flask equipped with a thermometer, a nitrogen inlet and a pressure reducing port, melt-mixed, and dried under reduced pressure at 105 ° C. for 3 hours.

Next, nitrogen was gradually introduced into the flask to return the inside of the flask to normal pressure, and at about 80 ° C., 18.3 parts by weight of diphenylmethane diisocyanate (MDI) was added, and 90
The reaction was performed at 3 ° C. for 3 hours to obtain a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group. The isocyanate group content in the above reactive hot melt adhesive was 2.6%, and the viscosity was 30,000 at 120 ° C.
It was 00 cps.

1,000 g of a reactive hot melt adhesive containing the urethane prepolymer having an isocyanate group synthesized above and 158 g of γ- (N-phenylamino) propyltrimethoxysilane as an arylamino group-containing silane coupling agent. Mix and 100 under nitrogen atmosphere
Reactive hot melt adhesive X containing a urethane prepolymer having an alkoxysilyl group by reacting at 1 ° C for 1 hour
-201 was obtained. No isocyanate group was detected in this X-201. The viscosity was also measured.

On the entire back surface of a 0.8 mm × 300 mm × 700 mm melamine decorative board, the X-201 obtained above was heated to 120 ° C. with a roll coater to melt it.
It is applied at a rate of 50 g / m ² , and a 1.2 mm x 300 mm x 700 mm size galvanized steel plate (bonded steel plate) is aligned and superposed on this adhesive-coated surface, 2 kg.
It was crimped at a pressure of / cm ² . The time from application to pressure bonding was 60 seconds, and the workability was good. 20-2
The reactive hot melt adhesive was left to stand in an atmosphere of 3 ° C. and 50 to 60% RH for 1 week to be moisture-cured. The top plate of the obtained melamine decorative plate / galvanized steel plate was examined for the presence or absence of blisters by touch with fingers and visually, but no blisters were found. The adhesive strength was also good. The results are shown in Table 1.

Example 2 In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group was mixed with 134 g of γ- (N-phenylamino) propyltrimethoxysilane. Then, the reaction was performed under a nitrogen atmosphere at 100 ° C. for 1 hour to obtain a reactive hot melt adhesive X-202 containing a urethane prepolymer having an alkoxysilyl group.

The isocyanate group content in the above reactive hot melt adhesive was 0.35%. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1. (Example 3) In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group and γ-aminopropyltriethoxysilane (KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
37 g were mixed and reacted at 80 ° C. for 1 hour under a nitrogen atmosphere to obtain a reactive hot melt adhesive X-203 containing a urethane prepolymer having an alkoxysilyl group.

No isocyanate group was detected in the reactive hot melt adhesive. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1. (Example 4) In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group and γ-mercaptopropyltrimethoxysilane (Toshiba Silicone as a silane coupling agent containing a mercapto group). Co., Ltd., TSL8380) 1
21 g were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere to obtain a reactive hot melt adhesive X-204 containing a urethane prepolymer having an alkoxysilyl group.

No isocyanate group was detected in the above reactive hot melt adhesive. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1. (Example 5) In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group and γ-glycidoxypropyltrimethoxysilane as an epoxy group-containing silane coupling agent. (Nippon Unicar Co., Ltd., A-187) 14
The reaction type hot melt adhesive X-205 containing a urethane prepolymer having an alkoxysilyl group was prepared by mixing 6.5 g, further adding a catalytic amount of ammonium bromide, and reacting at 140 ° C. for 3 hours in a nitrogen atmosphere. Was obtained.

No isocyanate group was detected in the above reactive hot melt adhesive. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1. (Example 6) In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group and 1,4-butanediol (B
118.7 g (manufactured by ASF Co., Ltd.) are mixed and the mixture is mixed in a nitrogen atmosphere at
The reaction was carried out at 0 ° C for 1 hour, and γ-isocyanatopropyltriethoxysilane (manufactured by Nippon Unicar Co., Ltd., Y-
9030) 152.5 g are mixed, and 100
Reactive hot melt adhesive X containing a urethane prepolymer having an alkoxysilyl group by reacting at 1 ° C for 1 hour
-206 was obtained.

No isocyanate group was detected in the above reactive hot melt adhesive. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1. (Comparative Example 1) A reactive hot melt adhesive containing a urethane prepolymer having an alkoxysilyl group was used in Example 1 as "ARX-1217" manufactured by Nitta Gelatin Co., Ltd. (isocyanate group content: 2.55% by weight). ),
Similarly to Example 1, the presence or absence of blisters and the adhesive strength of the top plate obtained by adhering the melamine decorative plate and the galvanized steel plate were examined.

Comparative Example 2 In the same manner as in Example 1, 1,000 g of a reactive hot melt adhesive containing a urethane prepolymer having an isocyanate group and 60.7 g of γ- (N-phenylamino) propyltrimethoxysilane. Were mixed and reacted for 1 hour at 100 ° C. under a nitrogen atmosphere to obtain a reactive hot melt adhesive X-207 containing a urethane prepolymer having an alkoxysilyl group.

The isocyanate group in the above reactive hot melt adhesive was 0.94%. Furthermore, the same evaluation as in Example 1 was performed, and the results are shown in Table 1.

[0046]

[Table 1]

Examples 1-6 and Comparative Examples 1-2 above
Then, the presence or absence of blisters on the top plate obtained by adhesion was evaluated as ◯ for no blisters, Δ for wavy lines, and x for blisters.
Further, the adhesive strength is the surface tensile strength of the top plate obtained by bonding at room temperature, the Shimadzu Universal Tensile Testing Machine Autograph AG-2000E (Crosshead speed: 50 mm /
Minutes). Furthermore, the value measured at 80 ° C. was defined as the heat resistant adhesive strength. The viscosity of the adhesive is Brookfi
It measured at 120 degreeC using the eld type | mold Thermsel system viscometer.

As shown in Table 1, in the examples, no blisters were generated and the adhesive strength was good, whereas in the comparative examples blisters were generated or the strength was low.

[0049]

The method for laminating a gas-impermeable material using the reactive hot-melt adhesive of the present invention uses a reactive hot-melt adhesive having an alkoxysilyl group, so that a siloxane bond is formed by a reaction with water. To generate. Since the polymer is polymerized through this siloxane bond, and further the reaction proceeds to crosslink and cure, carbon dioxide is not generated in this crosslink curing reaction, and blisters due to the generation of gas do not occur. It is possible to prevent deterioration of appearance and quality.

A reactive hot melt adhesive containing a urethane prepolymer having an alkoxysilyl group, which is obtained by reacting a urethane prepolymer having an isocyanate group with a silane coupling agent having an amino group, is one of the above gas impermeable materials. It is used in a laminating method, has excellent stability and handleability, does not cause blistering due to gas generation during the crosslinking and curing process, and can prevent deterioration of the appearance and quality of the laminated product. Here, when the amino group-containing silane coupling agent is represented by Formula 1, gelation can be prevented and the amino group and the isocyanate group can react under mild conditions. Further, since the aryl group is directly bonded to the amino group, it has excellent heat resistance.

In the laminating method of the present invention, since a reactive hot melt adhesive is used, a crosslinked structure is formed due to the progress of the curing reaction after coating, and the heat resistance becomes good. When using a reactive hot melt adhesive, unlike solvent-based rubber adhesives, it is not necessary to coat both sides, and since it does not contain an organic solvent, there is no adverse effect on the environment due to the solvent and workability is also excellent. There is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display area C09J 175/04 JFA // B29L 9:00 (72) Inventor Kazuaki Nakamura Futamata 2-chome, Yao City, Osaka No. 22 Nitta Zelatin Co., Ltd. Osaka factory

Claims (6)

[Claims] 1. A method of laminating a gas-impermeable first material and a second material with a reactive hot melt adhesive, wherein the reactive hot melt adhesive has an alkoxysilyl group as a reactive hot melt. A method for laminating a gas impermeable material, which comprises using an adhesive. 2. The method for laminating a gas impermeable material according to claim 1, wherein the first material is a resin decorative plate and the second material is a metal plate. 3. The laminating method according to claim 1, comprising a urethane prepolymer having an alkoxysilyl group obtained by reacting a urethane prepolymer having an isocyanate group with an amino group-containing silane coupling agent. Reactive hot melt adhesive. 4. The reactive hot melt adhesive according to claim 3, wherein the urethane prepolymer having an isocyanate group contains at least one selected from a crystalline urethane prepolymer and an amorphous urethane prepolymer. 5. The urethane prepolymer having an isocyanate group is further combined with a thermoplastic polymer to form a crystalline urethane prepolymer in a total amount of 100 parts by weight of the crystalline urethane prepolymer, the amorphous urethane prepolymer and the thermoplastic polymer. The reactive hot melt adhesive according to claim 4, which comprises 5 to 60 parts by weight of the polymer, 30 to 85 parts by weight of the non-crystalline urethane prepolymer and 10 to 30 parts by weight of the thermoplastic polymer. 6. The reactive hot melt adhesive according to claim 3, wherein the amino group-containing silane coupling agent is represented by Formula 1. [Chemical 1] (However, in the formula, Ar represents an aryl group having 6 to 10 carbon atoms, R
¹ is a divalent organic group having 1 to 10 carbon atoms, R ² and R ³ are alkyl groups having 1 to 5 carbon atoms, and n is an integer of 0 to 3. )