JP2001098228A - Method for bonding non-moisture-permeable members and lamination-bonded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for bonding non-moisture-permeable members, suited for obtaining a lamination-bonded product that does not need a long curing time, develops early excellent adhesiveness and heat resistance, and does not suffer blisters due to bubbles otherwise formed on the surface of the constituent non-moisture- permeable member and to provide a lamination-bonded product composed of non- moisture-permeable members bonded to each other by the method. SOLUTION: This method for bonding non-moisture-permeable members 1 and 1' to each other with a moisture-curing adhesive 4, comprises previously forming a pressure-sensitive-adhesive layer 2 backed with a mold release layer on part of the bonding surface of one of the members 1 and 1', applying the adhesive 4 to the bonding surface, peeling and removing the mold release layer from the layer 2, and lamination-bonding the layer 2 being in an exposed state to the other member 1' and a lamination-bonded product of non-moisture-permeable members 1 and 1', wherein a hardenable pressure-sensitive adhesive layer being a mixture of a moisture-curing adhesive layer 4 with a pressure-sensitive adhesive layer 2 formed so that its end is exposed to the end of the layer 4 is sandwiched between non-moisture-permeable members 1 and 1'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for bonding a moisture-impermeable member and a laminated body of the moisture-impermeable members bonded by the bonding method.

[0002]

2. Description of the Related Art Conventionally, when moisture-impermeable members are adhered to each other with a moisture-curable adhesive, a portion of the adhesive layer that comes into contact with moisture, such as an adhesive layer at the end of an adhesive body, is used. Although the moisture curing reaction proceeds promptly, the moisture does not enter the adhesive layer such as the adhesive layer near (inside) the center of the adhesive body in a short time, so that the moisture curing reaction is not sufficiently performed. If it does not progress and curing is insufficient, insufficient adhesive strength or poor heat resistance may occur, or bubbles mixed in the adhesive at the time of application or bubbles generated during the moisture curing reaction will form bubbles,
There are problems such as partial swelling of the surface of the impermeable member.

[0003] As an adhesion method using a moisture-curable adhesive, for example, Japanese Patent Publication No. 6-22956 discloses a method for manufacturing a sandwich structure panel in which a honeycomb core is used as a core material and a surface plate is adhered to the upper and lower surfaces thereof. A method of manufacturing a honeycomb sandwich structure panel, characterized in that a non-adhesive moisture-curable urethane-based hot-melt adhesive at room temperature is used as an adhesive and bonded by a hot press. "
Is disclosed.

[0004] However, for example, when a normal door panel is manufactured by the bonding method as disclosed in the above disclosure, the reinforcing portion of the frame material (normally a pentite steel plate) constituting the door frame and the face material constituting the surface decorative surface of the door are formed. Since both are moisture-impermeable members, even after curing for 3 days at room temperature after bonding, there is a problem that the inside of the adhesive layer remains uncured, and no adhesive strength or heat resistance is exhibited. is there.

[0005] As means for solving such problems,
A method that does not use an adhesive for bonding non-moisture-permeable members or a method that quickly cures a moisture-curable adhesive by minimizing the bonding area (application area of the adhesive) may be adopted. .

However, in the case of the latter method, an ordinary application device such as a roll coater or a spray generally used in the manufacture of a door panel strictly controls the adhesive application area and application pattern, and has a sufficient effect. There is a problem that it is quite difficult to develop adhesive strength and heat resistance.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems without requiring a long curing time.
A method for bonding a moisture-impermeable member suitable for obtaining a laminated adhesive body that expresses excellent adhesive strength and heat resistance at an early stage, and does not generate blisters due to bubbles on the surface of the moisture-permeable member, and
It is an object of the present invention to provide a laminated adhesive body of non-moisture permeable members bonded by the bonding method.

[0008]

According to a first aspect of the present invention, there is provided a method of bonding a moisture-impermeable member, wherein the moisture-impermeable members are bonded to each other with a moisture-curable adhesive. After forming a pressure-sensitive adhesive layer having a release material layer on the back surface on a part of the adhesive surface of the wet member, and then applying a moisture-curable adhesive to the adhesive surface, peeling off the release material layer of the pressure-sensitive adhesive layer And the other non-permeable member is laminated and adhered in a state where the pressure-sensitive adhesive layer is exposed.

According to a second aspect of the present invention, there is provided a method of bonding a moisture-impermeable member according to the first aspect, wherein the pressure-sensitive adhesive layer comprises a moisture-permeable adhesive or a water-containing adhesive. Alternatively, it is characterized by comprising a pressure-sensitive adhesive in which a moisture-permeable material or a water-containing material is laminated or contained.

According to a third aspect of the present invention, there is provided a method of bonding a moisture-impermeable member according to any one of the first and second aspects. In addition, the pressure-sensitive adhesive layer is formed such that an end of the pressure-sensitive adhesive layer is an end of the bonding surface.

According to a fourth aspect of the present invention, there is provided a laminated adhesive body between the non-moisture-permeable members, wherein the moisture-curable adhesive layer and the end are exposed at the end of the adhesive layer between the non-permeable members. Characterized in that a pressure-sensitive adhesive layer comprising a mixture of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer formed thereon is sandwiched.

The non-permeable member referred to in the present invention is ASTM.
The water vapor transmission rate measured according to -E96 is 100 g /
24 hours · m ² · atm or less means, for example,
Examples thereof include metal, glass, and a thermoplastic resin or a thermosetting resin whose surface is subjected to a waterproof treatment. In these non-moisture permeable members, the entire bonding surface may be non-moisture permeable, or a part of the bonding surface may be non-moisture permeable.

The moisture-curable adhesive used in the present invention is not particularly limited, and any adhesive can be used as long as it can cure by causing a moisture-curing reaction at room temperature. However, for example, a moisture-curable urethane-based adhesive containing a urethane prepolymer having isocyanate groups at both molecular terminals as a main component, or a polyoxyalkylene as a main chain, and a hydrolyzable silyl crosslinkable to at least one molecular terminal. A moisture-cured modified silicone-based adhesive mainly composed of a polymer having a group can be used, and is preferably used. These moisture-curable adhesives may be used alone or in combination of two or more in some cases.

These moisture-curable adhesives may be liquid at room temperature, semi-solid or solid. The moisture-curable adhesive liquid at room temperature can be applied and used as it is. Also, a semi-solid or solid moisture-curable adhesive at normal temperature is applied in a hot-melt state by heating, or used, for example, toluene, acetone,
It can be applied and used as a solvent-type adhesive dissolved in an organic solvent such as cyclohexane and dichloromethane.

The moisture-curable adhesive used in the present invention includes a tackifying resin for improving tackiness and adhesiveness, if necessary, as long as the achievement of the object of the present invention is not hindered, and an initial cohesive strength. Of waxes such as thermoplastic resins, paraffin wax and microcrystalline wax, inorganic fillers, organic fillers, thixotropic agents, softeners, plasticizers, surfactants, silane coupling agents, etc. Curing agents such as tertiary amines and organometallic compounds, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers,
One or more of various additives such as a coloring agent, a flame retardant, and an antistatic agent may be added.

Examples of the tackifier resin that may be added include rosin resins, terpene resins, aliphatic petroleum resins, and aromatic petroleum resins. These tackifying resins may be used alone or in combination of two or more.

The tackifying resin is not particularly limited, but preferably has a ring and ball softening point of 90 to 150 ° C.

The amount of the tackifying resin to be added is not particularly limited, but may be, for example, 100 parts by weight of the main component of a moisture-curable adhesive such as the urethane prepolymer or modified silicone polymer. And 0 to 200 parts by weight of a tackifier resin. The amount of the tackifying resin added is 20 per 100 parts by weight of the main component of the moisture-curable adhesive.
If the amount exceeds 0 parts by weight, heat resistance at high temperatures decreases,
May be brittle at low temperatures.

As the thermoplastic resin which may be added,
For example, an ethylene-vinyl monomer copolymer having a melt index (MI) of 100 or more can be used. Specific examples of the ethylene-vinyl monomer copolymer include, for example, ethylene-vinyl acetate copolymer (EVA) and ethylene-vinyl acetate such as ethylene-n-butyl acrylate.
Acrylic acid alkyl ester copolymers, ethylene-methacrylic acid copolymers and the like can be mentioned. These ethylene-
The vinyl monomer copolymer may be used alone or in combination of two or more.

The method for forming the pressure-sensitive adhesive layer in the present invention includes a method using a so-called double-sided pressure-sensitive adhesive tape, a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, and a light-curing pressure-sensitive adhesive. The adhesive is applied to a predetermined area of the moisture-impermeable member in a predetermined area and, if necessary, dried, cooled, and irradiated with light to form an adhesive layer. And a method of using a double-sided pressure-sensitive adhesive tape which is excellent in handleability and workability.

The double-sided pressure-sensitive adhesive tape may be a support-type double-sided pressure-sensitive adhesive tape comprising a release material layer / a pressure-sensitive adhesive layer / a support layer / a pressure-sensitive adhesive layer / a release material layer, or a release material layer / a pressure-sensitive adhesive layer / A non-support type double-sided pressure-sensitive adhesive tape composed of a release material layer may be used.

Examples of the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer include various pressure-sensitive adhesives generally used as pressure-sensitive adhesives for pressure-sensitive adhesive tapes such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Can be The form of the pressure-sensitive adhesive may be any form such as a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, and a light-curable pressure-sensitive adhesive.

Further, as the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer,
Using a moisture-permeable adhesive or a water-containing adhesive, or
It is preferable to use a pressure-sensitive adhesive in which a moisture-permeable material or a water-containing material is laminated or contained, since the curing of the moisture-curable adhesive applied near the center (inside) of the bonding surface is promoted.

Examples of the release material for forming the release material layer include various release materials generally used as release materials for adhesive tapes such as release paper and release films.

Examples of the support for forming the support layer include various supports generally used as a support for an adhesive tape such as paper, cloth, nonwoven fabric, cellophane, plastic film, plastic foam, and metal foil. Body.

Next, a method for bonding a moisture-impermeable member according to the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing a moisture-impermeable member having an adhesive layer formed thereon, and FIG. 2 is a perspective view showing an example of forming an adhesive layer on the moisture-impermeable member.

In the bonding method of the present invention, first, FIG.
As shown in FIG. 2, a pressure-sensitive adhesive layer 2 having a release material layer on the back surface at a part of the bonding surface of at least one of the moisture-impermeable members 1
Is formed. When the pressure-sensitive adhesive layer 2 is a double-sided pressure-sensitive adhesive tape, the release material layer on one side of the double-sided pressure-sensitive adhesive tape is peeled off and removed, and the exposed pressure-sensitive adhesive surface is fixed at a predetermined position on the moisture-impermeable member 1. It should just be pasted by area. Impermeable member 1
The form in which the pressure-sensitive adhesive layer 2 is formed is not particularly limited. As shown in FIGS. 1 and 2, the pressure-sensitive adhesive layer 2 may be formed over almost the entire area near the center of the bonding surface. Although it may be formed partially near the end or at the end,
In the present invention, since the portion where the pressure-sensitive adhesive layer 2 is formed is intended to be a path for moisture, the pressure-sensitive adhesive layer 2
Is preferably formed so that the end of the adhesive layer becomes the end of the bonding surface of the moisture-impermeable member 1, and the pressure-sensitive adhesive layer 2 communicates with any two ends of the bonding surface. Further, when the non-moisture permeable members 1 are bonded together by pressing with a roll, any two ends of the bonding surface become ends of the pressure-sensitive adhesive layer 2 and intersect with the axial direction of the roll. It is preferable to form the pressure-sensitive adhesive layer 2. By adopting such a method, air taken into the bonding surface or the adhesive layer at the time of pressing with a roll is discharged through the pressure-sensitive adhesive layer 2 and no air bubbles remain in the adhesive layer. preferable. Further, it is preferable to provide the adhesive layer 2 with the concave stripe 3 having an arbitrary pattern, since a moisture passage to the vicinity (inside) of the center of the bonding surface can be efficiently formed.

Next, the moisture-curable adhesive is applied to the adhesive surface of the moisture-impermeable member 1 having the adhesive layer 2 formed on a part of the adhesive surface. The method of applying the moisture-curable adhesive is not particularly limited, and for example, using various coating apparatuses such as a flow coater, a roll coater, a spray coating machine, a hand gun, and the like, at room temperature or in a state where the beads are heated and melted, It may be applied in a desired pattern such as shape, surface, spiral, foam and the like. The application of the moisture-curable adhesive may be applied to the entire surface of the adhesive surface or may be applied to a part of the adhesive surface.

Then, the release material layer on the back surface of the pressure-sensitive adhesive layer 2 is peeled off and removed, and the other non-permeable member is laminated and bonded in a state where the pressure-sensitive adhesive layer 2 is exposed. Is completed.

[0030]

According to the bonding method of the present invention, at the time of bonding the non-permeable members using a moisture-curable adhesive, at least one of the non-permeable members has a release material layer on the back surface in part of the bonding surface. After forming a pressure-sensitive adhesive layer, and then applying a moisture-curable adhesive to this bonding surface, the release material layer of the pressure-sensitive adhesive layer is peeled off and removed, and the other non-coated material is left in a state where the pressure-sensitive adhesive layer is exposed. Since the process passes through the step of laminating and adhering the moisture-permeable member, the adhesive was not applied to the portion where the pressure-sensitive adhesive layer was formed before the application of the moisture-curable adhesive. Therefore, the moisture-impermeable members are not bonded to each other in a large area, and the passage of moisture is secured, so that the curing proceeds quickly even in the vicinity (inside) of the center of the bonding surface, resulting in a decrease in bonding strength and poor heat resistance. And no swelling due to air bubbles occurs on the surface of the moisture-impermeable member.
Further, since the area in which the pressure-sensitive adhesive layer is formed can be freely changed, the application area of the moisture-curable adhesive and the area of the portion bonded with the moisture-curable adhesive can be arbitrarily and easily changed.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”. FIG. 3 is a perspective view showing the bonding method of the embodiment.

(Example 1)

(1) Preparation of moisture-curable adhesive Propylene glycol (molecular weight 3000, hydroxyl value 3
7) 1000 parts were heated and melted at 120 ° C. in a separable flask, and dehydrated under a reduced pressure of 700 mmHg for 1 hour. Then, after controlling the temperature of the melt to 100 ° C., diphenylmethane diisocyanate @ MDI (trade name “I
sonate125M ”, manufactured by Mitsubishi Kasei Dow)
And an amine catalyst (trade name "U-CAT2046", manufactured by Sun Apro Co., Ltd.)
The mixture was charged and reacted for 3 hours to prepare a moisture-curable urethane-based adhesive (A) which was liquid at room temperature. The isocyanate group (NC) of the obtained moisture-curable urethane-based adhesive (A)
The O) / hydroxyl (OH) ratio was 5.0.

(2) Preparation of Laminated Adhesive Body Width 25 mm and length 150 m used as a moisture-impermeable member
m, one pentite steel sheet 1 having a thickness of 0.8 mm
A 0 mm double-sided pressure-sensitive adhesive tape was adhered after removing the release material layer on the application surface, as shown in FIG. 3, to form an adhesive layer 2 having a release material layer on the back surface. Next, using the roll coater 5, the moisture-curable urethane-based adhesive (A) 4 supplied from the adhesive supply tank 6 was applied at a coating amount of 300 g / m ^2.
After application on one side at room temperature, the release material layer on the back surface of the pressure-sensitive adhesive layer 2 was peeled off and removed, and 20 seconds after application, the other pentite steel plate 1 ′ was laminated. Then, after hot pressing for 3 minutes at a temperature of 80 ° C. and a pressure of 0.1 kg / cm ² ,
The laminate was cold-pressed for 3 minutes at a temperature of 20 ° C. and a pressure of 0.1 kg / cm ² to produce a laminated adhesive.

(3) Evaluation After the laminated adhesive obtained above was cured in an atmosphere of 20 ° C. and 65% RH for 170 hours, T-peel strength (kgf / 25 mm) in an atmosphere of 20 ° C. and 80 ° C. Was measured. In addition, the destruction state was also visually observed. The results were as shown in Table 1.

Example 2 1000 parts of 1,6-hexane adipate (having a hydroxyl value of 43) was heated and melted at 120 ° C. in a separable flask, and 1 part was heated under a reduced pressure of 700 mmHg.
Dehydrated for hours. Then, after controlling the temperature of the melt to 100 ° C., 193 parts of MDI “Isonate 125M” and 10 parts of a moisture-curing promoting catalyst “U-CAT2046” are added, and the mixture is reacted for 3 hours to form a solid moisture-curable urethane at room temperature. A system adhesive (B) was produced. The NCO / OH ratio of the obtained moisture-curable urethane-based adhesive (B) was 2.0.

In the preparation of the laminated adhesive, the moisture-curable urethane-based adhesive (B) was heated and melted at 120 ° C., and the coating temperature was changed to 120 ° C. An adhesive was produced.

(Comparative Example 1) In the production of a laminated adhesive,
A laminated adhesive was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer was not formed on the pentite steel sheet.

Comparative Example 2 In the production of a laminated adhesive,
Moisture-curable urethane-based adhesive (A) using a spray coater without forming an adhesive layer on the pentite steel plate
Was applied in the same manner as in Example 1 except that was applied in a bead form, to produce a laminated adhesive.

Comparative Example 3 In the production of a laminated adhesive,
Moisture-curable urethane-based adhesive (A) using a spray coater without forming an adhesive layer on the pentite steel plate
Was laminated in the same manner as in Example 1 except that was applied spirally.

Comparative Example 4 In the production of the laminated adhesive,
A laminated adhesive was produced in the same manner as in Example 2 except that the pressure-sensitive adhesive layer was not formed on the pentite steel sheet.

Comparative Example 5 In the production of a laminated adhesive,
A moisture-curable urethane-based adhesive (B) that does not form an adhesive layer on a pentite steel sheet and uses a spray coater
Was applied in a bead form, and a laminated adhesive body was produced in the same manner as in Example 2.

Comparative Example 6 In the production of a laminated adhesive,
A moisture-curable urethane-based adhesive (B) that does not form an adhesive layer on a pentite steel sheet and uses a spray coater
Was laminated in the same manner as in Example 2 except that was applied spirally.

The T-peel strength (kgf / 25 mm) of the laminated adhesive obtained in Example 2 and Comparative Examples 1 to 6 was measured in Example 1.
The evaluation was performed in the same manner as in the above case. The results were as shown in Table 1.

[0045]

[Table 1]

As is clear from Table 1, the laminated adhesive bodies of Examples 1 and 2 produced by the bonding method of the present invention exhibited high T-peel strength at both 20 ° C. and 80 ° C. The state of destruction was also good.

On the other hand, the laminated adhesive bodies of Comparative Examples 1 to 3 in which the pressure-sensitive adhesive layer was not previously formed on the surface of the pentite steel plate were
The T-peel strength was low at both 20 ° C. and 80 ° C. as compared to the laminated adhesive of Example 1. Further, since the moisture curing reaction did not proceed to the inside of the adhesive layer, the destruction state was cohesive failure.

Similarly, the laminated adhesive bodies of Comparative Examples 4 to 6 in which the pressure-sensitive adhesive layer was not previously formed on the surface of the pentite steel plate,
The T-peel strength was low at both 20 ° C. and 80 ° C. as compared with the laminated adhesive of Example 2.

[0049]

As described above, according to the bonding method of the present invention, excellent bonding strength and heat resistance can be exhibited at an early stage without requiring a long curing time, and a moisture-impermeable member (adhered material) can be obtained. It is possible to obtain a laminated adhesive body of the non-moisture-permeable members without causing swelling due to bubbles on the surface of the (body). Also,
The laminated adhesive body of the moisture-impermeable members obtained by the above-described bonding method has high adhesive strength and heat resistance, and is a high-performance material that does not cause any abnormality such as swelling on the surface.

[0050]

[Brief description of the drawings]

FIG. 1 is a perspective view showing a moisture-impermeable member on which an adhesive layer is formed.

FIG. 2 is a perspective view showing an example of forming a pressure-sensitive adhesive layer on a moisture-impermeable member.

FIG. 3 is a perspective view showing a bonding method according to the embodiment.

[Explanation of symbols]

 1, 1 'Non-permeable member 2 Adhesive layer 3 Recess 4 Adhesive or adhesive layer 5 Roll coater 6 Adhesive supply tank

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB03 AR00A AR00B AR00G BA02 CB00 CB10G GB90 JD04A JD04B JJ03 JL11 JL13G 4J004 AA11 AA14 AB01 AB02 BA02 CA01 CA02 CA08 CB02 CC02 DB03 EA05 FA10 4J040 EA05 MA08 MA10 PA25 PA42

Claims (4)

[Claims] 1. A bonding method for bonding non-moisture-permeable members with a moisture-curable adhesive, wherein the pressure-sensitive adhesive layer has a release material layer on a back surface of a part of the bonding surface of at least one of the non-permeable members. Is formed, and then a moisture-curable adhesive is applied to the adhesive surface, the release material layer of the adhesive layer is peeled off and removed, and the other moisture-impermeable material is exposed in a state where the adhesive layer is exposed. A method for bonding a moisture-impermeable member, comprising laminating and bonding members. 2. The pressure-sensitive adhesive layer according to claim 1, wherein the pressure-sensitive adhesive layer comprises a moisture-permeable pressure-sensitive adhesive or a water-containing pressure-sensitive adhesive, or a pressure-sensitive adhesive in which a moisture-permeable material or a water-containing material is laminated or contained. The method for bonding a moisture-impermeable member according to the above. 3. The pressure-sensitive adhesive layer is formed partially on the bonding surface of the moisture-impermeable member so that the end of the pressure-sensitive adhesive layer becomes the end of the bonding surface. The method for bonding a moisture-impermeable member according to claim 1 or 2. 4. Adhesive bonding in which a moisture-curable adhesive layer and a pressure-sensitive adhesive layer having an end exposed at an end of the adhesive layer are interposed between non-permeable members. A laminated adhesive body of non-moisture permeable members, wherein an agent layer is sandwiched.