JPS60176757A - Manufacture of multilayer composite sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a multilayer composite sheet 1- that has excellent liquid-tightness, air-tightness, and mechanical durability under extremely low temperatures and high temperatures.

C1 has excellent liquid-tightness and airtightness in storage tanks that store cryogenic liquefied gas, etc., liquid barriers located around the outer periphery of these tanks, and various transfer pipes that transfer cryogenic fluids.
In addition, there is a desire to develop new materials (eg, Barrier Sea 1~, etc.) that have sufficient low-temperature properties.

For example, barrier sheets 1- used in low-temperature tanks that store extremely low-temperature liquid gas have traditionally been made of expensive metals, but in order to be economical and lightweight, they have been made of aluminum, for example, as shown in Figure 5. , reinforcing sheets 1 to 1 made of glass cloth or the like are placed on both sides of the metal sheet A made of stainless steel or the like.
Composite sheets 1 to G made by adhering protective sheets 1 to B and D have come to be used. I It is known that this composite sheet C can be manufactured by the current 2-no-j method.

<1> After applying a two-component reactive polyurethane adhesive, epoxy adhesive, or oil-based adhesive, etc. to metal sheet A, reinforcing sheet B is mounted and both A and B are bonded and covered. Method.

-2> A method of forming a laminate of the metal sheet 1-A and the reinforcing sheets I to 13 using a vinyl-based thermoplastic IJ4 plastic film such as polyethylene, polypropylene, etc. as an adhesive layer. However, the following problems remain to be solved in each of the two manufacturing methods described in F.

・This manufacturing method has problems with the curing time of the adhesive, workability, low-temperature properties, and water resistance. It is not suitable for

Regarding the manufacturing method (2), with regard to this manufacturing method, vinyl films such as polyethylene and polypropylene do not have low-temperature properties sufficient to withstand extremely low temperatures.

Therefore, it is not possible to expect durability under extremely low temperatures.

Furthermore, the softening point is low, and the composite sheet can be easily peeled off even under 8 degrees of temperature, such as hot water.

In view of the above points, the present invention has been developed to provide a C1 material that can secure sufficient adhesive strength between composite sheets even at extremely low temperatures or relatively high temperatures, and can be easily cut and destroyed. The purpose is to provide a method for manufacturing a composite sheet with excellent durability and liquid tightness.

Next, embodiments of the present invention will be described with reference to the drawings.

As shown in FIG. 1, the composite sheet according to the present invention]-1 is a reinforced metal foil 3 which has been pretreated with a silane coupling agent 2 on both sides of the metal foil 3, which has been pretreated with a silane coupling agent 2. The material 4 is positioned, an adhesive sheet 5 is interposed between the two materials 3 and 4, and the material is heated and formed.

Below is a brief explanation of each material.

E-1 Metal foil The metal foil 3 is a thin strip plate with excellent liquid tightness.

Although the metal foil 3 differs depending on the purpose of use, for example, aluminum foil, stainless steel foil, etc. can be used.

The thickness of the metal foil 3 can be selected depending on the material and purpose of use.
A thickness of ˜100 μM is preferred.

This metal foil 3 is pretreated with a silane coupling agent 2, which will be described later, to impart excellent thermal properties to the metal foil 3.

[Explanation] Reinforcing material The reinforcing material 4 is, for example, a cross-shaped sheet made of well-known glass fiber wound into a roll. (It is preferable to use a material with a basis weight of about 1/Tn2 or more.

[C] Adhesive sheet The adhesive sheet 5 is made of a known polyurethane material such as polyester or polyneedle.

In consideration of heat resistance properties, etc., it is preferable to use a material with a softening point of 150° C. or higher.

[21 Silane Coupling Agent One of the characteristics of the composite sheet 1 according to the present invention is that some of the sheets, that is, both the metal foil 3 and the reinforcing material 4, are pretreated with the silane coupling agent 2. do.

Although conventional composite sheets had excellent properties such as liquid-tightness and durability at low temperatures, they did not have sufficient weather resistance against changes in outside temperature and wind and rain.

For example, when performing the fresh water immersion test described below, the composite sheet was easily peeled off in a short time.

Therefore, as a result of research and development, the inventor of the present invention found that treatment with Silane Cobbler 2 shows amazing durability in a boiling water immersion test and improves properties such as durability even at low temperatures. was investigated.

Hereinafter, specific examples of the silane coupling agent 2 for each grain to be treated will be explained.

<For metal foil> The silane coupling agent 2 differs depending on the type of material to be treated, but for example, in the case of metal foil 3, γ-methacryloxy, γ-glycidoxy, γ-mercapto, or N
A compound having a GO group may be used alone, or it may be diluted with a solvent such as methanol, Improvyl alcohol, ethyl acetate, etc. and used at °C.

<For Reinforcing Materials> As the silane coupling agent 2 to be applied to the reinforcing material 4, for example, known aminosilane type, vinyl silane type, etc. can be used.

Next, a method for manufacturing the composite sheet 1 will be explained.

[B] Manufacturing method by heat fusion FIG. 2 shows a schematic diagram for heat fusion. This is a device for thermally fusing a plurality of sheets Y passing between fusing devices 6.

One end of the metal foil 3 wound up into a roll is pulled out from one end of the fusing device 6, and guided to a collecting section 7 where the composite sheet 1 produced through the fusing device 6 is rolled up. Next, the adhesive sheets 1 to 5 from the side closest to both sides of the metal foil 3, and one end of the sheet pulled out from the reinforcing material 4 on the outside of the adhesive sheet 5, are guided through the fusing device 6 to the collecting section 7, respectively. do.

A cooling means (not shown) for cooling the pressed sheets is arranged between the fusing device 6 and the collecting section 7.

In order to manufacture the composite sheet 1, the metal foil 3 and the reinforcing material 4 are preheated before arriving at the fusion splicer @6.
(not shown), all the sheets 1 to 3, 5, and 4 are laminated and fused as they pass through the fusing device 6, and are then cooled and hardened and recovered in the recovery section 7.

The fusion moisture level of fusion bonding N6 depends on the material, its thickness, etc.

Therefore, the temperature X is preferably higher than the temperature at which the adhesive sheet 5 starts melting, although it varies.

However, when heat-sealing adhesive sheet 1 to sheet 1 with VZ straight 6, it is necessary to fully consider the heat resistance temperature of adhesive sheet 1-5 and avoid completing the fusion in a short period of time9゜E口】 ■Extruder-T die lamination method Diagram 3 [I received a schematic diagram of the Extruder-T die lamination method.

In this h method, just before fusing the plural sheets 6Y, IYr
Adhesive sea 1 to 45 only, known extruder machine E3
After (extrusion molding and supplying between metal foil 3 and reinforcing material 4, all sheets) -3, 1, and 4 are crimped between 1 and 59, cold fJI hardening is performed.

Furthermore, ThfJIll! After forming the LL and completing the adhesion, the laminated sheet 1- is cured for a short period of time at a high temperature similar to the softening point of thermoplastic polyurethane (preferably 150 to 300°C). This is a method of forming the sheet 1.

Next, this example will be described with reference to some specific test examples.

[B] Test Example 1 T-glycidoxynorobil 1 to Lime(・xysilane 1
A 300 x 300 soft (300 x 300 soft) 7 lumi foil (thickness 80 μm) whose surface was treated with a 0% methanol solution and dried in a dryer at 70°C for about 3 minutes, and a fuminosilane-treated 30
A 300×300 adhesive sheet 5 (softening temperature: 160°C, thickness: 200 μm) is placed between 0×300 glass sheets L1
) and hot sprays 1 to 61 of the fusing device 6 at a surface humidity of 230°C to 240°C for 5 seconds! After checking the impression,
This was allowed to cool to form a "C" composite sheet.

This composite sheet 1 was then after-cured for 2 minutes in a dryer at 210°C to obtain a final composite sheet 1.

Physical properties of composite sheets 1-1 formed in this way (ill
is as shown in FIG.

In addition, in the figure, "A" indicates the manufacturing method by heat fusion,
10-1 shows a manufacturing method using an extruder ---1 tie lamination method.

[Open] Test Example 2 Metal positive 3, reinforcement 4. pretreated in the same manner as Test Example 1. f
4, add 1 adhesive pellet to 1 extruder.
The adhesive sheets 1 to 5 melted at about 200℃ at the outlet of the potspar [1] were continuously fed to the T-dye lamination machine C between the metal foil 3 and the reinforcing layer 4, and the rollers 9
The composite sheets were crimped and then cooled to 50 fZ to obtain composite sheets 1-1.

Furthermore, this composite sea 1-1 is heated to 160℃! 5
After being left for about a minute, it was left at room temperature.

The physical properties of the composite sheets 1 to 1 formed in this manner are as shown in FIG.

[CJ Comparative Example 1 Physical properties of composite sheets 1 to 1 obtained in the same manner as in Test Example 1 using a metal cylinder 3 (thickness 280 μM and reinforcement tΔ4) which was not treated with the silane bubbling agent 2. The values are as shown in FIG.

From these physical property values, it was found that the composite sheet 1 which had not been treated with the silane coupling agent 2 had a significant decrease in peel strength when boiled in clean water.

V2J Comparative Example 2 Composite sheet 1 was formed under the same conditions as Test Example 2, and e-composite sheet 1 was formed without subsequent after-curing 1'
Ru.

The physical properties of this composite sheet 1 ("1" are shown in FIG. 4).

As can be seen from this figure, composite sheets 1 to 1 that were not after-cured did not have a peel strength of -1 minute at room temperature.

[E1 Comparative Example 3 Is there any after-cooling under the manufacturing conditions of Test Example 1? The physical properties of the composite sheet 1 are as shown in FIG.

[Heco test example 3 Surface treatment with γ-mercaptopropyltrimethoxysilane 10% ethyl acetate solution, drying in a dryer at 80°C for about 3 minutes, Ic metal cylinder 3 (thickness near 0 μm) and aminosilane treatment An adhesive sheet 5 (softening temperature: 155°C, thickness 7,200 μm) was placed between the glass cloths using a fusing device 6.
Preheat to approximately 100°C before heating.

Furthermore, these sheet groups were heated to 200°C.
- Roll 6 1 'c- After being crimped, the composite sheet 1 is formed by cooling and hardening.

Then, this composite sheet 1 was after-cured for 5 minutes in a dryer at 180°C to obtain a composite sheet i~1 with a smooth curve.

The physical properties of this composite sheet 1 are as shown in FIG.

Since the present invention is as explained above, the following effects can be expected.

<B> While conventional composite sheets were low-temperature (a)
It has a disadvantage in that it has poor durability when exposed to outside air or wind and rain, and easily peels off under conditions of high temperatures, for example, about 100°C.

In the present invention, by treating a part of the composite sheet 1 with a silane coupling agent, it is possible to form a composite sheet 1- which is water-soaked and has fixed physical properties.

<Opening> The outermost part is protected with a reinforcing material and pre-treated with a silane coupling agent, so it is possible to give sufficient strength to the composite sheet 1~, and as a result, the durability of the composite sheet, which is easily damaged, is increased. can be improved.

<C> The composite sheet 1-, which is formed by pulling out a plurality of roll-shaped sheets and performing a simple fusing operation, has insufficient adhesive strength.

Therefore, by leaving this composite sheet at a high temperature of 150 DEG C. to 300 DEG C. for a short period of time to after-cure it, a composite sheet with high adhesive strength can be formed and covered.

Therefore, high quality composite sheets 1~
can be mass-produced. , (2) Excellent properties such as mechanical durability, physical TR4 usability, and liquid tightness can be maintained even under extremely low temperatures and high temperatures (boiling water infiltration test), so barrier seal 1 of cryogenic storage tanks can be maintained.・It can be used as an industrial material for many purposes other than t-1, and its versatility is wide.

[Brief explanation of the drawing]

1N: An explanatory diagram of an embodiment of the composite sea i~ according to the present invention. FIG. 2: Thermal FiA! An explanatory diagram of the manufacturing method of a composite sheet by dye lamination Figure 3: An explanatory diagram of your method for manufacturing composite sheets using the dye lamination method. Figure 5: Conventional composite sheet 1~ Illustration diagram 1: Composite sheet 2, Nijiran coupling agent 3: KinR sake 4: Reinforcement layer 5: Adhesive sheet 1 7: Collection department application Person Nisshinbo Co., Ltd. Taisei Kensetsu Co., Ltd. Procedural amendment 1. Indication of the case Special Order No. 59-32518 2, Name of the invention Method for manufacturing multilayer composite sheet 3, Person making the correction 6, Specification subject to amendment "Column j of Detailed Description of the Invention and Drawing 7, Contents of Amendment (1) The description of Detailed Description of the Invention is corrected as follows. (2) Addition of test method to Figure 4 of the drawing"

Claims (3)

[Claims] (1) A reinforcing material sheet made of durable and flexible metal foil sheet 1- and glass cloth is pretreated with a silane coupling agent, and an intermediate sheet made of thermoplastic polyurethane is placed between the metal foil and the reinforcing material sheet. After bonding without intervening, perform after-keying at high temperature to create a continuous composite seam [
- A method for producing a multilayer composite sheet, characterized by forming. (2) Special IT claims characterized in that the intermediate sheet is supplied by melt extrusion-T die lamination method (
1) Method for producing the multilayer composite sheet 1-. (3) The method for manufacturing a multilayer composite sheet according to claim (1), characterized in that the intermediate sheet between the reinforcing sheets made of metal foil and crow cloth is adhered by heat fusion. (4,) The method for producing a multilayer composite sheet according to claim (1), characterized in that after-curing is performed at 150°C to 300°C.