JPS6046239A - Manufacture of metallic 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 manufacturing a metal composite sheet using a water-crosslinkable polyethylene resin as an adhesive layer.
This term shall include foils and plates.

Conventionally, the method for producing this type of metal composite sheet is to extrude water-crosslinkable polyethylene resin into a film, and immerse this film in a dispersion of a silanol condensation catalyst, thereby producing a partially cross-linked polyethylene resin. There is a known method of manufacturing a metal composite sheet by making a film, then stacking the film with the film interposed between two metal sheets, and heating and pressing the laminate (Japanese Utility Model Publication No. 55-5313). (see publication).

However, such conventional methods require equipment for extruding water-crosslinkable polyethylene resin into a film or equipment for crosslinking a portion of the film in advance, which makes it difficult to manufacture metal composite sheets. The equipment became large and uneconomical. Furthermore, in order to improve adhesiveness, the degree of crosslinking of the water-crosslinkable polyethylene resin film had to be strictly controlled, making the production of metal composite sheets troublesome. Moreover, according to the conventional method, the adhesion of the crosslinked polyethylene resin film interposed between the metal sheets is insufficient, resulting in a problem that the peel strength of the metal composite sheet is low.

An object of the present invention is to provide a method for manufacturing a metal composite sheet that solves the above problems.

The method of this invention will be explained below with reference to the drawings.

The first method of the present invention is a method for manufacturing a metal composite sheet shown in FIG. A polyethylene resin powder is made, and a predetermined amount of silanol condensation catalyst and water are added to this powder.
A powder or slurry formulation is made and a metal sheet (
After forming a layer of the above compound on the surface of 1), overlaying another metal sheet (2) on the surface of this compound,
By heating and pressing these laminates, a metal composite sheet consisting of two metal sheets (+1+ +21) bonded to each other via a cross-linked polyethylene resin layer (3) is produced. be.

Next, the method of the second invention of the present invention is a method for manufacturing a metal composite sheet shown in FIG. 2 using a polyethylene resin sheet instead of the other metal sheet in the first invention, After forming a layer of the above compound on the surface of (1), a polyethylene resin sheet (4) is superimposed on the surface of this compound, and the laminate is heated and pressurized to form a crosslinked polyethylene resin layer (3). This method is characterized in that a metal composite sheet is produced, which is made up of a metal sheet (1) and a polyethylene resin sheet (4) that are bonded to each other via a metal sheet (1) and a polyethylene resin sheet (4).

Furthermore, the method of the third invention of the present invention produces a metal composite sheet shown in FIG. 3, in which another metal sheet is further joined to the surface of the polyethylene resin sheet joined to the metal sheet in the method of the second invention. The method comprises forming an IS of the above compound on the surface of a metal sheet (1), and then applying a polyethylene resin sheet (4) to the surface of the compound.
After layering the above-mentioned compound on the surface of this polyethylene resin sheet, another metal sheet (2) is layered on the surface of this compound, and these laminates are heated and pressurized. , is characterized in that it produces a metal composite sheet consisting of a metal sheet (1), a polyethylene resin sheet 4), and a metal sheet (2), each of which is sequentially bonded via a crosslinked polyethylene resin layer (3).

In the above, the metal sheet) f1+ +2) is
It is made of aluminum, copper, steel, stainless steel, lead, etc., and has a thickness of 0.05 to 1.0 mm, for example.

The polyethylene resin sheet 4) is made of low-density or high-density polyethylene, and has a thickness of, for example, 0.5 to 10.0 mm.

The thicknesses of the metal sheet fi+ [21 and the polyethylene resin sheet (4) can be determined as appropriate depending on the use of the metal composite sheet.

The above-mentioned water-crosslinkable polyethylene resin is composed of a polyethylene resin in which a hydrolyzable ethylenically unsaturated organic silane is bonded to the main chain or side chain, and this is described, for example, in JP-A-56-151561. There is.

Here, the ethylenically unsaturated organic silane has the general formula %formula% It is preferable to use one represented by

In the above formula, R is an ethylenically unsaturated hydrocarbyl group or a hydrocarbyloxy group, R' is an aliphatic saturated hydrocarbyl group, and Y is a hydrolyzable organic group, and when two or more Y's are present, they must not be the same. Good too. n represents 0, 1 or 2.

By copolymerizing ethylene with the above-mentioned hydrolyzable unsaturated organic silane, a water-crosslinkable polyethylene resin containing organic silane in the main chain is obtained.

In addition, by graft polymerizing the hydrolyzable unsaturated organic silane to prepolymerized polyethylene,
A wood non-crosslinkable polyethylene resin with organic silane bonded to the side chain is obtained.

When the unsaturated organic silane is included in the main chain, the unsaturated organic silane content of the water-crosslinkable polyethylene resin is, for example, 0.001 to 5% by weight, preferably 0.05 to 2% by weight.
and when an unsaturated organic silane is included in the side chain, the weight ratio is, for example, 0.01 to 10, preferably 0.105
~2105ru2 Water-crosslinkable polyethylene resin is usually commercially available in the form of pellets 14), and the pellets are crushed to produce water-crosslinkable polyethylene resin powder. This resin powder is, for example, 0.3
Preferably, the particles have a particle size of ˜0.8 mm. If the particle size of the powder is less than 0.3 mm, the cost of pulverization becomes very high, and if it exceeds 0.8 mm, the contact area with the silanol condensation catalyst becomes small, so it is difficult to obtain sufficient adhesion. is something that cannot be obtained.

Further, as the silanol condensation catalyst, generally used are carboxylic acid metal salt compounds such as tin, zinc, iron, lead, and cobalt, organic ring groups, inorganic acids, and organic acids.

Specifically, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethylamine, hexylamine, pyridine, sulfuric acid. , hydrochloric acid, toluenesulfonic acid, acetic acid, stearic acid, maleic acid, etc.

It is desirable to use the silanol condensation catalyst in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the water-crosslinkable polyethylene resin powder.

Here, if the silanol condensation catalyst is less than 0.5 parts by weight, the crosslinking reaction will not proceed sufficiently, and if it exceeds 10 parts by weight, the crosslinking reaction will be accelerated and the adhesion will be impaired.

The silanol condensation catalyst is mixed into a polyethylene resin in a required amount to form pellets, which are then crushed and used in the same manner as the water-crosslinkable polyethylene resin, or used as an aqueous dispersion.

In some cases, the silanol condensation catalyst is dissolved in an appropriate solvent and used.

A crosslinking reaction occurs by contacting water crosslinkable polyethylene resin powder with water in the presence of a silanol condensation catalyst.

The amount of water added is preferably in the range of 2.5 to 10 parts by weight per 100 parts by weight of the water-crosslinkable polyethylene resin.

Here, if the amount of water added is less than 2.5 parts by weight, sufficient crosslinking reaction will not occur and the desired adhesive strength will not be obtained. Also 1
If the weight exceeds 0, the reaction becomes too fast and uniform adhesive strength cannot be obtained.

A mixture is prepared by blending the water-crosslinkable polyethylene resin powder, a silanol condensation catalyst, and water as required, and this mixture is sprinkled on the surface of the metal sheet (1) or polyethylene resin sheet (4). Apply to form a uniform layer of the formulation. ) The compound is 50 to 1000 for metal sheet (1) or polyethylene resin sheet (4).
! It is preferable to spray or apply at a ratio of i'/i. Here, if the blend is less than 509 g/rye, sufficient adhesive strength cannot be obtained, and if it exceeds 1000 g/rye, it is economically disadvantageous.

The above-mentioned laminate is finally heated and pressurized to a temperature of 150 to 1
It is carried out under conditions of a temperature of 65° C. and a pressure of 50-60°/cl. This may be approximately the same as the press conditions used when molding polyethylene resin.

Next, this invention will be explained in detail.

Example: Water-crosslinkable polyethylene resin pellets (trade name: Linkron, manufactured by Mitsubishi Yuka Co., Ltd.) were crushed to obtain a π average particle size of 0.5.
A powder of mm was prepared. On the other hand, high density polyethylene resin 100i! To part f, 5 parts by weight of dibutyltin dilaurate as a silanol condensation catalyst was added, and these were made into pellets by extrusion, and then crushed in the same manner as above to obtain a powder with an average particle size of 0.5 mm. . Then, 5 parts by weight of resin powder containing this silanol condensation catalyst, 5.5 parts by weight of water, and 100 parts by weight of water-crosslinkable polyethylene resin powder were mixed to prepare a blend.

This mixture was then spread at a rate of 700 El/d onto a 0.1 ran thick stainless steel sheet, and a 0.1 mm thick stainless steel sheet was then placed on top of the layer of this formulation. After combining, these laminates were heated between a pair of hot plates at a humidity of 165° C. and a pressure of 50 K9.
/rJ to produce a crosslinking reaction and produce a metal composite sheet.

When the peel strength of the obtained metal composite sheet was measured at 180°C, it was found to be 11K9/2C11 width.

Example 2 The formulation prepared in Example 1 above was spread at a rate of 500!7/d onto a 2-thick high-density polyethylene sheet, and the surface of the layer of this formulation was further coated with a thickness of 0.7/d. After layering stainless steel sheets of one tone, the laminate was heated between a pair of hot plates at a temperature of 165°C and a pressure of 5oKy/
A metal composite sheet was produced by heating and pressurizing at cJ to cause a crosslinking reaction.

When the peel strength of the obtained metal composite sheet was similarly measured, it was found to be 14 KF/2 cm width.

Example 3 3 parts by weight of dibutyltin diurarate, which is a silanol condensation catalyst, was added to 100 parts by weight of water to prepare an aqueous dispersion of the catalyst. Next, 5 parts of this aqueous dispersion were added to 100 parts by weight of the water-crosslinkable polyethylene resin powder obtained by pulverization in Example 1, and mixed uniformly to prepare a blend.

Next, this compound is uniformly spread on the surface of a high-density polyethylene resin sheet as in the case of the second embodiment, and a stainless steel sheet is further stacked on the surface of the layer of this compound, and heated and pressurized to form a metal. A composite sheet was manufactured.

The peel strength of the obtained metal composite sheet was 11 kg/:
2, cm wide.

In the second and third embodiments above, the compound was spread on the surface of the polyethylene resin sheet and then the metal sheet was stacked on top of it, but on the contrary, after the compound was spread on the surface of the metal sheet, Of course, polyethylene resin sheets may be stacked on top of this.

The metal composite sheet produced by the method of the present invention is used for various materials such as building materials and face plates for signboards.

As described above, the method for manufacturing a metal composite sheet according to the present invention does not require any equipment for extruding a water-crosslinkable polyethylene resin into a film or equipment for crosslinking a portion of the film in advance, as in the past. Since only a crusher for water-crosslinkable polyethylene resin pellets is used, the metal composite sheet manufacturing equipment is simplified and therefore very economical. In addition, it may be necessary to strictly control the degree of crosslinking of the water-crosslinkable polyethylene resin film produced in advance as in the conventional method. , it has the effect that it can be effectively used for various purposes.

[Brief explanation of drawings]

1 to 3 are partially enlarged longitudinal cross-sectional views illustrating three types of metal composite sheets produced by the method of the present invention. (11+2)...Metal sheet, (3)...Crosslinked polyethylene resin layer, +41-...Polyethylene resin sheet. Figure 1: 4 other people

Claims (3)

[Claims] (1) Pellets of water-crosslinkable polyethylene resin containing hydrolyzable organic silane are pulverized to produce water-crosslinkable polyethylene resin powder, and a predetermined amount of silanol condensation catalyst and water are added to this powder to form a powder. After making a compound in the form of a solid or slurry and forming a layer of the above compound on the surface of a metal sheet, another metal sheet is superimposed on the surface of this compound, and the laminate is heated and pressurized. A method for manufacturing a metal composite sheet, which comprises manufacturing a metal composite sheet consisting of two metal sheets bonded to each other via a crosslinked polyethylene resin layer. (2) Grinding pellets of water-crosslinkable polyethylene resin containing hydrolyzable organic silane to prepare water-crosslinkable polyethylene resin powder, adding a predetermined amount of silanol condensation catalyst and water to the powder, After creating a powder or slurry compound and forming a layer of the above compound on the surface of a metal sheet, a polyethylene resin sheet is placed on the surface of this compound and the laminate is heated and pressurized. A method for manufacturing a metal composite sheet, comprising manufacturing a metal composite sheet consisting of a metal sheet and a polyethylene resin sheet that are bonded to each other via a crosslinked polyethylene resin layer. (3) Pellets of water-crosslinkable polyethylene resin containing hydrolyzable organic silane are crushed to produce water-crosslinkable polyethylene powder, and a predetermined amount of silanol condensation catalyst and water are added to this powder to form a powder. Alternatively, a slurry-like compound is made, a layer of the above compound is formed on the surface of a metal sheet, a polyethylene resin sheet is superimposed on the surface of this compound, and a layer of the above compound is further layered on the surface of this polyethylene resin sheet. After forming, another metal sheet is superimposed on the surface of this compound, and the laminate is heated and pressurized to form a metal sheet, a polyethylene resin sheet, and a A method for manufacturing a metal composite sheet, comprising manufacturing a metal composite sheet made of metal sheets.