JPS63231932A - Metal laminated plate - 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 [Object of the Invention] (Industrial Application Field) The present invention relates to a metal laminate in which a plurality of dissimilar metal plates are laminated and integrated via a heat-resistant prepreg.

(Prior art) Traditionally, the most commonly used metal sheet material has been economically advantageous steel. , which is usually compensated for by painting with organic polymer-based paints.

However, as is clear from the following example, there is a limit to the ability to add functionality and improve properties by simply applying such a coating.

In other words, a large number of living creatures such as Fujitbo and sea squirts live in the water of the sea, rivers, lakes, etc., but if they grow attached to ships, port facilities, buoys, etc., they can cause various harm to these underwater structures. I will give you. For example, if living organisms adhere to a ship's hull, the resistance to water will increase, leading to a decrease in fuel efficiency.Also, if living organisms adhere to port facilities, their individual functions will be inhibited, and the base materials will be damaged. It may also be eroded. For this reason, conventionally, an antifouling paint containing an antifouling agent having a bactericidal effect such as an organic tin compound or cuprous oxide has been applied. However, the effect of the antifouling agent blended in such paints is lost in a relatively short period of time due to the reduction of the paint film over time, so it is necessary to repeat the application periodically. Moreover, this painting work is extremely troublesome and imposes a large economic burden because the structure is large and located underwater.

On the other hand, there are materials known as functional metal materials that have excellent functions that steel materials do not have, and even surpass those of the above-mentioned coated steel materials.

In the example above, this is cupronickel. The sterilizing effect of copper ions precipitated from cupronickel prevents attachment of aquatic organisms over a long period of time. Furthermore, cupronickel has excellent (sea) water corrosion resistance, so painting is not necessary at all.

However, such functional metal materials are extremely expensive, and it is practically impossible to use such materials alone.

In this respect, it would be very advantageous to solve the above problem if a metal material having excellent properties and functions could be laminated onto the surface of an inexpensive steel material.

(Problems to be Solved by the Invention) However, this kind of adhesion of dissimilar metals has the following problems.

That is, when dissimilar metals come into direct contact, a local battery is formed at the contact area, resulting in electrolytic corrosion. If the parts are simply bonded with a normal adhesive, there is a risk that the adhesive may be partially missing, making it difficult to avoid electrolytic corrosion. The probability of this happening increases as the metal plate becomes larger.

Furthermore, since this type of metal plywood is subject to bending and welding during use, it is required to have strong adhesive strength and excellent heat resistance to withstand such processing.

Therefore, the present invention attempts to address these conventional circumstances, and is a useful material in which multiple dissimilar metals are laminated together without deterioration of performance, and which has strong adhesive strength and heat resistance that can withstand processing. Another object of the present invention is to provide a metal laminate that is also economically advantageous.

[Structure of the Invention (Means for Solving Problems)] The metal laminate of the present invention is produced by bonding a plurality of dissimilar metal plates through a heat-resistant prepreg made by semi-curing a heat-resistant insulating base material impregnated with an organometallic polymer paint. It is characterized by being made by stacking them together and thermo-compression bonding them together.

Heat-resistant insulating substrates used in the present invention include woven fabrics, nonwoven fabrics, vapors, etc. made of glass, ceramics, etc.

Furthermore, the organometallic polymer used in the present invention has a main chain of S
It consists of metal elements such as L, Ti, and B, as well as O, N, etc., and organic groups such as methyl and phenyl groups are bonded to the side chains. Siloxane, polycarbosilane, polysilastyrene, polysilazane.

Polytitanocarbosilane is suitable.

Although silicone resin (polysiloxane) is also a type of organometallic polymer, its use is not recommended because it has inferior heat resistance compared to other organometallic polymers. Useful when used within a range.

When the organometallic polymer of the present invention is heated and fired in an oxygen-free environment, it becomes a so-called non-oxide ceramic, and when fired in the atmosphere, the organic groups in the side chain are eliminated, and it finally becomes an oxide ceramic. Become.

(The following is a blank space) Table 1 (In the table, R represents an organic group) The organometallic polymer paint of the present invention can be prepared by dissolving one or more of such organometallic polymers in a known solvent. , or in addition to this, powders and flakes of insulating inorganic fillers such as gold R oxide, ceramics, and glass,
It is obtained by blending 11 fibers and the like and dissolving or dispersing them in a solvent.

Note that other additives may be added to this paint as necessary.

The heat-resistant prepreg used in the present invention is obtained by impregnating a heat-resistant insulating base material with the above-mentioned organometallic polymer paint and semi-curing it.

The degree of dryness of the impregnated paint is preferably within a range of 10 Wt$ or less of residual solvent, for the following reason.

That is, when an organometallic polymer paint is cured, the solvent first evaporates, then the organic groups in the side chains are eliminated, and finally the paint becomes inorganic.

In general, polymers need to be softened or melted by heat or pressure in order to bond, and in order to bond polymers that are difficult to soften, such as the organometallic polymer of the present invention, it is better to leave some solvent. On the other hand, when bonding by heat or pressure, if there is a large amount of residual solvent and a large amount of organic gas is generated due to the eliminated organic groups, blistering and peeling will occur during the production and welding of metal laminates.

In addition, the resin content in the heat-resistant prepreg is 30 to 50wt.
A range of % is preferred.

Generally speaking, the higher the resin content, the greater the adhesive strength, but if the content is too high, the probability of forming defects due to remaining air bubbles in the coating film increases, and the resin may flow out due to heat and pressure, making it difficult to maintain effective resin. This is because the adhesion force decreases as the amount decreases.

In the present invention, such a heat-resistant prepreg is placed between a plurality of dissimilar metal plates, such as a steel plate, and a thin plate-like functional metal material, such as a cupronickel plate, and is heated and pressed using a heat-pressing method, or The metal laminate of the present invention can be obtained by integrating by a post-heating method in which the metal laminates are pressed at room temperature and then heated and fused.

In addition, from the viewpoint of adhesiveness, the heating and pressing conditions at this time are a temperature of 150 to 400°C and a pressure of 2 to 30K.
ll/aJ range, and in the post-heating method, the temperature is 300~
A temperature range of 450° C. and a pressure of 30 to 150 kf/alI is suitable.

In addition, by making minute holes on the surface of the thin functional metal material, residual solvent gas generated from the heat-resistant prepreg and organic gas due to the elimination of organic groups can be smoothly removed without accumulating in the metal laminate. This is more preferable because the metal laminate can be discharged to the outside and the performance of the metal laminate can be improved.

Furthermore, if the metal plate is previously subjected to degreasing as a surface treatment, the adhesion force can be further improved, so it is preferable, and it is more preferable to perform sandblasting.

In addition to cupronickel, functional metal materials include copper alloys such as aluminum plus (seawater corrosion resistance), titanium (seawater corrosion resistance, high specific strength), and aluminum (weather resistance).

(Function) The metal WI laminate of the present invention is a heat-resistant insulating base material impregnated with an organometallic polymer paint and semi-cured. Since it is bonded, there is no risk of electrolytic corrosion, and it has enough properties to withstand bending and welding. Therefore, it is possible to provide a useful and inexpensive metal material.

(Example) Next, examples of the present invention will be described.

Example 1 A paint containing 50% by weight of polyborosiloxane (using solvent N-methyl-2-pyrrolidone) was prepared using polyborosiloxane from organometallic polymers having the structure and molecular weight shown in Table 2. This paint was applied to a size of 300 m x 300 m +'
A heat-resistant prepreg with a resin content of 40 wt % was obtained by impregnating a plain weave glass cloth (manufactured by Unitika) with a drying process of 200° C. for 20 minutes three times.

On the other hand, the size is 300 nx300 nX 1. On (Only the adhesion test in ■ below 30nm x 50m + x 1.On
im) cupronickel plate (Ni content 10%)
, Kobe #1) was degreased by ultrasonic cleaning in methyl ethyl ketone, pickled in concentrated nitric acid for 5 seconds, washed with water for 30 seconds, neutralized with 102 ammonia water for 5 seconds, and further
After washing with water for a minute, it was heated and dried at 70°C.

Also, the size is 300 u x 300 mi x 23n
(Only for the adhesion test in ■ below 30w x 50m x 2.3
After degreasing the steel material (51441 material manufactured by Kobe Steel, Ltd.) by ultrasonic cleaning in methyl ethyl ketone,
It was dried by heating at ℃.

After that, as shown in FIG. 1, a heat-resistant prepreg 3 is sandwiched between the surface-treated cupronickel plate 1 and the steel material 2, and the heat-resistant prepreg 3 is placed in a heating press at 250°C for 10 minutes.
The metal laminate 4 was manufactured by thermocompression bonding under the conditions of okg/aJ.

The following performance tests were conducted on the obtained metal laminate 4. The results are also shown.

■Adhesive strength The heat-resistant prepreg 3, cupronickel plate 1, and steel material 2 manufactured for the adhesive strength test were bonded together as shown in Figure 2.
A sample for adhesion test was prepared in the same manner as described above by overlapping 0w x 30mm, and the adhesive strength was measured at room temperature using an autograph.

The minimum value and average value of the five adhesive test samples were 108 kg/ad and 125 electr/-, respectively.

■Weldability: Seal the four sides of the metal laminate 4 with epoxy resin and arc weld it in a line at the center of the steel surface using a welding rod with a diameter of 2.3 m at 90A x 15 seconds with a beat length of 140m+. .

No peeling or swelling was observed.

■Place the bendable metal laminate plate 4 along a mandrel with a diameter of 18 mm.
09 The presence or absence of bending, misalignment, and peeling was examined.

The results were good.

■Sea immersion antifouling properties The antifouling properties of the metal laminate 4 were immersed in Sagami Bay, Kanagawa Prefecture for 12 months, and then their antifouling properties were observed.

There was no corrosion on the cupronickel surface, and no aquatic organisms were attached to it.

Examples 2 to 14 Organometallic polymer paints A1 to A9 were prepared using organometallic polymers having the structures and molecular weights shown in Table 2 and based on the compounding ratios shown in Table 3.

These paints were then applied in 300 tar pieces each.
× 300 wm × 0.15 m plain weave glass cloth (manufactured by Unitika) or size 300 mm × 300
It was impregnated with wX O, Shikaku ceramic cloth (manufactured by Olivest Co., Ltd.), and a drying process of 200° C. for 20 minutes was repeated three times to obtain B1-B12 heat-resistant prepregs. The paint, heat-resistant insulating base material, and resin content used are as shown in Table 4.

Thereafter, in the same manner as in Example 1, using the materials and conditions shown in Table 5, the heat-resistant prepreg was sandwiched between the steel material and the functional metal material, and they were bonded together by thermocompression. The performance results obtained in the same manner as in the examples are also shown in the same table.

(The following are blank spaces) Table 2 Table 3 Table 4 [Effects of the invention] As is clear from the above examples, the metal laminate of the present invention is produced by impregnating a heat-resistant insulating base material with an organometallic polymer paint. Since multiple dissimilar metal plates are bonded together through the heat-resistant prepreg obtained through this process, which has excellent heat resistance and adhesive strength, there is no risk of electrolytic corrosion, and it can withstand bending and welding processes. It has unique characteristics.

Therefore, it is possible to provide a metal material that is inexpensive and has excellent properties and functions.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing one embodiment of the present invention, and FIG. 2 is a perspective view showing the structure of a sample prepared for an adhesive force test. 1......Cupronickel plate 2...
...Steel material 3...Heat-resistant prepreg 4...Metal laminate rod 1 section vinegar 2 procedural amendment (July 31, 1981 incident) Indication Patent Application No. 66696 of 1988 2 Title of the invention Metal laminate plate 3 Relationship with the case of the person making the amendment Patent applicant (119) Kobe Steel, Ltd. (225) Showa Cable Denmo Co., Ltd. 4 Representative Director Tokyo 2-1-5 Kandatamachi, Chiyoda-ku, Tokyo Date of amendment order 5 Subject of amendment [Column for detailed explanation of the invention in book 1. Contents of amendment (1) Mei 1fE book, page 13, line 10, r2. 3fmll
Correct l to r2.6uJ. (2) Correct "beat length" on page 13, line 11 of Mingmun to "bead length." (3) In Table 4, page 17 of the specification, "eyeless plain woven glass" is corrected to "eyeless plain woven glass."that's all

Claims (5)

[Claims] (1) A metal laminate characterized in that a plurality of dissimilar metal plates are laminated via a semi-cured heat-resistant prepreg made by impregnating a heat-resistant insulating base material with an organic metal polymer paint and bonding them together by thermocompression. Board. (2) The organometallic polymer paint has one or more of polyborosiloxane, polycarbosilane, polysilastyrene, polysilazane, and polytitanocarbosilane as a main component according to claim 1. Metal laminate. (3) A patent in which the organometallic polymer paint contains one or more of polyborosiloxane, polycarbosilane, polysilastyrene, polysilazane, and polytitanocarbosilane as a main component, and contains an inorganic filler. A metal laminate according to claim 1. (4) Any one of claims 1 to 3, wherein one of the dissimilar metals is steel and the other is a functional metal material.
The metal laminate described in Section 1. (5) The metal laminate according to claim 4, wherein the functional metal material is cupronickel.