JPH09160504A - Sheet for forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for forming a pattern capable of being adhered to a steel product, or the like in the condition at which a high temperature is kept by making the sheet of a silicone resin sheet containing magnetic powder to be simply adhered through the magnetic force. SOLUTION: A sheet 1 for forming a pattern is made of the silicone resin sheet containing the magnetic powder. A pattern layer 2 and a hot body 3 to be fitted are provided in a pattern sheet to which the ink pattern is given to the sheet 1. The sheet 1 for forming the pattern is sufficient if it has a silicone resin sheet containing magnetic powder, and can be formed into an appropriate shape. The silicone resin sheet can be formed, for example, by a method in which the mixture of one or two kinds of silicone resin with the magnetic powder is formed on the sheet through the coating and extrusion system, or by a method capable of forming the sheet-shaped stuff such as impregnation in the reinforcement base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming sheet which can be adhered to a high temperature adherend by magnetic force.

[0002]

2. Description of the Related Art Steel products such as ingots and slabs taken out from a firing furnace, high-temperature products such as hot-rolled iron plates and melt-formed seamless pipes are given production numbers and the like at the high temperature maintenance stage to control production. The construction of a system that can be done has been a long-standing issue, and with the diversification of products such as the production system shifting to high-mix low-volume production, the construction of such a system becomes more important.

Conventionally, as a method of giving a serial number or the like to the above-mentioned high temperature maintaining product, there has been known a method of shooting a metal plate in which necessary information is written with a gun or the like. However, such a method is dangerous and has a problem that it is inferior in the efficiency of giving the serial number and the like. Although it is desired to give a serial number etc. by an adhesive type label via an adhesive layer etc., in the conventional labels, the adhesive layer does not withstand high temperature due to problems such as thermal decomposition of the adhesive layer and peeling of the label due to the generated gas, No label was known that could serve this purpose.

[0004]

DISCLOSURE OF THE INVENTION The present invention has an object to develop an adhesive type pattern forming sheet which can be applied to an adherend in a high temperature state and can also be applied to a curved surface adherend by giving a pattern on occasion. To do.

[0005]

The present invention provides a pattern-forming sheet comprising a magnetic resin-containing silicone resin sheet and, if necessary, a low-melting inorganic powder.

[0006]

EFFECT OF THE INVENTION According to the pattern forming sheet having the above structure, it can be easily adhered to a steel product or the like which can be easily adhered through a magnetic force and maintains a high temperature. Further, a pattern sheet can be formed by applying a necessary ink pattern by an appropriate printing method such as a thermal transfer printer or screen printing, and a flexible body having good curved surface adhesion can be easily formed. Furthermore, after the purpose of use of the pattern sheet is achieved, it can be separated and collected from the adherend by peeling it off against the magnetic adhesive force, and can be reused.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The pattern forming sheet of the present invention comprises
It is composed of a silicone-based resin sheet containing magnetic powder. An example is shown in FIG. 1 is a pattern forming sheet. In the illustrated example, a pattern sheet in which an ink pattern is applied to such a sheet is shown, and 2 is the pattern layer.
In addition, 3 is a high temperature adherend.

The pattern forming sheet may have a magnetic powder-containing silicone resin sheet and can be formed in an appropriate form. As an example, see FIG.
As shown in FIG. 2, a form of a single layer of the silicone resin sheet, as shown in FIG. 2, a form having an ink receiving layer 11 containing a colorant on the silicone resin sheet 1, FIG. As exemplified, the form in which the silicone-based resin sheet 1 is reinforced with a reinforcing base material 12 is exemplified.

The above-mentioned reinforcing mode is, for example, a method of interposing the reinforcing base material 12 in the silicone resin sheet 1 as shown in FIG. 3 or a method of impregnating the reinforcing base material with the forming material of the silicone resin sheet. As shown in FIG. 4, the reinforcing base material 1 is provided between the silicone resin sheet 1 and the ink receiving layer 11.
A suitable form that does not impede magnetic adhesion by the silicone-based resin sheet, such as a system in which 2 is interposed, can be adopted. As the reinforcing base material, fibers, cloths, non-woven fabrics, foils, and other sheet-like materials made of heat-resistant materials such as glass, ceramics, and metals, and nets may be used.

The silicone resin sheet is formed, for example, by molding a mixture of one or more kinds of silicone resin and magnetic powder into a sheet by an appropriate method such as a coating method or an extrusion method, or a reinforcing base material. It can be carried out by an appropriate method capable of forming a sheet-like material, such as a method of impregnating the sheet. When mixing the silicone-based resin and the magnetic powder, a surfactant such as a phosphoric acid ester and a dispersant such as a titanate-based coupling agent may be used together, if necessary, to prevent aggregation of the magnetic powder. It is also possible to use an antifoaming agent together to prevent bubbles from remaining in the molded sheet.

In the above, when preparing the mixture for coating, if necessary, a mixture such as toluene, xylene, butyl carbitol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone is prepared by a ball mill. can do. Further, the mixed liquid can be cast on a supporting material such as a reinforcing base material or a separator by an appropriate developing method using a roll coater, a knife coater or the like. In that case, the mixed solution is not limited, but it is preferable to prepare it so that the solid content concentration is 5 to 85% by weight from the viewpoint of casting property and the like.

On the other hand, a silicone-based resin and magnetic powder are mixed with a mixing roll or Banbury Mimasa without using a solvent, and the mixture is spread by a calender roll or the like on a supporting material such as a reinforcing base material or a separator. The silicone-based resin sheet can be formed also by such a method.

Examples of silicone resins include R ₃ Si
O, R ₃ SiO _1/2 , R ₂ SiO ₂ , R ₂ SiO, RSiO ₃ , S
iO ₂ , RSiO _3/2 (wherein R is an organic group such as an aliphatic hydrocarbon group such as a methyl group, an ethyl group and a propyl group, an aromatic hydrocarbon group such as a phenyl group, an olefin group such as a vinyl group) , Or a hydrolyzable group such as a bidoxyl group.) Or the like.

Generally, a curable polyorganosiloxane which is commercially available as a silicone varnish made of polymethylsiloxane, polyphenylmethylsiloxane or the like is used. Further, an alkyd-modified silicone resin, a phenol-modified silicone resin, a melamine-modified silicone resin, an epoxy-modified silicone resin, a polyester-modified silicone resin, an acryl-modified silicone resin, a urethane-modified silicone resin, and the like can also be used. The curable polyorganosiloxane is 200 to 30
The composition is cured by a heat treatment at about 0 ° C., and when the temperature is further increased, an organic group is released and finally changes to silica, and thus the composition is excellent in heat resistance.

Silicone resins which can be preferably used from the viewpoint of strength and the like have a rigidity after curing of 100,000 dyn / cm ² or more, such as ladder type and various straight type. Further, those having excellent flexibility are preferable in terms of adhesion to a curved surface. The silicone-based resin may be used alone or in combination of two or more, and the use ratio thereof can be appropriately determined according to the handleability and strength of the pattern forming sheet, but in general, the content ratio in the pattern forming sheet is Based on 10 to 90% by weight, especially 20 to 80% by weight, and especially 30 to 70% by weight.

As the magnetic powder, an appropriate one such as a hard type or a soft type can be used according to the temperature of the adherend to be adhered.
By the way, as an example, Al-Ni-Co magnetic powder,
Fe-Ni-Al-based magnetic powder, SmCo ₅ type or Sm ₂ Co ₁₇
Rare earth cobalt-based magnetic powders such as SmFeN and Nd
Rare earth iron-based magnetic powder such as FeB-based, ferrite-based magnetic powder such as barium ferrite or strontium ferrite, alnico-based magnetic powder, Fe-Cr-Co-based magnetic powder, C
Examples thereof include u-Ni-Fe magnetic powder. The magnetic powder that can be preferably used has a Curie temperature higher than the temperature of the adherend to be bonded. By the way, Al-Ni-C
The o-type magnetic powder has a high Curie temperature, and its applicable range is wide.

As the magnetic powder, one kind or two or more kinds can be used, and the amount of the magnetic powder can be appropriately determined according to the adhesive force due to the magnetic force and the like. Generally, from the viewpoint of adhesive strength and the like, it is preferably 20% by volume or more, especially 30 to 90% by volume, and particularly preferably 50 to 60% by volume based on the content rate in the silicone resin sheet. The particle size of the magnetic powder can be appropriately determined according to the sheet thickness and the like, but in general, it is 1 μm in view of the magnetizing processability.
m to 1 mm, especially 2 to 800 μm, especially 5 to 100 μm.

Upon formation of the silicone resin sheet, appropriate additives can be blended if necessary. By the way, it is preferable to add an inorganic powder having a low melting point from the viewpoint of compensating for the decrease in sheet strength due to the heat deterioration of the silicone resin, and when adhering to an adherend having a large heat capacity and maintaining a high temperature state for a long time. Especially useful. Further, the addition of an antioxidant or an antioxidant is useful for improving the weather resistance of the sheet. Further, an appropriate colorant may be added for the purpose of coloring the sheet, and an appropriate thermoplastic polymer may be added for the purpose of reinforcing the binder force with the silicone resin.

As the above-mentioned low-melting inorganic powder, one that softens or melts at a temperature below the temperature of the adherend to be bonded, especially 700 ° C. is preferably used. The kind is not particularly limited, and generally, glass powder such as lead glass type, lead borosilicate glass type, soda glass type and other glass frit, metal powder such as aluminum or tin, lead and solder alloy are used. It In particular, crystallized glass powder can be preferably used from the viewpoint of maintaining sheet strength. As the low melting point inorganic powder, one kind or two or more kinds may be used. From the viewpoint of sheet strength, the amount of silicone resin 10
200 parts by weight or less per 0 parts by weight, preferably 1 to 100 parts by weight, and particularly preferably 5 to 75 parts by weight.

On the other hand, as the colorant for imparting the ground color to the silicone resin sheet, inorganic powder composed of metal powder or ceramic powder can be preferably used. The colorant may be used alone or in combination of two or more depending on the desired background color, and the particle size is generally 50 μm or less, preferably 0.05 to 20 μm, but is not limited thereto. It should be noted that it is effective to improve the hiding power or reflectance by adhering the colorant to a flaky matrix such as mica and blending it as a flake powder.

Examples of commonly used colorants include white substances such as silica, titania, alumina, zinc white, zirconia, calcium oxide, mica, calcium carbonate and talc. In addition, for example, manganese oxide / alumina, chromium oxide / tin oxide, iron oxide, cadmium sulfide / selenium sulfide, red products, cobalt oxide, zirconia / vanadium oxide, chromium oxide / divanadium pentoxide, blue products, chromium oxide / oxidation. Black products such as cobalt, iron oxide, manganese oxide, chromate and permanganate, yellow products such as zirconium, silicon, praseodymium, vanadium, tin, chromium, titanium and antimony, chromium oxide, cobalt
Chromium, green materials such as alumina and chrome, aluminum
Examples include peach colored substances such as manganese, iron, silicon and zirconium.

The thickness of the silicone resin sheet can be appropriately determined, but is generally 10 μm in view of strength and magnetic force.
.About.1 mm, especially 20 to 500 .mu.m, especially 30 to 200 .mu.m. The magnetic force can be applied to the silicone resin sheet by an appropriate magnetizing treatment method such as a method of treating the magnetic powder in the sheet with an electromagnet or the like. In that case, it is advantageous from the viewpoint of stability of the adhesive force to perform the magnetizing treatment so that the N poles and the S poles are alternately arranged by the alternating current due to the coil current or the like.

The pattern forming sheet according to the present invention can also be formed as a superposed product having the ink receiving layer 11 on the surface as illustrated in FIGS. The ink receiving layer is
It is provided as necessary for the purpose of imparting a fine ink pattern with high accuracy, forming an ink pattern having a clear contrast, and the like.

The ink receiving layer can be formed as an appropriate resin layer or the like, but from the viewpoint of heat resistance and the like, it is preferably formed as a layer made of a colorant-containing silicone resin.
Further, the ink receiving layer may contain an inorganic powder having a low melting point for the purpose of compensating for thermal deterioration. The ink receiving layer can be formed according to the above-mentioned silicone resin sheet. Therefore, the silicone resin or colorant,
Examples of the low melting point inorganic powder include those exemplified for the silicone resin sheet.

The pattern-forming sheet of the present invention can be made into a porous form for the purpose of smooth volatilization of the thermal decomposition product. For example, a method of forming a large number of fine holes in a silicone resin sheet or the like by a punching method, a method of using a woven cloth or a non-woven cloth as a reinforcing substrate, or a method of using a metal foil or a net having a large number of fine holes, etc. It can be performed by an appropriate method.

The pattern-forming sheet of the present invention is excellent in heat resistance, weather resistance, chemical resistance, strength, etc. and is used as it is or in a high temperature state as a pattern sheet provided with a pattern.
For example, it can be adhered to an adherend at a temperature of 500 ° C. or more immediately after being taken out from the processing furnace, especially 600 ° C., especially 700 to 800 ° C. through magnetic force, and after it becomes unnecessary, the magnetic force from the adherend is increased. It can be easily removed without contamination by peeling it off against adhesion. Therefore, as the adherend, for example, iron or steel such as silicon steel, nickel, cobalt, chromium oxide, magnet, or the like, which has a property of adhering to a magnet, is used.

The pattern sheet is formed using the pattern-forming sheet of the present invention by providing the pattern-forming sheet with a pattern made of ink or an engraving pattern having holes or irregularities, or by using an appropriate pattern-forming sheet. It can be performed by punching into a form. It is also possible to form a pattern sheet having an arbitrary pattern such as a composite of the above pattern elements or a composite pattern of patterns formed by various other methods.

An appropriate ink such as a commercially available product can be used for forming the ink pattern, and the ink using the above-mentioned inorganic colorant is preferable from the viewpoint of heat resistance and the like. In addition, an ink prepared by mixing the colorant and the silicone-based resin with a solvent, if necessary, using a suitable kneading machine such as a roll mill or a pot mill to prepare a fluid such as a paste is also preferably used from the viewpoint of fixing property. sell. Carbon or metal powder may be used as the colorant.

As the silicone-based resin in the above-mentioned silicone-based ink, those exemplified in the above-mentioned pattern forming sheet are used. The use ratio of the colorant and the silicone resin is appropriately determined depending on the contrast with the sheet material, etc., but generally 10 to 500 parts by weight, and especially 50 to 200 parts by weight of the silicone resin per 100 parts by weight of the colorant. Is used. In the preparation of the ink, if necessary, suitable additives such as an organic binder, a wax, a dispersant, a softening agent, a foaming agent and the like according to the conventional ink may be blended.

An ink sheet such as a print ribbon is, for example,
It can be formed by holding a silicone-based ink on a supporting base material such as a film or cloth by a coating method, an impregnation method, or the like. As the supporting base material, customary materials such as a plastic film such as polyester, polyimide and fluororesin, and a cloth made of fibers such as polyamide and polyester may be used. The ink sheet can be prepared into various types, for example, for thermal transfer, for stamping, or for stamping transfer, depending on the object or method of pattern application.

The method of forming the pattern with ink is arbitrary. An appropriate pattern forming method such as a handwriting method, a coating method via a pattern forming mask, a transfer method of a pattern provided on a transfer paper, or a forming method by a printer may be adopted. The pattern forming method using a printer has an advantage that an appropriate pattern can be formed accurately and efficiently. As the printer, an appropriate printer such as a thermal transfer type printer, an XY plotter type printer, a wire dot type printer, an impact type printer, or an inkjet type printer can be used. The pattern to be formed is also arbitrary, and may be an arbitrary pattern such as a print pattern, a picture pattern, or a bar code pattern. When an identification label is formed, it is preferable that a good contrast or color difference is formed between the sheet material and the ink pattern.

The method of forming a pattern sheet obtained by engraving a pattern having holes or irregularities on a pattern forming sheet or a pattern sheet in a punching form, and the formation pattern thereof are arbitrary.

The step of forming the pattern sheet by imparting a pattern or form to the pattern forming sheet may be before or after adhering the pattern forming sheet to the adherend. When a pattern is formed by a printer, it is usual to apply a pattern in advance to form a pattern sheet and adhere the pattern sheet to an adherend. The pattern sheet formed in advance can be protected by temporarily attaching a separator to the pattern forming surface, if necessary, until it is put into practical use. The pattern forming sheet or the pattern sheet may be adhered to an adherend by an automatic adhering method using a robot or the like.

[0034]

【Example】

Example 1 A xylene solution containing 30 parts by weight of polyphenylmethylsiloxane having an average molecular weight of about 300,000 and a hydroxyl group content of 1 mol% (parts by weight; the same applies hereinafter) was treated with Fe having an average particle size of 5 μm.
-Ni-Al magnetic powder 15 parts, low melting point glass powder having an average particle size of 5 μm and a softening point of 400 ° C. 15 parts, and talc powder 15 parts having an average particle size of 0.8 μm were added and mixed homogeneously.
The dispersion was treated with a silicone release agent to a thickness of 70μ
A sheet having a thickness of 80 μm was formed by applying the composition on a separator made of glassine paper having a thickness of m by a doctor blade method and drying at 150 ° C. The sheet was magnetized to obtain a pattern forming sheet.

On the other hand, in a xylene solution containing 40 parts of carnauba wax, 30 parts of paraffin wax, and 30 parts of ethylene / vinyl acetate copolymer, an average particle diameter of 0.5 μm composed of chromium oxide, iron oxide, cobalt oxide, and manganese oxide.
100 parts of the black pigment are added and mixed homogeneously at 130 ° C. to prepare an ink, which is coated on a polyester film having a thickness of 6 μm with a hot melt gravure coater and dried to be retained, An ink sheet having an ink layer with a thickness of 5 μm was obtained.

A bar code pattern was formed on the pattern forming sheet through a commercially available thermal transfer printer and the ink sheet to obtain a pattern sheet.

Comparative Example A pattern forming sheet and a pattern sheet were obtained in the same manner as in Example 1 except that Fe-Ni-Al magnetic powder was not added.

Evaluation Test The pattern sheets obtained in Examples and Comparative Examples were adhered to an iron block maintained at 500 ° C. and left for 1 hour, and then the adhesion state and pattern state of the pattern sheets were examined. Further, after cooling the iron block, the pattern sheet was peeled off to examine the removability and the stain resistance of the adherend. The pattern sheet of the comparative example showed a bonded state by fusion at the initial stage with respect to the iron block.

The above results are shown in the following table.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example pattern sheet.

FIG. 2 is a sectional view of an example of a pattern forming sheet.

FIG. 3 is a cross-sectional view of another pattern forming sheet example.

FIG. 4 is a cross-sectional view of still another example of a pattern forming sheet.

[Explanation of symbols]

 1: Sheet for pattern formation 11: Ink receiving layer 12: Reinforcing base material 2: Pattern layer 3: High temperature adherend

Claims (7)

[Claims] 1. A pattern-forming sheet comprising a silicone-based resin sheet containing magnetic powder. 2. The pattern forming sheet according to claim 1, wherein the silicone-based resin sheet also contains an inorganic powder having a low melting point. 3. The pattern forming sheet according to claim 1, which has an ink receiving layer made of a silicone resin containing a colorant. 4. The pattern forming sheet according to claim 3, wherein the ink receiving layer contains a low melting point inorganic powder. 5. The pattern forming sheet according to claim 2, wherein the low melting point inorganic powder is crystallized glass. 6. The pattern forming sheet according to claim 1, which has a reinforcing base material. 7. A pattern sheet comprising the pattern forming sheet according to claim 1 having a pattern made of ink.