JPH04194974A - Pattern forming sheet - Google Patents

Abstract

PURPOSE:To easily and arbitrarily give a desired pattern comprising a heat resistant ink and to easily form identification patterns for multikind small scale production by providing a pattern comprising a heat resistant ink on a specified metal powder sheet and calcining the sheet to form a calcined pattern. CONSTITUTION:The metal powder sheet used consists of two or more kinds of aluminum-base powders having different particle shapes bound with a resin binder. A pattern comprising a heat resistant ink is provided on this metal powder sheet and then the sheet is calcined to form a calcined pattern. Thereby, any desired pattern comprising a heat resistant ink can be easily and arbitrarily given to the sheet to easily form an identification pattern for multikind small scale production. Moreover, the pattern can be easily adhered with using an adhesive layer which prevents dropout of the pattern and realizes easy adhesion of the pattern on a curved surface.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is characterized in that a pattern of heat-resistant ink is provided on an aluminum-based metal powder sheet to form a firing pattern, and the pattern is suitable for forming identification labels, etc. Relating to a formed sheet.

Conventional technologies and issues As production systems shift to high-mix, low-volume production, it is important to develop labels with excellent durability and heat resistance for use in managing products made of metal, glass, fired ceramics, etc., as well as semi-finished products and parts. provision has become an important issue.

Conventionally, substrate-type labels made of fired ceramics, metals, wax bodies, etc. have been known as management labels with excellent heat resistance.

However, there are problems such as lack of simple adhesion due to the time required for fixing screws, etc., lack of adhesion to curved surfaces due to rigidity, lack of flexible control label formation due to difficulty in applying patterns on-site, etc., and high-mix low-volume production system. There were problems such as a lack of ability to form labels for a wide variety of uses, which are necessary for the management of individual parts, etc.

In view of the above problems, a firing pattern sheet has been proposed in which a pattern of glass powder-containing ink is applied to a glass powder-containing sheet by screen printing. This adhesive adheres to the adherend while fusing the applied patterns during firing, and has flexibility and flexible label forming properties, and the fired product has excellent heat resistance.

However, in a high-mix, low-volume production system, the number of screens that must be prepared in advance is enormous, and the preparation takes a lot of time.
There were problems that required multilateral efforts.

Furthermore, even if an adhesive layer is provided on the firing pattern sheet to enable easy temporary attachment, the fired object will have poor adhesion to the adherend, and will easily peel off or fall off, especially during the rapid cooling process. There was a problem. In particular, in the case of sheets made of non-glass ceramic powder, there is a problem in that the firing fixing properties are extremely poor. Furthermore, there was also the problem that the fired pattern formed had poor clarity due to blurring and the like. In addition, the recognizability of the pattern should be improved by increasing the reflectance (when an inorganic coloring pigment is added, there is a problem that the firing fixation property is reduced).

Means for Solving the Problems The present invention overcomes the above-mentioned problems by using an aluminum-based metal powder sheet for the heath.

That is, in the present invention, a pattern made of heat-resistant ink is provided on a metal powder sheet made of a mixture of two or more types of aluminum-based powders having different particle shapes held together by a resin binder, and a pattern made of heat-resistant ink is formed by a baking process. The present invention provides a pattern-formed sheet characterized in that it is formed in such a way that the following patterns are formed.

Function: The pattern-forming sheet described above is flexible and has the ability to follow curved surfaces, and a pattern can be applied at any time by an appropriate printing method such as a thermal transfer printer. Further, by adding an adhesive layer, it can be easily temporarily attached to an adherend. On the other hand, by firing, the pattern-forming sheet preserves the pattern imparted thereto, becomes a fired body, and adheres to the adherend, thereby forming a fired pattern. At this time, when the adhesive layer contains aluminum powder, the powder adheres more firmly to the adherend due to adhesive action such as fusion and diffusion of the powder.

Furthermore, in addition to the reflectivity based on each particle, the formed firing pattern is based on the improvement of surface roughness by using two or more types of aluminum powder with different particle shapes. can be increased,
The visibility of the pattern is excellent.

Examples of Constituent Elements of the Invention The metal powder sheet used in the present invention is a mixture of two or more types of aluminum-based powders having different particle shapes, whose shape is maintained with a resin binder.

As the aluminum-based powder, aluminum powder, aluminum-based alloy powder, or metal powder that can be alloyed by mixing with aluminum and heating is used. Examples of aluminum-based alloys include aluminum-copper, aluminum-silicon, and aluminum-zinc. Examples of metals that can be alloyed by mixing with aluminum and heating include zinc and tin.

The combination of two or more types of aluminum-based powders having different particle shapes used to form the metal powder sheet is arbitrary, and there is no particular limitation on the particle shape. From the viewpoint of reflectivity, it is advantageous to use scaly powder, and from this point of view, it is preferable to use a combination of scaly powder and powder of other particle shapes. In this case, from the viewpoint of the balance between reflectance and firing fixity, it is desirable that the proportion of the scaly powder used be 10 to 90% by weight, particularly 20 to 80% by weight, based on the total powder. General particle shapes other than scale-like in aluminum-based powder include, for example, spherical, granular, and pulverized (amorphous) shapes. Note that the components of the aluminum-based powders used may be the same or different.

If necessary, a powder having a melting point lower than that of the aluminum-based powder used, such as glass powder or metal powder, may be added to the metal powder sheet for the purpose of improving adhesion to the adherend. The amount added may be appropriately determined depending on the purpose of use. Generally, it is 90% by weight or less, especially 20 to 50% by weight of the aluminum powder. The particle size of the powder such as aluminum powder used to form the metal powder sheet is 0.
．． A suitable thickness is 0.8 to 20 μm, among which 1 to 100 μm.

As the resin binder, one that is thermally decomposed and disappears during firing is used, and there are no particular limitations on its type. In general, hydrocarbon resins, vinyl or styrene resins,
Acetal resin, petitral resin, acrylic resin, polyester resin, urethane resin, cellulose resin, etc. are used. The amount of the resin binder used may be appropriately determined depending on the specific gravity and particle size of the aluminum-based powder used together. Generally, 5 to 100 parts by weight, particularly 15 to 50 parts by weight, are used per 100 parts by weight of aluminum powder. If the amount of resin binder used is too small, the sheet will have poor shape retention, and if it is too large, the sheet will be prone to cracking or foaming during firing.

Formation of a metal powder sheet can be carried out, for example, by mixing sheet-forming components using a solvent or the like in a ball mill or the like, spreading the mixed solution on a supporting substrate such as a separator using an appropriate method, and drying it. . As for the developing method, the doctor blade method is preferable in terms of layer thickness control accuracy.

It is preferable to carry out a sufficient defoaming treatment so that no air bubbles remain in the spreading layer, rather than using an antifoaming agent in combination. Note that when forming the metal powder sheet, appropriate additives such as a plasticizer and a dispersant may be added as necessary. The thickness of the metal powder sheet to be formed may be appropriately determined depending on the intended use, and is generally 10 to 500 m.

The pattern-formed sheet of the present invention is a metal powder sheet provided with a pattern made of heat-resistant ink.

The heat-resistant ink used is prepared so that the fired product adheres to the adherend through a firing process. Such heat-resistant inks usually contain one or more pigments or fillers, a fixing agent, a solvent, and, if necessary, appropriate additives such as a binder, plasticizer, and dispersant. The mixture is mixed in a ball mill or the like to form a fluid such as a paste. For example, optional components such as glass powder and inorganic pigments, or colored glass alone are mixed together with a binder, which are used in conventional direct coating methods such as screen printing methods, or transfer methods of coating patterns formed on transfer paper. Paste-like ink is a typical example.

The composition of the heat-resistant ink may be determined as appropriate depending on the contrast with the adherend, adhesion, etc. As the component that remains after firing to form the fired pattern, inorganic powders and fibers made of ceramics, metals, alloys, oxides thereof, etc. are generally used. Particle size is 0.1~20jt
It is appropriate to use a powder of 00 μm or less in diameter and a fiber with a length of 00 μm or less, but the present invention is not limited thereto. Specific examples of components forming the fired pattern include low melting point metals such as aluminum, zinc, and tin, silica, tunorsium carbonate, titanium oxide, zinc white, zirconia, calcium oxide, alumina,
carbonates that are oxidized to such oxides at temperatures below the calcination temperature;
White substances such as metal compounds such as nitrates and sulfates, iron, copper,
Contains metal ions such as gold, chromium, and selenium, such as red substances such as mankan oxide, alumina, chromium oxide, tin oxide, iron oxide, cadmium sulfide, and selenium sulfide, and metal ions such as mankan oxide, cobalt, copper, and iron. For example, blue materials such as cobalt oxide, zirconia/vanadium oxide, chromium oxide/divanadium pentoxide, iron, copper, manganese, chromium,
Examples include black substances containing metal ions such as cobalt, such as chromium oxide, cobalt oxide, iron oxide, mankanoxide, chromate, permanganate, and the like.

The adhesion imparting agent, which is used as necessary, imparts the property that the fired body adheres to the adherend when the heat-resistant ink is fired.For example, it melts below the firing temperature and does not disappear upon firing. It consists of substances that remain after washing. A typical example thereof is ceramic powder such as glass powder. The adhesion imparting agent to be used may be appropriately determined depending on the firing temperature based on the heat resistance of the adherend and the intended use of the pattern forming sheet.

As the binder, a material such as wax or resin that disappears by thermal decomposition below the firing temperature is used. Preferred waxes include paraffin waxes, natural waxes, ester waxes, higher alcohol waxes, and higher amide waxes.

Examples of the resin include the resins listed above as the materials for forming the metal powder sheet. The binder of the heat-resistant ink and the resin binder of the metal powder sheet have significantly different characteristics such as thermal decomposition temperature, and the seven-fired product is likely to suffer from poor appearance such as foaming or deformation. From this point of view, it is preferable that the binder of the heat-resistant ink and the resin binder of the metal powder sheet I are made of the same type of resin. The appropriate amount of the binder used, if necessary, is 5 to 80% by weight of the baked pattern forming components.

The method of forming the pattern on the metal powder sheet using the heat-resistant ink is arbitrary. Any suitable pattern forming method may be employed, such as a handwriting method, a coating method using a pattern forming mask, a method of transferring a pattern placed on a transfer paper, or a method of forming using a printer such as an inkjet type. The pattern to be formed is also arbitrary. Any pattern such as a print pattern, transfer pattern, picture pattern, or barcode pattern may be used. An ink sheet such as a printing ribbon, which is necessary when forming a pattern using a printer such as an XY plotter or a wire dot, is a method in which heat-resistant ink is held on a support base material such as a film or cloth using a coating method, an impregnation method, etc. It can be formed by As the supporting base material, conventional materials such as a plus deck film made of polyester, polyimide, fluororesin, etc., and cloth made of fibers such as nylon, polyester, etc. may be used. Pattern forming methods using printers have the advantage of being able to form appropriate patterns with high accuracy and efficiency.

The pattern may be applied to the metal powder sheet at an opportune stage, such as on-site. Note that the surface on which the pattern is formed may be protected by not pasting a separator, if necessary, until the pattern-formed sheet is baked. In the case of a transfer method, the transfer paper can be attached as is and used as a separator.

The pattern-formed sheet of the present invention may be provided with an adhesive layer, if necessary, to facilitate temporary attachment to an adherend. The step of providing the heat-resistant ink may be performed before or after providing the pattern of the heat-resistant ink on the metal powder sheet. The adhesive layer can be attached, for example, by applying an adhesive on a metal powder sheet, or by applying an adhesive layer on a separator to a metal powder sheet.
- It can be carried out by a method of transferring to. The thickness of the adhesive layer may be appropriately determined depending on the usage. Generally, it is Jm 2 0 0 (Jm 7). Note that it is desirable to attach a separator to the exposed surface of the adhesive layer to improve handling.

The adhesive used to form the adhesive layer has adhesive strength that allows it to temporarily adhere to the adherend, and disappears as it ages without being thermally decomposed below the firing temperature. From the standpoint of the firing process and the ability to form a good fired pattern, adhesives that can be preferably used are those whose resin component has a higher thermal decomposition temperature than the resin binder of the metal powder sheet. Generally, rubber adhesives, acrylic adhesives, vinyl alkyl ether adhesives, etc. are used. In particular, it consists of individual polymers such as natural rubber or similar synthetic rubber, butyl rubber, polyisoprene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, and styrene-butadiene-styrene block copolymer rubber. rubber adhesive,
Alternatively, to 100 parts by weight of a peeling polymer, add 10 to 300 parts by weight of an adhesive resin such as petroleum resin, terpene fruit resin, rosin resin, xylene resin, coumaron indene resin, etc. Rubber-based adhesives containing compounding agents such as softeners and anti-aging agents, and acrylic adhesives based on polymers of alkyl esters of acrylic acid or methacrylic acid are used.

The adhesive layer may contain a heat-resistant adhesive component such as glass powder or metal powder to ensure smooth firing and fixation to the adherend. As such a heat-resistant adhesive component, the aluminum-based powder exemplified in the above-mentioned metal powder sheet is preferably used. In particular, it is preferable to use at least one type of aluminum powder of the same type as that used for forming the metal powder sheet. The particle size of the aluminum powder is
0.1 to 504 m, especially 0.8 to 2011 m is suitable. The amount of the heat-resistant adhesive component to be used is appropriately determined depending on its specific gravity, particle size, etc. Generally, 20 to 400 parts by weight, particularly 50 to 250 parts by weight, are used per 100 parts by weight of the adhesive. If the content of the heat-resistant adhesive component in the adhesive layer is too high, the temporary adhesion strength will be poor, and if the content is too low, the effect of improving the adhesion of the adherend by firing will be poor.

The pattern-formed sheet of the present invention is preferably used for forming identification patterns such as barcodes, etc., for articles made of glass, ceramics, metals, etc. by attaching them to adherends as firing patterns. Patterns can be formed by adhering a pattern-forming sheet to an adherend via an adhesive layer, etc., and then baking it.The baking process eliminates the resin binder, etc., and creates a metal powder sheet or heat-resistant sheet. The residual component of the ink after firing is converted into a fired object while preserving the pattern, and is adhered to the adherend, ultimately fixing it to the adherend as a fired pattern.

In this case, when the adhesive layer contains a heat-resistant adhesive component such as aluminum powder, it contributes to the adhesion to the adherend.

The pattern-formed sheet of the present invention can be provided in any appropriate form, such as one in which predetermined pattern units are arranged in series, or one in which each pattern unit is labeled. The continuous body is preferably applied to an elongated adherend that is cut after the firing process, or a continuous body of adherends. Furthermore, since patterns can be efficiently applied and it is advantageous for forming uniform labels, it can also be used as a label base material for punching or cutting.

Effects of the Invention According to the pattern-forming sheet of the present invention, any pattern made of one heat-resistant ink can be easily and conveniently applied, and identification patterns for high-mix, low-volume production can also be easily formed. Furthermore, it can be easily adhered to the adherend through an adhesive layer, etc., and the pattern does not easily fall off (and can be easily adhered to curved surfaces.In addition, the fired pattern can be fixed to the adherend by the firing process, and the pattern can be easily adhered to the adherend. The fired pattern has excellent durability, heat resistance, and thermal shock resistance, as well as a high fouling rate and excellent pattern visibility and recognition.

Example: 75 parts of scaly powder (parts by weight, hereinafter) and 25 parts of granular powder
60 parts of mixed aluminum powder with an average particle size of 31vm, 40 parts of zinc powder with an average particle size of 31++11,
A slurry obtained by uniformly mixing 40 parts of polybutyl methacrylate 1, 2 parts of dibutyl phthalate, and 1 part of stearic acid in a ball mill using 100 parts of toluene was made into a polyester film with a thickness of 50μ■ using a doctor blade method. It was spread on top and dried to form a metal powder sheet with a thickness of 50 μm.

Next, 50 parts of zinc powder with an average particle size of 3 rtm, an average particle size of 1
A heat-resistant ink prepared by uniformly dispersing 10 parts of J1m chromate steel, 30 parts of stearic acid, and 10 parts of ethylene/vinyl acetate copolymer in toluene using a ball mill was applied to a 6jJm thick polyester film and dried. An ink sheet having a coating layer with a thickness of 8 vm was prepared, and a barcode pattern was applied to one side of the metal powder sheet using the ink sheet and a conventional thermal transfer printer.

Next, 60 parts of a mixed powder of 40 parts of granular aluminum powder with an average particle size of 3 μm and 20 parts of zinc powder with an average particle size of 3 μm,
A slurry obtained by uniformly mixing 40 parts of acrylic adhesive and 0.6 parts of stearic acid with 1.00 parts of toluene in a ball mill was mixed with Doctor Pray 1 and Method 1V x 381V.
A sheet having an adhesive layer with a thickness of 2 parts m, which is obtained by spreading it on a polyester film of 2 parts m and drying it, is laminated on the exposed surface of the metal powder sheet through the adhesive layer, thereby forming an adhesive layer. A pattern-formed sheet was obtained.

Next, the polyester film was peeled off from the resulting pattern-formed sheet, and it was temporarily attached to a 500 μm thick aluminum plate via the adhesive layer, and baked (in air) at 500° C. for 60 minutes. The organic components such as the metal powder sheet were burnt out by firing.

As a result of the above, a fired pattern was obtained that was firmly adhered to the aluminum plate. Moreover, the barcode pattern of the firing pattern was very AT bright.

Further, the pattern-formed sheet was flexible and could be easily temporarily attached to the three-dimensionally curved surface of the adherend, and had excellent adhesion after firing.

Comparative Example A pattern forming sheet I was obtained and a fired pattern was formed in the same manner as in the example except that granular aluminum powder having an average particle size of 3 um was used in place of the mixed aluminum powder.

Evaluation test The reflectance of the fired patterns obtained in Examples and Comparative Examples was investigated.

The results are shown in the table.

From the table, it can be seen that the reflectance is greatly improved by using together two or more types of aluminum powders having different particle shapes as in the examples.

Patent applicant: Nitto Denko Corporation

Claims (1)

[Scope of Claims] 1. A metal powder sheet made of a mixture of two or more types of aluminum powders with different particle shapes held together by a resin binder is provided with a pattern made of heat-resistant ink, and is baked by a baking process. A pattern-formed sheet characterized by being formed into a pattern. 2. The pattern-forming sheet according to claim 1, further comprising an adhesive layer containing aluminum-based powder.