JPH04120585A - Pattern forming sheet - Google Patents

Abstract

PURPOSE:To form the pattern formation sheet while easily adding an optional pattern upon occasion by providing a pattern made of heat-resisting ink on one surface of a metal powder sheet and a cohesive layer on the other surface, and forming a sintered pattern by a sintering process. CONSTITUTION:The metal powder sheet of an aluminum-based material is provided with the pattern of the heat-resisting ink to form the sintered pattern; and the metal powder sheet formed of aluminum-based powder by using a resin binder has the pattern of the heat-resisting ink on one surface and the cohesive layer, containing aluminum-based powder, on the other surface and the sintering process is performed to form the sintered pattern. Consequently, the pattern which is flexible and has curved-surface following-up performance is given upon occasion by a proper printing system such as a thermal printer. The pattern formation sheet which is formed by sintering is sintered and fixed to an adhered body to form the sintered pattern, and the sheet is adhered tightly to the adhered body at this time. Consequently, flexible and occasional label formation is available and the heat resistance of the sintered body is improved.

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 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 that was formed had poor clarity due to blurring and the like.

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

That is, the present invention has a metal powder sheet formed by holding aluminum powder with a resin binder, having a pattern made of heat-resistant ink on one side, and an adhesive layer containing aluminum powder on the other side, The present invention provides a pattern-formed sheet characterized in that a fired pattern is formed by firing treatment.

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 that time, the adhesive layer firmly adheres to the adherend due to adhesive action such as fusion and diffusion of the aluminum powder contained in the adhesive layer.

Examples of Constituent Elements of the Invention The metal powder sheet used in the present invention is formed by holding aluminum powder in shape with a resin binder.

As the aluminum-based powder, aluminum powder, aluminum-based alloy powder, or metal powder that is alloyed by mixing with aluminum and heating is used. Examples of aluminum-based alloys include aluminum-copper, aluminum-silicon, and aluminum-zinc. Further, examples of metals that can be alloyed by mixing with aluminum and heating include zinc and tin. The metal powder sheet is formed using one or more types of aluminum-based powder. 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 not more than 90% by weight of aluminum powder, especially 20% by weight
~50% by weight. The particle size of the powder such as aluminum powder used to form the metal powder sheet is 0.1 to 1 Ohm.
, in particular, 0.8 to 2 hm is suitable.

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, butyral 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, particle size, etc. 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 the 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 support base 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 perform a sufficient defoaming treatment such as by using an antifoaming agent in combination so that no air bubbles remain in the spreading layer. 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 μm.

The pattern-formed sheet of the present invention has a pattern made of heat-resistant ink on one side of a metal powder sheet, and an adhesive layer containing aluminum powder on the other side.

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, a binder,
The mixture is mixed in a ball mill or the like in combination with appropriate additives such as plasticizers and dispersants to form a fluid such as a paste.

Optional ingredients such as glass powder and inorganic pigments, which were used in conventional direct coating methods such as screen printing methods and transfer methods of coating patterns formed on transfer paper,
A typical example is a paste-like ink made by mixing a colored glass alone with a binder.

The composition of the heat-resistant ink may be appropriately determined depending on the contrast with the adherend, adhesion, etc. Inorganic powders and fibers made of ceramics, metals, alloys, oxides thereof, etc. are generally used as components that remain after firing to form the fired pattern. It is appropriate to use powder with a particle size of 0.1 to 20 μm and fibers with the same diameter and a length of 100 μm or less, but are not limited thereto. Specific examples of components forming the fired pattern include low melting point metals such as aluminum, zinc, and tin, silica, calcium carbonate, titanium oxide, zinc white, zirconia, calcium oxide, alumina, and oxides that are oxidized below the firing temperature. White substances such as metal compounds such as carbonates, nitrates, and sulfates, and metal ions such as iron, copper, gold, chromium, and selenium, such as manganese oxide, alumina, chromium oxide, tin oxide, iron oxide, and sulfide. Red substances such as cadmium and selenium sulfide, manganese, cobalt,
Blue materials containing metal ions such as copper and iron, such as cobalt oxide, zirconia/vanadium oxide, chromium oxide and divanadium pentoxide; containing metal ions such as iron, copper, manganese, chromium, and cobalt, such as chromium oxide - Black substances such as cobalt oxide, iron oxide, manganese oxide, chromate, and permanganate are listed.

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. Typical examples include ceramic powder such as glass powder. The adhesion imparting agent to be used may be appropriately determined based on the heat resistance of the adherend, etc. (according to the firing temperature and the purpose of use of the pattern forming sheet).

The binder used is one that disappears by thermal decomposition below the firing temperature, such as wax or resin. Preferred vine 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. If the binder of the heat-resistant ink and the resin binder of the metal powder sheet have significantly different properties such as thermal decomposition temperature, defects in appearance such as foaming and deformation are likely to occur in the fired product. 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 are made of the same type of resin. The amount of binder used as necessary is
A suitable amount is 5 to 80% by weight of the fired pattern forming components.

The method of forming the pattern on the metal powder sheet using the heat-resistant ink is arbitrary. Handwriting method, coating method using pattern forming mask, transfer method of pattern on transfer paper, forming method using Pnonta such as inkjet type, etc.
Any suitable pattern forming method may be employed. The pattern to be formed is also arbitrary. Any pattern such as a printed pattern, a transfer pattern, a picture pattern, a barcode pattern, etc. may be provided. An ink sheet such as a printing ribbon, which is necessary when forming a pattern using a printer such as an XY plotter, wire dot type, thermal transfer type, or impact type, is made by applying heat-resistant ink from a film or cloth using a coating method, an impregnation method, etc. It can be formed by holding it on a supporting base material. As the supporting base material, conventional materials such as plastic films 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 patterning of the metal powder sheet may be done at an ad hoc stage in the field. Note that the surface on which the pattern has been formed may be protected without pasting a separator, if necessary, before the pattern forming sheet is subjected to the baking process. In the case of a transfer method, the transfer red can be attached as is and used as a separator.

The pattern-forming sheet of the present invention is provided with an adhesive layer to facilitate attachment to the adherend, and the adhesive layer is provided with an adhesive layer in order to increase the tightness of attachment to the adherend during firing. It contains aluminum powder.

The step of providing the adhesive layer may be performed either before or after providing the heat-resistant ink pattern on the metal powder sheet. The adhesive layer can be attached, for example, by applying an adhesive containing aluminum powder onto a metal powder sheet, or by transferring an adhesive layer containing aluminum powder provided on a separator onto a metal powder sheet. This can be done by The thickness of the adhesive layer may be determined as appropriate depending on the intended use. Generally, it is 1 to 200 μm. 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 be temporarily attached to an adherend, and disappears by thermal decomposition at a temperature below the firing temperature. From the standpoint of the firing process and the ability to form a good firing pattern, the vine adhesive is preferably one whose resin component has a lower thermal decomposition temperature than the resin binder of the metal powder sheet. Generally, rubber-based adhesives, acrylic, IL-based adhesives, vinyl alkyl ether-based 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. Add 10 to 30 parts by weight of a tackifying resin such as petroleum resin, terpene resin, rosin resin, xylene resin, or coumaron indene resin to 100 parts by weight of a rubber adhesive or such polymer.
Rubber adhesives containing 0 parts by weight, other compounding agents such as softeners and anti-aging agents, and acrylic adhesives mainly composed of polymers of alkyl esters of acrylic acid or methacrylic acid are used.

As the aluminum-based powder to be contained in the adhesive layer, those exemplified in the above-mentioned metal powder sheet can be used.

Among these, those of the same type as those used for forming the metal powder sheet are preferably used. The particle size of the aluminum-based powder used is suitably 0.8 to 20 μm, preferably 0.1 to 50 μm. The amount of aluminum powder to be used is appropriately determined depending on its specific gravity, particle size, etc., and is generally used in an amount of 20 to 400 parts by weight, especially 50 to 250 parts by weight, per 100 parts by weight of the adhesive. If the content of aluminum-based powder in the adhesive layer is too large, temporary adhesion will be poor, and if it is too small, adhesion to the adherend upon firing will be poor.

The pattern-forming sheet of the present invention is fixedly applied to an adherend as a fired pattern, and is preferably used for forming identification patterns such as bar codes on articles made of glass, ceramic, metal, etc. The formation of the firing pattern is
This can be done by adhering a pattern-forming sheet to an adherend via an adhesive layer and then performing a baking treatment. The resin binder, etc. disappears during the firing process, and the components remaining after firing in the metal powder sheet and heat-resistant ink form a fired object while preserving the pattern, adhere to the adherend, and ultimately form a fired pattern on the adherend. stick. At that time, the aluminum powder contained in the adhesive layer contributes to improving 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 a long adherend that is cut after firing, a continuous body of adherends, and the like. 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 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 an adherend through an adhesive layer, the pattern does not easily fall off, and it is easy to adhere to curved surfaces.

In addition, the firing process allows the fired pattern to be firmly attached to the adherend, and the formed fired pattern has excellent durability and
Excellent heat resistance and thermal shock resistance.

Example 100 parts of mixed powder of 60 parts (by weight, the same applies below) of aluminum powder with an average particle size of 3 μm and 40 parts of zinc powder with an average particle size of 3 μm, 40 parts of polybutyl methacrylate, 2 parts of dibutyl phthalate, and 1 part of stearic acid. , toluene 1
A slurry obtained by uniformly mixing 00 parts with a ball mill was spread on a 50 μm thick polyester film using a doctor blade method and dried to form a 50 μm thick metal powder sheet.

Next, 50 parts of zinc powder with an average particle size of 3 μm, 10 parts of copper chromate with an average particle size of 1 μm, 30 parts of stearic acid, and ethylene.
A heat-resistant ink prepared by uniformly dispersing 10 parts of vinyl acetate copolymer in l.luene using a ball mill was applied to a thickness of 6 cm.
coated on a polyester film and dried to a thickness of 8 μm.
An ink sheet having a coating layer of m was prepared, and a barcode pattern was applied to one side of the metal powder sheet using the ink sheet and an ordinary thermal transfer printer.

Then, 60 parts of a mixed powder of 40 parts of aluminum powder with an average particle size of 3 μm and 20 parts of zinc powder with an average particle size of 3 ul, 40 parts of an acrylic adhesive, and 0.6 parts of stearic acid were mixed in a ball mill using 100 parts of toluene. The slurry obtained by uniform dispersion is spread on a polyester film with a thickness of 38 um using a doctor blade method, and dried to form a sheet having an adhesive layer with a thickness of 20 μm. A pattern-formed sheet was obtained by laminating the exposed surface with an adhesive layer.

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. By firing, the organic components such as the metal powder sheet were burnt out, and a fired pattern that firmly adhered to the aluminum plate was obtained. Moreover, the barcode pattern of the firing pattern was very clear. Furthermore, the pattern-formed sheet was flexible and could be easily attached temporarily to a three-dimensionally curved surface of an adherend, and had excellent adhesion after firing.

On the other hand, the patterned sheet was temporarily attached to a 500 μm thick aluminum plate through its adhesive layer, and
After being fired for a period of time (in air), it was immediately immersed in water and quenched, and the fired pattern adhered firmly to the aluminum plate without falling off, and the barcode pattern was also very clear.

Comparative Example A pattern-formed sheet was obtained in the same manner as in the example except that the adhesive layer provided on one side of the metal powder sheet was formed using only an acrylic adhesive.

The above pattern-formed sheet was coated with a thickness of 50 mm through its adhesive layer.
When it was temporarily attached to a 0 μm aluminum plate and fired at 500°C for 3 hours (in air), it was immediately immersed in water to rapidly cool it, and the fired pattern peeled off.

Claims (1)

[Claims] 1. A metal powder sheet made of aluminum-based powder held in shape with a resin binder has a pattern made of heat-resistant ink on one side, and an adhesive layer containing aluminum-based powder on the other side. A pattern-formed sheet characterized by forming a fired pattern.