JPS6280100A - Muffle painting method to base body with vitreous or ceramicsurface - 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 [Industrial Application Field] The present invention is applicable to substrates having a vitreous or ceramic surface, that is, generally glass products, or ceramics, cement molded products, enameled products, bricks, etc. The present invention relates to a method for painting ceramic molded products made of

[Prior Art] Methods for painting on a substrate having a glassy or ceramic surface include direct drawing with ink containing colored glass frit, and printing pattern layer using printing ink containing fired pigment. There are methods of transferring the printed pattern layer of a transfer film having the following.

[Problems to be Solved by the Invention] By the way, among the above-mentioned painting methods, the former method of direct drawing has the disadvantage that it is not possible to obtain a large quantity of products of the same standard and is also expensive; The method using a transfer film has the disadvantage that it cannot be applied unless the surface to be painted is flat.

On the other hand, the method of painting a substrate having a glassy or ceramic surface according to the present invention eliminates all the drawbacks of the conventional painting method, and is limited by the shape of the surface to be painted. Although this may not be the case, the painting, which has excellent adhesion strength between the surface of the substrate to be painted and the pattern layer of the painting, has provided a method by which a large quantity of products with the same standard pattern can be obtained. .

[Means for Solving the Problems] The method of painting a substrate having a glassy or ceramic surface according to the present invention comprises a thermoformable thermal Q( The printed pattern layer of the transfer sheet made of plastic film is subjected to vacuum, compressed air,
Alternatively, the colorant in the printed pattern layer on the transfer sheet is transferred to the transfer surface by a vacuum pressure method, and then the colorant in the printed pattern layer on the transfer sheet is
It is firmly fixed to the surface to be transferred.

That is, the method of painting a substrate having a glassy or ceramic surface according to the present invention involves forming a release layer on one side of a transfer base sheet made of a thermoformable thermoplastic film, and then applying a baking layer to the surface of the release layer. A first step of forming a printing pattern layer with a printing ink containing pigment to obtain a transfer sheet, and a step of transferring a substrate having a glassy or ceramic surface, the surface of which is subjected to primer treatment, if necessary. A second step in which the surface and the printed pattern layer surface of the transfer sheet come into contact with each other, and the transfer sheet is heated and deformed by a vacuum, compressed air, or vacuum-pressure method to form a glass or ceramic material. a third step of closely pressing the transfer surface of the substrate having a textured surface, and peeling off the transfer base sheet of the transfer sheet, and transferring the printed pattern layer of the transfer sheet to the transfer surface of the glass material; or fourth to obtain a substrate with a ceramic surface.
process, the transferred surface of the substrate having a glassy or ceramic surface and the fired pigment in the printed pattern layer are melted,
A fifth step is performed in which the substrate is fired at a temperature higher than the temperature at which it comes into close contact, and the fired pigment is fixed on the transferred surface.

In the method for painting a substrate having a glassy or ceramic surface according to the present invention having the following configuration,
Although the above steps of the present invention may be carried out directly on the substrate to be painted, a glass frit slurry or a squeegee may be applied to the glass or ceramic surface of the substrate to be painted.
The above steps of the present invention may be carried out after applying a primer treatment such as applying oil and drying, or forming a coating layer with an acrylic binder mixed with glass lift. Of course.

In particular, when forming the single layer of primer, if the amount of coating is too large, uneven coating will occur, and cracks may occur in the baking process in the fifth step in the areas where the amount of coating is large, so form the single layer of primer as much as possible. It is better to make it thinner.

The squeegee oil used in the primer treatment is mineral oil, vegetable oil, 2 synthetic drying oils, various solvents, and plasticizers as necessary. , a fluid substance containing resins, etc., which does not pass through the silk screen plate just by placing it on the plate, but has a viscosity that allows it to pass through the plate by pressurization with a squeegee or FfIJ motion. For example, turpentine oil, butyl carpitol acetate, turpentine, xylene, butyl cellosolve, turbine oil, cellosolve acetate, various alkyl alcohols,
Acetate, propionate, higher alkyl ester,
Acrylic acid ester resin, pine oil, etc. as needed.
Methacrylic acid resins, these copolymer resins, butyral resins, cellulose acetate butyrate, nitrocellulose, cellulose acetate, cellulose acetate propionate, ethyl cellulose, methyl cellulose and other cellulose resins, alkyd resins, polyethylene oxide, phenolic resins, lily 7 resin.

Melamine resin, polyester, melamine-alkyd resin, vinyl resin, etc. are added. Similarly, the glass frit is 1, for example, pbo 78%*5
t0210%, 820312% or Ranal low melting point Karasuya, PbO-B2O3 system, pbo-B203-5in2 system, PbO-ZnO-B2O5/1. 5nO2-T
iO-8in2- PbO-CdOM etc. 57. A particle size of about 2 to 30 mm is used. Furthermore.

Glass frit slurry is made by adding the above-mentioned glass lift to the above-mentioned squeegee oil or water and kneading it. Generally, about 40 to 80 parts by weight of glass frit is kneaded with 1001 parts by weight of squeegee oil. things are used.

The above-mentioned primer treatment is generally carried out by spraying, dipping, etc., but for painting, if the substrate is enamel and the primer treatment bath is aqueous, electrophoresis can be used. You can also. Further, for forming a single layer of primer by primer treatment, it is most preferable to use an acrylic binder that generates a hot lump of metal in the fifth firing step and easily sublimates.

Next, as the transfer base sheet in the transfer sheet used in the method of the present invention, thermoformable thermoplastic films are used, such as polypropylene, polystyrene, ABS, nylon, acrylonitrile, and methyl methacrylate.

Thickness 50~5 made of PVC, or even a mixed resin of these, etc.
00 pot, preferably about 70 to 200 liters of film.

The release layer formed on one side of the transfer base sheet is made of silicone, wax, rosin, cellulose resin, etc., and usually has a thickness of about 1 to 5 g (dry)/m'', such as gravure coating or roll coating 'J. Although it is formed by a manufacturing method, a release layer made of rosin or cellulose is suitable when considering the sublimation property after firing in the fifth step.

The printed pattern layer formed on the surface of the peeled S layer mentioned above is as follows.

It is formed from a printing ink containing a coloring agent made of fired pigment as an essential component, and the fired pigment that is an essential component in the printing ink includes, for example, oxides of Fe, Cr, Zn, etc. Group...
...brown Zn, Co, kl oxides
...Old...Song...Blue Ti, Zn,
Co, Ni+ Cr oxides...Green Ti, Ba, Ni.

Oxides of Pb, Sb, Cd ・・・・・・・・・
...Yellow Cd, Se, S oxide ...
・・・・・・・・・・・・・・・ Red Fe, Cu
, Mn, Cr+ Co oxides, etc., including black, CdS, CaO, etc. are used.

As mentioned above, it is essential that the printing ink for forming the printed pattern layer contains a colorant made of fired pigment, but generally, it is composed of fired pigment + glass frit...・・・・・・・・・・・・・・・・・・(Powder content) 85% Sublimable binder 10 Slow drying solvent ・・・・・・・・・(Squeegee oil content) 15% Forming a printed pattern layer by silk screen printing using component printing inks has the advantage that a pattern layer with a high degree of coloration can be obtained. However, when printing a pattern layer using a silk screen ink with a powder content of 85% and a squeegee oil content of 15%, the fixing effect of the printed pattern layer is not sufficient due to the large amount of powder in the ink components. It is also possible to cover the surface of the printed pattern layer with a heat sealing layer to create a heat sealing effect, but if this heat sealing layer is thick, cracks may occur in the firing process, which is the fifth step, or the pattern layer may be damaged. There are disadvantages such as shrinkage phenomenon. Therefore, it is preferable to subject the surface to be painted to a primer treatment in advance using a primer treatment bath containing glass frit to improve the adhesion between the printed pattern layer and the surface to be painted.

In addition, examples of the sublimable binder used in the printing ink suitable for forming the printed pattern layer include acrylic acid ester resins, methacrylic acid resins, copolymer resins thereof, butyral resins, and cellulose resins. , alkyd resin, polyethylene oxide, phenolic resin, urea resin, melamine resin, polyester, melamine-alkyd resin, vinyl resin, maleic resin, rosin and its modified products, etc. can be used, but cellulose resin and rosin are the most preferred. suitable. Also,
Slow-drying solvents include, for example, pentane, hexane, heptane, octane, etc., or mixtures thereof such as gasoline, petroleum, benzine, mineral spirits, aliphatic hydrocarbons such as petroleum naphtha, benzene, toluene, xylene, and cyclohexane. .

Aromatic hydrocarbons such as ethylbenzene, halogenated hydrocarbons such as trichlorethylene, perchlorethylene, chloroform, carbon tetrachloride, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol,
Monohydric alcohols such as aluminum alcohol, benzyl alcohol, diacetone alcohol, and ethylene glycol.

Polyhydric alcohols such as propylene glycol and glycerin, acetone, and methyl ethyl ketone.

Methyl isobutyl ketone, cyclohexanone.

Ketones such as methylcyclohexanone and isophorone, ethyl ether, isopropyl ether.

Ethylene glycol mono-methyl ether.

Ethylene glycol mono-ethyl ether.

Diethylene glycol mono-methyl ether.

Diethylene glycol mono-ethyl ether.

Diethylene glycol mono-butyl ether.

Ethers such as diethylene glycol di-butyl ether, ethylene glycol mono-methyl ether 0 acetate, ethylene glycol mono-ethyl ether acetate, diethylene glycol mono-methyl acetate.

Diethylene glycol mono ethyl ether acetate, diethylene glycol mono butyl ether
Single or mixed solvents such as acetate esters such as acetate, esters such as butyrate, nitrohydrocarbons, nitriles, amines, other acetals, acids, and furans are used.

As a means for forming a printed pattern layer on the surface of the release layer, known means such as an intaglio printing method, a lithographic printing method, a letterpress printing method, a screen printing method, etc. can be used. If glass frit is mixed in the printing ink, the doctor blade may be worn out (R), so it is not preferable to use a printing stage that uses a doctor blade.

Note that the printed pattern layer is formed in an arbitrary shape such as a character, a symbol, a pattern, or the like.

The process of overlapping the transfer sheet and the substrate to be painted so that the printed pattern layer on the transfer sheet and the transfer surface of the substrate to be painted are in contact with each other and bringing them into close contact can be carried out by, for example, a vacuum press method or a vacuum pressure method. , a vacuum method, a compressed air method, etc., but in this process, it is sufficient to temporarily adhere the printed pattern layer on the transfer sheet to the transfer surface, and usually 100 to 1
It is carried out under heating conditions of about 50°C.

The substrate on which the printed pattern layer is temporarily adhered to the transferred surface, that is, the substrate on which the printed pattern layer has been transferred to the transferred surface, is fired, and the fired pigment in the printed pattern layer and the transferred surface are integrated. Although the transfer sheet is fixed and the painting is completed, it goes without saying that the transfer base sheet of the transfer sheet is peeled off prior to the firing process.

The firing temperature in the firing step may be any temperature higher than the temperature at which the binder resin in the printed pattern layer temporarily adhered to the surface of the substrate for the decoration is fired; The temperature of the surface to be transferred is 550-600℃ if the surface is made of low-melting glass, and 750-8℃ if it is floating.
The temperature is 50°C, 800 to 900°C for ceramics, and 1000 to 1300°C for porcelain.

[Example] Hereinafter, the specific structure of the painting method of the present invention will be explained with reference to the drawings and examples.

Example 1 Mixed resin film of polyvinyl chloride resin and polystyrene resin with a thickness of 0.16 mm [manufactured by Royal Resin Co., Ltd.: NP]
3 g (
The film was coated uniformly over the entire surface at a ratio of dry)/trr' and dried to form a release layer 2.

' -7 Polyethylene glycol・・・・・・・・・20
Weight part rosin ・・・・・・・・・・・・・・・
・・・・・・・toz, 1 part diluting solvent ・・・・
・・・・・・・・・・・・・・・70 parts by weight (ethyl acetate: toluene: IPA=l:l:l) Next, on the two sides of the above-mentioned release layer, the following material containing a fired pigment was applied. A three-color printing pattern layer 3 was formed using printing inks [A], [B], and [C] by a silk screen method to obtain a transfer sheet 4.

Sai ink A 1 Ink acrylic resin ・・・・・・・・・・・・・・・・・・
・・・・・・40 parts by weight fired pigment ・・・・・・・
・・・・・・・・・・・・・・・・・・10 parts by weight (Ti
, mixture of oxides of Sb and Cr) glass frit
・・・・・・・・・・・・・・・・・・・・・・・・・・・ 5
Part by weight Diluent ・・・・・・・・・・・・・・・
・・・・・・・・・45 parts by weight (cyclohexanone:xylene:inholon=20:20:5) Ink B
1 Ink acrylic resin ・・・・・・・・・・・・・・・・・・
・・・40 parts by weight fired pigment ・・・・・・・・・
・・・・・・・・・・・・ Bow 0 tonne part (Zr, Si,
Cd, S, Se (1) Oxide mixture) Glass frit ・・・・・・・・・・・・・・・・・・
・・・ 5 parts by weight diluent solvent ・・・・・・・・・
・・・・・・・・・・・・45 parts by weight (cyclohexanone: xylene: isophorone = 20: 20: 5) Ink C ink acrylic resin ・・・・・・・・・・・・・・・・・・
・・・40 parts by weight fired pigment ・・・・・・・・・
・・・・・・・・・・・・10 parts by weight CA9. ．． Co
mixture of oxides) glass frit...
・・・・・・・・・・・・・・・ 5 parts by weight diluent solvent
・・・・・・・・・・・・・・・・・・・・・4
5 parts by weight (cyclohexanone:xylene:inholon=20:20:5) On the other hand, the thickness was 0.
A molded body made by press-molding a 5mm iron plate into the shape of a door is coated with antimony glaze, then coated with a water-based titanium glaze paint, dried, further baked at 820°C for 3 minutes, and then allowed to cool naturally to give a shape of approx. When cooled to 60°C, the molded body was placed in a vacuum press molding machine.

Subsequently, the door-shaped molded body in the vacuum press molding machine was
After preheating to °C, the above-mentioned transfer sheet 4 is placed on the surface of the packed molded product, and the printed pattern layer 3 of the sheet is placed in contact with the surface of the surface, and vacuum press using a silicone rubber plate is carried out. The test was conducted at 110°C for 1 minute.

After that, the laminate of the transfer sheet 4 and the door-shaped molded body was taken out from the vacuum press molding machine, cooled, and the transfer base sheet l of the transfer sheet 4 was peeled off.
The product was fired in an electric furnace for "'OXS" and allowed to cool naturally to obtain a door-shaped molded product with a painted surface.

Example? An iron plate with a thickness of 0.5 mm is press-molded into the shape of a door. After applying antimony glaze, a water-based titanium glaze paint is applied and dried, and then immersed in a primer treatment bath with the following composition and dried. A door-shaped press molded body whose surface was coated with a single layer of primer having a thickness of about 2001 L was obtained.

Primer ゝAcrylic resin・・・・・・・・・・・・・・・・・・
...30 parts by weight glass frit ...
・・・・・・・・・・・・10 parts by weight diluent solvent
・・・・・・・・・・・・・・・・・・60 parts by weight (ethyl acetate: toluene: MI BK=50:3
0:20) The primer-treated door-shaped press molded body was used as a base for decoration, and the same process as in Example 1 was carried out to obtain a door-shaped molded body whose surface was painted.

[Operations and Effects of the Invention] The method of painting a substrate having a glass or ceramic surface according to the present invention is as described above, and includes printing on the surface of a transfer sheet formed by a printing means. Since the pattern layer is transferred onto the glass or ceramic surface of the substrate having a glass or ceramic surface, the same standard can be produced in large quantities and quickly. This function and effect is achieved.

In addition, in the method of the present invention, the step of transferring the printed pattern layer on the surface of the transfer sheet to the glass or ceramic surface and temporarily adhering it is carried out using vacuum, pressure-pressure, or vacuum-pressure molding. Even if the surface of the substrate to which the printed image layer on the transfer sheet is transferred has a complex shape other than a flat surface, the transfer sheet is brought into close contact with the surface to be transferred, ensuring orderly transfer without distortion. The effect is that a printed pattern can be formed on a glass or ceramic surface.

Furthermore, in the method of the present invention, since the painting is applied by firing the fired pigment on the glassy or ceramic surface, it is possible to create a painting in which the fired pigment adheres to the glassy or ceramic surface with strong adhesive force. It also has the function and effect of being able to obtain a pattern.

[Brief explanation of drawings]

The figure is a cross-sectional view of a model showing an example of a transfer sheet used in the method of painting a substrate having a vitreous or ceramic surface according to the present invention. 1: Transfer base sheet, 2: Peeling layer, 3: Printed pattern layer, 4
: Transfer sheet.

Claims (4)

[Claims] (1) A release layer is formed on one side of a transfer base sheet made of a thermoformable thermoplastic film, and then a printed pattern layer is formed on the surface of the release layer using printing ink containing a fired pigment to form a transfer sheet. a second step of superimposing the transfer surface of the decorative substrate having a glass or ceramic surface and the printed pattern layer surface of the transfer sheet so that they are in contact with each other; or a third step of closely pressing the transfer sheet against the transfer surface of the substrate having a glassy or ceramic surface by heat deformation and pressing action using a vacuum pressure method; and a transfer base sheet in the transfer sheet. A fourth step of peeling off and obtaining a substrate having a vitreous or ceramic surface on which the printed pattern layer of the transfer sheet has been transferred to the transfer surface, and printing on the transfer surface of the substrate having a glass or ceramic surface. A fifth step of firing the substrate on which the printed pattern layer has been transferred to the transferred surface at a temperature higher than the temperature at which the fired pigment in the pattern layer melts and comes into close contact with the fired pigment, and fixing the fired pigment on the transferred surface.
A method for painting a substrate having a glass or ceramic surface, the method comprising the steps of: (2) A patent in which the transfer surface of a painting substrate having a glass or ceramic surface and the printed pattern layer surface of a transfer sheet are heated in advance when they are superimposed so that they are in contact with each other. A method for painting a substrate having a vitreous or ceramic surface according to claim 1. (3) Claims 1 or 2, wherein the transfer surface of a painting substrate having a glassy or ceramic surface is subjected to primer treatment with an acrylic binder mixed with glass frit. A method of painting a substrate having a vitreous or ceramic surface as described. (4) The glassy or ceramic surface according to claim 1, 2, or 3, wherein the pattern layer printed by the printing ink containing the fired pigment is a pattern layer printed by silk screen printing. A method of painting onto a substrate.