JPS63256584A - Manufacturing method of cosmetic ceramic body - 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 relates to a method for manufacturing a decorative ceramic body with a decorated surface, and is used for building materials for interior and exterior panels, enameled tableware, and ceramic housing equipment. The present invention provides a method for obtaining a decorative ceramic body for use in, for example.

[Conventional technology]

Conventionally, methods for manufacturing cosmetic ceramic surfaces include (1)
A method of hand-painting a ceramic body before or after bisque firing, (2) a method of applying heat transfer to a ceramic body before bisque firing using thermal transfer paper, and then firing it, and (3) a method of applying paper/water-soluble resin. A transfer sheet with a release layer/fired ink layer structure is floated on the water surface with the ink layer facing up to separate the ink layer from the paper, and the ink layer is transferred to the surface of the ceramic body, followed by drying and firing. There are methods etc.

However, among the above-mentioned conventional methods for producing decorative ceramic bodies, method (1) using hand-painting not only requires skill but also has the disadvantage of being extremely difficult to mass-produce. Methods that use paper have drawbacks such as a blocking phenomenon that easily occurs when the thermal transfer paper is stored (this causes trouble), and a thermal transfer machine is required, making the device larger. In addition, in method (2), the large plate of the ceramic body is generally not flat, so it tends to cause transfer omissions (also, it is difficult to improve the adhesion between the thermal transfer paper and the ceramic body). Therefore, if the heat-sealing layer in thermal transfer paper is thickened, there are drawbacks such as cracks occurring in the coating film obtained by firing.Furthermore, the method using water pressure transfer method (13) is a method that uses thin fired ink. Since this method transfers only the printed layer, it has the disadvantage that it cannot be applied to large objects.

[Problem that the invention seeks to solve]

The present invention aims to solve the problems that exist in conventional methods of manufacturing decorative ceramic bodies, which have poor mass productivity.
Blocking of thermal transfer paper and related troubles occur; Requires a thermal transfer machine, which increases the size of the device; Transfer failure is likely to occur on large ceramic plates; When the heat seal layer is thick, cracks occur in the coating film. do, and
The disadvantages of the hydraulic transfer method, such as the inability to apply it to large-sized objects, could not be solved at the same time.

[Means for solving problems]

According to the present inventors, 1. It has been discovered that the firing ink layer can be easily transferred by using an adhesive as the material for the adhesive layer to transfer the fired ink layer to the ceramic body. It has been found that all the shortcomings of the prior art can be eliminated by using the method.

This invention is based on the following method: ``A fired ink layer that is integrated with the ceramic base material of the transferred object when fired, and an adhesive layer that has the property of sublimated when fired are sequentially formed on a releasable base sheet that has the property of sublimating when fired. A method for manufacturing a decorative ceramic body, which comprises: adhering the transferred transfer sheet to a ceramic base material using the adhesive layer, then peeling off the releasable base sheet, and then firing the ceramic base material. ” is the key phrase.

[Effect]

In the present invention, since the transfer sheet is transferred using an adhesive layer, it can be attached by placing the transfer layer on the surface of the ceramic base material and pressing lightly, and then only the base sheet can be easily peeled off. be able to.

(Example) The releasable base sheet used in the present invention, which has the property of sublimating upon firing, is an organic sheet that sublimes at 500 to 600°C, and those containing nitrogen components cause carbonization. In particular, it is preferable to use a material that does not contain a nitrogen component, such as cellophane, polypropylene film, polyethylene film, or polyester film.

In addition, for materials containing halogen atoms, such as PvC films, the halogen ions act as reducing agents, which may cause carbonization, and halogenated hydrocarbons may be generated, such as heaters in furnaces, etc. This is not preferable because it may cause corrosion of metal parts.

The thinner the releasable base sheet is, the more preferable it is.

Further, the releasable base sheet may be a sheet provided with a releasable layer on the surface.

The fired ink applied to the releasable base sheet necessarily contains a sublimable vehicle, a fired pigment, and a solvent, and can be used to form a fired ink layer by the best printing method or coating method, The thickness of the layer is approximately 10 μm or less.

In addition, if the fired ink contains glass, it is better to avoid gravure printing, and gravure printing and offset printing are also undesirable because the amount of ink applied is too small. Further, when using the gravure printing method and wishing to obtain a decorative ceramic body having a glassy surface, it is preferable to add a glassy substance to the glaze.

Examples of the sublimable vehicle contained in the fired ink include acrylic ester resins, methacrylic acid resins, copolymer resins thereof, butyral resins, cellulose resins, alkyd resins, polyethylene oxide resins, phenolic resins, urea resins, These include melamine resin, polyester resin, melamine-alkyd resin, vinyl resin, maleic acid resin, and the like.

In addition, the solvent in the firing ink is a solvent that does not corrode the surface of the ceramic base material, for example,
Pentane, hexane, heptane, octane, etc., or mixtures thereof, aliphatic hydrocarbons such as gasoline, petroleum, benzene, mineral sublift, petroleum naphtha, etc.
Aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, ethylbenzene, halogenated hydrocarbons such as trichlorethylene, perchlorethylene, chloroform, carbon tetrachloride, methyl alcohol, catyl alcohol, propyl alcohol, butyl alcohol, amyl m-alcohols such as alcohol, benzyl alcohol, and diacetone alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, isophorone, ethyl ether, isopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol Nithyls such as dibutyl ether, acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol motsubutyl ether acetate, esters such as butyric acid esters,
Single or mixed solvents such as nitrohydrocarbons, nitriles, amines, other acetals, acids, and furans can be used.

In addition, as the fired pigment in the fired ink, for example, Fe, Cr, Zn (7) M compound...- Listen to one song...-
・Listen・Between songs・Brown Zn, Co, AI (7)
Oxide-song=-・・-song...then-・--・-song-・
- Curved blue oxides of Ti, Zn, Co, Ni, Cr - Curved - 1... - Green Ti, Ba, Ni, Pb, Sb,
Oxide of Cd・-Curved one mountain・Curved yellow Oxide of Cd, Se, S・−・−・−・・−・−・−−−−−−−−
・-・-Between songs - Red oxides of Fe, Cu, Mn, Cr, and Co. --- Turns - Between songs, including black colors, CdS,
Calcined pigments such as CaO are used, but for high temperature firing, blue (Co), green (Cr), brown (Fe, Ni, Cr) pigments are used.
, Co, Sb) % Yellow (Tt+Sb), Black (Fe, M
n) is used.

Furthermore, as the glassy material, for example, PbO78%, Slo
Low melting point glass consisting of 10% W and 12% B105,
PbO-B, O, system, PbOBtus Si0g system,
pbO-ZnO-Btus series, Snow-Tilt
Sing PbO-CaO glass with particle size 2~
A material of about 30 μm is used.

The adhesive layer formed on the fired ink layer is mainly composed of an adhesive substance that sublimes when fired or a rewet adhesive that becomes sticky when rewetted.The adhesive layer is usually an acrylic-based adhesive. It is composed of resin or acrylic-based resin. Additionally, glass frit may be added to the adhesive layer in order to prevent coating cracking due to shrinkage during firing.In addition, if the adhesive layer is composed only of acrylic resin, Because the sublimation rate is too fast, there is a risk that the baked ink layer in the decorative adhesive sheet will break through and the pattern will come off, so another resin that is compatible with the acrylic resin and has a slow sublimation rate is mixed. It is preferable to use

If the thickness of the adhesive layer is too thick, shrinkage will occur during firing, so it is preferable to set the thickness to about several microns.

In addition to the above, a releasable base sheet constituting the transfer sheet,
The firing ink vehicle, adhesive layer, etc. must not only contain nitrogen components, but also materials with extremely high heat resistance such as epoxy and silicone. This should be kept in mind.

Furthermore, when using a glaze, it should not contain silicone, as this may cause the glaze to be repelled during painting.

Ceramic substrates to be transferred include, for example, products such as enamel molded products, inorganic plates, lightweight concrete plates, glass plates, ceramics, and porcelain, as well as the above-mentioned products having fired coatings on their surfaces.

Note that the transfer sheet applied to the ceramic base material can also be used after being previously formed into a predetermined shape using a slitter or punching.

・The process of firing the ceramic substrate onto which the fired ink layer has been transferred is preferably carried out in an oxidizing atmosphere, as carbonization of organic substances is likely to occur if carried out in a reducing atmosphere, which can cause blackening.The firing time and As for the temperature, the longer and lower the temperature, the less the pattern will come off due to shrinkage of the resin.

Furthermore, the firing temperature varies depending on the type of transfer sheet, that is, the material of the firing ink layer and the material of the adhesive layer, but it is better to bake at a low temperature for 2 to 3 minutes than to bake at a high temperature (700 to 1000°C) at once. (400-600℃) After firing to remove organic substances, the surface of the ceramic base material and the fired ink are bonded to each other by a two-step process in which high-temperature firing (600-1300℃) is performed for several tens of seconds, either subsequently or after cooling. Preferably, the layer is integrated.

〔Effect of the invention〕

The method for manufacturing a decorative ceramic body of the present invention uses a transfer sheet having a fired ink layer and an adhesive layer to transfer the material to a ceramic base material and then fires it. related (can be carried out,
Since there is no need for a transfer machine, there are advantages such as the device being simplified.

Furthermore, since the transfer sheet can be subjected to punching, slitting, etc., it has the advantage of being able to be decorated with a sophisticated design.

Furthermore, the method of the present invention has the advantage that the transfer sheet can be applied to either a ceramic substrate before drying or a ceramic substrate in a dry state. .

[Specific examples]

Hereinafter, the specific structure of the method for manufacturing a decorative ceramic body of the present invention will be explained using Examples.

Acrylic resin brimer (
One layer of primer was provided by gravure printing using SLM Brimer (manufactured by Showa Ink Al) using a solid plate with a plate depth of 45 μm.

On a single layer of brimer, a yellow firing ink (an ink that turns yellow after firing) using a 2/1 mixed resin of acrylic resin/ethyl cellulose resin as a vehicle is applied by gravure printing.
A fired ink layer was formed by printing using a pigment (see below).

- Sumire "Self-view" - Hajime Otobe acrylic resin ・・・・・・−・・−・・−・・−
・ 6 parts by weight ethyl cellulose resin ---
・・・・−Triple 1 part chromium oxide ・−・−−−
−−−−・・・−・−・−10 parts by weight glass frit
・−・・−・−・−・−・・−・・ 10 parts by weight dissolved
agent ・・・・・・・・・−・−・−−1−−−
・ 70 parts by weight Furthermore, on the entire surface including the fired ink layer,
Already on the release paper is a 3μ thick film made of acrylic resin as the main component.
The adhesive layer was applied with an adhesive tape formed by a coating method to obtain a transfer sheet with a release paper, and this was further slit to a width of 5 cm to obtain a striped cane tape.

! A 60 cm square ceramic plate (manufactured by Freburn Co., Ltd., Brisera), unglazed, with a rising top and a thickness of 2+n+, was dried at 80°C for 2 hours, then a glaze (made by Nippon Frit ■) was applied, and 1
A ceramic base material was prepared by baking at 000°C for 1 hour.

First, the prepared stripe tape is attached to a part of the ceramic base material using the adhesive layer made of an adhesive substance while removing the release paper from the tape. The ethylene terephthalate film was peeled off.

The powder was then fired at 400°C for 10 minutes in an oxidizing atmosphere using an electric furnace, and then fired at 850°C for an hour.

The thus obtained ceramic plate had a yellow striped pattern, resulting in a ceramic body with a high design effect.

Claims (8)

[Claims] (1) Transfer in which a fired ink layer that integrates with the ceramic base material of the transferred object when fired and an adhesive layer that has the property of sublimating when fired are sequentially formed on a releasable base sheet that has the property of sublimating when fired. A method for manufacturing a decorative ceramic body, which comprises adhering a sheet to a ceramic base material using its adhesive layer, then peeling off the releasable base sheet, and then firing the ceramic base material. (2) The method for producing a decorative ceramic body according to claim (1), wherein the releasable base sheet is cellophane, a polypropylene film, a polyethylene film, a nylon film, or a polyester film. (3) The method for producing a decorative ceramic body according to claim 1, wherein the adhesive layer in the transfer sheet has a thickness of 5 μm or less. (4) The method for manufacturing a decorative ceramic body according to claim (1), wherein the adhesive layer in the transfer sheet contains glass frit. (5) The method for manufacturing a decorative ceramic body according to claim (1), wherein the ceramic base material is fired in an oxidizing atmosphere. (6) Firing of the ceramic substrate is performed by a first stage firing performed at the sublimation temperature of the organic substance and a second stage firing performed at the welding temperature of the fired ink layer. ) A method for producing a decorative ceramic body as described in item 2. (7) Claim (1) characterized in that a transfer sheet having a glaze layer that becomes transparent upon firing is used between the releasable base sheet and the fired ink layer.
A method for producing a decorative ceramic body as described in Section 1. (8) A glaze layer that becomes transparent upon firing is formed on the surface of the ceramic base material after the first stage firing, and then the second stage firing is performed. A method for producing a decorative ceramic body.