JP2009185379A - Porcelain enamel member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porcelain enamel member which uniformly has specific metallic luster on a porcelain enamel surface, is industrially excellent in reproducibility, and to which a coloring layer is applied to enable mass production. <P>SOLUTION: The surface 10 of an underlying body 1 baked with porcelain enamel glaze (ground coat enamel 12, cover coat enamel 13) on an iron body 11 is coated with an aqueous or organic solvent-based coating film forming liquid containing a metal component, more preferably a titanium component, and the coating is dried and baked, and is thereby provided with color layers 2 composed of iris layers indicating patterns, such as grid patterns a, dot patterns b, and stripe patterns c. Coloring portions 10a, 10b of the underlying body surface 10, and the color portions 2a, 2b of the coloring layer are alternately repeated, for example, the continual patterns composed of the lattice patterns, the continual patterns composed of the spot patterns, or the continual patterns composed of the stripe patterns are formed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hollow member used as an interior / exterior material of a kitchen cooker, and particularly relates to an improvement of a hollow member having a high design property.

  Conventionally, as one of the methods of decorating ceramics, there is a decorating method called an iris hand (raster coloring: Luster). This decoration method is an ultra-thin color-developing layer that shows a metallic luster by forming a coating containing metal components such as gold, silver, copper, etc. on the smooth surface of glazed ceramics and firing it in a low-temperature reducing atmosphere. Is formed. This ultra-thin color-developing layer has an interference color of incident light and reflected light in addition to the original color of metal oxide, and exhibits a unique metallic luster called iridescent or iris color (hereinafter, this color-developing layer) Is called the iris layer).

  As a technique for coloring the metallic luster by such an iris layer, for example, Patent Document 1 discloses that a liquid mixture of an organic compound of gold, copper, bismuth, titanium, and molybdenum and a resin solvent is applied to a surface of ceramic, tile, or glass at 800 ° C. A method for decorating with an iris layer having antibacterial properties to be baked in is disclosed.

  Although the coloring by this iris layer is a unique technique that provides a heavy metallic luster, the principle that interference colors such as iridescent or iris color change delicately and variously depending on the construction conditions, especially the thickness of the iris layer. Have instability. Therefore, in the case of an iris layer covering a large area of an object, the coloring situation varies greatly depending on the location, and the color image obtained by the coloring varies depending on the object, and a specific color image cannot be obtained. There were various circumstances.

  Therefore, in applications such as ceramic containers, a color image consisting of a variety of unexpected colors, shadows, and patterns will appear, which may be prized, but it is necessary to reproduce specific designs and patterns uniformly. In the field of certain industrial products, there is a problem that a uniform appearance product cannot be obtained. There is a problem with this reproducibility, it is not suitable for mass production of the same pattern, there are problems such as scratches and wear easily occurring during use, and the unique interference color caused by the iris layer gives an odd and eerie feeling In some cases, there was a problem that it did not spread widely

  Furthermore, in recent years, the use of enameled steel sheet materials has expanded, and it has come to be used for interior and exterior materials for kitchen cookers, including gas or microwave ovens, ovens, refrigerators, system kitchen tables, door face materials, and the like. In such applications, it is expected as a decorative face material that requires durability, so it is difficult to see partial minor scratches and discoloration along with high durability (scratch resistance, corrosion resistance, discoloration resistance, etc.). Development of coloring design to come to be required.

JP 08-32080 A: Claims, paragraphs 0005 and 0012

  The present invention has been made to solve the above-mentioned problems. The enamel surface has a unique metallic luster uniformly, is provided with a colored layer that is industrially reproducible and capable of mass production, and is durable. Provided is an enamel member excellent in design that is useful as an interior / exterior material for kitchen cookers.

  The above problem is that the surface of the base body onto which the enamel glaze has been baked is provided with an inorganic coloring layer showing one or more combinations of a spotted pattern, a lattice pattern, and a striped pattern. This can be solved by the enamel member according to the present invention, wherein a pattern in which the color portion of the chromatic layer is alternately repeated and intermittent is formed.

Further, the coloring layer of the present invention is premised on an inorganic layer baked and fixed on the enamel base surface, and the coloring layer is an iris layer composed of a thin film mainly composed of titanium, and has a thickness of A form formed into a linear shape having a width of 0.5 μm or less and a width of 10 mm or less or a point shape having a diameter of 10 mm or less, or the coloring layer is a pigment baking layer made of a thin film mainly composed of an inorganic pigment and glass flux. Thus, the present invention can be embodied in a form in which the thickness is 50 μm or less and the shape is a linear shape having a width of 10 mm or less or a point shape having a diameter of 10 mm or less.
In addition, the iris layer or pigment baking layer, which is the coloring layer, is formed in a predetermined pattern by screen printing or transfer paper, or is applied to an enamel steel plate material and used as a kitchen cooker interior / exterior material. Preferably there is.

  Since the enamel member of the present invention forms a pattern in which the iris layer or the pigment baking layer is intermittently formed as described above, the unstable color tone, gloss, and texture inherent in the raster color in the iris layer are eliminated. Moreover, in the case of a pigment baking layer, it becomes possible to improve durability. As described above, according to the present invention, an industrially reproducible material excellent in mass productivity can be provided as a decorative member exhibiting a uniform metallic luster.

  In addition, when used as an exterior material such as a kitchen cooker's top plate and door plate in an iris layer using titanium metal, it is possible to obtain a high-quality heavy face material, and because the surface hardness is large, it is difficult to be damaged and hard to wear. Has an excellent effect. In the case of a pigment baking layer mainly composed of an inorganic pigment and a glass flux, in addition to the above-mentioned advantages, the pigment baking layer is particularly excellent in durability (such as long-term stable scratch resistance, corrosion resistance, and discoloration resistance). Therefore, the present invention has an extremely large industrial value as an enamel member that has solved the conventional problems.

Next, an embodiment according to the enamel member of the present invention will be described with reference to FIG.
In the present invention, an iris layer or a pigment baking layer, which will be described later, is applied to an enameled steel sheet material and used as a kitchen cooker exterior material. However, it goes without saying that the present invention is not limited to this.

(Iris layer)
A feature of the enamel member of the present invention is that a water-based or organic material containing a metal component, preferably a titanium component, on the surface 10 of the base body 1 obtained by baking enamel glaze (lower arm 12, upper arm 13) on an iron substrate 11. By applying a solvent-based coating film forming solution, drying, and baking, a colored layer 2 composed of an iris layer showing a pattern such as a speckled pattern b, a lattice pattern a, or a striped pattern c is applied. 10a, 10b and the color portions 2a, 2b of the iris layer are alternately repeated and intermittently, for example, a pattern consisting of a spotted pattern b, a pattern consisting of a lattice pattern a, a pattern consisting of a striped pattern c, etc. It is in the point formed.

  In the present invention, the base body 1 on which the coloring layer 2 for forming the pattern is applied is, for example, a steel plate having a thickness of about 1.0 to 2.0 mm in the case of a hollow member suitable for a kitchen cooker exterior material. The enamel surface is engraved with a hollow enamel 12 and the enamel 13 is formed on a two-layer structure with a thickness of 0.1 to 0.5 mm. Used steel plate is used. Usually, a transparent or opaque color shade according to the purpose, such as white, color tone, and gloss, is applied to the enamel upper shade 13, but the surface enamel shade can also be used in the case of a one-layer structure. Such a material is obtained by a known enamel processing technique.

In order to form the iris layer of the present invention, a conventional raster color technique can be applied.
As a coloring metal, spray, flow, organic solvent-based film forming liquid consisting of a mixture of conventionally known metal components such as gold, silver, copper, resin solutions such as resin balsam, organic solvents such as turpentine oil, The iris layer can be obtained by applying by a coating method such as spin, dip, roll, and baking at 500-700 ° C. However, those using these metal components are generally not suitable for the present invention because of their low surface hardness.

  In the present invention, titanium is preferable as the metal component because an iris layer having excellent hardness can be obtained. For example, in addition to a film-forming liquid composed of a titanium compound such as titanium abietic acid and the organic solvent system, an aqueous system can be used.

  Examples of aqueous coating film forming liquids include titanium tetraisopropoxide, tetraethoxy titanium, tetra n-propoxy titanium, tetramethoxy titanium, and other titanium alkoxides, carboxylates, or alkoxylate compounds, glycol ethers, acrylic acid, and cellulose. An aqueous mixed solution prepared by adding a derivative or the like is used.

  A predetermined spotted pattern, lattice pattern, or striped pattern is formed by coating the above-described enamel base body 1 with these coating film forming liquids. As a coating method, in order to obtain a predetermined coating thickness and a predetermined pattern as described later, screen printing using a squeegee is finished, which is most preferable from the viewpoint of cost. In this case, a screen plate made of tetron fine wires or stainless fine wires is suitable, and a screen having a mesh size of 250 to 300 mesh is suitable.

  After coating, it is dried and baked in the range of 500-700 ° C. in an oxidizing atmosphere furnace. Thus, the iris layer of the present invention can be obtained, and the thickness thereof is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less from the viewpoint of coloring of the iris layer and difficulty of scratching. The lower limit for obtaining the minimum color development is 0.02 μm.

  The main point of the present invention is to form a pattern such as a speckled pattern b, a lattice pattern a, or a striped pattern c by the iris layer. FIG. 1 illustrates a part of these patterns. In the case of a dot pattern, the size of the point is 10 mm or less in diameter, preferably 5 mm or less, and the shape is not limited to a circle, but may be a polygon, an indefinite shape, or the like. Well, the arrangement can be either regular or random.

  And between the color portions (2a, 2b, etc.) of the iris layer of the chromatic layer 2, the color portions (10a, 10b, etc.) of the base body surface 10 are interposed, and the color portions of the iris layer are continuous. The present invention is characterized in that the intermittent pattern is formed without occupying a large area.

  Thus, according to the present invention, the iris layer arranged on the enamel base body 1 does not occupy a large continuous area, so that each iris layer itself has an unstable color tone, gloss, and texture. Even if it is, since it is blocked by the color portion of the base body surface 10 between the iris layers, the uncomfortable feeling becomes difficult to recognize, and as a whole, a high-grade appearance brought about by the metallic luster is obtained. Therefore, it can be used as a decorative member that exhibits metallic luster and is industrially reproducible and excellent in mass productivity.

  Such an effect is not particularly limited because the iris layer only needs to be visually blocked by the color portion of the base body surface 10 between them. It will also be understood that the iris layer pattern is the same in the case of the lattice pattern a, the striped pattern c, etc. in addition to the speckled pattern b described above. The combination pattern obtained by appropriately combining these patterns is also preferable. In the case of the lattice pattern a and the striped pattern c, since a continuous line shape is recognized, the width is naturally limited, and the width is 10 mm or less, preferably 5 mm or less.

  It was found that the iris layer thus obtained exhibited a metallic luster having excellent chemical resistance with Mohs hardness of 5 or higher, acid resistance and alkali resistance of class 1 or higher. Raster-colored Mohs hardness of metal components such as conventional gold, silver, copper, etc .: 4 or less, acid resistance and alkali resistance were good compared with class 2 or less. The enamel member with the iris layer of the present invention applied to the enamel steel plate material, combined with the original characteristics such as heat resistance, contamination resistance, and wear resistance, is combined with gas or microwave oven, oven, refrigerator, system kitchen table, It becomes the most suitable exterior material for kitchen cookers including door face materials.

  In addition, acid resistance and alkali resistance were measured and evaluated according to a room temperature citric acid test and a room temperature sodium carbonate test of JIS R 4301.

(Pigment baking layer)
A feature of the enamel member of the present invention is that a colored inorganic pigment made of various metal oxides, mica, etc. are formed on the surface 10 of the base body 1 obtained by baking enamel glaze (lower iron 12, upper iron 13) on the iron base 11. A coloring layer 2 composed of a pigment baking layer showing a pattern such as a speckled pattern b, a lattice pattern a, or a striped pattern c is applied by coating a water-based or organic solvent-based coating film forming liquid containing the glossy pigment, drying, and baking. Applied, a pattern in which the color portions 10a and 10b of the base body surface 10 and the color portions 2a and 2b of the pigment baking layer are alternately and repeatedly interrupted, for example, a pattern consisting of a spotted pattern b, a pattern consisting of a lattice pattern a Or a pattern formed of a striped pattern c.

  In the present invention, the base body 1 to which the coloring layer 2 composed of the pigment baking layer forming the pattern is applied is the same as in the case of the above-described iris layer. For example, in the case of a hollow member suitable for a kitchen cooker exterior material, a steel plate having a thickness of about 1.0 to 2.0 mm is used as the base 11, a hollow enamel 12 is provided on the surface, and an enamel upper iron 13 is provided thereon. The thickness is a two-layer structure with a thickness of 0.1 to 0.5 mm, and a hollow-processed steel plate backed up with a hollow enamel 14 is used on the back surface. Usually, a transparent or opaque color shade according to the purpose, such as white, color tone, and gloss, is applied to the enamel upper shade 13, but the surface enamel shade can also be used in the case of a one-layer structure. Such a material is obtained by a known enamel processing technique.

  Conventional ceramic coloring techniques can be applied to form the pigment baking layer of the present invention. Spray, flow, spin, dip, roll, screen printing, organic solvent-based film-forming liquid consisting of a mixture of inorganic pigments consisting of metal oxides known in the art and ink media consisting of organic solvents as color pigments, It can be applied by a coating technique such as transfer paper and baked at a high temperature of 750 ° C. or higher to obtain a colored layer 2 in which a pigment has developed. In the case of this pigment baking layer, baking can be performed at a higher temperature than in the case of the iris layer, and therefore, there is an advantage that a thin film having excellent wear resistance and chemical resistance and having high durability can be formed.

The example of the organic solvent type coating-film formation liquid used for the pigment baking layer of this invention is shown below.
This coating film forming liquid (hereinafter simply referred to as ink) comprises 5 parts of colored pigment powder made of metal oxide, 10 parts of glossy pigment such as mica, and 30 parts of flux (particle size of 10 μm or less) made of alkali borosilicate glass powder. It is obtained by blending with 100 parts of ink medium. In this case, the mica is composed of fine flakes having an outer diameter of about 30 μm, and gives the finished chromatic layer a metallic luster having a fine irregular reflection-like luster, whereby a color layer that is particularly preferable as the chromatic layer of the enamel member of the present invention.・ A design effect consisting of gloss can be obtained.

  The ink medium can be obtained by mixing a methacrylic acid ester copolymer, a phthalic acid ester, an aromatic hydrocarbon, an ester solvent, a cellulose derivative, and the like. For this, ceramic or enamel coloring media can also be used. The blending ratio of the ink medium is variable in the range of 80 to 120 in order to obtain desired ink properties.

  The blending ratio of the flux and glossy pigment mica can be adjusted to obtain the desired fine reflection gloss and favorable stain resistance. However, if the flux is excessive, it is difficult to obtain the fine reflection gloss and is too low. Since contamination resistance decreases, the range of 25 to 35 parts of flux and 5 to 15 parts of glossy pigment mica is preferred.

This ink is prepared by the following procedure.
The material excluding the glossy pigment mica is weighed, blended and stirred to obtain an ink paste. Next, solid particles are dispersed by sufficiently kneading by passing through a three-roll mill twice. Next, a predetermined amount of glossy pigment mica having an average particle size of about 30 μm is added to the kneaded paste and mixed with a stirrer. In this case, considering that the mica particles are not destroyed, it is better not to knead with a three-roll mill.

  A predetermined spotted pattern, lattice pattern, or striped pattern is formed by coating these inks on the enamel base body 1 described above. As a coating method, in order to obtain a predetermined coating thickness and a predetermined pattern as described later, screen printing using a squeegee is finished, which is most preferable from the viewpoint of cost. In this case, a screen plate surface made of tetron fine wires or stainless fine wires is suitable, and a screen having an opening of 200 to 300 mesh is suitable.

After coating, drying is performed, and the baking temperature is baked in an oxidation atmosphere furnace at a temperature higher than 750 ° C., preferably 780 ° C. to 820 ° C., higher than that of the iris layer (500 to 700 ° C.). Thus, although the pigment baking layer of the present invention is obtained, the thickness does not need to be 50 μm or more because the pigment baking layer of the present invention has a sufficient color density and scratching strength.
Unlike the iris layer, the pigment baking layer uses a metal oxide as a coloring element, so the boundary with the color portion (10a, 10b, etc.) of the base body surface 10 becomes clear, and a clear pattern, pattern It was found that there is an advantage that can be obtained.

  The main point of the present invention is to form a clear pattern such as a speckled pattern b, a lattice pattern a, and a striped pattern c as shown in FIG. 12 by the pigment baking layer. The color layer (10a, 10b, etc.) of the base body surface 10 is interposed between the color portions (2a, 2b, etc.) of the pigment baking layer, and the pigment baking layer. This is the same as in the case of the iris layer, in that the color portion of does not occupy a continuous large area and forms an intermittent pattern.

Thus, the pigment baking layer of the present invention disposed on the enamel base body 1 does not occupy a continuous wide area and is blocked by the color portion of the base body surface 10 of the pigment baking layer. Since the coloring property is more stable, it is possible to obtain a high-grade appearance brought about by metallic luster composed of clearer spot patterns b, lattice patterns a, striped patterns c, and the like. Therefore, as a decorative member exhibiting a metallic luster, it can be used as an industrially reproducible material with excellent mass productivity and high durability.
Furthermore, the requirements regarding the pattern of the pigment baking layer, the interval between the patterns and the combination of the patterns are exactly the same as those of the iris layer.

  The pigment baking layer thus obtained is confirmed to be completely wiped by a wear resistance test in accordance with JIS-R4301, a similar acid resistance and alkali spot test, and a wiping test after leaving the black magic ink drawn portion for 12 hours. It was confirmed that there was no abnormality in the contamination resistance test. Thus, the enamel member obtained by applying the pigment baking layer of the present invention to the enamel steel plate material is combined with the original characteristics such as heat resistance, contamination resistance, wear resistance, corrosion resistance, and the like, and the gas or microwave oven, oven, refrigerator It becomes the most suitable as the interior / exterior material of the kitchen cooker that requires the harder performance including the system kitchen table and the door face material.

Moreover, in the case of this pigment baking layer, when the surface was defective for some reason after the baking step of the pigment baking layer, it was found that it could be regenerated without any problem by applying the enamel top ridge 13 again. . This point seems to be due to the fact that the pigment baked layer itself has excellent fusing property with the enamel top, but it also has the advantage of reducing the number of defective products and excellent mass productivity.

The principal part cross section and perspective view for demonstrating the enamel member of this invention.

Explanation of symbols

1: Base body, 10: Surface, 10a, 10b: Color part of base body surface 10, 11: Iron base, 12: Lower arm, 13: Upper arm 2: Color layer, 2a, 2b: Color portion of color layer
a: Lattice pattern, b: Spotted pattern, c: Striped pattern

Claims (5)

      The surface of the base body onto which the enamel glaze has been baked is provided with an inorganic coloring layer showing one or two or more of a speckled pattern, a lattice pattern, or a striped pattern, and the color portion of the base body surface and the color of the coloring layer An enamel member characterized by forming a pattern in which the portion is alternately repeated and intermittent.       The colored layer is an iris layer composed of a thin film mainly composed of titanium, and is formed in a linear shape having a thickness of 0.5 μm or less and a width of 10 mm or less or a point shape having a diameter of 10 mm or less. The enamel member described in 1.       The colored layer is a pigment baking layer made of a thin film mainly composed of an inorganic pigment and glass flux, and has a thickness of 50 μm or less, a linear shape having a width of 10 mm or less, or a point shape having a diameter of 10 mm or less. Item 5. The enamel member according to item 1.       The enamel member according to claim 2 or 3, wherein the iris layer or the pigment baking layer is formed in a predetermined pattern by screen printing or transfer paper. The enamel member according to any one of claims 2 to 4, wherein the iris layer or the pigment baking layer is applied to an enamel steel plate material and used as an interior / exterior material of a kitchen cooker.

Images