JP2023073046A - Glass forming agent and use thereof - Google Patents

Abstract

To provide a technique that can suitably improve alkali resistance of a decorative film formed on a glaze layer, the glaze layer provided on a substrate.SOLUTION: A glass forming agent disclosed herein forms a glass film for protecting a decorative film formed on a glaze layer, the glaze layer provided on a substrate. The glass forming agent comprises an amorphous oxide forming organic compound that comprises at least an Si organic compound comprising Si as a constituent element, and a crystalline oxide forming organic compound comprising a crystalline oxide forming element as a constituent element. Here, based on TG-DTA, burnthrough temperature TSi of the Si organic compound and burnthrough temperature TX of the crystalline oxide forming organic compound have a relationship satisfying the following formula (I): TX<TSi.SELECTED DRAWING: None

Description

The present invention relates to glass formers and their uses.

A decorative film containing a noble metal component is sometimes formed on the surface of articles such as ceramics, glassware, and enamelware in order to give an elegant or luxurious impression. This type of article is typically formed by applying a decorative composition containing predetermined components onto a substrate and then performing a baking treatment.

By the way, this type of article includes, for example, articles that are expected to be immersed in an alkaline detergent (for example, tableware). At this time, the decorative film formed on the substrate may be damaged by the alkaline detergent. Therefore, in recent years, decorative compositions have been proposed that are capable of forming decorative films with excellent alkali resistance. For example, Patent Literature 1 discloses a liquid metal for ceramic overglaze coating containing an element such as nickel for improving alkali resistance.

Japanese Patent No. 3784973

By the way, in order to further enhance the water resistance, etc., a base material to which a glaze layer is applied is sometimes used. Further, according to the studies of the present inventors, it has been found that such a glaze layer tends to be easily damaged by an alkaline solution such as an alkaline detergent, and as a result, the decorative film formed on the glaze layer is easily peeled off. rice field. Therefore, there is a demand for the development of a technique that can suitably prevent the decorative film from peeling off due to an alkaline solution, even when a substrate having a glaze layer is used as the base material, for example.

The present invention has been made in view of such circumstances, and its main object is to suitably improve the alkali resistance of a decorative film formed on a glaze layer of a base material to which the glaze layer is applied. It is to provide technology that can

In order to achieve such an object, the present invention provides a substrate, a glaze layer formed on the substrate, a decorative film formed on the glaze layer, and any glass disclosed herein. An article is provided comprising a glass film formed from a forming agent, the glass film being between the glaze layer and the decorative film and/or on the decorative film. The glass film comprises an amorphous oxide containing an amorphous oxide-forming element containing at least Si as a constituent element, and crystalline particles containing a crystalline oxide containing a crystalline oxide-forming element as a constituent element. and are mixed.

The present inventors have found that an article having a structure in which a glass film formed from the glass former disclosed herein is provided between the glaze layer and the decorative film and/or on the decorative film has, for example, alkaline The glass film protects the glaze layer even when it is exposed to a solution, and thus the inventors have found that peeling of the decorative film can be suitably suppressed, leading to the completion of the present invention. In addition, although not intended to be a particularly limited interpretation, the glass film contains a mixture of amorphous oxides and crystalline particles, and such crystalline particles are difficult for alkali components to permeate. Since it has a structure, it can be considered that penetration of alkali components into the amorphous oxide region can be suppressed. Therefore, since the glass film protects the glaze layer from alkaline components, it can be considered that the alkali resistance of the decorative film can be suitably improved.

In one preferred aspect of the article disclosed herein, the glass film has an average thickness of 20 nm to 500 nm. By providing the article with a glass film having such a small average thickness, the color and texture of the decorative film can be favorably exhibited.

In the article disclosed here, for example, at least the surface of the substrate is made of ceramics. Also, the articles disclosed herein can constitute tableware, for example.

In another aspect, the present invention provides a glass former for forming a glass film for protecting a decorative film formed on a glaze layer of a substrate on which the glaze layer is applied. Such a glass-forming agent includes an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element, and a crystalline oxide-forming organic compound containing a crystalline oxide-forming element as a constituent element. contains. Here, the relationship between the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound satisfies the following formula (I) based on TG-DTA.
T _X < T _Si (I)

Further, the present invention further provides a glass-forming compound containing an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element, and crystalline particles containing a crystalline oxide-forming element as a constituent element. provide drugs.

The present inventors found that when the burn-through temperature _Tx of the crystalline oxide-forming organic compound is lower than the burn-through temperature _TSi of the Si organic compound, the crystalline oxide-forming organic compound is preferentially decomposed and decomposed during firing. found to be calcined. It was also found that the crystalline oxide produced by such a firing treatment cannot form the skeleton of the amorphous oxide region by itself, and precipitates as crystalline particles. Therefore, according to the glass forming agent having such a constitution, it is possible to form a glass film in which amorphous oxides and crystalline particles are mixed. In addition to the amorphous oxide-forming organic compound, the glass film having the structure described above can also be formed by using a glass-forming agent to which crystalline particles are added in advance.

A preferred embodiment of the glass-forming agent disclosed herein contains Zr and/or Ti as the crystalline oxide-forming element. In a glass former containing Zr and/or Ti as a crystalline oxide forming element, it is possible to more suitably improve the alkali resistance of the decorative film formed on the glaze layer of the substrate to which the glaze layer is applied. can.

A preferred embodiment of the glass-forming agent disclosed herein further contains a Bi organic compound containing Bi as a constituent element as the amorphous oxide-forming organic compound. In a glass forming agent further containing a Bi organic compound as an amorphous oxide-forming organic compound, the alkali resistance of the decorative film formed on the glaze layer of the substrate provided with the glaze layer is more preferably improved. be able to.

The glass-forming agent disclosed herein is, for example, a substrate whose surface is made of ceramics, and which is provided with a glaze layer. It can be suitably applied to the formation of a glass film.

It is a figure which shows typically the cross-section of the goods which concern on 1st Embodiment. FIG. 5 is a diagram schematically showing a cross-sectional structure of an article according to a second embodiment; It is a figure which shows typically the cross-section of the goods which concern on 3rd Embodiment. 3 is an XRD chart of a glass film included in a top coat sample of Example 3. FIG. 4 is an XRD chart of a glass film included in a top coat sample of Example 6. FIG. 10 is an XRD chart of the glass film included in the top coat sample of Example 9. FIG.

Preferred embodiments of the technology disclosed herein are described below. Matters other than those specifically mentioned in this specification that are necessary for implementation (for example, detailed preparation means for glass-forming agents, decorative compositions, glazes, manufacturing procedures for articles, etc.) It can be understood based on the technical content taught by this specification and the general technical knowledge of those skilled in the art. The content of the technology disclosed here can be implemented based on the content disclosed in this specification and common general knowledge in the field. In this specification, the notation "A to B" indicating the range means from A to B. Therefore, the case above A and below B is included.

<Glass forming agent>
The glass former disclosed herein is used to form a glass film for protecting a decorative film formed on a glaze layer of a base material to which the glaze layer is applied. The glass-forming agent disclosed herein includes an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element, and a crystalline oxide containing a crystalline oxide-forming element as a constituent element. forming organic compounds; Here, based on TG-DTA, the relationship between the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound is expressed by the following formula (I): T _X <T _Si is characterized by satisfying Each component will be described below.

(1) Amorphous oxide-forming organic compound The amorphous oxide-forming organic compound contains an amorphous oxide-forming element and an organic substance as constituent elements. When such an amorphous oxide-forming organic compound is calcined, an amorphous oxide (amorphous oxide region) is formed by oxidizing the amorphous oxide-forming element after burning the organic matter. In the present specification and claims, the term "amorphous oxide-forming element" means an amorphous oxide region ( In other words, it is a concept that includes metal elements and metalloid elements capable of constructing a glass matrix. Examples of such amorphous oxide-forming elements include Al, Ti, Zr, Si, Bi, Sm, Y, La, Ce, Pr, Nd, Sm, Dy, Sn, Zn, Be, Mg, Ca, Sr. , Ba, Li, Na, K, Rb, B, V, Fe, Cu, P, Sc, Pm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Ni, In, Co, Cr, etc. mentioned. Amorphous oxide-forming organic compounds may also take the form of metal resinates, complexes, polymers, and the like.

Here, the organic substance that constitutes the amorphous oxide-forming organic compound is not particularly limited as long as the effects of the technology disclosed herein are exhibited. For example, when a metal resinate is used as the amorphous oxide-forming organic compound, conventionally known resin materials that can be used for this type of metal resinate can be used without particular limitation. Examples of such resin materials include carboxylic acids having a high carbon number (for example, 8 or more carbon atoms) such as octylic acid (2-ethylhexanoic acid), abietic acid, naphthenic acid, stearic acid, oleic acid, linolenic acid, and neodecanoic acid. ; sulfonic acid; resin acid contained in rosin; turpentine oil, resin containing essential oil components such as lavender oil; be done. As the metal resinate, for example, commercially available products can be used.

Further, for example, when a complex is used as an amorphous oxide-forming organic compound, conventionally known ligands that can be used for this type of complex can be used without particular limitation as such an organic substance. Examples of such ligands include alkoxide ligands, diketone ligands, carboxylate ligands, amine ligands, and the like. As the complex, for example, a commercially available one can be used.

As described above, the amorphous oxide-forming organic compound disclosed herein contains a Si organic compound containing at least Si as a constituent element. The Si organic compound contains Si (silicon) and an organic substance as constituent elements. When such a Si organic compound is calcined, the organic matter is burned off and Si is oxidized to form SiO ₂ . Such SiO ₂ can then construct the skeleton of the amorphous oxide region (in other words, the glass matrix) and become the main component of the amorphous oxide region.

The content of Si (mol%) when the total number of moles of the amorphous oxide-forming element and the crystalline oxide-forming element in the glass forming agent is 100 mol% (hereinafter simply referred to as "Si content in the glass forming agent content”) is not particularly limited as long as the effect of the technology disclosed herein is exhibited. The content of Si in the glass forming agent may be, for example, 40 mol % or more, 50 mol % or more, or 60 mol % or more. In addition, the content of Si in the glass forming agent is generally 99 mol% or less, and may be, for example, 95 mol% or less, or may be 90 mol% or less, 80 mol% or less, or 70 mol% or less. good.

Here, as the Si organic compound, for example, one type of Si resinate (or Si complex) may be used, or two or more types of Si resinate may be used as long as the effect of the technology disclosed herein is exhibited. (or Si complex) may be mixed and used, or Si resinate and Si complex may be mixed and used. The same is true for other amorphous oxide-forming organic compounds and crystalline oxide-forming organic compounds.

Further, the glass forming agent disclosed herein preferably further contains Bi (bismuth) as a glass matrix element. Bi can be added to the glass former in the form of a Bi organic compound. The Bi organic compound contains Bi and an organic substance as constituent elements. Bi is an element that becomes bismuth oxide (Bi ₂ O ₃ ) after firing treatment and can constitute a part of the skeleton of the glass matrix. Since such Bi ₂ O ₃ has the effect of softening the glass, it is said that the adhesion of the glass film to other layers (or films) is improved. Such an improvement in adhesion can suitably prevent peeling of the glass film when exposed to an alkaline solution. From the viewpoint of more preferably exhibiting the effect of the addition of Bi, the content of Bi (mol %) (hereinafter also simply referred to as “the content of Bi in the glass forming agent”) may be, for example, 1 mol % or more, 3 mol % or more, or 5 mol % or more. Further, the upper limit of the content of Bi in the glass matrix element may be, for example, 30 mol% or less, or may be 25 mol% or less, 20 mol% or less, 15 mol% or less, or 10 mol% or less. .

As long as the effect of the technique disclosed here can be obtained, the glass forming agent disclosed here can be, for example, an element other than Si and Bi among the above-described amorphous oxide forming elements (hereinafter referred to as "arbitrary element ”) and an organic substance as constituent elements. The arbitrary elements may be used singly or may be contained in combination of two or more. In addition, the content (mol%) of the arbitrary element when the total number of moles of the amorphous oxide-forming element and the crystalline oxide-forming element in the glass forming agent is 100 mol% (hereinafter simply referred to as "in the glass forming agent When two or more types are contained, it means the total mol % of them.) is not particularly limited, and may be 0.1 mol % or more, and may be 0.1 mol % or more. It may be 5 mol % or more, or 1.0 mol % or more. On the other hand, from the viewpoint of preventing a relative decrease in the content of active ingredients (such as crystalline oxide-forming elements described later) that affect the alkali resistance of the glass film, the upper limit of the content of any element in the glass-forming agent is is preferably 10 mol % or less, more preferably 5 mol % or less.

(2) Crystalline Oxide-Forming Organic Compound The crystalline oxide-forming organic compound contains a crystalline oxide-forming element and an organic substance as constituent elements. Such an organic substance can be selected from, for example, those described in the description of the amorphous oxide-forming organic compound. In the present specification and claims, the term “crystalline oxide-forming element” means an element that forms a crystalline oxide when a glass film (typically, an oxide glass film) is formed. It is a concept that includes metal elements and metalloid elements to be obtained. Examples of such crystalline oxide-forming elements include Ga, Li, Ca, Sc, Ti, V, Zn, Y, Zr, In, Sn, Te, La, Na, K, Rb, Cs, Sr, and Cd. be done. The crystalline oxide-forming element may be contained singly or in combination of two or more. Among the above elements, Ti and Zr are particularly suitable as crystalline oxide forming elements. Since crystalline particles containing Ti or Zr are difficult to dissolve in an alkaline solution, peeling of the decorative film during alkaline cleaning can be suppressed more favorably.

As described above, in the glass forming agent disclosed herein, the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound are based on TG-DTA. satisfies the following formula (I): T _X <T _Si . When the glass-forming agent having such a structure is fired, the crystalline oxide-forming organic compound having a relatively low burn-through temperature is preferentially decomposed and fired to form a crystalline oxide. In addition, since the crystalline oxide cannot form the framework of the amorphous oxide (amorphous oxide region) by itself, it may precipitate in the form of crystalline particles. After the formation of such crystalline particles, the Si organic compound can be decomposed and fired to form the skeleton of the amorphous oxide region. By forming an amorphous oxide region in the presence of crystalline particles in this manner, a glass film in which amorphous oxide and crystalline particles are mixed can be formed.

The burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound are not particularly limited as long as the above formula (I) is satisfied. For example, each burn-through temperature is preferably lower than the firing temperature _TF from the viewpoint of suppressing deterioration in quality due to residual organic matter. For example, when the firing temperature T _F is set to 800° C., the burn-through temperature T _Si of the Si organic compound is preferably 600° C. to 750° C., more preferably 625° C. to 725° C., still more preferably 650° C. °C to 700 °C. At this time, the combustion temperature T _X of the crystal-forming organic compound is preferably 450° C. to 560° C., more preferably 460° C., from the viewpoint of satisfying the above formula (I) and appropriately forming crystalline particles. to 550°C, more preferably 470°C to 540°C. The burn-through temperature of each organic compound can be easily adjusted by changing the type of organic substance that bonds with the metal element. That is, the crystalline oxide-forming organic compound can be obtained by selecting a predetermined crystalline oxide-forming element and appropriately selecting the type of organic substance so that it burns at a temperature lower than the combustion temperature T _Si of the Si organic compound. can be done.

Further, as the glass forming agent, in addition to those mentioned above, an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element, and a crystal containing a crystalline oxide-forming element as a constituent element Substances containing particles can also be used. That is, in addition to the amorphous oxide-forming organic compound, the glass film having the structure described above can also be formed by using a glass-forming agent to which crystalline particles are added in advance.

Here, the configuration (for example, shape, size, etc.) of the crystalline particles is not particularly limited as long as the effects of the technology disclosed herein are exhibited. Such crystalline particles may be, for example, in the state of independent primary particles, or may be in the state of secondary particles in which a neck is formed between a plurality of primary particles. The crystallite size (particle size of primary particles) of the crystalline particles is generally 1 nm or more, preferably 2 nm or more, and more preferably 3 nm or more. By using crystalline particles having a sufficient size in this manner, a glass film having excellent alkali resistance can be obtained, which is preferable. On the other hand, if the crystalline particles become too large, the light entering the amorphous oxide region is scattered by the crystalline particles, which may adversely affect the color development of the decorative film. From this point of view, the crystallite size of the crystalline particles is generally 20 nm or less, preferably 16 nm or less, and more preferably 10 nm or less. The crystallite diameter of the crystalline particles is calculated based on the peak half width in XRD analysis of a glass film.

In addition, mol % of the crystalline oxide forming element when the total number of moles of the amorphous oxide forming element and the crystalline oxide forming element is 100 mol % (hereinafter simply referred to as "crystalline oxide in the glass forming agent Also referred to as "content of substance-forming elements". When two or more types are included, it means the total mol % of them.) is not particularly limited as long as the effect of the technology disclosed herein is exhibited. The content of the crystalline oxide-forming element in the glass-forming agent may be, for example, 1 mol % or more, 2 mol % or more, or 3 mol % or more. The content of the crystalline oxide-forming element in the glass-forming agent may be, for example, 50 mol % or less, 45 mol % or less, 40 mol % or less, or 35 mol % or less.

(3) Other Components The amorphous oxide-forming element and the crystalline oxide-forming element contained in the glass-forming agent disclosed herein have been described above. In addition to the components described above, the glass forming agent disclosed herein preferably contains various components in consideration of formability of the glass film. Other components that may be included in the glass formers disclosed herein are described below. However, as the other components described below, conventionally known components that can be used in glass forming agents can be used without any particular limitation, as long as they do not significantly hinder the effects of the technology disclosed herein. That is, in the glass-forming agent disclosed herein, components other than the essential components described above can be appropriately changed depending on the application and the like.

Further, in a glass former containing an amorphous oxide-forming organic compound or a crystalline oxide-forming organic compound as described above, a solvent (typically an organic solvent) for dispersing or dissolving each compound is preferably used. As such an organic solvent, for example, conventionally known organic solvents used for this type of glass forming agent and resinate paste can be used without particular limitation. Examples of such organic solvents include 1,4-dioxane, 1,8-cineole, 2-pyrrolidone, 2-phenylethanol, N-methyl-2-pyrrolidone, p-tolualdehyde, benzyl benzoate, butyl benzoate, eugenol, caprolactone, geraniol, methyl salicylate, cyclohexanone, cyclohexanol, cyclopentyl methyl ether, citronellal, di(2-chloroethyl) ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dihydrocarbon, dibromomethane, dimethyl sulfoxide, dimethylformamide, nitrobenzene, Pyrrolidone, propylene glycol monophenyl ether, pulegone, benzyl acetate, benzyl alcohol, benzaldehyde, various oils such as turpentine oil and lavender oil. In addition, these organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type. Since the metal resinate is commercially available as, for example, a resinate paste, such a resinate paste may be used as it is.

The content of the organic solvent (if two or more types are contained, the total content thereof) is not particularly limited, and may be appropriately selected depending on the means for applying the glass forming agent to another layer (or film). preferably adjusted. For example, when using inkjet printing or a spin coater, it is required to control the viscosity of the glass forming agent to a relatively low range (for example, about 10 mPa·s to 500 mPa·s). Therefore, in the glass former for inkjet printing, the weight of the organic solvent is preferably adjusted within the range of 10% by weight to 99% by weight when the total weight of the glass former is 100% by weight. On the other hand, when brush coating or screen printing is used, it is preferable to form a sufficiently thick glass film with a single application, so the content of the organic solvent should be within the range of about 0% to 10% by weight. It is preferable to adjust the viscosity of the glass forming agent so as to have a viscosity of about 500 mPa·s to 100000 mPa·s.

Further, the glass forming agent disclosed herein may contain other additional components as long as they do not significantly impair the effects of the technology disclosed herein. Examples of such additional components include organic binders, protective agents, surfactants, thickeners, pH adjusters, preservatives, antifoaming agents, plasticizers, stabilizers and antioxidants. As these, for example, commercially available products can be used. As the organic binder, for example, an organic binder resin such as a cellulose-based resin can be used. can be within the range. In addition, when using an additional component containing a metal element or a metalloid element in the technology disclosed herein, the content of the element derived from the additional component is also taken into consideration, and the above-mentioned Si content and It is required to prepare the glass former so that the content of the rare earth element is the desired value.

When the amorphous oxide-forming organic compound or the crystalline oxide-forming organic compound takes a form other than the metal resinate, the solvent and additional components described above may be appropriately changed according to the usage form. preferable. For example, when containing in a form that does not dissolve in a solvent such as fine particles, it is preferable to select a solvent that can appropriately disperse the fine particles and add a dispersant or the like as an additional component.

<Composition of goods>
Next, one embodiment (first embodiment) of an article provided with a glass film formed from the glass forming agent disclosed herein will be described with reference to FIG. In addition, the following description is not intended to limit the article disclosed here to the following forms.

FIG. 1 is a diagram schematically showing the cross-sectional structure of an article according to the first embodiment. As shown in FIG. 1, an article 1 according to the first embodiment includes a substrate 2, a glaze layer 3 formed on the substrate, a decorative film 5 formed on the glaze layer, A glass film formed from any of the glass formers disclosed herein, wherein the glass film 4 is present between the glaze layer and the decorative film. Thus, according to the article 1 having the glass film 4 between the glaze layer 3 and the decorative film 5, the glaze layer 3 is protected by the glass film 4 having excellent alkali resistance even when exposed to an alkaline solution, for example. Therefore, peeling of the decorative film 5 can be suppressed appropriately. Further, with such a configuration, the decoration film 5 can be the outermost surface, so that it is less likely to be affected by the coloration caused by coating with the glass film 4, which is preferable. In the glass film 4, the amorphous oxide 6 containing an amorphous oxide forming element containing at least Si as a constituent element and the crystalline particles 7 containing a crystalline oxide as a constituent element are mixed. It is characterized by Each component will be described below.

(1) Base material 2
First, as the substrate included in the article disclosed herein, one having at least the surface made of ceramics can be preferably used. In the first embodiment, the substrate 2 is made of ceramics. Here, in the present specification and claims, "ceramics" (hereinafter also referred to as "ceramic components") are inorganic compounds that are not limited to oxides, and are inorganic compounds that do not correspond to glass (amorphous structure). It can be a compound or the like. In addition, the above-mentioned "composed of ceramics" means that, among the components constituting the base material, the component contained in the largest amount on a weight basis is the ceramic component. Such substrates may contain 95% or more, 97% or more, or 99% or more by weight of the ceramic component. Components other than the ceramic component may include, for example, various metallic elements and non-metallic elements as unavoidable impurities. Examples of such ceramic components include Al ₂ O ₃ , MgO, BeO, ZrO ₂ , TiO ₂ , Y ₂ O ₃ , mullite, forsterite, steatite, boron nitride (BN), aluminum nitride (AlN), silicon nitride. (Si ₃ N ₄ ), boehmite (AlOOH) and the like. In addition, these may be used individually by 1 type, and may be used in combination of 2 or more types. The average value (that is, the average thickness of the substrate 2) of the thickness (that is, the width in the X direction in FIG. 1) of the substrate 2 is not particularly limited, and can be, for example, within the range of 0.1 mm to 1 mm. In the present specification and claims, the "average thickness" typically means the upper and lower surfaces of the substrate, film, and layer (for example, two surfaces in the X direction in FIG. 1) under microscope observation. When the shortest distance between is randomly measured at 3 points, it can mean the average value of the 3 points. Further, the substrate included in the article disclosed herein may be made of a metal material such as Cu (copper), W (tungsten), or the like.

(2) Glaze layer 3
The glaze layer 3 may be formed from conventionally known glazes used in this type of technology. Examples of the glaze include an alkali-MgO--CaO--Fe ₂ O ₃ --Al ₂ O ₃ --SiO ₂ glaze and an alkali-ZnO--Al ₂ O ₃ --SiO ₂ glaze. The one used in the examples described later is one such example. Here, the alkali means an oxide of an alkali metal element such as Na ₂ O, for example. Although it is not intended to be a particularly limited interpretation, many glazes contain such an alkaline component, and the alkaline component cuts the Si—O bond with an alkaline solution to form HSiO ₃ ^— or SiO ₃ ^2— The glaze layer can be considered to have poor alkali resistance because it can induce a reaction that produces such as. In addition, since the technique disclosed here is related to the glass former, the detailed explanation of the method for preparing the glaze is omitted. The average value (ie, the average thickness of the glaze layer 3) of the thickness (ie, the width in the X direction in FIG. 1) of the glaze layer 3 is not particularly limited, and can be, for example, within the range of 100 nm to 5000 nm. In addition, the thing in which the glaze layer 3 was previously formed can also be used as a base material.

(3) Glass film 4
Glass membrane 4 is formed from any of the glass formers disclosed herein. As described above, the glass film 4 formed from the glass formers disclosed herein is characterized by a mixture of amorphous oxides 6 and crystalline particles 7 . Since the crystalline particles 7 have a structure that makes it difficult for alkali components to permeate, it is thought that the penetration of the alkali components into the amorphous oxide (amorphous oxide region) 6 can be suitably prevented. obtain. Further, as described above, among various crystalline oxides, oxides of Zr and Ti have extremely high chemical resistance as single materials. Therefore, by allowing the crystalline oxide of Zr or Ti to exist in the amorphous oxide region 6, peeling of the decorative film 5 during alkaline cleaning can be suppressed particularly favorably. The crystalline oxides of Zr and Ti may be not only ZrO ₂ and TiO ₂ but also composite oxides such as ZrTiO ₄ and Ti ₂ Bi ₂ O ₇ . It has been confirmed that these composite oxides are also excellent in alkali resistance.

The crystalline oxide-forming element forming the crystalline particles 7 may or may not be contained in the amorphous oxide region 6 . Specifically, for example, when crystalline particles 7 containing ZrO ₂ are formed, the amorphous oxide region 6 may or may not contain ZrO ₂ . This point does not greatly affect the effect produced by the technology disclosed herein. Moreover, in the amorphous oxide region 6 of the glass film 4 in this embodiment, a plurality of types of crystalline particles 7 having different main components may exist. Specifically, for example, even when two types of crystalline particles, ie, crystalline particles containing ZrO ₂ and crystalline particles containing ZrTiO ₄ exist as the crystalline particles 7 in the amorphous oxide region 6, the decorative film 5 It has been confirmed that the delamination can be suitably suppressed. The crystalline particles 7 in the glass film 4 can be confirmed, for example, by X-ray diffraction measurements (XRD) on the glass film 4 by peaks indicating crystalline oxides.

The average value (that is, the average thickness of the glass film 4) of the thickness (that is, the width in the X direction in FIG. 1) of the glass film 4 is not particularly limited. For example, from the viewpoint of suitably exhibiting the color and texture of the decorative film provided on the article, it is preferably in the range of 20 nm to 500 nm, more preferably in the range of 20 nm to 150 nm.

(4) Decorative film 5
The decorative film 5 may be formed from a conventionally known decorative composition used in this type of technology. Examples of decorative compositions include Pt--Si--Bi based decorative compositions and Au--Si--Bi based decorative compositions. The one used in the examples described later is one such example. Since the technique disclosed here relates to a glass forming agent, detailed descriptions of the composition and preparation method of the decorative composition are omitted. The average value of the thickness of the decorative film 5 (that is, the width in the X direction in FIG. 1) (that is, the average thickness of the decorative film 5) is not particularly limited, and can be, for example, within the range of 50 nm to 200 nm.

<Product manufacturing method>
Next, a method for manufacturing the article 1 will be described, but it is not intended to limit the manufacturing method to the following method. If necessary, steps can be deleted or added as appropriate. Moreover, the order of each process can be changed and implemented as needed.
First, the base material 2 is prepared. Then, a glaze is applied (applied) to the surface of the base material 2, dried at a predetermined temperature (for example, about 50° C. to 100° C.), and kept at a predetermined temperature (for example, about 900° C. to 1300° C.) for a predetermined time. (For example, about 10 to 30 minutes) calcination treatment is performed. In addition, the thing which the glaze layer was previously provided can also be used as a base material. Next, the glass forming agent disclosed herein is applied (applied) to the surface of the fired glaze, dried at a predetermined temperature (for example, about 50 ° C. to 100 ° C.), and then dried at a predetermined temperature (for example, , 600° C. to 1000° C.) for a predetermined time (for example, about 10 to 30 minutes). Subsequently, a decorative composition is applied (applied) to the surface of the fired glass-forming agent, dried at a predetermined temperature (for example, about 60° C.), and then dried at a predetermined temperature (for example, 700° C. to 800° C.). ℃) for a predetermined time (for example, about 10 to 30 minutes), the article 1 can be manufactured.

The articles disclosed herein can constitute tableware, for example. Since tableware is expected to be immersed in, for example, an alkaline detergent, it is suitable as an object to which the technology disclosed herein is applied.

<Other embodiments>
An embodiment (first embodiment) of the article disclosed herein has been described above. In addition, the above-described embodiment shows an example to which the technique disclosed here is applied, and is not intended to limit the technique disclosed here.

For example, FIG. 2 is a diagram schematically showing the cross-sectional structure of an article according to the second embodiment. As shown in FIG. 2, an article 10 according to the second embodiment includes a substrate 12, a glaze layer 13 formed on the substrate, a decorative film 15 formed on the glaze layer, a glass membrane formed from any of the glass formers disclosed herein, the glass membrane 14 overlying the decorative membrane. Thus, according to the article 10 having the glass film 14 on the decorative film 15, the glass film 14 having excellent alkali resistance protects the glaze layer 13 even when exposed to an alkaline solution, for example. Detachment of the film 15 can be suitably suppressed. In addition, by arranging the glass film 14 near the surface of the article 10, the article 10 can be given luster (raster), which is preferable. As with the article 1, the glass film 14 included in the article 10 is characterized by a mixture of amorphous oxides 16 and crystalline particles 17. FIG. The base material 12, the glaze layer 13, the glass film 14, and the decoration film 15 can be configured in the same manner as the base material 2, the glaze layer 3, the glass film 4, and the decoration film 5, respectively. The article 10 can be produced, for example, by changing the formation order of the glass film and the decorative film in the method for producing the article 1 described above.

For example, FIG. 3 is a diagram schematically showing the cross-sectional structure of an article according to the third embodiment. As shown in FIG. 3, an article 20 according to the third embodiment includes a substrate 22, a glaze layer 23 formed on the substrate, a decorative film 25 formed on the glaze layer, A glass film formed from any of the glass formers disclosed herein, comprising glass films 24a, 24b present between the glaze layer and the decorative film and on the decorative film. goods. Thus, according to the article provided with the glass films 24a and 24b between the glaze layer and the decorative film and on the decorative film, the glass films 24a and 24b have excellent alkali resistance even when exposed to an alkaline solution, for example. Since the glaze layer 23 is protected from above and below by 24b, peeling of the decorative film 25 can be more suitably suppressed. As with the article 1, the glass films 24a and 24b included in the article 20 are characterized by a mixture of amorphous oxide 26a and crystalline particles 27a, and amorphous oxide 26b and crystalline particles 27b. The base material 22, the glaze layer 23, the glass films 24a and 24b, and the decoration film 25 can be configured in the same manner as the base material 2, the glaze layer 3, the glass film 4, and the decoration film 5, respectively. The article 20 can be manufactured by referring to the manufacturing method of the article 1 described above.

Further, for example, the articles according to Embodiments 1 to 3 above include only the base material, the glaze layer, the glass film, and the decorative film, but are not limited to this, and may further include other layers (or films). good. The shape of the article can be changed as appropriate according to the intended use.

[Test example]
Test examples relating to the technology disclosed here will be described below, but the technology disclosed here is not intended to be limited to such test examples.

1. Preparation of sample <Preparation of glass former>
In this test example, 18 kinds of glass formers with different glass matrix element contents were prepared (Examples 1 to 18). Table 1 shows the content of each element in Examples 1-18. Each numerical value in Table 1 represents the content (mol% ). In addition, the preparation of the glass forming agent in this test example was carried out by mixing various raw materials (see "raw materials of each element") in an ointment pot and was used to mix for 2 minutes at a rotation speed of 1800 rpm. The glass forming agent is prepared by adding a diluent solvent (WA oil) manufactured by Noritake Co., Ltd. so that the viscosity at 25° C.-100 rpm (measured with a Brookfield DV viscometer) is about 10 to 15 mPa s. bottom.

<Preparation of decorative composition>
A decorative composition was then prepared. In this test example, the weight ratio of the total weight of the metal element and metalloid element contained in the decorative composition to 100% by weight was as follows: Pt: 86.1% by weight, Si: 5.9% A decorative composition was prepared so that weight %, Bi; 8.0% by weight. In addition, to prepare the decorative composition in this test example, various raw materials (see "raw materials of each element") were mixed in an ointment pot, and a stirrer manufactured by Thinky Co., Ltd. ) and mixed for 2 minutes at 1800 rpm. The decorative composition has a viscosity of about 10 to 15 mPa s at 25° C.-100 rpm (measured with a Brookfield DV viscometer) by adding a diluted solvent (WA oil) manufactured by Noritake Co., Ltd. prepared.

<Raw materials for each element>
Further, each element in Table 1 described above is added to the glass forming agent in the following conditions. Here, for Si, two types of Si organic compounds (Si-1 and Si-2) having different burn-through temperatures T _Si were used. As for Bi, the following Bi organic compound was used. In addition, for Ti, two types of Ti organic compounds (Ti-1, Ti-2, Ti-3) with different burnout temperatures T _Ti and titanium oxide (TiO ₂ ) nanoparticles (Ti-4) are used. bottom. As for Zr, Zr organic compounds (Zr-1, Zr-2) and zirconium oxide (ZrO ₂ ) nanoparticles (Zr-3) were used. As such raw materials, commercially available ones were used. The burn-through temperatures of these components are also listed below. Si-1 was used as the raw material of Si in the composition for decoration, and Bi-r was used as the raw material of Bi.
Si-1: Si resinate (Si resinate, burn-through temperature T _Si : 680.8° C.)
Si-2: Si resinate (Si resinate, burn-through temperature T _Si : 378.5° C.)
Bi-r: Bi resinate (Bi resinate, burn-through temperature T _Bi : 561.2° C.)
Ti-1: Ti resinate (Ti resinate, burn-through temperature T _Ti : 512.9°C)
Ti-2: Ti resinate (Ti resinate, burn-through temperature T _Ti : 542.3°C)
Ti-3: Ti complex (a complex having an alkoxide ligand and a diketone ligand, combustion temperature T _Ti : 501.5° C.)
Ti-4: _TiO2 nanoparticles (crystallite size: 15.8 nm)
Zr-1: Zr resinate (Zr resinate, combustion temperature T _Zr : 532.9°C)
Zr-2: Zr complex (complex with alkoxide ligand and diketone ligand, combustion temperature T _Zr : 557.7° C.)
Zr-3: _ZrO2 nanoparticles (crystallite size: 6.8 nm)
Pt: Pt resinate (platinum resin sulfide balsam)

All of the burn-through temperatures described above are based on TG-DTA using a thermogravimetry device (TG-DTA/H) manufactured by Rigaku Corporation. Specifically, the target metal organic compound is placed in an environment with an air flow rate of 300 ml / min, and the temperature is raised from room temperature (20 ° C.) to 1000 ° C. at a heating rate of 10 ° C. / min. The temperature at which weight loss no longer occurred was considered the burn-through temperature. In this measurement, it was determined that the weight did not decrease when the weight when the heating temperature was raised by 3° C. was within ±0.03% of the weight before the temperature was raised.

<Preparation of sample>
In this test example, for each example, a sample having a structure in which a base material, a glaze layer, a glass film, and a decorative film are laminated in this order as shown in FIG. 2 (hereinafter also simply referred to as "top coat sample") having a structure in which a base material, a glaze layer, a decorative film, and a glass film are laminated in this order. A method for producing the top coat sample and the undercoat sample will be described below.
First, a white porcelain flat plate (length: 15 mm, width: 15 mm, thickness: 20 mm) on which a glaze layer was previously formed was prepared, and this white porcelain flat plate was prepared. Here, the glaze has the following composition in terms of oxides in terms of molar ratio: SiO ₂ : 70.8 mol %, Al ₂ O ₃ : 16.4 mol %, Fe ₂ O ₃ : 0.1 mol %, CaO; 4.2 mol%, MgO; 4.0 mol%, K2O; 3.4 mol%, Na2O; _0.6 mol% _, ZnO; 0.5 mol%.

Next, for the upper coat sample, the decorative composition prepared as described above was applied onto the glaze layer, dried at 60°C for 60 minutes, and then fired at 800°C for 10 minutes. Onto that layer was applied the glass former prepared as above and dried at 60° C. for 60 minutes. Also, for the undercoated samples, the order of application of the glass former and the decorative composition was reversed. The application of the glass forming agent and the decorative composition was performed using a spin coater: Opticoat MS-A-150 manufactured by Mikasa Co., Ltd. under the spin conditions of 5000 rpm for 10 seconds. The obtained laminate was dried on a hot plate heated to 60° C. for 1 hour, and then baked at 800° C. for 10 minutes to obtain an upper coat sample and an undercoat sample. Here, as a result of observing the cross section of each upper and lower sample after firing using FE-SEM (SU-8200, manufactured by Hitachi High-Technologies Corporation), the average thickness of the glaze layer was 1000 nm to 3000 nm, and the decorative film The average thickness of the glass film was in the range of 100 nm to 200 nm, and the average thickness of the glass film was in the range of 50 nm to 150 nm.

2. Evaluation test <Analysis of glass film after baking>
Further, in this test, XRD measurement (X-ray diffraction measurement) was performed on the glass films included in the upper coat sample and the undercoat sample according to each example to investigate the composition of the glass film. As an example, the XRD charts of the glass films included in the upper coat samples of Examples 3, 6, and 9 are shown in FIGS. 4 to 6, respectively. In addition, the conditions of the X-ray diffraction measurement in this test are as follows. However, the following XRD measurement conditions do not limit the technology disclosed herein. XRD measurement conditions can be appropriately changed to conditions that allow the composition of the particulate component to be detected appropriately.

[XRD conditions]
Measuring instrument: Fully automatic multi-purpose X-ray diffractometer SmartLab (manufactured by Rigaku Co., Ltd.)
Scan speed: <5.00°/min
Step width: 0.01°
Scan range: 2θ (5° to 80°)
Incident angle: ω = 0.2° to 1.5°

As a result of the XRD measurement, a peak of ZrO ₂ was confirmed for the glass films included in the upper coat samples and undercoat samples according to Examples 2 to 4 and 10 to 14, and the upper coat samples and undercoat samples according to Examples 5 to 7. A peak of at least one oxide of ZrO ₂ , Ti ₂ Bi ₂ O ₇ and TiO ₂ was confirmed for the glass film included in the sample, and the top coat samples and undercoat samples according to Examples 8, 9, 15 to 17 A peak of at least one oxide of Ti ₂ Bi ₂ O ₇ and TiO ₂ was confirmed in the glass film of the sample. In Example 18, no crystalline oxide peaks were identified.

<Evaluation of alkali resistance>
In this test example, each sample was immersed in a 0.5% by weight Na ₂ CO ₃ aqueous solution (3 L) heated to 100° C. and boiled for 30 minutes. After the immersion, the sample was washed with water and subjected to a rubbing test in which zircon paper was rubbed back and forth 10 times to observe whether or not the decorative film was damaged. In this test example, the immersion time was extended in units of 30 minutes, and the maximum immersion time during which 30% or more of the decorative film remained was regarded as "endurance time (h)." When the durability time is 0.5 hours or more, it is evaluated as having sufficient alkali resistance, and when the durability time is 1.0 to 1.5 hours, it is evaluated as having excellent alkali resistance. is 2.0 hours, it is evaluated to have particularly good alkali resistance. The results for each topcoat sample are shown in Table 2 in the appropriate column. Moreover, although not clearly shown in Table 2, it was found that the undercoat samples according to Examples 1 and 18 did not have sufficient alkali resistance (in other words, the durability time was less than 0.5 hours). confirmed. On the other hand, 5 samples (Examples 3, 6, 9, 12 and 15) were randomly selected from Examples 2 to 17, and the base coat samples according to each example were evaluated for alkali resistance. It was confirmed that it has alkali resistance (in other words, durability time is 0.5 hours or more).

As shown in Table 1, an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element and a crystalline oxide-forming organic compound containing a crystalline oxide-forming element as a constituent element , and the relationship between the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound based on TG-DTA is the following formula: T _X <T _Si Examples 2-17, which have glass films formed from glass formers that satisfy the durability requirements, compare to Example 1, which has glass films formed from glass formers that do not contain crystalline oxide-forming organic compounds. It was confirmed that the time was 0.5 hours or more and sufficient alkali resistance was obtained. On the other hand, the glass formed from the glass forming agent satisfies the following formula: T _X ≧T _Si , where the relationship between the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound is satisfied. In Example 18 with a membrane, the endurance time was less than 0.5 hours, and the alkali resistance was not excellent.
From the above results, it can be seen that the glass forming agent disclosed herein preferably improves the alkali resistance of the decorative film formed on the glaze layer of the base material to which the glaze layer is applied.

Specific examples of the technology disclosed herein have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

1, 10, 20 Articles 2, 12, 22 Substrates 3, 13, 23 Glaze layers 4, 14, 24a, 24b Glass films 5, 15, 25 Decorative films 6, 16, 26a, 26b Amorphous oxide regions ( amorphous oxide)
7, 17, 27a, 27b crystalline particles

Claims (9)

A glass forming agent for forming a glass film for protecting a decorative film formed on a glaze layer of a base material to which the glaze layer is applied,
an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element;
a crystalline oxide-forming organic compound containing a crystalline oxide-forming element as a constituent element;
contains
Here, the relationship between the burn-through temperature T _Si of the Si organic compound and the burn-through temperature T _X of the crystalline oxide-forming organic compound based on TG-DTA satisfies the following formula (I): .
T _X < T _Si (I) A glass forming agent for forming a glass film for protecting a decorative film formed on a glaze layer of a base material to which the glaze layer is applied,
an amorphous oxide-forming organic compound containing at least an Si organic compound containing Si as a constituent element;
crystalline particles containing a crystalline oxide-forming element as a constituent element;
A glass former comprising: 3. The glass former according to claim 1 or 2, comprising Zr and/or Ti as said crystalline oxide forming elements. The glass forming agent according to any one of claims 1 to 3, further comprising a Bi organic compound containing Bi as a constituent element as the amorphous oxide-forming organic compound. The glass forming agent according to any one of claims 1 to 4, wherein at least the surface of said substrate is made of ceramics. a substrate;
a glaze layer formed on the substrate;
a decorative film formed on the glaze layer;
A glass film formed from the glass former according to any one of claims 1 to 5, wherein the glass film is present between the glaze layer and the decorative film and/or on the decorative film ,
An article comprising
The glass film is
an amorphous oxide containing an amorphous oxide-forming element containing at least Si as a constituent element;
crystalline particles containing a crystalline oxide containing a crystalline oxide-forming element as a constituent element;
are mixed, goods. 7. The article of claim 6, wherein the glass film has an average thickness of 20 nm to 500 nm. 8. The article according to claim 6 or 7, wherein at least the surface of said substrate is made of ceramics. The article according to any one of claims 6 to 8, which constitutes tableware.

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