• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Red paint for ceramic decoration. The present invention provides a red paint for ceramic decoration, which includes a glass matrix and a red dye and a protective material that are intermixed in the glass matrix. The red dye contains gold nanoparticles and silver nanoparticles. The protective material contains silica nanoparticles. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2698260A2
    申请号:ES201890054
    申请日:2017-03-17
    公开日:2019-02-01
    发明作者:Hiromichi Hayashi；Jun Shiota；Tomoshi Kumazawa
    申请人:Noritake Co Ltd；
    IPC主号:
    专利说明:

    [0001]
    [0002] RED PAINT FOR CERAMIC DECORATION
    [0003]
    [0004] TECHNICAL FIELD
    [0005]
    [0006] The present invention refers to a red paint for ceramic decoration. More particularly, the present invention relates to a red paint containing gold nanoparticles (Au) and silver nanoparticles (Ag) as a red dye.
    [0007]
    [0008] The present application claims priority based on Japanese Patent Application No. 2016-068160, filed on March 30, 2016, the total contents of which are incorporated herein by reference.
    [0009]
    [0010] STATE OF ART
    [0011]
    [0012] An example of ceramic production represented by porcelain, tiles and the like involves first kneading and molding prepared soils such as kaolin, silica, and feldspar, as starting materials, followed by drying and cooking to produce a substrate. Next, enamel or paint is applied to the surface of the substrate, and decorating is done. As a result, a decorated piece of pottery having a color or pattern burned onto the surface thereof can be obtained.
    [0013]
    [0014] Red is a color highly demanded in ceramic decoration, by virtue of being associated with national flags, corporate logos, characters, Christmas, and so on. Cadmium-based materials, such as selenium-cadmium red, have been widely used, conventionally as red dyes contained in red paints, since said materials provide an intense red coloration. There is a trend, however, towards restricting the use of selenium-cadmium red, due to the toxicity of cadmium.
    [0015]
    [0016] Appointment list
    [0017] Patent Bibliography
    [0018] Patent Bibliography 1: Publication of Japanese Patent Application No. 2013 023735.
    [0019]
    [0020] BRIEF DESCRIPTION OF THE INVENTION
    [0021]
    [0022] In view of the foregoing considerations, it is an object of the present invention to provide a red paint for ceramic decoration (with paint) which gives rise to an intense red coloration.
    [0023]
    [0024] The present invention provides a red paint for decorating ceramics, including a glass matrix, and a red dye and a protective material that are intermixed in the glass matrix. The red dye contains gold nanoparticles and silver nanoparticles. The protective material contains silica nanoparticles.
    [0025]
    [0026] Gold nanoparticles produce a bluish-red (red-purple) coloration, called "garnet", due to the absorption of green light to light blue.The silver nanoparticles provide a yellow coloration through the absorption of blue light. Therefore, the concomitant use of gold nanoparticles and silver nanoparticles as a red dye allows the silver nanoparticles to absorb the blue light in the "garnet" obtained from the gold nanoparticles. As a result, intense red coloration can be achieved. In addition, dispersing the red dye in the vitreous matrix together with the protective material makes the red dye less susceptible to penetrate the vitreous matrix during decorating, and allows to achieve a carefully nuanced red coloration.
    [0027]
    [0028] Unless otherwise indicated, the term "nanoparticles" in the present specification indicates particles having an arithmetic mean value (particle size D50) of 1 to 100 mm of an equivalent circle diameter, based on an electron microscope , for example, a transmission electron microscope (MET).
    [0029]
    [0030] Unless otherwise indicated, the term "ceramic" in the present specification indicates non-metallic inorganic materials in general, for example, Porcelain materials, glass materials, etc., are examples encompassed within the term ceramic in the present specification.
    [0031]
    [0032] The patent literature 1 discloses a red enamel containing copper nanoparticles. In the patent literature 1, a red coloration is achieved by decorating the previous red enamel in an oxidizing atmosphere. However, even a little copper (II) oxide is not generated by the oxidation of copper when the copper nanoparticles disclosed in Patent Literature 1 are fired in an oxidizing atmosphere (for example, an air atmosphere) . When the previous red enamel is used, therefore, a decorative part in red acquires a dark and dull color tone, derived from an insufficient brightness or an insufficient yellow tint (for example, a value L * and a value b * in the color space L * a * b *). Therefore, the previous red enamel is not suitable to become an alternative to, for example, the red selenium-cadmium that provides an intense red.
    [0033]
    [0034] In a preferred embodiment of the red paint disclosed in the present patent, the volume ratio of the gold nanoparticles and the silver nanoparticles satisfies the ratio of gold nanoparticles: silver nanoparticles = 80:20 to 20:80. As a result, the effect of concomitant use of gold nanoparticles and silver nanoparticles can be brought to a higher level, and an intense red coloration can be achieved even more stably.
    [0035]
    [0036] In a preferred embodiment of the red paint disclosed in the present patent, the proportion of gold nanoparticles is 0.05 parts by volume to 0.5 parts by volume, with respect to 100 parts by volume as the total of the glass matrix and the protective material. As a result, the value a * in the direction of red in the L * a * b * increases, and the development of the red color can thus be improved. In addition, it increases the L * value of the brightness in the L * a * b * color space, and an intense and bright tint can be achieved in an adequate way. Moreover, costs can be kept low by preventing red paint from becoming excessively expensive.
    [0037]
    [0038] In a preferred embodiment of the red paint disclosed in the present patent, the proportion of silver nanoparticles is 0.05 parts by volume to 0.4 parts by volume with respect to 100 parts by volume as the total of the glass matrix and the protective material. As a result, it increases the value of b * in the direction of yellow, in the color space L * a * b *, which allows suppressing the bluish coloration in gold nanoparticles at a high level. Therefore, a further development of the red color can be achieved. Moreover, costs can be kept low by preventing red paint from becoming excessively expensive.
    [0039]
    [0040] In a preferred embodiment of the red paint disclosed in the present patent, the volume of the protective material is 20 times or more the volume of the red dye. As a result, this returns the penetration of the red dye into the vitreous matrix during decorating even less likely, and the discoloration of the red is better suppressed. An excellent development of the red color can be realized as a result, at an even higher level.
    [0041]
    [0042] In a preferred embodiment of the red paint disclosed in the present patent, the proportion of the protective material is 10% by volume to 40% by volume with respect to 100% by volume as the total of the glass matrix and the protective material. In addition to the development of the red color, a decorative red part with high specular gloss and an excellent appearance in the perception of brightness can be achieved as a result.
    [0043]
    [0044] In another aspect, the present invention also provides a ceramic product having a decorative part of red color. The decorative part of red color contains glass, gold and silver. The decorative part of red color satisfies the following conditions in the color space L * a * b *, based on Japanese industrial standards JIS Z8729 (2004): the value of L * is from 35 to 70; the value of a * is 20 or greater, and the value of b * is 15 or greater.
    [0045]
    [0046] In a preferred embodiment, a 45 degree specular gloss of the red decorative part based on Japanese industrial standards JIS Z8741 (1997) is 70% or greater.
    [0047]
    [0048] BRIEF DESCRIPTION OF THE DRAWINGS
    [0049]
    [0050] Fig. 1 is a flow chart for explaining a method for producing a red paint according to an embodiment of the present invention.
    [0051] Fig. 2 is a matrix indicating the relationship between the ratio of the dye content and brightness and the chromaticity in the color space L * a * b *.
    [0052]
    [0053] DESCRIPTION OF THE REALIZATIONS
    [0054]
    [0055] Preferred embodiments of the present invention will now be explained. Any characteristic other than the characteristics specifically set forth in the present description and which may be necessary to realize the present invention, can be considered as an example of the design matter, for a person skilled in the art, based on conventional techniques in the field technical in question. The present invention can be made based on the disclosure of the present specification and common technical knowledge in the relevant technical field. In the present specification a range of numerical values annotated as A to B (where A and B are arbitrary numerical values), indicates a value equal to or greater than A, and equal to or less than B.
    [0056]
    [0057] «Red paint >>
    [0058] The red paint disclosed in the present patent is a red paint to form a decorative part of red color in a piece of ceramics, as an object to be decorated, covering the surface of the ceramic with the red paint and then carrying out the firing of decorated. The red paint has a vitreous matrix, and a red dye and protective material dispersed in the vitreous matrix, where the red dye contains gold nanoparticles (Au) and silver nanoparticles (Ag), and the protective material contains silica nanoparticles . Other properties are therefore not particularly limited, and can be established arbitrarily in view of various criteria, for example, through the addition of various components and the modification of the compositions thereof. The various constituent components will be explained below in order.
    [0059]
    [0060] The vitreous matrix has the properties of a reticular matrix to disperse the red dye and the protective material. The red dye and the protective material are intermixed in the vitreous matrix. The glass component, the red dye component and the protective material component are usually in the form of a compact sintered product which is the result of the integral sintering of the above.
    [0061] The vitreous matrix is a component that functions as an inorganic binder of the red dye. The vitreous matrix also has the function of improving the adherence between the red dye and the ceramic that is the object that is going to be decorated. The coefficient of linear thermal expansion (average coefficient of the linear expansion measured in a temperature region of 25 ° C to 500 ° C using a thermomechanical analyzer, also hereinafter) of the glass constituting the glass matrix is not particularly limited and it can be identical to that of ceramics as an object to be decorated. As an example, the coefficient of linear thermal expansion of the glass can be approximately (coefficient of thermal expansion of the object to be decorated) ± 2x 10-6 K-1. The coefficient of linear thermal expansion of the glass can be found, for example, in the range of 4.0x 10-6 K-1 to 8.0x 10-6 K-1. As a result, the difference between the contraction factors of the object to be decorated (ceramic) and the red paint at the time of decorating becomes smaller, and the appearance of chipping, cracking and so on at the site decorated with the dye Red becomes less likely.
    [0062]
    [0063] The glass transition point (value of Tg based on differential scanning calorimetry, also hereinafter) of the glass constituting the glass matrix is not particularly limited. For example, the glass transition point may be from about 400 ° C to 1500 ° C, based on the relationship described below with respect to the sintering temperature. Within the above range, the glass transition point can be from about 900 ° C to 1300 ° C in enamel decoration applications and immersion applications. The glass transition point in enamel decoration applications can be from about 500 ° C to 900 ° C.
    [0064]
    [0065] Examples of types of glass that can have such properties (coefficient of thermal expansion and glass transition point) include, for example, SiO 2 -RO glass (where RO represents an oxide of a group II element, for example MgO) , CaO, SrO and BaO, also hereinafter), SiO2-RO-R2O glass (where R 2 O represents an oxide of an alkali metal element, for example Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and Fr2O, in particular Li2O, also hereinafter), SiO2-RO-ZnO glass, SiO2-RO-ZrO2 glass, SiO2-RO-Al2O3 glass, SiO2-RO-Bi2O3 glass, SiO2-R2O glass, SiO2- glass ZnO, SiO2-ZrO2 glass, SiO2-Al2O3 glass, RO-R2O glass, glass RO-ZnO or similar. The above types of glass may contain one, or two or more components in addition to the main constituent components provided in the above denomination. The glass can be common amorphous glass, or crystallized glass containing crystals.
    [0066]
    [0067] In a preferred embodiment, the SiO2 is half (50 mol%) or more with respect to 100 mol% as full glass. The glass transition point tends, generally, to increase with an increasing proportion of SiO 2 . Accordingly, the proportion of SiO 2 can be maintained at, or below, about 80 mol% in the case, for example, in which the sintering temperature described below is adjusted to be low.
    [0068]
    [0069] Adding components such as RO, R2O, and B2O3 is effective from the point of view of reducing the glass transition point and, thereby, increasing the glass's fusibility. In contrast, the coefficient of thermal expansion of glass tends to become higher with an increasing content of the above components. In a preferred embodiment, the RO is approximately 15 to 35 mol% with respect to 100 mol% as the whole of the glass. In another preferred embodiment, the R2O is from 0 to 5 mol% with respect to 100 mol% as the whole of the glass.
    [0070]
    [0071] In a preferred embodiment, the glass is constituted by a multicomponent system of four or more components (for example, five or more components). The physical stability of the decorative part of red color is increased as a result. In applications involving, for example, dishware decoration, the red decorative part is required to show sufficient acid resistance to acidic foods, and sufficient alkali resistance to alkaline detergents. In these cases, it is effective to add, for example, a component such as Al2O3, ZnO, and CaO, for example in a proportion of 1 mol% or greater, in addition to the main constituent components provided in the above denomination. The chemical durability of the decorative part of red color can be improved more optimally as a result. Preferably, also the wear resistance can be improved.
    [0072]
    [0073] In a preferred embodiment, the glass contains substantially no component that may have an adverse impact on human health or the environment, Examples include arsenic components, lead components or cadmium components. In tableware decoration applications, in particular, it is preferable not to actively add any component of this type (which can, however, be permissibly mixed in the glass as unavoidable impurities).
    [0074]
    [0075] The proportion of the vitreous matrix in the red paint is not particularly limited. The proportion of the vitreous matrix is about 50% by volume or greater, usually 60% by volume or greater, and for example 70% by volume or greater, with respect to 100% by volume in the form of all of the red paint, from the point of view of improving the adherence with the ceramic piece, which is the object to be decorated. The proportion of the vitreous matrix is about 95% by volume or less, usually 90% by volume or less, and for example 80% by volume or less, with respect to 100% by volume in the form of all of red paint, from the point of view of increasing the development of the red color. For identical reasons, the proportion of the vitreous matrix is about 50% by volume or greater, usually 60% by volume or greater, and for example 70% by volume or greater, and is about 95% by volume or smaller, usually 90% by volume or less, and for example 80% by volume or less, with respect to 100% by volume as the total of the glass matrix and the protective material.
    [0076]
    [0077] The red dye is a component that imparts red color to the surface of the ceramic that is the object to be decorated. The red dye is intermixed with the protective material in the vitreous matrix. The red dye and the protective material may be present one independently of the other, or they may be present as groupings that are the result of the aggregation of the protective material around the red dye. The red dye contains gold nanoparticles and silver nanoparticles as metal nanoparticles.
    [0078]
    [0079] Metal nanoparticles show specific optical characteristics (for example, bands of strong light absorption) in the visible to ultraviolet regions, which arise from surface plasmon resonance (SPR, for its acronym in English). For example, gold nanoparticles (Au) absorb light of a wavelength close to 530 nm (green light to light blue light) and show a bluish red (red-purple) color called "garnet." For example, nanoparticles of silver (Ag) they absorb light (blue light) at a wavelength close to 420 nm and show a yellow coloration. Through the concomitant use of gold nanoparticles and silver nanoparticles, therefore, the bluish wavelength of the gold nanoparticles is absorbed by the silver nanoparticles, and in this way an intense red coloration is produced. The gold nanoparticles and the silver nanoparticles can be in the form of respective single particles, or they can be in alloy state. Provided that the effect of the technology disclosed in the present patent is not significantly impaired in this way, the red dye may include metal nanoparticles other than those of gold and silver, for example, in a volume ratio no greater than 1/10 of the total volume of gold nanoparticles and silver nanoparticles.
    [0080]
    [0081] The D50 particle size of the gold nanoparticles and the silver nanoparticles is a nanometric size (approximately 1 to 100 nm), in terms of a compensation with the previous surface plasmon resonance. The effect of the surface plasmon resonance of the metal nanoparticles can vary depending on the particle size. The effect of surface plasmon resonance can be better exploited through the proper adjustment of particle size to a nanometric size.
    [0082]
    [0083] In a preferred embodiment, each particle size D50 of the gold nanoparticles and silver nanoparticles is 5 nm or greater, usually 10 nm or greater and for example 15 nm or greater. In another preferred embodiment, each particle size D50 of the gold nanoparticles and the silver nanoparticles is about 80 nm or less, usually 50 nm or less, and for example 30 nm or less. Establishing that the particle size D50 is within the above ranges allows to increase the absorbance at the specific wavelengths of the metal nanoparticles, while achieving a good red coloration with small amounts of addition. In addition, a precise decoration can be made, with little irregularity in the color.
    [0084]
    [0085] The ratio of the mixture of gold nanoparticles and silver nanoparticles is also affected, for example, by the particle size and the particle size distribution of the metal nanoparticles, and therefore is not particularly limited. For example, the volume ratio can be adjusted from so that the volume of the gold nanoparticles is greater, or so that the volume of the silver nanoparticles is greater. In a preferred embodiment, the ratio of the volume of gold nanoparticles and silver nanoparticles satisfies the following, gold nanoparticles: silver nanoparticles = 80:20 to 20:80, for example gold nanoparticles: silver nanoparticles = 72: 28 to 36:64. As a result, the effect of the technology disclosed in the present patent can be presented at a high level, and an intense red coloration can be made even more stable.
    [0086]
    [0087] The proportion of red dye in red paint is not particularly limited. The proportion of the red dye is about 0.1% by volume or greater, for example 0.15% by volume or greater, and is about 1% by volume or less, usually 0.8% by volume or less, and for example, 0.7% by volume or less, with respect to 100% by volume, in the manner of the entire red paint, for example, from the point of view of improving the development of the red color and in terms of cost. For identical reasons, the proportion of the red dye may be about 0.1 parts by volume or more, for example 0.15 parts by volume or more, and may be about 1 part by volume or less, usually 0.8 parts. by volume or less and for example 0.7 parts by volume or less, with respect to 100 parts by volume as the total of the glass matrix and the protective material.
    [0088]
    [0089] In a preferred embodiment, the volume of the red dye is from about 1/100 to 1/200, for example 1/120 to 1/180, of the volume of the glass matrix. A homogenous red coloration can be achieved stably as a result.
    [0090]
    [0091] In a preferred embodiment, the proportion of gold nanoparticles is about 0.05 parts by volume or more, preferably 0.1 parts by volume or more, and for example 0.11 parts by volume or more, with respect to 100 parts. by volume as the total of the vitreous matrix and the protective material. By establishing that the proportion of gold nanoparticles is equal to or greater than a predetermined value, it is possible to increase the value a * in the direction of red, in the color space L * a * b *, and thus improve the development of color Red. In addition, the L * value of the brightness can also be increased, and an intense and bright dye can be achieved more optimally.
    [0092] In another preferred embodiment, the proportion of gold nanoparticles is about 0.5 parts by volume or less, usually 0.45 parts by volume or less, preferably 0.35 parts by volume or less, and for example 0.32 parts. by volume or less, with respect to 100 parts by volume as the total of the vitreous matrix and the protective material. By establishing that the proportion of gold nanoparticles is equal to or less than a predetermined value, it is possible to increase the L * value of the brightness in the color space L * a * b *, and to optimally perform an intense and bright dye. In addition, costs can be kept low.
    [0093]
    [0094] In a preferred embodiment, the proportion of silver nanoparticles is about 0.05 parts per volume or more, preferably 0.1 parts per volume or more, and for example 0.11 parts per volume or more, with respect to 100 parts. by volume as the total of the vitreous matrix and the protective material. By establishing that the proportion of the silver nanoparticles is equal to or greater than a predetermined value, it is possible to increase the value b * in the direction of yellow, in the color space L * a * b *, and achieve a development of the red color even superior.
    [0095]
    [0096] In another preferred embodiment, the proportion of silver nanoparticles is about 0.4 parts by volume or less, preferably 0.35 parts by volume or less, and for example 0.32 parts by volume or less, with respect to 100 parts. by volume as the total of the vitreous matrix and the protective material. By establishing that the proportion of silver nanoparticles is equal to or less than a predetermined value, it is possible to increase the L * value of the brightness in the color space L * a * b *, and to optimally perform an intense and bright dye. In addition, costs can be kept low.
    [0097]
    [0098] The protective material is a component to suppress the discoloration of the red dye during decorating and to enhance the development of the red color. Specifically, the protective material has a higher melting point than a decorating cooking temperature described below. As a result, the red dye (nanometal) and the glass do not easily come into contact with each other during decorating, thanks to the fact that the red paint contains the protective material. Consequently, it is possible to prevent the red dye from being absorbed as a constituent component of the glass, in other words, to suppress the dissolution of the red coloring in the glass. The state in which the red dye is dispersed in the glass in the form of metal particles, also after the decorating firing, can be maintained, as a result, stably. Therefore, a carefully nuanced red coloration can be achieved that boasts an excellent color development. The protective material is intermixed with the red dye in the vitreous matrix. The protective material can be in a state independent of the state of the red dye, or it can for example be adhered to, as a bond or in coordinated fashion with the surface of the red dye.
    [0099]
    [0100] The protective material contains silica nanoparticles. The transparency of the silica increases when it is sintered. An effect is caused as a result of accentuating the development of color in the decorative part of red color, and reinforcing the perception of brightness. In addition, silica is commercially available at a comparatively low cost, and is therefore preferable in terms of availability and cost. Provided that the effect of the technology disclosed in the present patent is not significantly impaired in this way, the protective material may contain ceramic nanoparticles other than silica nanoparticles, for example, in a volume ratio lower than that of the silica nanoparticles. Concrete examples of the same include, for example, zirconium oxide nanoparticles, alumina nanoparticles and titanium oxide nanoparticles.
    [0101]
    [0102] The particle size D50 of the protective material is nanometric in size (from about 1 to 100 nm). The particle size D50 of the protective material (usually silica nanoparticles) is usually identical to, or less than, the particle size D50 of the metal nanoparticles. In a preferred embodiment, the particle size D50 of the protective material is about 50 nm or less, usually 30 nm or less and, for example, 20 nm or less. By establishing that the particle size D50 is equal to or less than a predetermined value, the specific surface area of the particle size increases, and the effect of suppressing the discoloration of the red dye during the decorating firing is most optimally caused. It is therefore possible to achieve a superior red coloration even more stable.
    [0103]
    [0104] In a preferred embodiment, the volume of the protective material is about 5 times or more, usually 10 times or more, preferably 20 times or more, per example 30 times or more the volume of the red dye. As a result, the effect of suppressing the discoloration of the red dye during decorating cooking can be more optimally produced.
    [0105]
    [0106] In another preferred embodiment, the volume of the protective material is about 90 times or less, usually 80 times or less, preferably 70 times or less, for example 60 times or less, and more preferably 50 times or less the volume of the red dye. As a result, a decorative part with improved appearance (perception of brightness, brightness, and color tone) can be realized.
    [0107]
    [0108] The proportion of protective material in red paint is not particularly limited. The proportion of the protective material can be about 10% by volume or greater, for example 20% by volume or greater, with respect to 100% by volume as the total of the red paint, from the point of view of an improvement of the development of the red color. The proportion of the protective material may be about 40% by volume or less, for example 30% by volume or less, with respect to 100% by volume of the entire red paint, from the point of view of increasing the perception of brightness, or brightness. For similar reasons, the proportion of the protective material may be about 10% by volume or greater, for example 20% by volume or greater, and may be about 40% by volume or less, for example 30% by volume or less, with respect to 100% in volume as the total of the vitreous matrix and the protective material.
    [0109]
    [0110] The red paint disclosed in the present patent may be constituted of the above three components (glass, red dye and protective material), or may have other components added thereto, as appropriate, for example within a range of less than about 10% by volume, with respect to 100% by volume in the manner of the entire red paint, provided that the effect of the technology disclosed in the present patent is not significantly impaired in doing so. Examples of additional components include, for example, organic binders, reaction accelerators, surfactants, dispersants, thickeners, pH adjusting agents, preservatives, antifoaming agents, plasticizers, stabilizers, antioxidants and the like.
    [0111] In a preferred embodiment, the red paint contains substantially no components that can exert an adverse impact on human health or on the environment, for example, arsenic components, lead components or cadmium components (which can nevertheless be found mixed permissibly in red paint as unavoidable impurities). In decorative ware applications, in particular, it is preferable that the red paint does not contain said components.
    [0112]
    [0113] The red paint disclosed in the present patent can be adjusted in various ways depending on the desired application. For example, red paint can be prepared in the form of a glass hull, in the form of powders, in the form of a frit, a granule form, a plate form or a paste form. As an example, in a case for example in which a fine decoration is to be imparted to the surface of the object to be decorated, the red paint can be prepared as a paste by the addition of a solvent (for example, a solvent watery) to red paint.
    [0114]
    [0115] «Method to produce red paint >>
    [0116] The method for producing said red paint is not particularly limited, and for example may involve adding a glass frit to a mixture of the red dye and the protective material, with additional mixing, drying and sintering, followed by spraying, to thereby produce the red paint. The various steps will be explained below in reference to the flow chart of Fig. 1.
    [0117]
    [0118] The production method illustrated in Fig. 1 includes the following steps: (step S1) preparing a first liquid mixture by mixing a red dye and a protective material according to a wet method; (step S2) mix a glass frit in the first mixture, to prepare a second mixture; (step S3) subjecting the second mixture to a heat treatment, to thereby produce a compact sintered product in which the red dye and the protective material are intermixed in the glass matrix; and (step S4) spraying the sintered compact. This production method makes it possible to produce a red paint of the present embodiment in simple steps, i.e., mixing and a heat treatment. Therefore, the above method of production is preferable in terms of convenience, workability and productivity of the mass compared to, for example, a method production that requires a step of forming a silica coating film on the surface of the metal nanoparticles.
    [0119]
    [0120] In step S1, the red dye and the protective material are mixed. At least gold nanoparticles and silver nanoparticles are prepared as the red dye. At least silica nanoparticles are prepared as a protective material. The nanoparticles have high cohesiveness, and are therefore usually commercially available in the form of dispersions in which the particles have been stabilized in a dispersion solvent. In the present embodiment, therefore, respective nanoparticle dispersions are weighed and mixed in such a way that the gold nanoparticles, silver nanoparticles and silica nanoparticles obey predetermined volume ratios. The affinity of the red dye and the protective material can be increased by mixing the red dye and the protective material beforehand, prior to the addition of the glass frit. The mixing operation can be carried out for example using a magnetic stirrer or counting with ultrasonic waves. A first liquid mixture is thus prepared.
    [0121]
    [0122] In step S2 the glass frit is mixed, at a predetermined ratio, in the first liquid mixture. In the present embodiment a highly homogeneous mixture can be obtained by mixing the first mixture and the glass frit, according to a wet method. A second liquid mixture is thus prepared.
    [0123]
    [0124] In step S3 the second mixture is subjected to heat treatment. For example, the second mixture is first dried in a region of temperature not higher than 100 ° C, to remove the dispersion medium to a certain degree. The resulting mixture is then heated to a temperature equal to or greater than the glass transition point of the glass frit, in order to thereby integrally sinter the mixture. The sintering temperature can be adjusted to be in the range of approximately one glass transition point from 0 ° C to 300 ° C. In the production, for example, of a paint for decoration on enamel the sintering temperature can be adjusted to approximately 800 ° C to 900 ° C, in a case where the glass transition point of the glass frit is 600 ° C at 800 ° C. The sintering time can be adjusted in an ordinary way to be in a range of about 0.1 to several hours. The atmosphere that is used at the moment of the sintering can be an air atmosphere, an oxidizing atmosphere, an inert gas atmosphere or the like. As a result of said thermal treatment an integral sintered compact product is obtained in which the red dye and the protective material are intermixed in the vitreous matrix.
    [0125]
    [0126] In step S4 the compact product is pulverized (eg, crushed) and / or sized to a desired size. The spraying operation can be achieved for example using a vibratory mill, a planetary mill, a stirrer or the like. The shape and size of the red paint are not particularly limited, and for example the average particle size based on the scattering of the light by laser diffraction can be adjusted to approximately 10 p, or less, usually in the range of 0, 1 to 10 p, m, and for example from about 0.5 to 5 p, m, for example, in terms of workability.
    [0127]
    [0128] The red paint obtained is used to decorate the surface of a ceramic piece such as the object to be decorated. The decoration operation can be achieved by applying the red paint on the surface of a ceramic, followed by the decorating firing at a predetermined temperature. For example, in the "decoration under enamel", in which the decoration is imparted on a baked substrate, and in the "immersion" where the red paint is incorporated into an enamel, the red paint can be applied to the surface of a ceramic , followed by decorating at an elevated temperature, from approximately 1200 ° C to 1400 ° C. In the decoration "on enamel", in which the decoration is imparted on an enamelled substrate (after enameling), the red paint can be applied to the surface of the ceramic, followed by decorating at an average temperature of approximately 700 ° C to 1000 ° C. The red paint of the present embodiment can produce a particularly good red coloration through cooking at the above average temperature.
    [0129]
    [0130] The decorating firing after the red paint application can usually be carried out in an air atmosphere (oxidizing atmosphere). For example, cinnabar (cuprous oxide) widely used as a red dye requires decorating firing under a reducing atmosphere. In contrast, the red paint disclosed in the present patent develops a red coloration through cooking in an air atmosphere, and therefore no equipment is required to maintain a reducing atmosphere, which is advantageous in terms of ease of use.
    [0131] A ceramic product having a decorative part of red color can be obtained in this way as described above. The term "ceramic product" encompasses in the present patent pottery, porcelain, earthenware, ceramic stoneware, glass, etc. Specific articles include, for example, tableware, decorative jugs, various wall and floor tiles, sanitary ceramics, tiles, bricks, clay pipes, ceramic pipes and the like.
    [0132]
    [0133] The decorative red part of the ceramic product is a baked body that contains at least glass, gold and silver. The red decorative part of the present embodiment results in a unique intense red coloration. The appearance (color tone and brightness perception) of this red decorative part allows to improve the aesthetics and the quality sensation of the ceramic, and contributes to provide articles that accumulate high customer satisfaction.
    [0134]
    [0135] The color tone of the red decorative part of the present embodiment in the color space L * a * b * according to the JIS Z8729 (2004) standard can adequately satisfy the following conditions:
    [0136] • the L * value is in the range of 35 to 70 (preferably 35 to 55); • the value a * is 20 or greater (preferably 30 or greater, and for example 50 or less);
    [0137] • the value b * is 15 or greater (preferably 20 or greater, and for example 40 or less).
    [0138]
    [0139] An intense and bright dye can be made by establishing that the L * value of brightness is equal to or greater than a predetermined value. A deep warm tint can be made by setting the L * value of brightness to be equal to or less than a predetermined value. The development of the red color can be increased, and a clear and sharp tint can be made, establishing that a value of a * in the direction of red is equal to or greater than a predetermined value. Setting that the value of b * in the direction of yellow is equal to or greater than a predetermined value, in other words, keeping the value of -b * small in the direction of blue, it is possible to perform an intense red coloration by suppressing the purple coloration to blue, for example, as in the color "garnet".
    [0140] The brightness perception of the red decorative part of the present embodiment involves a specular brightness of 45 degrees according to JIS Z8741 (1997), which can satisfy a value of 70% or greater, preferably 80% or greater, and particularly preferably 90% or greater. As a result, the decorative part of red emits brightness when irradiated with light, which translates into an improvement in the perception of brightness. In addition, it increases the smoothness of the surface and a beautiful, luxurious appearance can be achieved.
    [0141]
    [0142] Next, some examples pertaining to the technology disclosed in the present patent will be explained, but the invention is not intended to be limited by the following examples.
    [0143]
    [0144] <I. Evaluation of the color tone>
    [0145] In the present test example, gold nanoparticles and silver nanoparticles were prepared as a red dye, and the color tone was evaluated through the modification of the content ratios of the gold nanoparticles and the silver nanoparticles.
    [0146]
    [0147] Specifically, first, a dispersion (commercial product) of gold nanoparticles with a D50 particle size of 20 nm, a dispersion (commercial product) of silver nanoparticles with a D50 particle size of 20 nm and a dispersion is mixed. (commercial product) of silica nanoparticles with a D50 particle size of 20 nm, to produce a first mixed solution. Then, a glass frit (glass transition point: 640 ° C) with the composition provided in Table 1 was added to the first mixed solution, with further mixing of the whole, to thereby produce a second mixed solution. The second mixed solution was dried in an oven, and thereafter subjected to a heat treatment in an air atmosphere at a temperature of 800 ° C to 900 ° C for 30 minutes, to thereby produce a compact sintered product. Each compact sintered product was disintegrated using an Ishikawa mixing and grinding machine, followed by spraying using a vibratory mill and a planetary mill, in this order, to produce a red powder paint with an average particle size of 0.5 to 5. p.m.
    [0148] The first mixed solution and the second mixed solution were prepared so that, in the state of red paint, the glass was 80% by volume, silica as a protective material was 20% by volume, and the gold nanoparticles (Au) and the silver nanoparticles (Ag), such as the red dye, were present in the proportion (parts by volume) that is provided in Table 2 with respect to the total (100 parts by volume) of glass plus silica.
    [0149]
    [0150] Table 1 Composition of the glass frit
    [0151]
    [0152]
    [0153]
    [0154]
    [0155] Table 2 Relationship of red dye content and evaluation results
    [0156]
    [0157]
    [0158]
    [0159]
    [0160] Each red paint produced was applied to the surface of a ceramic piece (test piece), and decorating was done from 700 ° C to 900 ° C in an air atmosphere (oxidizing atmosphere), to thereby produce a respective piece of ceramic with a decorative part of red color. Each red decorative part was measured to determine its brightness (L *) and chromaticity (a *, b *) in the color space L * a * b *, according to the JIS standard Z8729 (2004), using a spectrophotometer from Konica Minolta, Inc. Results are shown in Table 2 in the corresponding columns.
    [0161]
    [0162] The "Determination" columns in Table 2 show the determination results based on criteria (1) of Table 3. The column "Determination 1" in Table 2 establishes the results of determination of the value of L *. The column "Determination 1" establishes the annotation "E (Excellent)" where the value of L * is "®" (excellent), the annotation "G (good)" where the value of L * is "O" (good) , and the annotation "P (Poor)" where the value of L * is "X" (poor). The results of chromaticity determination (a *, b *) are shown in the "Determination 2" column. The column "Determination 2" shows the annotation "E (Excellent)" where both the value of a * and the value of b * are "®" (excellent), the annotation "G (good)" where one of the value from a * and the value of b * is "®" (excellent) and the other is "O" (Good), or where both the value of a * and the value of b * are "O" (good), and shows the annotation "P (Poor)" where at least one of the value of a * and the value of b * is "X" (poor).
    [0163]
    [0164] Table 3 Criteria (1)
    [0165]
    [0166]
    [0167]
    [0168]
    [0169] Fig. 2 is a matrix that indicates the relationship between the ratio of red dye content and brightness and chromaticity in the color space L * a * b *. As illustrated in Table 2 and Fig. 2, a red decorative part of an intense coloration with good chromaticity (a *, b *) could be made using the red dyes of Examples 1 to 8, which contain gold nanoparticles and silver nanoparticles. Among the previous ones, the brightness (L *) was improved and an intense and bright dye could be achieved more optimally by using the red paints of Examples 2 to 8, in which the proportion of gold nanoparticles and nanoparticles of silver was 0.32 parts by volume or less with respect to the total vitreous matrix plus the protective material. In particular, the blue tendency was further suppressed and it was able to achieve a decorative part of red color that shows a remarkably clear red coloration by using the red paints of Examples 4 to 8, in which the proportion of gold nanoparticles and silver nanoparticles is in the range of 0, 11 to 0.32 parts by volume with respect to the total of the vitreous matrix plus the protective material.
    [0170]
    [0171] <II. Brightness perception evaluation>
    [0172] In the present test example, gold nanoparticles and silver nanoparticles were prepared as the red dye, and the color tone was evaluated through the modification of the content ratios of the gold nanoparticles and the silver nanoparticles. Red paints were obtained in the same manner as in section I above, but in the present section the red paints were prepared so that, in the state of the first mixed solution and the second mixed solution, the glass and the protective material were present in the proportions shown in Table 4, and the content of gold nanoparticles as the red dye was 0.3 parts by volume and the content of silver nanoparticles was 0.2 parts by volume, with respect to total (100 parts by volume) of the glass plus silica. A respective decorative part of red color was formed using each red paint, and the "appearance (color tone and brightness perception)" was measured.
    [0173]
    [0174] The method to measure the color tone is the same as in section I above. The perception of brightness was measured according to JIS standard Z8741 (1997) using a brightness meter manufactured by Nippon Denshoku Industries Co., Ltd. Table 5 establishes the criteria for determining "color tone" and "Brightness", where the results of the determination are given in the corresponding columns of Table 4. The criterion for the color tone provided in Table 5 is identical to the criterion "®" (Excellent) in the test example I. Therefore, the Examples where the criteria in the color tone column in Table 4 are satisfied are shown as "E (Excellent)". Examples that do not meet the criteria in Table 5 are indicated by an asterisk (*) in the brightness column of Table 4. In the complete determination of Table 4, the examples in which the color tone was "E "And the brightness was 90% or higher were classified as" E (Excellent) ", while the examples in which the color tone was" E "and the brightness was 80% or higher were classified as" G ( Good)".
    [0175] Table 4 Proportion of glass, protective material and red coloring
    [0176]
    [0177]
    [0178]
    [0179]
    [0180] Table 5 Criteria (2)
    [0181]
    [0182]
    [0183]
    [0184]
    [0185] As Table 4 reveals, decorative parts could be achieved in which the color tone and gloss were both particularly good in Examples 10 to 13, in which the proportion of the protective material was 10 to 40% by volume with respect to the 100% by volume as the total of the vitreous matrix and the protective material. Among the above, a decorative part of particularly high brightness perception, with a brightness of 90% or more, could be achieved using the red paints of Examples 10 and 11.
    [0186]
    [0187] Concrete examples of the technology disclosed in the present patent have been explained in detail above, but the specific examples are merely illustrative and are not intended to limit the scope of the claims in any way. The technology set forth in the claims includes variations and modifications of the specific examples illustrated above.
    权利要求:
    Claims (8)
    [1]
    1. Red paint for ceramic decoration, comprising: a vitreous matrix; and a red dye and a protective material that are intermixed in the vitreous matrix,
    where the red dye contains gold nanoparticles and silver nanoparticles, and the protective material contains silica nanoparticles.
    [2]
    Red paint according to claim 1, wherein the volume ratio of the gold nanoparticles and the silver nanoparticles satisfies the ratio of gold nanoparticles: silver nanoparticles = 80:20 to 20:80.
    [3]
    Red paint according to claim 1 or 2, wherein the proportion of the gold nanoparticles is 0.05 parts by volume to 0.5 parts by volume with respect to 100 parts by volume as the total of the glass matrix and the protective material.
    [4]
    Red paint according to any one of claims 1 to 3, wherein the proportion of the silver nanoparticles is 0.05 parts by volume to 0.4 parts by volume with respect to 100 parts by volume as the total of the glass matrix and the protective material.
    [5]
    Red paint according to any one of claims 1 to 4, wherein the volume of the protective material is 20 times or more the volume of the red dye.
    [6]
    Red paint according to any one of claims 1 to 5, wherein the proportion of the protective material is 10% by volume to 40% by volume with respect to 100% by volume as the total of the glass matrix and the protective material.
    [7]
    7. A ceramic product comprising a decorative part of red color, where the decorative part of red color contains glass, gold and silver, and
    the decorative part of red color satisfies the following conditions in the color space L * a * b *, based on Japanese industrial standards JIS Z8729 (2004):
    the value of L * is 35 to 70;
    the value of a * is 20 or greater; Y
    the value of b * is 15 or greater.
    [8]
    8. Ceramic product according to claim 7, wherein a 45-degree specular gloss of the red decorative part, based on Japanese industrial standards JIS Z8741 (1997), is 70% or greater.
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    PCT/JP2017/010934|WO2017169905A1|2016-03-30|2017-03-17|Red paint for ceramic decoration|
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