Dental ceramic coloring liquid with shielding property

Abstract

The invention relates to a dental ceramic coloring liquid with shielding property. The present invention provides a dental ceramic coloring liquid which is capable of suppressing a decrease in mechanical strength of a dental ceramic after sintering, has good storage stability, and is capable of imparting shielding properties. The present invention relates to a dental ceramic coloring liquid comprising an organosilicon compound. The organosilicon compound is preferably hydrophilic. The organosilicon compound is preferably a silicone compound. The organosilicon compound is preferably an alkylsilane compound.

Description

[0001] This application is a divisional application of PCT Patent Application No. PCT / JP2021 / 042508, entitled "Dental Ceramic Coloring Liquid with Masking Property", the parent application entered China as Application No. 202180077834.0. TECHNICAL FIELD

[0002] The present application relates to a coloring liquid for dental ceramics. More specifically, it relates to a coloring liquid for dental ceramics, for example, which is used for the production of dental prostheses such as inlays, onlays, veneers, crowns, bridges, abutments, posts, dentures, denture bases, implant components (fixtures, abutments), and the like, which are obtained by cutting processing using a dental CAD / CAM system. BACKGROUND

[0003] In the past, as dental products (e.g., dental prostheses such as representative covering crowns, tooth crowns, dental crowns, attached dentures, and the like, orthodontic products, and dental implant products), metals have often been used. However, the color of metals is significantly different from that of natural teeth, and has the disadvantage of lacking aesthetic properties, and sometimes also causes allergies due to the elution of metals. Thus, in order to solve the problems associated with the use of metals, ceramic materials such as alumina (aluminum oxide) and zirconia (zirconium oxide) have been increasingly used as alternative materials to metals for dental products. In particular, zirconia is excellent in strength and also has relatively good aesthetic properties, and thus, in particular, in conjunction with the recent reduction in price, the demand is increasing.

[0004] In recent years, CAD / CAM systems that use a computer to design and use a milling device to cut and process final shapes of dental prostheses and large implant prostheses are becoming widespread. As the raw material of the cutting material, i.e., the polishing blank, used in this system, zirconia is often used in view of aesthetic properties, and in particular, in recent years, zirconia that has high transmittance and satisfies aesthetic requirements to reproduce the color of natural teeth is becoming widespread. In addition, for color tones that are difficult to reproduce, high aesthetic requirements are satisfied by further coloring the surface of the ceramic shaped into a dental prosthesis with a dental ceramic.

[0005] However, in recent years, as the transmittance of zirconia has been improved, cases where the high total light transmittance of the zirconia significantly affects the color observed due to discoloration of the residual tooth serving as a base, or the color of the residual tooth or dental prosthesis or the like serving as a base other than the color possessed by the zirconia (hereinafter also referred to as "base color"), such as the color of a dental prosthesis such as an implant bridge base, a metal core, or the like, have gradually increased. Therefore, if a dental prosthesis made of zirconia is covered on these bases, the shade of the dental prosthesis that should be reproduced becomes dark, and the aesthetic property is impaired, and thus a dental material capable of masking the influence of the base color is sought.

[0006] As one method of solving this problem, a dental ceramic coloring liquid having masking properties is generally used, and the following methods have been proposed.

[0007] Patent Document 1 discloses that zirconia is opacified by containing a phosphorus component.

[0008] Patent Document 2 discloses the use of a nitrate salt as a masking agent.

[0009] Patent Document 3 discloses an opacity imparting liquid containing a water-soluble aluminum compound and / or a water-soluble lanthanum compound.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: U.S. Patent Application Publication No. 2017 / 105818

[0013] Patent Document 2: International Publication No. 2020 / 155446

[0014] Patent Document 3: Japanese Patent Application Publication No. 2019-181179. SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] However, it is known that, with respect to the phosphoric acid and the phosphoric acid salt or the like disclosed in Patent Literature 1, it is presumed that the surface of the sintered zirconia becomes rough, and the strength of the zirconia sintered body decreases. In addition, Patent Literature 1 aims at making the zirconia white with masking properties, and does not suggest the implementation of coloring that reproduces the color of natural teeth. In addition, in Patent Literature 2, the nitrate salt decomposes due to heating to a temperature at which the ceramic is calcined, and toxic gas is generated or explosion is induced, and there is a problem in terms of safety. Furthermore, the present inventors and the like have found as a result of research that, in Patent Literature 3, the masking properties with respect to the metal abutment tooth are insufficient, and the color of the abutment tooth is seen through by visual observation. In addition, Patent Literature 3 aims at imparting masking properties to the zirconia, and does not suggest the implementation of coloring that reproduces the color of natural teeth.

[0017] Thus, an object of the present application is to provide a dental ceramic coloring liquid that can inhibit a decrease in mechanical strength of a dental ceramic after sintering, has good storage stability, and can impart masking properties. In addition, an object of the present application is to provide a dental ceramic coloring liquid that can impart masking properties and impart a desired color tone to a dental ceramic even when a coloring component is contained.

[0018] Means for solving the problem

[0019] The present inventors and the like have repeatedly conducted intensive research in order to solve the above-described problem, and as a result, have found that a coloring liquid that can impart high masking properties can be obtained by containing an organosilicon compound, and have further repeatedly conducted research to complete the present application.

[0020] That is, the present application includes the following technical solutions.

[0021] [1] A dental ceramic coloring liquid comprising an organosilicon compound.

[0022] [2] The coloring liquid according to [1], wherein the organosilicon compound is hydrophilic.

[0023] [3] The coloring liquid according to [1] or [2], wherein the organosilicon compound is a silicone compound.

[0024] [4] The coloring liquid according to [3], wherein the silicone compound is a functional group-modified silicone compound.

[0025] [5] The coloring liquid according to [3] or [4], wherein the silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound.

[0026] [6] The coloring liquid according to [5], wherein the polyether-modified silicone compound or the polyol-modified silicone compound is a compound represented by General Formula (1).

[0027] [Chemical Formula 1]

[0028]

[0029] (in the formula, each R 1 identical or different, represents a linear or branched alkyl group optionally having a substituent, or an aryl group optionally having a substituent. m is an integer of 1 or more. Each R 2 identical or different, represents a polyether group or a polyhydric alcohol group).

[0030] [7] The colored liquid according to [6], wherein the aforementioned silicone compound is a compound in which all R 1 are methyl groups.

[0031] [8] The colored liquid according to any one of [3] to [7], wherein the aforementioned silicone compound is a liquid at ordinary temperature.

[0032] [9] The colored liquid according to any one of [3] to [8], wherein the content ratio of the aforementioned silicone compound is 0.1 to 60 mass%.

[0033]

[10] The colored liquid according to [1] or [2], wherein the aforementioned organosilicon compound is an alkylsilane compound.

[0034]

[11] The colored liquid according to

[10] , wherein the aforementioned alkylsilane compound is a compound represented by the following general formula (2).

[0035] [Chem. 2]

[0036]

[0037] (in the formula, R 3 represents a linear or branched alkyl group optionally having a substituent; R 4 represents a linear or branched alkyl group optionally having a substituent, an aryl group optionally having a substituent, or a halogen atom. n is an integer of 0 to 3. X represents -R 5 -Y 1 , -Y 1 , -R 5 -B 1 -A 1 , -R 5 -A 1 , or -A 1 . R 5 is a linear or branched alkylene group or a cycloalkylene group optionally having a substituent, the aforementioned alkylene group or the aforementioned cycloalkylene group optionally containing -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O-, or -O- group. R 6represents a linear or branched alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, or an aryl group optionally having a substituent. Y 1 represents a hydroxyl group, an alkoxy group optionally having a substituent, an amino group optionally having a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt optionally having a substituent. B 1 represents -C(O)-O-, -C(O)-S-, -C(O)-NH-, -NH-C(O)-NH-, -NH-C(O)-S-, or -NH-C(O)-O-. A 1 represents H2C=CH-, H2C=C(CH3)-, or H2C=CH-C6H4- (C6H4 represents a phenylene group).

[0038]

[12] The coloring liquid according to

[11] , wherein, in the compound represented by the aforementioned general formula (2), X represents -R 5 -Y 1 or -Y 1 ; Y 1 is a hydroxyl group, an amino group optionally having a substituent, an epoxy group, or an amine salt optionally having a substituent.

[0039]

[13] The coloring liquid according to

[12] , wherein, in the compound represented by the aforementioned general formula (2), X represents -R 5 -Y 1 ; R 5 is a linear or branched alkylene group optionally having a substituent, the aforementioned alkylene group optionally containing -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O-, or an -O- group.

[0040]

[14] The coloring liquid according to any one of

[10] to

[13] , wherein the alkylsilane compound is at least one compound selected from the group consisting of trimethylsilanol, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3- aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3- phenylaminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3- aminopropyltriethoxysilane.

[0041]

[15] The coloring liquid according to any one of

[10] to

[14] , wherein the content ratio of the alkylsilane compound is 0.1 to 60 mass%.

[0042]

[16] The coloring liquid according to any one of [1] to

[15] , further comprising a coloring component.

[0043]

[17] The coloring liquid according to

[16] , wherein the coloring component is an ion or a complex.

[0044]

[18] The coloring liquid according to

[16] or

[17] , wherein the coloring component contains at least one selected from the group consisting of Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb, and Er.

[0045]

[19] The coloring liquid according to any one of [1] to

[18] , further containing water or / and an organic solvent.

[0046]

[20] The coloring liquid according to

[19] , wherein the organic solvent contains at least one selected from the group consisting of alcohols, diols, triols, and ketones.

[0047]

[21] The coloring liquid according to any one of [1] to

[20] , wherein the dental ceramic contains zirconia as a main component.

[0048]

[22] A dental ceramic having a silicone compound supported on a surface thereof.

[0049]

[23] The dental ceramic according to

[22] , wherein the silicone compound is hydrophilic.

[0050]

[24] The dental ceramic according to

[22] or

[23] , wherein the silicone compound is a silicone compound.

[0051]

[25] The dental ceramic according to

[24] , wherein the silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound.

[0052]

[26] The dental ceramic according to

[22] or

[23] , wherein the silicone compound is an alkylsilane compound.

[0053]

[27] The dental ceramic according to

[26] , wherein the alkylsilane compound is a compound represented by the following general formula (2).

[0054] [Chemical Formula 3]

[0055]

[0056] (In the formula, R 3 represents a linear or branched alkyl group optionally having a substituent; R 4 represents a linear or branched alkyl group optionally having a substituent, an aryl group optionally having a substituent, or a halogen atom. n is an integer of 0 to 3. X represents -R5 -Y 1 , -Y 1 , -R 5 -B 1 -A 1 , -R 5 -A 1 or -A 1 . R 5 is a linear or branched alkylene group or a cycloalkylene group optionally having a substituent, the aforementioned alkylene group or the aforementioned cycloalkylene group optionally containing -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O- group. R 6 represents a linear or branched alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, or an aryl group optionally having a substituent. Y 1 represents a hydroxyl group, an alkoxy group optionally having a substituent, an amino group optionally having a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt optionally having a substituent. B 1 represents -C(O)-O-, -C(O)-S-, -C(O)-NH-, -NH-C(O)-NH-, -NH-C(O)-S- or -NH-C(O)-O-. A 1 represents H2C=CH-, H2C=C(CH3)- or H2C=CH-C6H4- (C6H4 represents a phenylene group).

[0057]

[28] The dental ceramic according to

[27] , wherein, in the compound represented by the aforementioned general formula (2), X represents -R 5 -Y 1 or -Y 1 ; Y 1 represents a hydroxyl group, an amino group optionally having a substituent, an epoxy group, or an amine salt optionally having a substituent.

[0058]

[29] The dental ceramic according to any one of

[22] to

[28] , further carrying a coloring component.

[0059]

[30] The dental ceramic according to

[29] , wherein the aforementioned coloring component is an ion or a complex.

[0060]

[31] The dental ceramic according to

[29] or

[30] , wherein the aforementioned coloring component contains at least one kind selected from Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb and Er components.

[0061] Effects of the Invention

[0062] The dental ceramic coloring liquid of the present application can inhibit a decrease in mechanical strength of dental ceramic after sintering, has good storage stability, and can impart masking properties. In addition, the dental ceramic coloring liquid of the present application can impart masking properties and impart a desired color tone to dental ceramic even when a coloring component is contained. Furthermore, the dental ceramic coloring liquid of the present application does not need to have characteristics required for dental ceramic, such as a coefficient of thermal expansion that matches a ceramic frame for good adhesion to the ceramic frame, and durability in the oral cavity, and is thus easy to use compared to dental ceramic. DETAILED DESCRIPTION

[0063] The present application is a coloring liquid for coloring dental ceramic, characterized by containing a silicone compound.

[0064] <silicone compound>

[0065] First, the silicone compound contained in the coloring liquid of the present application is described as a masking component for imparting masking properties to dental ceramic. The silicone compound of the present application can impart white color to the color tone of dental ceramic by masking the influence of discoloration of residual teeth of the substrate or the substrate color of a metal dental prosthesis such as an implant bridge base, a metal core, and the like. In addition, the silicone compound used in the present application has good storage stability. Furthermore, by using the silicone compound, a decrease in mechanical strength of a sintered body obtained after sintering of dental ceramic can be inhibited. In the present application, not only coloring other than white color, but also imparting white color simply by masking the influence of the substrate color is regarded as "coloring", and a liquid preparation used for "coloring" is referred to as a "coloring liquid". On the other hand, the "coloring component" described later refers to an optional component for coloring dental ceramic into a color other than white (for example, imparting a prescribed chroma to dental ceramic).

[0066] The reason why the dental ceramic coloring liquid containing a silicone compound can improve the masking properties of dental ceramic after calcination is not certain, but the present inventors and the like have made the following conjecture. That is, it is conjectured that at least a part of the silicone compound applied to dental ceramic forms silicon dioxide (SiO2) in calcination, a part of which is combined with zirconia (ZrO2) to partially form zircon (ZrSiO4), and a crystalline phase different from that of sintered ceramic is locally mixed, thereby causing scattering of incident light and becoming opaque.

[0067] The coloring liquid of the present application can impart masking properties required in dental use to dental ceramic. Thus, the surface of the object can be made opaque by reducing transparency and masking the influence of the substrate color. With respect to the color tone of dental ceramic after coloring and sintering, the L * a* b * The colorimetric system (JIS Z8781-4:2013 Colorimetry - Part 4: CIE 1976 L*a*b* color space) (L) * ,a * ,b * ), measuring lightness (Lw) when measuring chromaticity against a white background. * ) and lightness (Lb) when measuring chromaticity against a black background. * ), as the difference between the two (ΔL) * =(Lw * )-(Lb * That is, transparency (ΔL) * From the viewpoint of maintaining the brightness of sintered dental ceramics that should be reproduced in the oral cavity as required for dental use, it is preferably 11 or less, more preferably 10 or less, and even more preferably 9 or less. Transparency (ΔL) * The evaluation can be performed using methods described, for example, in the embodiments described later.

[0068] Furthermore, when the coloring liquid of the present invention contains the coloring components described later, it is possible to impart opacity to dental ceramics and to impart the desired hue to dental ceramics for dental applications. Regarding the colored and sintered dental ceramics based on L... * a * b * Color scheme (L) * ,a * ,b * ), as a * Preferably -5 to 5, more preferably -4 to 4, and even more preferably -3 to 3. As b * Preferably 0.5 to 25, more preferably 1 to 22, and even more preferably 2 to 20. As per a * and b * The calculated chroma (C) * =((a) * ) 2 +(b * ) 2 ) 1 / 2 The concentration is preferably 0.5–25, more preferably 1–22, and even more preferably 2–20. As L * Preferably, it is 70-97, more preferably 75-96, and even more preferably 80-95. * b * and L * The determination can be performed using, for example, the methods described in the embodiments.

[0069] The silicone compound of the present application is preferably a hydrophilic compound from the viewpoint of the impregnation in dental ceramics and the solubility in water and the like. The hydrophilicity in the present application means that the solubility in water at 25°C and pH 7 is 0.5% by mass or more, and the solubility is preferably 5% by mass or more. As the silicone compound, a silicone compound, an alkylsilane compound, and the like can be exemplified. The silicone compound can be used alone or in combination with two or more kinds.

[0070] The content of the silicone compound contained in the coloring liquid is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and further preferably 0.5 to 55% by mass, relative to the total amount of the coloring liquid. In the case where the content of the silicone compound is 0.1% by mass or more, masking properties with respect to the base color such as discoloration of the remaining teeth can be obtained, and in the case where the content is 60% by mass or less, the impregnation in dental ceramics is excellent.

[0071] In addition, as one embodiment, the silicone compound used in the coloring liquid of the present application is preferably a silicone compound from the viewpoint of high storage stability and high masking properties after calcination of dental ceramics. Thus, the silicone compound will be described next. In the present application, the silicone compound is preferably a high molecular compound having a siloxane bond as a main skeleton.

[0072] <silicone compound>

[0073] The silicone compound of the present application is a polymer obtained by bonding an organic group having an alkyl group or an aryl group as a main body to silicon having a siloxane bond including silicon and oxygen as a skeleton. In the present application, as described above, the silicone compound is preferably a hydrophilic silicone compound. Thus, as the silicone compound, from the viewpoint of the impregnation in dental ceramics and the solubility in water and the like, a functional group-modified silicone compound having an organic functional group for imparting hydrophilicity is preferable, from the viewpoint of more excellent storage stability, a polyether-modified silicone compound and / or a polyol-modified silicone compound are more preferable, and further, a compound represented by General Formula (1), that is, a polyether-modified silicone compound and / or a polyol-modified silicone compound are further preferable. The functional group possessed by the organic functional group-modified silicone compound is not particularly limited as long as the functional group is one having excellent impregnation in dental ceramics and high solubility in water and the like, and can be selected.

[0074] [Chemical Formula 4]

[0075]

[0076] (In the formula, each R 1 identical or different, represents a linear or branched alkyl group optionally having a substituent, or an aryl group optionally having a substituent. m is an integer of 1 or more. Each R2 identical or different, represents a polyether group or a polyol group.

[0077] as R 1 linear or branched alkyl group optionally having a substituent, is not particularly limited, is preferably an alkyl group having 1 to 6 carbon atoms, is more preferably an alkyl group having 1 to 4 carbon atoms, and is further preferably an alkyl group having 1 to 3 carbon atoms from the viewpoints of the impregnability in the dental ceramic and the solubility in water and the like. As the alkyl group of R 1 and R 2 , there can be mentioned methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, t-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group. As the aryl group of R 1 optionally having a substituent, there can be mentioned, for example, phenyl group, naphthyl group and the like. As the substituent, there can be mentioned, for example, an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (preferably an alkoxy group having 1 to 3 carbon atoms), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group and the like. As to the number of the substituents, there is no particular limitation as long as the silicone compound has the impregnability in the dental ceramic and the solubility in water and the like, and can be 1 to 6, can be 1 to 4, and can be 0.

[0078] as R 1 from the viewpoints of the impregnability in the dental ceramic and the solubility in water and the like, is preferably a linear or branched alkyl group optionally having a substituent.

[0079] as R 2 polyether group, is not particularly limited as long as it is a group containing a polyalkylene glycol structure, and there can be mentioned, for example, a group of polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer and the like. As the polyol group, it is not particularly limited as long as it is a group having 2 or more hydroxyl groups (for example, an aliphatic group and the like), and there can be mentioned, for example, a group of polyether polyol, polyester polyol and the like.

[0080] In the silicone compound, the main chain having a siloxane bond (hereinafter referred to as a siloxane main chain) is preferably a dimethylpolysiloxane group in which all of R 1 are methyl groups. It is presumed that by making the siloxane main chain a dimethylpolysiloxane group, a helical skeleton structure is obtained, and the impregnability in the dental ceramic is improved.

[0081] From the viewpoints of the impregnability in the dental ceramic and the solubility in water and the like, the silicone compound is preferably a liquid at ordinary temperature (20 to 35°C). In the case of being rubbery or solid at ordinary temperature, it is possible that the impregnability in the dental ceramic is insufficient due to an increase in the molecular weight or a decrease in the hydrophilicity, and the masking property cannot be sufficiently obtained.

[0082] In addition, regarding the silicone compound, from the viewpoints of the impregnability in the dental ceramic and the solubility in water or the like, the number of siloxane bonds in the siloxane main chain is preferably 2000 or less (in the case of the compound represented by General Formula (1), m is 1998 or less). If the number of siloxane bonds exceeds 2000, it is possible that the impregnability in the dental ceramic is insufficient due to an increase in the molecular weight and a decrease in the hydrophilicity, and the masking property cannot be sufficiently obtained.

[0083] Regarding the silicone compound, from the viewpoints of the impregnability in the dental ceramic and the solubility in water or the like, as a solubility parameter (Solubility Parameter, hereinafter referred to as "SP value"), 8.2 (cal / cm 3 ) 1 / 2 More preferably, 8.4 (cal / cm 3 ) 1 / 2 Further preferably, 8.6 (cal / cm 3 ) 1 / 2 Above. In the case where the SP value is less than 8.2 (cal / cm 3 ) 1 / 2 , it is possible that the impregnability of the dental ceramic is insufficient, the masking property cannot be sufficiently obtained, and the solubility in the aqueous solvent is low, causing sedimentation, separation, or the like.

[0084] The aforementioned SP value is expressed by the square root of the cohesive energy density CED (Cohesive Energy Density) between molecules, which is the mutual attraction force. Note that the CED refers to the energy required to evaporate 1 mL of a substance.

[0085] As the aforementioned SP value, it can be calculated by the Fedors method using the following Formula (A).

[0086] SP value = (CED value) 1 / 2 = (E / V) 1 / 2 Formula (A)

[0087] In the aforementioned Formula (A), E is the cohesive energy (cal / mol), and V is the molar volume (cm 3 / mol). The calculation method of the SP value is various, but the Fedors method, which is generally used, is used in the present application.

[0088] As data of each of the aforementioned calculation method, cohesive energy E, and molar molecular volume V, the method described in Paint Research No. 152, issued in October 2010, pp. 41-46 ("Correlation Study on Solubility Parameters of Additives", Nobuyoshi Ueda, Tomonori Yamada, Masami Sugishima) can be referred to; and data (E of Table 2 on p. 42, molar molecular volume, Fedors value of Table 3, etc.); and the method and data described in R. F. Fedors, Polymer Engineering & Science. Feb, Vol. 14, No. 2, 147-154 (1974) can be referred to. coh and molar molecular volume, Fedors value of Table 3, etc.); and the method and data described in R. F. Fedors, Polymer Engineering & Science. Feb, Vol. 14, No. 2, 147-154 (1974) can be referred to.

[0089] As the silicone compound, a commercially available product can be used. As the commercially available product, polyether-modified silicone such as trade name "KP-120", "KP-106", "KP-110", "KP-101", "KP-125", "KP-112" (manufactured by Shin-Etsu Chemical Co., Ltd.), polyol-modified silicone such as trade name "KP-104", "KP-105" (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like can be exemplified.

[0090] As the content ratio of the silicone compound contained in the coloring liquid, it is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and further preferably 0.5 to 55% by mass, with respect to the total amount of the coloring liquid. In the case where the content ratio of the silicone compound is 0.1% by mass or more, masking properties with respect to the base color of the discoloration of the residual tooth, etc. can be obtained, and in the case where it is 60% by mass or less, the penetration properties in the dental ceramic are excellent.

[0091] In addition, as another embodiment, from the viewpoint of high storage stability and high masking properties of the dental ceramic after calcination, the organosilicon compound used in the coloring liquid of the present application is preferably an alkylsilane compound. Thus, the alkylsilane compound will be described next.

[0092] <Alkylsilane compound>

[0093] First, the alkylsilane compound contained in the dental ceramic coloring liquid of the present application will be described. The alkylsilane compound of the present application can color the dental ceramic by imparting a white color to the color tone of the dental ceramic by masking the influence of the base color of the discoloration of the residual tooth or the base color of the metal dental prosthesis such as an implant bridge base, a metal core, etc. In addition, the storage stability of the alkylsilane compound used in the present application is good. Furthermore, by using the alkylsilane compound, the mechanical strength of the sintered body obtained after sintering the dental ceramic can be suppressed from decreasing. Note that, in the present application, the alkylsilane compound refers to a silane compound having an alkyl group, and the aforementioned alkyl group can optionally have a substituent.

[0094] The alkylsilane compound of the present application is preferably hydrophilic from the viewpoint of the impregnation property in dental ceramics and the solubility in water or the like.

[0095] The alkylsilane compound of the present application preferably has a molecular structure of a compound represented by the following general formula (2) from the viewpoint of further more excellent storage stability and masking property and further reduction of the decrease in the mechanical strength of the sintered body.

[0096] [Chemical Formula 5]

[0097]

[0098] (In the formula, R 3 represents a linear or branched alkyl group optionally having a substituent; R 4 represents a linear or branched alkyl group optionally having a substituent, an aryl group optionally having a substituent, or a halogen atom. n is an integer of 0 to 3. X represents -R 5 -Y 1 , -Y 1 , -R 5 -B 1 -A 1 , -R 5 -A 1 or -A 1 . R 5 is a linear or branched alkylene group or a cycloalkylene group optionally having a substituent, the aforementioned alkylene group or the aforementioned cycloalkylene group optionally containing -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O- group. R 6 represents a linear or branched alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, or an aryl group optionally having a substituent. Y 1 represents a hydroxyl group, an alkoxy group optionally having a substituent, an amino group optionally having a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt optionally having a substituent. B 1 represents -C(O)-O-, -C(O)-S-, -C(O)-NH-, -NH-C(O)-NH-, -NH-C(O)-S- or -NH-C(O)-O-. A 1 represents H2C=CH- (vinyl group), H2C=C(CH3)- (1-methylethenyl group) or H2C=CH-C6H4- (C6H4 represents a phenylene group).

[0099] R 3 and R 4The optional straight-chain or branched alkyl group having substituents is not particularly limited, but is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. As R 3 and R 4 Alkyl groups, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, and n-hexyl. Halogen atoms, including fluorine, chlorine, bromine, and iodine. As R... 4 The optional aryl group having substituents can be exemplified by, for example, phenyl, naphthyl, etc., with phenyl being preferred. As R 3 and R 4 alkyl groups and R 4 Examples of substituents for the aryl group include alkyl groups with 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), alkoxy groups with 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), phenyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), hydroxyl groups, etc. The number of substituents is not particularly limited, as long as the alkylsilane compound has impregnation in dental ceramics and solubility in water, etc., and can be 1 to 6, 1 to 4, or even 0. In one embodiment, in the compound shown in general formula (2), R... 3 R represents an unsubstituted straight-chain or branched alkyl group. 4 It indicates an unsubstituted straight-chain or branched alkyl group, an unsubstituted phenyl group, or a halogen atom.

[0100] As R 5 The alkylene group can be a straight-chain or branched alkylene group with substituents, without particular limitation, preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, further preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. Examples of alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, n-pentylene, and n-hexylene. 5 The alkylene group is either straight-chain or branched, and is not particularly limited, but preferably a alkylene group with 3 to 10 carbon atoms, more preferably a alkylene group with 4 to 8 carbon atoms, and even more preferably a alkylene group with 4 to 7 carbon atoms. Examples of alkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene (e.g., 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene). 5 The type and number of substituents in alkylene and cycloalkylene compounds are related to R. 3 and R 4 The alkyl substituents are the same.

[0101] Additionally, R 5The aforementioned alkylene group or the aforementioned cycloalkylene group can contain -CH2-C6H4- (C6H4represents phenylene group), -S-, -NH-, -NR 6 -C(O)-O-, -O- group as a bonding group. In other words, the aforementioned alkylene group or the aforementioned cycloalkylene group is optionally interrupted by -CH2-C6H4- (C6H4represents phenylene group), -S-, -NH-, -NR 6 -C(O)-O-, -O- group. Specifically, R 5 may be -C2H4-NH-C3H6-, -CH2-NH-C2H4-NH-C3H6-, -CH2-O-C3H6-, etc. R 6 The alkyl group, the aryl group and R 4 of R 6 The cycloalkyl group of R 6 The kinds and the number of the substituents of the alkyl group, the cycloalkyl group and the aryl group of R 3 are the same as those of the alkyl group of R 4 .

[0102] B 1 is preferably -C(O)-O-, -C(O)-NH-, -NH-C(O)-NH- or -NH-C(O)-O-. A 1 is preferably H2C=CH- or H2C=C(CH3)-. Y 1 is preferably hydroxyl group, amino group optionally having a substituent, epoxy group, or amine salt optionally having a substituent.

[0103] Among these, more preferably, X represents -R 5 -Y 1 or the compound represented by -Y 1 , from the viewpoints of the impregnability in dental ceramics and the solubility in water, etc., it is further preferable that X represents -R 5 -Y 1 or -Y 1 , Y 1 is hydroxyl group, amino group optionally having a substituent, epoxy group, or amine salt optionally having a substituent. In a certain suitable embodiment, a dental ceramic coloring liquid can be exemplified in which, in the compound represented by General Formula (2), X represents -R 5 -Y 1 ; R 5 is linear or branched alkylene group, and the aforementioned alkylene group optionally contains -CH2-C6H4- (C6H4represents phenylene group), -S-, -NH-, -NR 6 -C(O)-O- or -O- group. The kinds and the number of the substituents of the alkoxy group, the amino group and the amine salt of Y 1 are the same as those of the alkyl group of R3 and R 4 the substituents of the alkyl group are the same as those of the alkyl group of R1.

[0104] As specific compounds, there can be mentioned, for example, amino-containing alkylsilane compounds such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, and the like; epoxy-containing alkylsilane compounds such as 3-triethoxysilyl-N-(l,3-dimethyl-butylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, and the like; vinyl-containing alkylsilane compounds such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; hydroxyl-containing alkylsilane compounds such as trimethylsilanol, trimethylsilylmethyl alcohol, trimethylsilyl ethanol, and the like. Of these, at least one selected from the group consisting of trimethylsilanol, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3- aminopropyltriethoxysilane is preferred, and at least one selected from the group consisting of 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane is more preferred.

[0105] The content of the alkylsilane compound contained in the coloring liquid of the present application is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and further preferably 0.5 to 55% by mass, relative to the total amount of the coloring liquid. In the case where the content of the alkylsilane compound is 0.1% by mass or more, masking properties with respect to the base color of the residual teeth, such as discoloration, can be obtained, and in the case where the content is 60% by mass or less, the storage stability is excellent.

[0106] As one other embodiment, a dental ceramic coloring liquid containing an organosilicon compound (for example, a silicone compound, an alkylsilane compound) and a coloring component can be cited. In the present application, the organosilicon compound contained in the coloring liquid has excellent storage stability and does not react with the coloring component, and thus it is presumed that the coloring component can be contained, and the dental ceramic can be imparted with masking properties and imparted with a desired color tone. Note that the coloring component in the present application refers to a component that colors the ceramic sintered body when the coloring liquid is applied to the ceramic pre-sintered body or unsintered body and sintering is performed.

[0107] As the coloring component, there is no particular limitation, and ions, complexes, and the like can be cited, and metal ions are particularly preferable. The coloring component can be used alone as one kind, or two or more kinds can be used in combination.

[0108] The ions and complexes of the coloring component used in the present application are described. The ions and complexes contain one or more coloring cations. "Coloring" refers to having a significant absorption in the spectrum (for example, the range of wavelengths of 380 to 790 nm) visible to the human eye. The coloring cation in the present application develops color after sintering. The ions and complexes of the present application can dissolve the coloring cation, and thus the coloring cation is applied to the ceramic pre-sintered body or unsintered body, and the ceramic sintered body can be colored after sintering.

[0109] As the aforementioned coloring cation, ions of at least one component (element) selected from the group consisting of Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb, and Er are preferable, ions of at least one component selected from the group consisting of Al, K, Cr, Fe, Na, V, Ni, Mn, Co, and Er are more preferable, and ions of at least two components selected from the group consisting of Al, K, Cr, Fe, Na, V, Ni, Mn, Co, and Er are further preferable. The ion solution can contain only one kind of the cation, or two or more kinds of cations can be contained in combination.

[0110] The aforementioned coloring cation can be added to the solvent described later in the form of a salt containing the cation and an anion. As the anion, for example, OAc - , NO3 - , NO2 -, CO3 2- , HCO3 - , ONC - , SCN - , SO4 2- , SO3 2- , glutarate, lactate, gluconate, propionate, butyrate, glucuronate, benzoate, phenate, halogen anion (fluoride, chloride, bromide), acetate, etc. Ac means acetyl group.

[0111] As a suitable embodiment of the present application, in order to color the dental ceramic to yellow tone, a coloring solution in which coloring components include V (vanadium) components can be exemplified.

[0112] The ion or complex of V can be added to the coloring solution in the form of a salt including cation and anion of V or a complex including V and ligand. As the anion or ligand, for example, OAca - , NO3 - , NO2 - , CO3 2- , HCO3 - , ONC - , SCN - , SO4 2- , SO3 2- , glutarate, lactate, gluconate, propionate, butyrate, glucuronate, benzoate, phenate, halogen anion (fluoride, chloride, bromide), acetate, etc.

[0113] As the vanadium compound, from the viewpoint of storage stability, ease of handling, a vanadium compound of +IV and / or +V valence is preferable, and a vanadium oxide compound is more preferable.

[0114] As specific examples of the compound of the component V, vanadium acetylacetonate, vanadyl acetylacetonate, vanadium naphthenate, vanadium benzoylacetate, vanadyl oxalate, bis(maltolato)oxovanadium (IV), bis(l-phenyl-l,3-butanedionato)oxovanadium, triisopropoxyoxovanadium (V), vanadium (V) trichloride oxide, vanadium (IV) dichloride oxide, vanadium (III) chloride hydrate (hexahydrate), vanadium (III) chloride anhydride, vanadium disilicide, vanadium (III) trioxide, vanadium (IV) tetroxide, vanadium (V) pentoxide, tetravanadium dideuterium trideuteride, vanadyl sulfate (IV) hydrate, vanadium (III) bromide, vanadyl oxalate (vanadyl oxalate (IV)), vanadyl acetate (IV) (VO[OC(O)CH3]2), vanadyl nitrate (V) (VO(NO3)3), vanadyl glycolate, vanadium hydride, vanadium selenide, vanadium carbide (VC), vanadium nitride (VN), potassium divanadate, potassium vanadate, potassium metavanadate (KVO3) (V), sodium metavanadate (NaVO3) (V), sodium divanadate (Na4V2O7), sodium vanadate (Na3VO4), sodium vanadate hydrate, lithium metavanadate (LiVO3), rubidium divanadate (Rb4V2O7), rubidium metavanadate (RbVO3), rubidium vanadate (Rb3VO4), vanadium diboride, vanadium boride (VB), vanadium (III) sulfide (V2S3), and the like can be listed. Among these, from the viewpoint of excellent storage stability of the coloring solution and excellent handling properties, vanadyl oxalate, vanadyl nitrate, vanadyl acetate are preferred. The vanadium component can be used alone as one kind or in combination with two or more kinds.

[0115] In addition, as one suitable embodiment of the present application, a coloring solution containing a Cr component as a coloring component can be listed.

[0116] The ion or complex of Cr can be added to the coloring solution in the form of a salt containing a cation and anion of Cr or a complex containing Cr and a ligand thereof. As the anion or ligand, for example, OAc - , NO3 - , NO2 - , CO3 2- , HCO3 - , ONC - , SCN - , SO4 2- , SO3 2- , glutarate, lactate, gluconate, propionate, butyrate, glucuronate, benzoate, phenate, halogen anion (fluoride, chloride, bromide), acetate, and the like can be listed.

[0117] As examples of specific compounds of the Cr component, mention can be made of compounds of valence 3 and 4, with preference being given to chromium compounds of valence 3. Mention can be made of, for example, chromium (III) chloride, chromium (III) chloride hydrate (hexahydrate), chromium (III) bromide hydrate (hexahydrate), chromium (III) nitrate hydrate (nonahydrate), chromium (III) sulfate hydrate (n-hydrate), chromium (III) acetate hydrate (monohydrate), chromium (III) formate hydrate (n-hydrate), etc., with preference being given to chromium (III) nitrate hydrate (nonahydrate), chromium (III) chloride hydrate (hexahydrate), chromium (III) acetate hydrate (monohydrate) from the viewpoint of excellent solubility in water and organic solvents. The Cr component can be used alone or in combination with two or more.

[0118] The coloring liquid of the present application preferably further contains water and / or an organic solvent as a solvent. The water and / or the organic solvent dissolves the aforementioned organosilicon compound (e.g., silicone compound, alkylsilane compound), and improves the penetration of the coloring liquid into the dental ceramic. By dissolving the aforementioned organosilicon compound in water, the dental ceramic coloring liquid of the present application is easily applied, and has excellent workability. The solvent can be used alone or in combination with two or more.

[0119] The water needs to be water that is substantially free of impurities that adversely affect the effects of the present application, and is preferably purified water, distilled water, ion-exchange water, pure water. The content of water in the dental ceramic coloring liquid is preferably 40 to 99.9 mass%, more preferably 42 to 99.7 mass%, and further preferably 45 to 99.5 mass%. "Substantially free of impurities" means that impurities in an amount that does not interfere with the effects of the present application are acceptable, and impurities in an amount that interferes with the effects of the present application are not acceptable, and the amount of impurities varies depending on the type of impurity, for example, the content of impurities can be less than 0.01 mass%, or less than 0.001 mass%.

[0120] The SP value calculated by the aforementioned method for the organic solvent is preferably 8.6 (cal / cm 3 ) 1 / 2 More preferably, 8.8 (cal / cm 3 ) 1 / 2 More preferably, 8.8 (cal / cm 3 ) 1 / 2 In the case where the SP value is 8.6 (cal / cm 3 ) 1 / 2In the above case, on the basis of being able to obtain the aforementioned sufficient masking property, the solubility of the coloring component is also sufficient, sufficient penetration of the coloring liquid into the dental ceramic can be obtained, and sufficient coloring can be obtained.

[0121] As the organic solvent, at least one selected from the group consisting of alcohols, diols, triols, and ketones is preferably contained. As specific examples, methanol, ethanol, 1-propanol, 2-propanol, isopropanol, 1-butanol, 2-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-l-pentanol, 3-methyl-l-pentanol, 4-methyl-l-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 2,2-dimethyl-l-butanol, 2-ethyl-l-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobenzyl ether, propylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, benzyl alcohol, 2-(benzyloxy)ethanol, 3-(benzyloxy)-l-propanol, 2-(benzyloxy)-l-butanol, 5-(benzyloxy)-l-pentanol, and the like alcohols; 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 2,5-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight: 200 to 600), propylene glycol, dipropylene glycol, polypropylene glycol, 1-methyl-l,3-propanediol, 2-methyl-l,3-propanediol, 2-methyl-l,4-butanediol, 3-methyl-l,3-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-l,5-pentanediol, 2,4-diethyl-l,5-pentanediol, 2-ethyl-l,3-hexanediol, and the like diols; glycerol, 1,2,4-butanetriol, 1,2,3-butanetriol, 1,2,6-hexanetriol, and the like triols; acetone, 2-butanone, 2-pentanone, cyclohexanone, and the like ketones. These organic solvents can be used alone or in combination of two or more as appropriate. In addition, the organic solvent can be used for adjusting the viscosity as a thickening agent described later.

[0122] The content of the organic solvent in the coloring liquid of the present application is preferably 40 to 99.9% by mass, more preferably 42 to 99.7% by mass, and further preferably 45 to 99.5% by mass.

[0123] As a certain embodiment, a dental ceramic coloring liquid can be exemplified, which contains an organosilicon compound (e.g., a silicone compound, an alkylsilane compound), a solvent, a complexing agent, and a thickening agent, and contains water and / or an organic solvent as the solvent, and the content of the solvent is 40 to 99.7 mass%. In the foregoing embodiment, the content of the solvent is preferably 41 to 99.6 mass%, more preferably 42 to 99.5 mass%, and further preferably 45 to 99.2 mass%.

[0124] In a certain embodiment, the pH of the coloring liquid of the present application (e.g., a coloring liquid containing a silicone compound, a coloring liquid containing an alkylsilane compound) is preferably 0 to 12, more preferably 1 to 11, and further preferably 2 to 10. Since the organosilicon compound contained in the present application has good storage stability and is not easily affected by pH, a wide range of pH can be applied. In the case where the pH is outside the above range, the silicone compound or the coloring component sometimes starts to precipitate from the solution. The pH can be measured using a commercially available pH meter (e.g., a small pH meter LAQUA twin manufactured by HORIBA, Ltd., or the like).

[0125] The coloring liquid of the present application can contain a complexing agent within a range that does not impair the effects of the present application. The addition of a complexing agent is sometimes beneficial for improving the storage stability of the coloring component in the coloring liquid, promoting the dissolution process of the salt added to the coloring liquid, and / or increasing the amount of the salt that can be dissolved in the coloring liquid.

[0126] The complexing agent can generally form a complex with the metal ion present in the coloring liquid. The complex formed must be soluble in the solvent. For example, the molar amount of the complexing agent with respect to the ion of the coloring component contained in the coloring liquid can be used at least in a stoichiometric ratio, and good results can be obtained if the molar ratio of the complexing agent with respect to the cation of the coloring liquid is about 1 or about 2 or about 3 or more.

[0127] As examples of the complexing agent, N,N-bis(2-hydroxyethyl)glycine, acetylacetone, crown ether, cryptand, ethylenediaminetriacetate and salts thereof, ethylenediaminetetraacetate and salts thereof, nitrilotriacetate and salts thereof, citric acid and salts thereof, triethylenetetramine, porphyrin, polyacrylate, polyaspartate salt, acidic peptide, phthalocyanine, salicylate, glycine salt, lactate, propylenediamine, ascorbate, oxalic acid and salts thereof, and mixtures thereof can be exemplified. The complexing agent can be used alone or in combination of two or more as appropriate.

[0128] The content of the complexing agent in the coloring solution of the present application is not particularly limited as long as the effects of the present application are exhibited, and for example, it is preferable to contain an amount sufficient to dissolve the cations in the solution or to prevent precipitation of the cations. Specifically, in the coloring solution, it is preferable to be 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more. In addition, there is no particular upper limit to the content, and it is preferable to be 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. If the amount of the complexing agent used is too small, it can not be completely dissolved, and if the amount of the complexing agent used is too large, an excess amount of the complexing agent itself can remain without being dissolved.

[0129] The coloring solution of the present application preferably has an appropriate viscosity so as to not only be applied to the ceramic surface in a necessary amount but also be able to move in the fine pores of the ceramic unfired body or the ceramic pre-fired body. As the appropriate viscosity, for example, it is preferable to be 0.1 to 10,000 mPa at 20°C, more preferably 0.5 to 6,000 mPa, and further preferably 1 to 3,000 mPa. In the case where the viscosity is too high, it can not be contained in the fine pores of the ceramic unfired body or the ceramic pre-fired body. The method of measuring the viscosity is not particularly limited, and it can be measured at 25°C using a Brookfield viscometer.

[0130] In the coloring solution of the present application, one or more thickening agents can be contained within a range that does not impair the effects of the present application for the purpose of making an appropriate viscosity.

[0131] As the thickening agent, the viscosity can be adjusted by selecting from the aforementioned organic solvents, or it can be selected from the following thickening agents. As the thickening agent other than the aforementioned organic solvents, polysaccharide compounds such as methyl cellulose, carboxy cellulose, hydroxyethyl cellulose, xanthan gum, guar gum, carrageenan, tamarind gum, pectin, sugar alcohol compounds such as sorbitol, erythritol, xylitol, trehalose, synthetic polyol compounds such as diglycerin, triglycerin, polyglycerin, polyvinyl alcohol, solid organic compounds such as sodium polyacrylate, ammonium polyacrylate, polyethylene oxide, polyethylene glycol (molecular weight of 1,000 or more), polyvinylpyrrolidone, calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, polyethylene glycol monostearate, 12-hydroxystearic acid, stearamide, oleamide, ethylene bisoleamide, and the like. These thickening agents can be used alone or in combination of two or more as appropriate.

[0132] The content of the thickening agent in the coloring solution of the present application is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and further preferably 0.2 to 5% by mass.

[0133] The coloring liquid of the present application can contain other additives, other masking agents, within a range not impairing the effects of the present application.

[0134] As the other additives, stabilizers (e.g., methoxyphenol, hydroquinone, Topanol A (2,4-dimethyl-6-tert-butylphenol and the like and mixtures thereof and the like (excluding stabilizers capable of inhibiting the phase transition of zirconium oxide)), buffers (e.g., acetate, amino buffers and mixtures thereof and the like), antibacterial agents (e.g., chlorhexidine gluconate and the like gluconic acids), preservatives (e.g., sorbic acid, benzoic acid and mixtures thereof and the like), other silane compounds and mixtures thereof can be exemplified. As the other masking agents, aluminum nitrate and the like nitrates; phosphorus components such as phosphoric acid; sodium silicate pentahydrate, water-soluble aluminum compounds, water-soluble lanthanum compounds can be exemplified. The other additives and the other masking agents can be used singly in one kind, or in combination in two or more kinds. The content of the additives and the masking agents in the coloring liquid of the present application can be set to 0.01 to 10 mass%, can be 0.05 to 5 mass%, or can be 0.1 to 3 mass%, for example.

[0135] The dental ceramic coloring liquid of the present application can contain other components within a range to exert the effects of the present application. As the other components, phosphorus-containing components such as phosphoric acid and phosphates (ammonium salts and the like), phosphate esters; nitrates such as potassium nitrate, magnesium nitrate, cobalt (II) nitrate, nickel (II) nitrate, praseodymium (III) nitrate, cerium (III) nitrate, neodymium (III) nitrate; chlorides such as erbium chloride, yttrium chloride, iron chloride; water-soluble aluminum compounds (aluminum nitrate and the like) and water-soluble lanthanum compounds can be exemplified. The content of the other components can be set to less than 10 mass%, can be less than 5 mass%, can be less than 1 mass%, or can be less than 0.01 mass%, for example. In a certain suitable embodiment, a dental ceramic coloring liquid not containing the aforementioned other components can be exemplified. In addition, by using the dental ceramic coloring liquid of the present application in place of a dental ceramic material, it is possible to mask the influence of the base color of a metal dental prosthesis such as a residual tooth which cannot be masked without laminating multiple layers in the case of using a dental ceramic material, an implant abutment, a metal core and the like. Therefore, in a certain suitable embodiment, the dental ceramic coloring liquid of the present application does not contain glass components (SiO2, Al2O3, Li2O, Na2O, K2O and the like) contained in a dental ceramic material. On the other hand, in order to obtain a dental prosthesis more excellent in aesthetics, it can also be combined with a dental ceramic material.

[0136] The dental ceramic colored with the coloring liquid of the present application can be any ceramic used in dentistry, and is not particularly limited, and examples thereof include a ceramic containing zirconia (also referred to as "zirconia" or "Zr02"), alumina (also referred to as "alumina" or "AI2O3"), feldspar glass, disilicate glass, ceramic material, and the like. The dental ceramic preferably contains zirconia and / or alumina, and more preferably contains zirconia as a main component. The "main component" is as described later in the description of the zirconia calcine.

[0137] The dental ceramic colored with the coloring liquid of the present application can be any ceramic used in dentistry, and is not particularly limited, and examples thereof include a ceramic containing zirconia (also referred to as "zirconia" or "Zr02"), alumina (also referred to as "alumina" or "AI2O3"), feldspar glass, disilicate glass, ceramic material, and the like. The dental ceramic preferably contains zirconia and / or alumina, and more preferably contains zirconia as a main component. The "main component" is as described later in the description of the zirconia calcine.

[0138] As another embodiment of the present application, a dental ceramic (colored ceramic calcine or colored uncalcine) having an organic silicon compound (e.g., silicone compound, alkylsilane compound) supported on the surface thereof can be exemplified. The content of the organic silicon compound is not particularly limited as long as the effect of the present application is exerted, and can be appropriately adjusted by the coating amount of the coloring liquid of the present application and the like, according to the strength of the masking property after sintering and the like. In addition, the range of support of the organic silicon compound can be adjusted to not only the surface but also the inside of the surface, according to the application of the coloring liquid of the present application and the like, and by capillary phenomenon, into the space of the ceramic calcine or uncalcine communicating with the outside. Note that the support is usually in a state of being attached to the carrier, and in the present application, is in a state of being attached to the ceramic by adsorption and the like.

[0139] The dental ceramic of the present application, after calcination, can impart the desired masking property required in dental applications, and in the case of containing a coloring component, can impart the desired coloring at the same time. As such an embodiment, a dental ceramic having a coloring component supported thereon can be exemplified. The coloring component is the same as that described in the coloring liquid.

[0140] As described above, the ceramic pre-sinter or uncalcined body preferably contains zirconia as a main component. Hereinafter, the embodiment in which the dental ceramic contains zirconia as a main component will be described. Note that, in the present application, the pre-sinter before coloring with the coloring liquid is simply referred to as "ceramic pre-sinter" or "zirconia pre-sinter", and the pre-sinter after coloring is simply referred to as "colored ceramic pre-sinter" or "colored zirconia pre-sinter" to distinguish between them. Note that, the coloring liquid of the present application can also be used to color a zirconia uncalcined body, in which case, a zirconia sintered body is produced without going through a pre-sinter. In the case where such a sintered body is envisaged, the conditions described below in the relevant description of the zirconia pre-sinter can be applied mutatis mutandis as appropriate to the zirconia uncalcined body. The ceramic pre-sinter and uncalcined body can have a shape such as a block or a disc.

[0141] A zirconia pre-sinter of the present application will be described. The zirconia pre-sinter refers to a substance in which zirconia (Zr02) is a main component and the zirconia is pre-sintered (a state in which zirconia particles (powder) are not completely sintered). The zirconia pre-sinter can have a shape obtained by processing according to the target dental product. The main component can be 50% by mass or more. The content of zirconia in the zirconia pre-sinter of the present application is preferably 60% by mass or more, more preferably 65% by mass or more, further preferably 70% by mass or more, more further preferably 75% by mass or more, particularly preferably 80% by mass or more, and most preferably 85% by mass or more. For example, if used in the application of dental restorations or dental implant products, the zirconia powder can be press-formed using a known technique, and the disc or block obtained thereby can be processed by pre-sintering and the like to produce the zirconia pre-sinter. The content of zirconia in the zirconia uncalcined body is the same as that of the zirconia pre-sinter. The density of the zirconia pre-sinter is preferably 2.7 g / cm 3 The density of the zirconia pre-sinter is preferably 4.0 g / cm 3 The density of the zirconia pre-sinter is more preferably 3.8 g / cm 3 The density of the zirconia pre-sinter is further preferably 3.6 g / cm 3The density of the pre-sintered body can be calculated, for example, as (mass of the pre-sintered body) / (volume of the pre-sintered body). In addition, the three-point bending strength of the zirconia pre-sintered body is preferably 15 to 70 MPa, more preferably 18 to 60 MPa, and further preferably 20 to 50 MPa. The aforementioned bending strength can be measured by using a test piece having a thickness of 5 mm, a width of 10 mm, and a length of 50 mm, and measuring in accordance with ISO 6872:2015, except for the size of the test piece. The faces and C-faces (faces obtained by chamfering the corners of the test piece at an angle of 45°) of the test piece are surface-finished in the length direction using sandpaper of No. 600. The test piece is disposed with the widest face facing the vertical direction (direction of the load). In the bending test measurement, the span is set to 30 mm, and the crosshead speed is set to 0.5 mm / minute.

[0142] The zirconia pre-sintered body in the present application preferably contains a stabilizer (hereinafter also simply referred to as "stabilizer") that can inhibit phase transition of zirconia. For example, the zirconia before sintering preferably contains a stabilizer.

[0143] As the stabilizer, oxides such as yttria (Y2O3) (hereinafter referred to as "yttria"), calcium oxide (CaO), magnesium oxide (MgO), ceria (CeO2), scandia (Sc2O3), niobia (Nb2O5), lanthana (La2O3), erbia (Er2O3), praseodymia (Pr6O 11 ), samaria (Sm2O3), europia (Eu2O3), and thulia (Tm2O3) can be exemplified, and yttria is preferable. They can be used alone as one kind or in combination with two or more kinds. In a certain suitable embodiment, a coloring liquid can be exemplified in which the dental ceramic that is the coloring target contains zirconia as the main component, and further contains yttria as the stabilizer, and the stabilizer is substantially only yttria. In the aforementioned suitable embodiment, the stabilizer is substantially only yttria means that the content rate of the stabilizer other than yttria is less than 0.1 mol%, preferably 0.05 mol% or less, more preferably 0.01 mol% or less, and further preferably 0.001 mol% or less, in 100 mol% of the total of zirconia and the stabilizer. The content rate of the stabilizer can be measured by, for example, inductively coupled plasma (ICP) emission spectroscopy, fluorescence X-ray analysis, or the like.

[0144] In the case where the dental ceramic contains zirconia as a main component and further contains a stabilizer, the content of the stabilizer is preferably 0.1 to 18 mol%, more preferably 1 to 15 mol%, and further preferably 1.5 to 10 mol% in 100 mol% of the total of zirconia and the stabilizer. The kind and content of the stabilizer in the zirconia uncalcined body are the same as those in the zirconia calcined body. In a certain suitable embodiment, the content of yttria in the dental ceramic containing zirconia as a main component is preferably 2.5 to 9.5 mol%, more preferably 3.0 to 9.0 mol%, and further preferably 3.5 to 8.5 mol% in 100 mol% of the total of zirconia and the stabilizer.

[0145] The zirconia uncalcined body and the zirconia calcined body of the present application can contain, as needed, a coloring agent (including a pigment, a composite pigment, and a fluorescent agent), alumina (AI2O3), titania (TiO2), silica (SiO2), and the like. These components can be used singly in one kind or in a mixture of two or more kinds. As the aforementioned pigment, an oxide of at least one component selected from the group of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Sn, Sb, Bi, Ce, Pr, Sm, Eu, Gd, Tb, and Er can be exemplified. As the aforementioned composite pigment, (Zr, V)O2, Fe(Fe, Cr)2O4, (Ni, Co, Fe)(Fe, Cr)2O4 · ZrSiO4, (Co, Zn)AI2O4, and the like can be exemplified. As the aforementioned fluorescent agent, Y2SiO5:Ce, Y2SiO5:Tb, (Y, Gd, Eu)BO3, Y2O3:Eu, YAG:Ce, ZnGa2O4:Zn, BaMgAl 10 O 17 : Eu, and the like.

[0146] A general production method of the zirconia calcined body of the present application is described. First, zirconia raw material particles containing a stabilizer are prepared, and are press-molded into a block or a disc, or the like. Next, a CIP (Cold Isostatic Pressing) treatment is performed on the molded body (uncalcined body) as needed. The pressure at this time is, for example, 50 to 500 MPa. Next, a pre-calcination treatment is performed thereon. With respect to the pre-calcination, by slowly raising the temperature from room temperature to 800 to 1200°C and leaving for about 1 to 6 hours, a zirconia calcined body can be obtained. The obtained zirconia calcined body is subjected to cutting processing using a publicly known device according to the final dental product. For example, in the case where the dental product is a dental prosthesis, cutting processing is performed into a crown shape using CAD / CAM, or the like.

[0147] The manufacturing method of the colored zirconia pre-sinter body of the present application includes a step of allowing the zirconia pre-sinter body after cutting to contain the aforementioned dental ceramic coloring liquid. As the method of allowing the zirconia pre-sinter body to contain the aforementioned dental ceramic coloring liquid, for example, a method of applying the dental ceramic coloring liquid to the zirconia pre-sinter body using a pen or the like, or a method of immersing the zirconia pre-sinter body in a container containing the coloring liquid, or a method of spraying the zirconia pre-sinter body using a sprayer or the like can be used, and known devices can be used. Note that in the case of manufacturing the zirconia sintered body directly from an uncalcined body without including the pre-sintering step, the aforementioned dental ceramic coloring liquid can be allowed to contain the zirconia uncalcined body after cutting.

[0148] The present application also includes a zirconia sintered body obtained by sintering the aforementioned colored zirconia pre-sinter body. The manufacturing method of the zirconia sintered body includes a step of calcining the aforementioned colored zirconia pre-sinter body. The calcination temperature (maximum calcination temperature) can be appropriately changed depending on the type of zirconia, and is not particularly limited as long as the coloring component is colored, and is preferably 1350°C or higher, more preferably 1450°C or higher, and further preferably 1500°C or higher. The upper limit of the calcination temperature is not particularly limited, and is preferably, for example, 1600°C or lower. Note that the zirconia sintered body of the present application includes not only a sintered body obtained by sintering a formed zirconia powder under normal pressure and / or without pressure, but also a sintered body obtained by densifying it through high-temperature pressurization treatment such as HIP (Hot Isostatic Pressing).

[0149] The content of the stabilizer in the zirconia sintered body and the zirconia pre-sinter body of the present application can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry, fluorescence X-ray analysis, or the like.

[0150] The zirconia sintered body of the present application preferably has at least one of partially stabilized zirconia and fully stabilized zirconia as a matrix phase. In the zirconia sintered body, the main crystal phase of the zirconia is at least one of tetragonal and cubic crystal systems. The zirconia sintered body can contain both tetragonal and cubic crystal systems. The zirconia sintered body preferably substantially does not contain a monoclinic crystal system. Note that zirconia obtained by adding a stabilizer to partially stabilize it is referred to as partially stabilized zirconia (PSZ), and zirconia obtained by adding a stabilizer to fully stabilize it is referred to as fully stabilized zirconia.

[0151] The present application includes a dental product formed of the aforementioned zirconia sintered body. As the dental product, dental prostheses, products for orthodontic treatment, or dental implant products, and the like can be cited. As the dental prostheses, inlays, onlays, laminate veneers, and crowns made of zirconia, and the like can be used, for example.

[0152] In the above-described embodiments, the kind, the content rate, and the like of each component can be appropriately changed, and for optional components, addition, deletion, and the like can be changed. In addition, in the above-described embodiments, the values of the composition and the properties of the coloring liquid can be appropriately changed and combined.

[0153] The present application includes embodiments obtained by various combinations of the above-described configurations within the scope of the technical idea of the present application as long as the effects of the present application are exerted.

[0154] Examples

[0155] Hereinafter, the present application will be described in more detail by examples, but the present application is not limited to the following examples.

[0156] [Examples 1-1 to 1-24, 2-1 to 2-18, and Comparative Examples 1-1 to 1-6]

[0157] The coloring liquid of each example and comparative example was prepared as follows, and the properties thereof were evaluated. The results are shown in Tables 1 to 4.

[0158] [Method for evaluating solubility of silicone compound in water]

[0159] After 2.985 g and 2.85 g of water at pH 7 were added to 0.015 g and 0.15 g of the silicone compound, respectively, the solubility was evaluated by stirring for 1 hour at 25°C and observing by visual observation according to the following criteria.

[0160] A: solubility in water at 25°C was 5% by mass or more.

[0161] B: solubility in water at 25°C was 0.5% by mass or more and less than 5% by mass.

[0162] C: solubility in water at 25°C was less than 0.5% by mass.

[0163] [Preparation of coloring liquid]

[0164] The coloring liquid was prepared by mixing each component described in Tables 1 to 4 at the % by mass described in the table at room temperature. Note that, for the silicone compound used, the following was used. The solubility in water was evaluated according to the criteria described later.

[0165] <silicone compound>

[0166] KP-120: polyether-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 10.0 (cal / cm 3 ) 1 / 2 Solubility in water: A

[0167] KP-106: polyether-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 8.9 (cal / cm 3 ) 1 / 2 Solubility in water: A

[0168] KP-110: polyether-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 8.3 (cal / cm 3 ) 1 / 2 Solubility in water: B

[0169] KP-104: polyol-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 11.6 (cal / cm 3 ) 1 / 2 Solubility in water: A

[0170] <Alkylsilane compound>

[0171] KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: A

[0172] KBM-602: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: A

[0173] KBM-903: 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: A

[0174] Trimethylsilanol: manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: B

[0175] [Evaluation of storage stability of colored liquid]

[0176] After 12 ml of the colored liquid subjected to the aforementioned adjustment was filled into a container of ES Liquid (manufactured by Kuraray Noritake Dental Co., Ltd.), and stored at 40°C, 50°C, and 60°C for 60 days in consideration of the environment at the time of transportation and storage environment of the colored liquid actually used, the evaluation was performed in accordance with the following criteria.

[0177] O: no separation of components and gelation of the colored liquid were confirmed by visual observation.

[0178] X: separation of components or gelation of the colored liquid was confirmed by visual observation.

[0179] [Manufacture of zirconia calcined body]

[0180] Next, a method for producing the zirconia calcined body to be coated with the aforementioned coloring solution will be described.

[0181] First, a zirconia powder containing a stabilizer was produced. To 90.1 mass% of the zirconia powder, 9.9 mass% (5.5 mol%) of yttria as a stabilizer was added to produce a mixture. Next, the mixture was added to water to produce a slurry, and the mixture was wet-pulverized using a ball mill to an average particle diameter of 0.13 μm or less. The pulverized slurry was dried using a spray dryer, and the resulting powder was calcined at 950°C for 2 hours to produce a powder (primary powder). Note that the aforementioned average particle diameter can be obtained by a laser diffraction scattering method. Specifically, the laser diffraction scattering method can be performed using, for example, a laser diffraction particle size distribution measuring device (SALD-2300: Shimadzu Corporation), using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium, and measuring on a volume basis.

[0182] To the resulting primary powder, water was added to produce a slurry, and the mixture was wet-pulverized using a ball mill to an average particle diameter of 0.13 μm or less. After a binder was added to the pulverized slurry, the mixture was dried using a spray dryer to produce a powder (secondary powder). The produced secondary powder was used as a raw material powder for producing the zirconia calcined body described later.

[0183] Next, a method for producing the zirconia calcined body will be described. The aforementioned raw material powder 1.32 g was filled into a mold having a diameter of 19 mm, and one-press molding was performed using a single-screw press molding machine at a surface pressure of 57.5 kN for 20 seconds. The resulting one-press molded body was calcined at 1000°C for 2 hours to produce a zirconia calcined body.

[0184] [Measurement of color of sintered body]

[0185] The aforementioned prepared coloring solution was applied to the aforementioned produced zirconia calcined body with a pen, and calcination was performed under the calcination conditions described in Tables 1 to 4 to obtain a zirconia sintered body. The obtained zirconia sintered body was ground and processed into a round plate having a diameter of 15 mm and a thickness of 1.2 mm, and the colorimetric value (L * a * b * Colorimetric value based on L * a * b * a color space) was measured using a spectrophotometer "Crystal Eye" (Olympus Corporation) under the following measurement conditions: measurement mode: 7 band LED light source, white background, and n = 3. The average value of the measured values is shown in Tables 1 to 4. In addition, the a * and b* The chroma C is calculated as an average value of the chroma C * = ((a * ) 2 +(b * ) 2 ) 1 / 2 .

[0186] [Measurement of transparency of sintered body]

[0187] The coloring liquid prepared as described above was applied to the zirconia pre-sintered body produced as described above, and calcination was performed under the calcination conditions described in Tables 1 to 4 to obtain a sintered body. The obtained sintered body was ground and processed into a round plate having a diameter of 15 mm and a thickness of 1.2 mm, and the brightness (Lw * ) when the chroma was measured in the measurement mode: 7 band LED light source, white background, and the brightness (Lb * ) when the chroma was measured in the measurement mode: 7 band LED light source, black background, were measured using a spectrophotometer "Crystal Eye" manufactured by Olympus Corporation, for the same test piece and using the same measuring device, measurement mode, and light source. The difference (ΔL * = (Lw * ) - (Lb * )) was taken as the transparency (ΔL * ) (n = 3). The average value of the calculated values is shown in Tables 1 to 4. In addition, the change rate of the transparency was calculated using the following formula, taking the zirconia sintered body which was not colored with the coloring liquid (Comparative Example 1-1) as a reference.

[0188] Change rate of transparency (%) = {(transparency of sintered body obtained by applying the coloring liquid and performing calcination - transparency of zirconia sintered body which was not colored) / transparency of zirconia sintered body which was not colored} x 100

[0189] [Evaluation of masking degree of sintered body]

[0190] A dental milling machine (trade name: DWX-51D, manufactured by Roland DG Corporation) was used to cut a crown shape from the zirconia pre-sintered body produced as described above, and the coloring liquid prepared as described above was applied to the inside of the crown shape, and calcination was performed under the calcination conditions described in Tables 1 to 4 to obtain a sintered body. The sintered body in the shape of a crown was placed over a metal abutment, and the evaluation of the masking degree was performed according to the following criteria.

[0191] O: The color of the metal abutment was not seen through with the naked eye (high masking degree) compared to the sintered body to which the coloring liquid was not applied.

[0192] Δ: The color of the metal abutment was seen through with the naked eye, but was slightly not seen through compared to the sintered body to which the coloring liquid was not applied (slightly high masking degree).

[0193] X: The color of the metal bridge abutment was seen through or was the same degree (low degree of masking or no masking) compared with the sintered body to which no coloring liquid was applied, by visual observation.

[0194] [Measurement of Biaxial Flexural Strength of Sintered Body]

[0195] The coloring liquid prepared as described above was applied to the zirconia pre-sintered body produced as described above, and calcination was performed under the calcination conditions described in Tables 1 to 4, to obtain a sintered body having a diameter of 15 mm and a thickness of 1.2 mm. The biaxial flexural strength of the obtained sintered body was measured (n = 3) at a crosshead speed of 0.5 mm / min using an automatic plotter of a universal testing machine (trade name "AG-I 100kN") manufactured by Shimadzu Corporation in accordance with JIS T 6526:2012. The average of the measured values is shown in Tables 1 to 4. In addition, the change rate of the biaxial flexural strength was calculated in accordance with the following formula, taking the zirconia sintered body which was not colored with the coloring liquid (Comparative Example 1-1) as a reference.

[0196] Change rate (%) of biaxial flexural strength = {(biaxial flexural strength of sintered body obtained by applying the coloring liquid and performing calcination - biaxial flexural strength of zirconia sintered body which was not colored) / biaxial flexural strength of zirconia sintered body which was not colored} x 100

[0197]

[0198]

[0199]

[0200]

[0201] In Comparative Examples 1-2 and 1-3 containing inorganic silicon compounds, the storage stability was poor, and it was confirmed by visual observation that gelation occurred during storage. In Comparative Example 1-4 in which phosphoric acid was compounded, it was confirmed that the biaxial flexural strength of the zirconia sintered body was reduced. In addition, it was confirmed that in Comparative Examples 1-5 and 1-6 in which water-soluble aluminum was compounded, the color of the metal bridge abutment was seen through, and the masking property was insufficient.

[0202] On the other hand, in Examples 1-1 to 1-24 and 2-1 to 2-18 containing organic silicon compounds, the strength of the zirconia sintered body was not reduced, the storage stability was good, and excellent masking property was confirmed. Furthermore, it was confirmed that in Examples 1-5 to 1-7, 1-10, 1-11, 1-17 to 1-24, 2-5 to 2-8, 2-10, 2-12 to 2-18 containing coloring components, the storage stability was good and excellent masking property was exhibited, and at the same time, desired coloring could be imparted.

[0203] Industrial applicability

[0204] The dental ceramic coloring liquid of the present application can inhibit the decrease in mechanical strength of dental ceramics after sintering, has good storage stability, and can impart masking properties. In addition, when the dental ceramic coloring liquid of the present application contains a coloring component, it can impart masking properties to dental ceramics and impart a desired color tone. Therefore, it can be suitably used as a coloring liquid for coloring dental ceramics. In particular, the demand for ceramic dental crowns is increasing, and as personal aesthetic requirements increase, it is predictable that the frequency of use of dental ceramic coloring liquids will increase, and therefore, the dental ceramic coloring liquid of the present application having masking properties is useful.

Claims

1. Dental ceramic staining solution containing organosilicon compounds. The organosilicon compound is selected from at least one of silicone compounds or alkylsilane compounds. The silicone compound is a functionalized silicone compound. The content of the silicone compound relative to the total amount of coloring solution is 0.1% to 60% by mass. The alkylsilane compound is a compound represented by the following general formula (2). The content of the alkylsilane compound relative to the total amount of coloring liquid is 0.1% to 60% by mass. In the formula, R 3 Indicates a straight-chain or branched alkyl group that may optionally have substituents; R 4 This indicates a straight-chain or branched alkyl group optionally having a substituent, an aryl group optionally having a substituent, or a halogen atom; n is an integer from 0 to 3; X represents -R 5 -Y 1 -Y 1 -R 5 -B 1 -A 1 -R 5 -A 1 or -A 1 ; R 5 The alkylene or cycloalkylene group is optionally a straight-chain or branched alkylene or cycloalkylene group having substituents, wherein the alkylene or cycloalkylene group optionally comprises -CH2-C6H4-, -S-, -NH-, or -NR. 6 -, -C(O)-O- or -O- radical, where, C6H4 represents phenylene; R 6 This indicates a straight-chain or branched alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, or an aryl group optionally having a substituent; Y 1 The term represents a hydroxyl group, an alkoxy group optionally having a substituent, an amino group optionally having a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt optionally having a substituent; B 1 represents -C(O)-O-, -C(O)-S-, -C(O)-NH-, -NH-C(O)-NH-, -NH-C(O)-S- or -NH-C(O)-O-; A 1 It represents H2C=CH-, H2C=C(CH3)- or H2C=CH-C6H4-, where C6H4 represents phenylene.

2. The coloring liquid according to claim 1, wherein, The organosilicon compound is hydrophilic.

3. The coloring liquid according to claim 1 or 2, wherein, The organosilicon compound is a silicone compound.

4. The coloring liquid according to any one of claims 1 to 3, wherein, The silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound.

5. The coloring liquid according to claim 4, wherein, The polyether-modified silicone compound or the polyol-modified silicone compound is a compound represented by general formula (1). In the formula, each R 1 "Same" or "different" indicates either a straight-chain or branched alkyl group with substituents, or an aryl group with substituents; m is an integer greater than or equal to 1 and less than 1998; each R 2 The same or different indicates polyether group or polyol group.

6. The coloring liquid according to claim 5, wherein, In general formula (1), As R 1 The optional alkyl group having substituents, either straight-chain or branched, is an alkyl group having 1 to 6 carbon atoms. As R 1 The optional aryl group with substituents is phenyl or naphthyl.

7. The coloring liquid according to claim 5 or 6, wherein, In general formula (1), As R 1 The alkyl group may be a straight-chain or branched alkyl group with a substituent, having 1 to 4 carbon atoms.

8. The coloring liquid according to any one of claims 5 to 7, wherein, When a substituent is present, it is selected from alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogen atoms, or hydroxyl groups.

9. The coloring liquid according to any one of claims 5 to 8, wherein, The number of substituents when substituents are present is 0 to 6.

10. The coloring liquid according to any one of claims 5 to 9, wherein, The silicone compound has all R in its main chain. 1 It is a compound of dimethylpolysiloxane with methyl groups.

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