Dental ceramic staining liquid with masking properties

Abstract

The present invention provides a dental ceramic coloring liquid that can suppress a decrease in mechanical strength of sintered dental ceramics, exhibits excellent storage stability, and imparts opacifying 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

Technical Field

[0001] The present invention relates to a coloring liquid for dental ceramics. More specifically, it relates to a coloring liquid for dental ceramics suitable for use in the production of dental restorations such as inlays, onlays, veneers, crowns, bridges, abutments, post pins, dentures, denture gums, and implant components (fixtures, abutments) obtained by machining using a dental CAD / CAM system. Background Art

[0002] In the past, metals were often used as dental products (e.g., representative dental restorations such as overlay crowns, crowns, crowns, attached dentures, orthodontic products, and dental implant products). However, the color of metal is significantly different from that of natural teeth, and it lacks aesthetic appeal. In addition, metals can sometimes cause allergies due to the dissolution of metals. Therefore, in order to solve the problems associated with the use of metals, ceramic materials such as aluminum oxide (aluminum oxide) and zirconium oxide (zirconia) are gradually being used for dental products as alternative materials to metals. In particular, zirconium oxide is excellent in strength and relatively excellent in aesthetic appeal, and therefore, demand is increasing, particularly in conjunction with the recent trend toward lower prices.

[0003] In recent years, CAD / CAM systems, which use computers to design the final shape of dental restorations and large implant prostheses and then perform cutting processes using milling equipment, have become increasingly popular. Zirconia, the raw material for the cut material used in these systems, or the polished blanks, is often used due to its emphasis on aesthetics. Recently, zirconia, which has increased its transmittance and aesthetic appeal to reproduce the color of natural teeth, has become increasingly popular. Furthermore, for color tones that are difficult to reproduce, the surface of the ceramic formed into the shape of the dental restoration is further colored with dental ceramics to meet high aesthetic demands.

[0004] However, in recent years, as the transmittance of zirconium oxide has increased, the high total light transmittance of zirconium oxide has increasingly led to significant color effects, such as discoloration of the remaining teeth that form the substrate, or the color of metal dental restorations such as implant abutments and metal cores, which are other than the color of zirconium oxide. Therefore, when dental restorations made of zirconium oxide are placed over these substrates, the intended color tone of the dental restoration becomes darker, impairing its aesthetic appeal. Consequently, dental materials that can mask the influence of the base color are being sought.

[0005] As one method for solving such a problem, a dental ceramic coloring liquid having a masking property is generally used, and the following method has been proposed.

[0006] Patent Document 1 discloses that zirconium oxide becomes cloudy due to the inclusion of a phosphorus component.

[0007] Patent Document 2 discloses the use of nitrate as a shielding agent.

[0008] Patent Document 3 discloses an opacity-imparting liquid containing a water-soluble aluminum compound and / or a water-soluble lanthanum compound.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: U.S. Patent Application Publication No. 2017 / 105818

[0012] Patent Document 2: International Publication No. 2020 / 155446

[0013] Patent document 3: Japanese Patent Application Publication No. 2019-181179. Summary of the Invention

[0014] Problems to be solved by the invention

[0015] However, it is known that: regarding the phosphoric acid and phosphates disclosed in Patent Document 1, it can be inferred that the surface of the zirconia after sintering becomes rough, and the strength of the zirconia sintered body is reduced. In addition, the purpose of Patent Document 1 is to make the zirconia white with a masking property, and it does not suggest the implementation of coloring that can reproduce the natural tooth color. In addition, in Patent Document 2, nitrates are decomposed by heating to a temperature at which the ceramic is calcined, producing toxic gases or causing explosions, which poses a problem in terms of safety. Furthermore, the results of research by the present inventors show that: in Patent Document 3, the masking property for metal abutments is insufficient, and the color of the abutments can be seen through by visual observation. In addition, the purpose of Patent Document 3 is to give masking properties to zirconia, and it does not suggest the implementation of coloring that can reproduce the natural tooth color.

[0016] Therefore, an object of the present invention is to provide a dental ceramic coloring liquid that can suppress a decrease in the mechanical strength of sintered dental ceramics, has excellent storage stability, and can impart masking properties. Another object of the present invention is to provide a dental ceramic coloring liquid that, when containing a coloring component, can impart masking properties to dental ceramics and a desired color tone.

[0017] Means used to solve problems

[0018] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that a coloring liquid capable of imparting high hiding properties can be obtained by containing an organosilicon compound. Further studies have led to the completion of the present invention.

[0019] That is, the present invention includes the following technical solutions.

[0020] [1] A dental ceramic coloring liquid comprising an organosilicon compound.

[0021] [2] The colored liquid according to [1], wherein the organosilicon compound is hydrophilic.

[0022] [3] The colored liquid according to [1] or [2], wherein the organosilicon compound is a silicone compound.

[0023] [4] The colored liquid according to [3], wherein the silicone compound is a functional group-modified silicone compound.

[0024] [5] The colored liquid according to [3] or [4], wherein the silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound.

[0025] [6] The colored liquid according to [5], wherein the polyether-modified silicone compound or the polyol-modified silicone compound is a compound represented by the general formula (1).

[0026] [Chemistry 1]

[0027]

[0028] (In the formula, each R 1 are the same or different and represent a linear or branched alkyl group which may have a substituent, or an aryl group which may have a substituent. m is an integer greater than 1. 2 are the same or different, representing a polyether group or a polyol group).

[0029] [7] The colored liquid according to [6], wherein the silicone compound has all R 1 A compound containing a methyl dimethylpolysiloxane group.

[0030] [8] The colored liquid according to any one of [3] to [7], wherein the silicone compound is a liquid at room temperature.

[0031] [9] The colored liquid according to any one of [3] to [8], wherein the content of the silicone compound is 0.1 to 60% by mass.

[0032]

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

[0033]

[11] The colored liquid according to

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

[0034] [Chemistry 2]

[0035]

[0036] (Where R 3 represents a linear or branched alkyl group which may have a substituent; R 4 represents an optionally substituted linear or branched alkyl group, an optionally substituted aryl group, 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 It is a linear or branched alkylene or cycloalkylene group which may have a substituent, wherein the alkylene group or the cycloalkylene group may contain -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O-. 6 represents a linear or branched alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. 1 represents a hydroxyl group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt which may have a substituent. 1 Indicates -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- (C6H4 represents a phenylene group).

[0037]

[12] The colored liquid according to

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

[0038]

[13] The colored liquid according to

[12] , wherein X represents -R 5 -Y 1 ; R 5 It is a linear or branched alkylene group which may have a substituent, and the aforementioned alkylene group may include -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR6 , -C(O)-O- or -O- group.

[0039]

[14] The coloring liquid according to any one of

[10] to

[13] , wherein the alkylsilane compound is at least one compound selected from 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.

[0040]

[15] The colored liquid according to any one of

[10] to

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

[0041]

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

[15] , further comprising a coloring component.

[0042]

[17] The colored liquid according to

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

[0043]

[18] The coloring liquid according to

[16] or

[17] , wherein the coloring component comprises 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.

[0044]

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

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

[0045]

[20] The coloring liquid according to

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

[0046]

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

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

[0047]

[22] Dental ceramics having an organosilicon compound supported on the surface.

[0048]

[23] The dental ceramic according to

[22] , wherein the organosilicon compound is hydrophilic.

[0049]

[24] The dental ceramic according to

[22] or

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

[0050]

[25] The dental ceramic according to

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

[0051]

[26] The dental ceramic according to

[22] or

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

[0052]

[27] The dental ceramic according to

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

[0053] [Chemistry 3]

[0054]

[0055] (Where R 3 represents a linear or branched alkyl group which may have a substituent; R 4 represents an optionally substituted linear or branched alkyl group, an optionally substituted aryl group, 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 It is a linear or branched alkylene or cycloalkylene group which may have a substituent, wherein the alkylene group or the cycloalkylene group may contain -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O-. 6 represents a linear or branched alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. 1 represents a hydroxyl group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt which may have a substituent. 1 Indicates -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- (C6H4 represents a phenylene group).

[0056]

[28] The dental ceramic according to

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

[0057]

[29] The dental ceramic according to any one of

[22] to

[28] , further comprising a coloring component.

[0058]

[30] The dental ceramic according to

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

[0059]

[31] The dental ceramic according to

[29] or

[30] , wherein the coloring component comprises 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.

[0060] Effects of the Invention

[0061] The dental ceramic coloring liquid of the present invention can suppress the reduction in mechanical strength of sintered dental ceramics, exhibits excellent storage stability, and imparts opacifying properties. Furthermore, when containing a coloring component, the dental ceramic coloring liquid of the present invention can impart opacifying properties and a desired color tone to the dental ceramic. Furthermore, the dental ceramic coloring liquid of the present invention does not require the properties required of dental ceramics, such as a thermal expansion coefficient that matches the ceramic frame for good bonding and durability in the oral cavity. This distinguishes it from dental ceramics and makes it easier to use than dental ceramics. DETAILED DESCRIPTION

[0062] The present invention is a coloring liquid for coloring dental ceramics, characterized by containing an organosilicon compound.

[0063] <Organic silicon compounds>

[0064] First, as a masking component that imparts masking properties to dental ceramics, the organosilicon compound contained in the coloring liquid of the present invention is described. The organosilicon compound of the present invention can impart white to the color tone of dental ceramics by masking the discoloration of the residual teeth that serve as the base or the influence of the base color of metal dental restorations such as implant abutments and metal cores. In addition, the organosilicon compound used in the present invention has good storage stability. Furthermore, by using the organosilicon compound, when dental ceramics are sintered, the mechanical strength of the sintered body obtained after sintering can be suppressed. In the present invention, not only coloring other than white, but also simply imparting white by masking the influence of the base color is regarded as "coloring", and the liquid preparation used for "coloring" is recorded as "coloring liquid". On the other hand, the "coloring component" mentioned below refers to an optional component for coloring dental ceramics into a color other than white (for example, giving a predetermined chroma to dental ceramics).

[0065] The reason why applying a dental ceramic coloring liquid containing an organosilicon compound improves the opacity of dental ceramics after firing is uncertain, but the present inventors speculate as follows. Specifically, they speculate that at least a portion of the organosilicon compound applied to the dental ceramic forms silicon dioxide (SiO2) during firing, a portion of which combines with zirconium oxide (ZrO2) to partially form zircon (ZrSiO4). This partially intermingles a crystalline phase different from that of the sintered ceramic, scattering incident light and rendering it opaque.

[0066] The coloring liquid of the present invention can impart the masking properties required for dental applications to dental ceramics. This can reduce transparency and render the surface of the object opaque, thereby masking the influence of the base color. * a * b * Color system (JIS Z8781-4:2013 Color Measurement - Part 4: CIE 1976 L*a*b* color space) (L * , a * , b * ), measure the lightness when measuring chromaticity on a white background (Lw * ) and the lightness when measuring chromaticity against a black background (Lb * ), as the difference between the two (ΔL * =(Lw * )-(Lb * )) Transparency (ΔL * ), from the viewpoint of maintaining the brightness of the dental ceramic after sintering that should be reproduced in the oral cavity required for dental use, it is preferably 11 or less, more preferably 10 or less, and even more preferably 9 or less. Transparency (ΔL* ) can be evaluated by, for example, the method described in the Examples below.

[0067] In addition, when the coloring liquid of the present invention contains the coloring component described below, it can impart masking properties to the dental ceramic and impart the desired color tone for dental use to the dental ceramic. * a * b * Color system (L * , a * , b * ), as a * , preferably -5 to 5, more preferably -4 to 4, further preferably -3 to 3. * , preferably 0.5 to 25, more preferably 1 to 22, further preferably 2 to 20. * and b * The calculated chroma (C * =((a * ) 2 +(b * ) 2 ) 1 / 2 ), preferably 0.5 to 25, more preferably 1 to 22, and even more preferably 2 to 20. * , preferably 70 to 97, more preferably 75 to 96, further preferably 80 to 95. * 、b * and L * For example, the measurement can be performed by the method described in the Examples.

[0068] From the perspective of permeability into dental ceramics and solubility in water and the like, the organosilicon compound of the present invention is preferably a hydrophilic compound. Hydrophilicity in the present invention means a solubility of 0.5% by mass or greater in water at 25°C and pH 7, preferably 5% by mass or greater. Examples of organosilicon compounds include silicone compounds and alkylsilane compounds. Organosilicon compounds may be used alone or in combination of two or more.

[0069] The content of the organosilicon compound in the coloring liquid is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and even more preferably 0.5 to 55% by mass, relative to the total amount of the coloring liquid. When the content of the organosilicon compound is 0.1% by mass or greater, sufficient shielding against the underlying color, such as residual tooth discoloration, is achieved. When the content is 60% by mass or less, excellent permeability into dental ceramics is achieved.

[0070] In one embodiment, the organosilicon compound used in the coloring liquid of the present invention is preferably a silicone compound from the perspective of high storage stability and high masking properties of the dental ceramic after firing. Therefore, the silicone compound will be described below. In the present invention, the silicone compound is preferably a polymer compound having a siloxane bond as its main backbone.

[0071] <Silicone Compound>

[0072] The silicone compound of the present invention is a polymer having a siloxane bond containing silicon and oxygen as a skeleton and an organic group mainly composed of an alkyl group or an aryl group bonded to the silicon. In the present invention, as described above, the silicone compound is preferably a hydrophilic silicone compound. Therefore, as a silicone compound, from the perspective of permeability in dental ceramics and solubility in water, etc., it is preferably a functional group-modified silicone compound having an organic functional group for making it hydrophilic. From the perspective of better storage stability, it is more preferably a polyether-modified silicone compound and / or a polyol-modified silicone compound, and further preferably a compound represented by general formula (1), i.e., a polyether-modified silicone compound and / or a polyol-modified silicone compound. The functional group possessed by the organic functional group-modified silicone compound is not particularly limited as long as it is a functional group that has excellent permeability in dental ceramics and high solubility in water, etc., and can be selected.

[0073] [Chemistry 4]

[0074]

[0075] (In the formula, each R1 is the same or different and represents a linear or branched alkyl group optionally having a substituent, or an aryl group optionally having a substituent. m is an integer greater than 1. Each R2 is the same or different and represents a polyether group or a polyol group).

[0076] The linear or branched alkyl group optionally having a substituent as R1 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 further preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of permeability into dental ceramics and solubility in water or the like. 1 and R 2 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, and n-hexyl. 1Examples of the aryl group that may have a substituent include phenyl and naphthyl. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), alkoxy groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), halogen atoms (fluorine, chlorine, bromine, or iodine), and hydroxyl groups. The number of substituents is not particularly limited as long as the silicone compound has permeability into dental ceramics and solubility in water and the like, and may be 1 to 6, 1 to 4, or even 0.

[0077] As R 1 From the viewpoint of permeability into dental ceramics and solubility in water or the like, a linear or branched alkyl group which may have a substituent is preferred.

[0078] As R 2 The polyether group is not particularly limited as long as it is a group containing a polyalkylene glycol structure, and examples thereof include polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers. The polyol group is not particularly limited as long as it is a group having two or more hydroxyl groups (e.g., an aliphatic group), and examples thereof include polyether polyols and polyester polyols.

[0079] In the silicone compound, the main chain having siloxane bonds (hereinafter referred to as the siloxane main chain) is preferably composed of all R 1 It is speculated that by using a dimethylpolysiloxane group as the main chain of siloxane, a helical skeleton structure is obtained, and the permeability into dental ceramics is improved.

[0080] From the perspective of permeability into dental ceramics and solubility in water, etc., the silicone compound is preferably liquid at room temperature (20-35°C). If it is rubbery or solid at room temperature, the increased molecular weight and decreased hydrophilicity may result in insufficient permeability into dental ceramics, and sufficient shielding properties may not be achieved.

[0081] Furthermore, from the perspective of permeability into dental ceramics and solubility in water, etc., the number of siloxane bonds in the siloxane main chain of the silicone compound 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, the permeability into dental ceramics may be insufficient due to an increase in molecular weight and a decrease in hydrophilicity, and sufficient shielding properties may not be achieved.

[0082] The silicone compound preferably has a solubility parameter (hereinafter referred to as "SP value") of 8.2 (cal / cm2) from the viewpoint of permeability into dental ceramics and solubility in water or the like. 3 ) 1 / 2 More preferably, 8.4 (cal / cm 3 ) 1 / 2 More preferably, 8.6 (ca1 / cm 3 ) 1 / 2 Above. When the SP value is less than 8.2 (cal / em 3 ) 1 / 2 In such cases, the dental ceramic may have insufficient permeability, failing to achieve sufficient shielding properties, or may have low solubility in aqueous solvents, causing sedimentation, separation, and the like.

[0083] The SP value is expressed as the square root of the mutual attraction between molecules, namely the cohesive energy density (CED). Note that CED refers to the energy required to evaporate 1 mL of a substance.

[0084] The SP value can be calculated using the following formula (A) by the Fedors method.

[0085] SP value = (CED value) 1 / 2 =(E / V) 1 / 2 ...Formula (A)

[0086] In the above formula (A), E is the cohesive energy (cal / mol), V is the molar molecular volume (cm 3 There are many different methods for calculating the SP value, but the commonly used Fedors method is used in the present invention.

[0087] The calculation method, cohesive energy E, and molar molecular volume V can be calculated by referring to the method described in Coating Research No. 152, published in October 2010, pages 41 to 46 ("Research on the Solubility Parameters of Additives," by Shinichi Ueda, Kyoo Yamada, and Masami Sugishima); and the data (E in Table 2 on page 42). coh and molar molecular volume, Fedors values ​​in Table 3, etc.); and the methods and data described in RF Fedors, Polymer Engineering & Science. Feb, Vol. 14, No. 2, 147-154 (1974).

[0088] Commercially available silicone compounds can be used. Examples of commercially available silicone compounds include polyether-modified silicones such as "KP-120," "KP-106," "KP-110," "KP-101," "KP-125," and "KP-112" (all manufactured by Shin-Etsu Chemical Co., Ltd.); and polyol-modified silicones such as "KP-104" and "KP-105" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0089] The content of the silicone compound in the coloring liquid is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and even more preferably 0.5 to 55% by mass, relative to the total amount of the coloring liquid. A silicone compound content of 0.1% by mass or greater provides excellent shielding against base color, such as residual tooth discoloration. A content of 60% by mass or less provides excellent permeability into dental ceramics.

[0090] In another embodiment, the organosilicon compound used in the coloring liquid of the present invention is preferably an alkylsilane compound from the viewpoint of high storage stability and high shielding properties of the dental ceramic after firing.

[0091] <Alkylsilane Compound>

[0092] First, the alkylsilane compound contained in the dental ceramic coloring liquid of the present invention is described. The alkylsilane compound of the present invention can impart white color to the color tone of the dental ceramic by shielding the discoloration of the residual teeth that serve as the base or the influence of the base color of metal dental restorations such as implant bridges and metal cores. In addition, the alkylsilane compound used in the present invention has good storage stability. Furthermore, by using the alkylsilane compound, when the dental ceramic is sintered, the mechanical strength of the sintered body obtained after sintering can be suppressed. It should be noted that in the present invention, the alkylsilane compound refers to a silane compound having an alkyl group, and the aforementioned alkyl group optionally has a substituent.

[0093] The alkylsilane compound of the present invention is preferably hydrophilic from the viewpoint of permeability into dental ceramics and solubility in water or the like.

[0094] The molecular structure of the alkylsilane compound of the present invention is preferably a compound represented by the following general formula (2) from the viewpoint of achieving better storage stability and shielding properties and further reducing the reduction in mechanical strength of the sintered body.

[0095] [Chemistry 5]

[0096]

[0097] (Where R3 represents a linear or branched alkyl group which may have a substituent; R 4 represents an optionally substituted linear or branched alkyl group, an optionally substituted aryl group, 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 It is a linear or branched alkylene or cycloalkylene group which may have a substituent, wherein the alkylene group or the cycloalkylene group may contain -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O-. 6 represents a linear or branched alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. 1 represents a hydroxyl group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt which may have a substituent. 1 Indicates -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-(vinyl group), H2C=C(CH3)-(1-methylvinyl group) or H2C=CH-C6H4-(C6H4 represents phenylene group).

[0098] As R 3 and R 4 The linear or branched alkyl group which may have a substituent 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 further preferably an alkyl group having 1 to 3 carbon atoms. 3 and R 4 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, and n-hexyl. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. 4 The aryl group optionally having a substituent includes, for example, phenyl and naphthyl, and is preferably phenyl. 3 and R 4 The alkyl group and R 4The substituents of the aryl group include, for example, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), a phenyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, and the like. The number of substituents is not particularly limited as long as the alkylsilane compound has permeability in dental ceramics and solubility in water, etc. The number of substituents may be 1 to 6, 1 to 4, or 0. In one embodiment, in the compound represented by the general formula (2), R 3 represents an unsubstituted straight-chain or branched alkyl group, R 4 represents an unsubstituted linear or branched alkyl group, an unsubstituted phenyl group, or a halogen atom.

[0099] As R 5 The linear or branched alkylene group which may have a substituent is not particularly limited, but is 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 the alkylene group include methylene, ethylene, n-propylene, isopropylene, n-butylene, n-pentylene, and n-hexylene. 5 The linear or branched cycloalkylene group is not particularly limited, but is preferably a cycloalkylene group having 3 to 10 carbon atoms, more preferably a cycloalkylene group having 4 to 8 carbon atoms, and even more preferably a cycloalkylene group having 4 to 7 carbon atoms. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene (e.g., 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene). 5 The type and number of substituents of alkylene and cycloalkylene are the same as R 3 and R 4 The substituents of the alkyl groups are the same.

[0100] In addition, R 5 The aforementioned alkylene group or the aforementioned cycloalkylene group may contain -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 In other words, the aforementioned alkylene group or the aforementioned cycloalkylene group may be replaced by -CH2-C6H4- (C6H4 represents phenylene), -S-, -NH-, -NR 6 -, -C(O)-O-, -O- groups are interrupted. Specifically, R 5 It can be -C2H4-NH-C3H6-, -CH2-NH-C2H4-NH-C3H6-, -CH2-O-C3H6-, etc. 6 The alkyl, aryl and R 4 Same as R 6Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. 6 The type and number of substituents of alkyl, cycloalkyl and aryl groups are related to R 3 and R 4 The substituents of the alkyl groups are the same.

[0101] B 1 Preferred is -C(O)-O-, -C(O)-NH-, -NH-C(O)-NH- or -NH-C(O)-O-. 1 Preferably, it is H2C=CH- or H2C=C(CH3)-. 1 Preferred are a hydroxyl group, an amino group which may have a substituent, an epoxy group, or an amine salt which may have a substituent.

[0102] Among these, it is more preferable that X represents -R 5 -Y 1 Compounds or compounds representing -Y 1 From the viewpoint of permeability in dental ceramics and solubility in water, etc., it is further preferred that: 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. In a preferred embodiment, the following dental ceramic coloring liquid can be cited: In the compound represented by the general formula (2), X represents -R 5 -Y 1 ; R 5 is a linear or branched alkylene group, wherein the alkylene group may optionally include -CH2-C6H4- (C6H4 represents a phenylene group), -S-, -NH-, -NR 6 -, -C(O)-O- or -O-. 1 The types and numbers of substituents of alkoxy, amino and amine salts are similar to those of R 3 and R 4 The substituents of the alkyl groups are the same.

[0103] Specific examples of the compound include amino group-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, and 3-phenylaminopropyltrimethoxysilane; 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 2-(3,4- Alkylsilane compounds containing epoxy groups such as epoxy) cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; alkylsilane compounds containing vinyl groups such as the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; alkylsilane compounds containing hydroxyl groups such as trimethylsilanol, trimethylsilylmethanol, and trimethylsilylethanol. Among these, preferably selected from 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, At least one of oxysilane and 3-aminopropyltriethoxysilane, more preferably at least one selected from 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0104] The content of the alkylsilane compound in the coloring liquid of the present invention is preferably 0.1 to 60% by mass, more preferably 0.3 to 58% by mass, and even more preferably 0.5 to 55% by mass, relative to the total amount of the coloring liquid. When the content of the alkylsilane compound is 0.1% by mass or greater, shielding against the underlying color, such as residual tooth discoloration, is achieved. When the content is 60% by mass or less, excellent storage stability is achieved.

[0105] Another embodiment includes a dental ceramic coloring liquid containing an organosilicon compound (e.g., a silicone compound or an alkylsilane compound) and a coloring component. In the present invention, the organosilicon compound contained in the coloring liquid has good storage stability and does not react with the coloring component. Therefore, it is speculated that the coloring component can be included to impart masking properties and a desired color tone to the dental ceramic. It should be noted that the coloring component in the present invention refers to a component that colors the sintered ceramic body when the coloring liquid is applied to a calcined or uncalcined ceramic body and then sintered.

[0106] The coloring component is not particularly limited, and examples thereof include ions and complexes, with metal ions being particularly preferred. The coloring component may be used alone or in combination of two or more.

[0107] The ions and complexes of the coloring components used in the present invention are described. The ions and complexes contain one or more coloring cations. "Coloring" means having significant absorption within the spectrum visible to the human eye (e.g., a wavelength range of 380 to 790 nm). The coloring cations in the present invention develop color after calcination. The ions and complexes of the present invention can dissolve the coloring cations, thereby being applied to a pre-calcined or uncalcined ceramic body, and can color the ceramic sintered body after calcination.

[0108] The coloring cation is preferably an ion of at least one 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, more preferably an ion of at least one element selected from the group consisting of Al, K, Cr, Fe, Na, V, Ni, Mn, Co, and Er, and even more preferably an ion of at least two elements selected from the group consisting of Al, K, Cr, Fe, Na, V, Ni, Mn, Co, and Er. The ionic solution may contain only one of these cations or a combination of two or more cations.

[0109] The coloring cation can be added to the solvent described later in the form of a salt containing the cation and an anion. Examples of the anion include 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.

[0110] As a preferred embodiment of the present invention, a coloring liquid containing V (vanadium) as a coloring component can be used to color dental ceramics in a yellow tone.

[0111] The ion or complex of V can be added to the coloring liquid in the form of a salt containing a cation and an anion of V or a complex containing V and a ligand. Examples of the anion or ligand include OAc. - 、NO3 - 、NO2 - 、CO3 2- 、HCO3 - ONC - 、SCN - 、SO4 2- 、SO3 2- , glutarate, lactate, gluconate, propionate, butyrate, glucuronate, benzoate, phenolate, halogen anion (fluoride, chloride, bromide), acetate, etc.

[0112] As the vanadium compound, from the viewpoint of storage stability and ease of handling, a vanadium compound having a valence of +IV and / or +V is preferred, and a vanadium oxide compound is more preferred.

[0113] Examples of specific compounds of the component V include vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoyl acetonate, vanadyl oxalate, bis(maltol)oxyvanadium(IV), bis(1-phenyl-1,3-butanedione)oxyvanadium, vanadium(V) triisopropoxide, vanadium(V) oxytrichloride, vanadium(IV) oxydichloride, vanadium(III) chloride hydrate (hexahydrate), vanadium(III) chloride anhydrate, vanadium disilicide, vanadium(III) trioxide, vanadium(IV) tetroxide, vanadium(V) pentoxide, tetravanadium diiron trioxide, vanadium(IV) sulfate hydrate, vanadium(III) bromide, vanadium(IV) oxalate (vanadium(IV) oxalate) ), vanadium (IV) acetate (VO[OC(O)CH3]2), vanadium (V) nitrate (VO(NO3)3), vanadium oxyglycolate, 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), etc. Among these, vanadium oxyoxalate, vanadium oxynitrate, and vanadium oxyacetate are preferred from the viewpoint of excellent storage stability and excellent handling of the coloring liquid. The vanadium component can be used alone or in combination of two or more.

[0114] Furthermore, as a preferred embodiment of the present invention, a coloring liquid containing a Cr component as a coloring component can be cited.

[0115] Cr ions or complexes can be added to the coloring liquid in the form of a salt containing Cr cations and anions or a complex containing Cr and its ligands. Examples of the anions or ligands include OAc. - 、NO3 - 、NO2 - 、CO3 2- 、HCO3 - ONC - 、SCN - 、SO4 2- 、SO3 2- , glutarate, lactate, gluconate, propionate, butyrate, glucuronate, benzoate, phenolate, halogen anion (fluoride, chloride, bromide), acetate, etc.

[0116] Specific examples of the Cr component include trivalent and tetravalent compounds, preferably trivalent chromium compounds. Examples include 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), and chromium (III) formate hydrate (n-hydrate). Chromium (III) nitrate hydrate (nonahydrate), chromium (III) chloride hydrate (hexahydrate), and chromium (III) acetate hydrate (monohydrate) are preferred due to their excellent solubility in water and organic solvents. The Cr component may be used alone or in combination of two or more.

[0117] The coloring liquid of the present invention preferably further contains water and / or an organic solvent as a solvent. Water and / or an organic solvent dissolves the aforementioned organosilicon compound (e.g., a silicone compound, an alkylsilane compound), thereby improving the coloring liquid's permeability into the dental ceramic. Dissolving the aforementioned organosilicon compound in water makes the dental ceramic coloring liquid of the present invention easy to apply and has excellent workability. One solvent may be used alone or in combination of two or more.

[0118] The water used must be substantially free of impurities that would adversely affect the effects of the present invention, and is preferably purified water, distilled water, ion-exchanged water, or pure water. The water content in the dental ceramic coloring liquid is preferably 40 to 99.9% by mass, more preferably 42 to 99.7% by mass, and even more preferably 45 to 99.5% by mass. "Substantially free of impurities" means that any amount of impurities that do not interfere with the effects of the present invention is acceptable. The amount of impurities that do not interfere with the effects of the present invention varies depending on the type of impurity; for example, the impurity content can be less than 0.01% by mass or less than 0.001% by mass.

[0119] The SP value of the organic solvent calculated by the above method is preferably 8.6 (cal / cm 3 ) 1 / 2 More preferably, 8.8 (cal / cm 3 ) 1 / 2 In the embodiment without coloring components, the SP value is 8.6 (cal / cm 3 ) 1 / 2 In the above case, the dissolved organosilicon compound (especially hydrophilic silicone compound, hydrophilic alkylsilane compound) can be sufficiently permeated into the dental ceramic, and sufficient shielding properties can be obtained. In the embodiment containing the coloring component, when the SP value is 8.6 (cal / cm 3 ) 1 / 2In the above case, in addition to achieving the aforementioned sufficient shielding properties, the solubility of the coloring component is also sufficient, sufficient permeability of the coloring liquid into the dental ceramic is achieved, and sufficient coloring can be achieved.

[0120] The organic solvent preferably contains at least one selected from alcohols, diols, triols and ketones. Specific examples include 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-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2-ethyl-1-butanol, ethylene glycol monomethyl ether ... Ethyl 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)-1-propanol, 2-(benzyloxy)-1-butanol, 5-(benzyloxy)-1-pentanol and other alcohols; 1,2 -Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 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 200-600), propylene glycol, dipropylene glycol, polypropylene glycol, 1-methyl-1,3-propanediol Diols such as 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 3-methyl-1,3-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-ethyl-1,3-hexanediol; triols such as glycerol, 1,2,4-butanetriol, 1,2,3-butanetriol, and 1,2,6-hexanetriol; and ketones such as acetone, 2-butanone, 2-pentanone, and cyclohexanone. These organic solvents can be used alone or in appropriate combinations of two or more. Furthermore, organic solvents can be used as thickeners, described below, to adjust viscosity.

[0121] The content of the organic solvent in the colored liquid of the present invention is preferably 40 to 99.9% by mass, more preferably 42 to 99.7% by mass, and even more preferably 45 to 99.5% by mass.

[0122] In one embodiment, a dental ceramic coloring liquid includes an organosilicon compound (e.g., a silicone compound, an alkylsilane compound), a solvent, a complexing agent, and a thickener, and includes water and / or an organic solvent as the solvent, wherein the solvent content is 40 to 99.7% by mass. In the aforementioned embodiment, the solvent content is preferably 41 to 99.6% by mass, more preferably 42 to 99.5% by mass, and even more preferably 45 to 99.2% by mass.

[0123] In a certain embodiment, the pH of the coloring liquid of the present invention (for example, 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 even more preferably 2 to 10. Since the organosilicon compound contained in the present invention has good storage stability and is not easily affected by pH, a wide range of pH values ​​can be applied. When the pH is outside the above range, the silicone compound or the coloring component sometimes begins to precipitate from the solution. The pH can be measured using a commercially available pH meter (for example, a small pH meter LAQUA twin manufactured by Horiba, Ltd.).

[0124] The colored liquid of the present invention may contain a complexing agent within a range that does not impair the effects of the present invention. Adding a complexing agent may be beneficial for improving the storage stability of the coloring component in the colored liquid, facilitating the dissolution of a salt added to the colored liquid, and / or increasing the amount of salt that can be dissolved in the colored liquid.

[0125] Complexing agents are generally capable of forming complexes with metal ions present in the coloring liquid. The complexes formed must be soluble in the solvent. For example, the complexing agent can be used in at least a stoichiometric molar ratio relative to the ions of the coloring component in the coloring liquid. Good results are achieved when the molar ratio of the complexing agent to the cations in the coloring liquid is approximately 1, 2, or 3 or more.

[0126] Examples of the complexing agent include N,N-bis(2-hydroxyethyl)glycine, acetylacetone, crown ethers, cryptands, ethylenediaminetriacetate and its salts, ethylenediaminetetraacetate and its salts, nitrilotriacetate and its salts, citric acid and its salts, triethylenetetramine, porphine, polyacrylates, polyasparagine salts, acidic peptides, phthalocyanine, salicylates, glycinates, lactates, propylenediamine, ascorbate, oxalic acid and its salts, and mixtures thereof. The complexing agent may be used alone or in combination of two or more.

[0127] The content of the complexing agent in the coloring liquid of the present invention is not particularly limited as long as the effects of the present invention are achieved. For example, it is preferably contained in an amount sufficient to dissolve the cations in the solution or to prevent the precipitation of these cations. Specifically, in the coloring liquid, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more. In addition, there is no specific upper limit for this content, but it is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. If the amount of complexing agent used is too small, it is possible that the complexing agent will not dissolve at all. If the amount of complexing agent used is too large, the excess complexing agent itself may remain and not dissolve.

[0128] The coloring liquid of the present invention preferably has an appropriate viscosity so that the required amount can be applied to the ceramic surface and can also move within the pores of the unfired ceramic or pre-fired ceramic. The appropriate viscosity is, for example, preferably 0.1 to 10,000 mPa at 20°C, more preferably 0.5 to 6,000 mPa, and even more preferably 1 to 3,000 mPa. If the viscosity is too high, it may not be contained in the pores of the unfired ceramic or pre-fired ceramic. The method for measuring the viscosity is not particularly limited, and it can be measured using a Brookfield viscometer at 25°C.

[0129] The colored liquid of the present invention may contain one or more thickeners for the purpose of adjusting the viscosity to an appropriate level, within a range that does not impair the effects of the present invention.

[0130] The thickener can be selected from the aforementioned organic solvents to adjust the viscosity, or from the following thickeners. Examples of thickeners other than the aforementioned organic solvents include polysaccharides such as methylcellulose, carboxycellulose, hydroxyethylcellulose, xanthan gum, guar gum, carrageenan, tamarind gum, and pectin; sugar alcohols such as sorbitol, erythritol, xylitol, and trehalose; synthetic polyols such as diglycerol, triglycerol, polyglycerol, and polyvinyl alcohol; and solid organic compounds such as sodium polyacrylate, ammonium polyacrylate, polyethylene oxide, polyethylene glycol (molecular weight of 1000 or greater), polyvinyl pyrrolidone, calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, polyethylene glycol monostearate, 12-hydroxystearic acid, stearamide, oleamide, and ethylenebisoleamide. These thickeners can be used alone or in appropriate combinations of two or more.

[0131] The content of the thickener in the colored liquid of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and even more preferably 0.2 to 5% by mass.

[0132] The colored liquid of the present invention may contain other additives and other masking agents within a range that does not impair the effects of the present invention.

[0133] Other additives include stabilizers (e.g., methoxyphenol, hydroquinone, Topanol A (2,4-dimethyl-6-tert-butylphenol, etc., and mixtures thereof (excluding stabilizers that inhibit the phase transition of zirconium oxide)), buffers (e.g., acetates, amino buffers, and mixtures thereof), antibacterial agents (e.g., gluconic acids such as chlorhexidine gluconate), preservatives (e.g., sorbic acid, benzoic acid, and mixtures thereof), other silane compounds, and mixtures thereof. Other masking agents include nitrates such as aluminum nitrate; phosphoric acid and other phosphorus components; sodium silicate pentahydrate, water-soluble aluminum compounds, and water-soluble lanthanum compounds. Other additives and other masking agents may be used alone or in combination of two or more. The content of these additives and masking agents in the colored liquid of the present invention may be, for example, 0.01 to 10% by mass, 0.05 to 5% by mass, or 0.1 to 3% by mass.

[0134] The dental ceramic coloring liquid of the present invention may contain other ingredients within the scope of the present invention. As other ingredients, phosphorus-containing ingredients such as phosphoric acid and phosphates (ammonium salts, etc.), phosphate esters, etc., nitrates such as potassium nitrate, magnesium nitrate, cobalt (II) nitrate, nickel (II) nitrate, praseodymium (III) nitrate, cerium (III) nitrate, neodymium (III) nitrate, etc., chlorides such as erbium chloride, yttrium chloride, and ferric chloride, water-soluble aluminum compounds (aluminum nitrate, etc.), and water-soluble lanthanum compounds, etc. The content of other ingredients can be set to, for example, less than 10% by mass, less than 5% by mass, less than 1% by mass, or less than 0.01% by mass. In a suitable embodiment, a dental ceramic coloring liquid that does not contain the aforementioned other ingredients can be listed. In addition, by using the dental ceramic coloring liquid of the present invention instead of dental ceramics, it is possible to shield the discoloration of residual teeth, the base color of metal dental restorations such as implant abutments and metal cores, etc., which cannot be shielded without stacking multiple layers when using dental ceramics. Therefore, in a preferred embodiment, the dental ceramic coloring liquid of the present invention does not contain glass components (such as SiO2, Al2O3, Li2O, Na2O, and K2O) contained in dental ceramics. Alternatively, the coloring liquid may be combined with dental ceramics to obtain a more aesthetically pleasing dental restoration.

[0135] The dental ceramic colored with the coloring liquid of the present invention is not particularly limited as long as it comprises a ceramic used in dentistry. Examples thereof include materials containing zirconium oxide (also known as "zirconium oxide" or "ZrO2"), aluminum oxide (also known as "alumina" or "Al2O3"), feldspar glass, disilicate glass, and ceramics. The dental ceramic preferably contains zirconium oxide and / or aluminum oxide, and more preferably contains zirconium oxide as the main component. The "main component" is as described below in the description of the zirconium oxide calcined body.

[0136] The dental ceramic colored with the coloring liquid of the present invention may be a pre-sintered ceramic, an unfired body, or a pre-calcined body. From the perspective of penetration of the coloring liquid, when the dental ceramic contains zirconium oxide as a main component, the dental ceramic is preferably a pre-calcined zirconium oxide body.

[0137] As other embodiments of the present invention, dental ceramics (colored ceramic pre-fired bodies or colored unfired bodies) having an organosilicon compound (e.g., a silicone compound, an alkylsilane compound) supported on its surface can be cited. The content of the organosilicon compound is not particularly limited as long as the effect of the present invention is exerted, and can be appropriately adjusted by the amount of coating of the coloring liquid of the present invention, etc., according to the desired degree of shielding after sintering. In addition, as the supporting range of the organosilicon compound, it can be based on the application of the coloring liquid of the present invention, etc., and by utilizing the capillary phenomenon to immerse it into the space connected to the outside of the ceramic pre-fired body or the unfired body, so that not only the support on the outermost surface can be adjusted, but also the support to the inside of the surface can be adjusted. It should be noted that support is usually a state of being attached to a carrier, and in the present invention, it is a state of being attached to the ceramic by adsorption, etc.

[0138] After firing, the dental ceramic of the present invention can impart the desired masking properties required for dental applications, and when containing a coloring component, can also impart the desired coloring. Examples of such embodiments include dental ceramics that carry a coloring component. The coloring component is the same as that described for the coloring solution.

[0139] As described above, the ceramic calcined body or uncalcined body preferably contains zirconium oxide as the main component. The following describes an embodiment in which the dental ceramic contains zirconium oxide as the main component. It should be noted that, in the present invention, the calcined body before being colored with the coloring liquid is abbreviated as "ceramic calcined body" or "zirconia calcined body", and the calcined body after being colored is abbreviated as "colored ceramic calcined body" or "colored zirconia calcined body" to distinguish them. It should be noted that the coloring liquid of the present invention can also be used to color the zirconia uncalcined body. In this case, the zirconia sintered body is manufactured without undergoing pre-calcination. In the case of envisioning such a sintered body, as a suitable embodiment of the zirconia uncalcined body, the various conditions in the following description of the zirconia calcined body can be similarly applied. The ceramic calcined body and the uncalcined body can have a shape such as a block or a disk.

[0140] The zirconia calcined body of the present invention is described. The zirconia calcined body refers to a substance obtained by pre-calcining zirconia with zirconia (ZrO2: zirconia) as the main component (the zirconia particles (powder) are in a state where they are not completely sintered). The zirconia calcined body can have a shape obtained by processing according to the target dental product. The main component only needs to be 50% by mass or more. The content of zirconia in the zirconia calcined body of the present invention is preferably 60% by mass or more, more preferably 65% ​​by mass or more, further preferably 70% by mass or 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 it is used in the application of dental restorations or dental implant products, the zirconia calcined body can be made by press-forming the zirconia powder using a known technique and pre-calcining the resulting disk or block. The content of zirconia in the uncalcined zirconia body is the same as that of the zirconia calcined body. The density of the zirconia calcined body is preferably 2.7 g / cm 3 In addition, the density of the zirconia calcined body is preferably 4.0 g / cm 3 Below, more preferably 3.8g / cm 3 Below, more preferably 3.6 g / cm 3Below. If it is within this density range, forming processing can be easily performed. The density of the calcined body can be calculated, for example, in the form of (mass of the calcined body) / (volume of the calcined body). In addition, the three-point bending strength of the zirconia calcined body is preferably 15 to 70 MPa, more preferably 18 to 60 MPa, and further preferably 20 to 50 MPa. The above-mentioned bending strength can be measured as follows: using a test piece with a thickness of 5 mm × a width of 10 mm × a length of 50 mm, the measurement is carried out in accordance with ISO 6872:2015 except for the size of the test piece. The surface and C surface of the test piece (the surface obtained by chamfering the corners of the test piece at an angle of 45°) are surface-finished along the length direction using No. 600 sandpaper. The test piece is arranged in a manner such that the widest surface faces the vertical direction (load direction). In the bending test measurement, the span is set to 30 mm and the crosshead speed is set to 0.5 mm / min.

[0141] The calcined zirconium oxide in the present invention preferably contains a stabilizer (hereinafter also referred to as a "stabilizer") capable of suppressing the phase transformation of zirconium oxide. For example, the zirconium oxide before calcination preferably contains a stabilizer.

[0142] Examples of stabilizers include yttrium oxide (Y2O3) (hereinafter referred to as "yttrium oxide"), calcium oxide (CaO), magnesium oxide (MgO), cerium oxide (CeO2), scandium oxide (Sc2O3), niobium oxide (Nb2O5), lanthanum oxide (La2O3), erbium oxide (Er2O3), praseodymium oxide (Pr6O3), and tantalum oxide (TfO3). 11 ), samarium oxide (Sm2O3), europium oxide (Eu2O3) and thulium oxide (Tm2O3), preferably yttrium oxide. They can be used alone or in combination of two or more. In a suitable embodiment, the following coloring liquid can be listed: the dental ceramic to be colored contains zirconium oxide as a main component, and further contains yttrium oxide as a stabilizer, and the stabilizer is essentially only yttrium oxide. In the aforementioned suitable embodiment, the stabilizer is essentially only yttrium oxide, which means that the content of the stabilizer other than yttrium oxide is less than 0.1 mol% in the total 100 mol% of zirconium oxide and the stabilizer, preferably 0.05 mol% or less, more preferably 0.01 mol% or less, and further preferably 0.001 mol% or less. The content of the stabilizer can be measured by, for example, inductively coupled plasma (ICP; Inductively Coupled Plasma) emission spectrometry, fluorescent X-ray analysis, etc.

[0143] When a dental ceramic contains zirconium oxide 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 even more preferably 1.5 to 10 mol%, based on 100 mol% of the total of zirconium oxide and the stabilizer. The type and content of the stabilizer in the uncalcined zirconium oxide body are the same as those in the calcined zirconium oxide body. In a preferred embodiment, the content of yttrium oxide in the dental ceramic containing zirconium oxide as a main component is preferably 2.5 to 9.5 mol%, more preferably 3.0 to 9.0 mol%, and even more preferably 3.5 to 8.5 mol%, based on 100 mol% of the total of zirconium oxide and the stabilizer.

[0144] The uncalcined zirconium oxide body and the calcined zirconium oxide body of the present invention may contain a colorant (including a pigment, a composite pigment, and a fluorescent agent), aluminum oxide (Al2O3), titanium oxide (TiO2), silicon dioxide (SiO2), etc. as needed. These components may be used alone or in combination of two or more. Examples of the aforementioned pigment include oxides of at least one component selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Sn, Sb, Bi, Ce, Pr, Sm, Eu, Gd, Tb, and Er. Examples of the aforementioned composite pigment include (Zr, V)O2, Fe(Fe, Cr)2O4, (Ni, Co, Fe)(Fe, Cr)2O4·ZrSiO4, and (Co, Zn)Al2O4. Examples of the fluorescent agent include Y2SiO5:Ce, Y2SiO5:Tb, (Y, Gd, Eu)BO3, Y2O3:Eu, YAG:Ce, ZnGa2O4:Zn, BaMgAl 10 O 17 :Eu et al.

[0145] The general manufacturing method of the zirconia calcined body of the present invention is described. First, zirconia raw material particles containing a stabilizer are prepared and pressurized into a shape such as a block or a disk. Then, the formed body (uncalcined body) is subjected to CIP (Cold Isostatic Pressing) treatment as needed. The pressure at this time is, for example, 50 to 500 MPa. Then, it is subjected to a calcination treatment. Regarding calcination, a zirconia calcined body can be obtained by slowly heating from room temperature to 800 to 1200°C and keeping it for about 1 to 6 hours. The obtained zirconia calcined body is cut using existing well-known devices according to the final dental product. For example, when the dental product is a dental restoration, it is cut into the shape of a crown using CAD / CAM or the like.

[0146] The method for producing a colored zirconia calcined body of the present invention includes the step of impregnating the machined zirconia calcined body with the aforementioned dental ceramic coloring liquid. Examples of methods for impregnating the zirconia calcined body include applying the dental ceramic coloring liquid to the zirconia calcined body using a pen, immersing the zirconia calcined body in a container containing the coloring liquid, or spraying the zirconia calcined body with a sprayer. Conventionally known instruments and devices can be used. It should be noted that when producing a zirconia sintered body directly from an uncalcined body without a pre-calcining step, the dental ceramic coloring liquid can be impregnated into the machined uncalcined zirconia body.

[0147] The present invention also includes a zirconia sintered body obtained by sintering the aforementioned colored zirconia calcined body. The method for manufacturing the zirconia sintered body includes the step of calcining the aforementioned colored zirconia calcined body. The calcination temperature (maximum calcination temperature) can be appropriately changed according to the type of zirconia, and is not particularly limited as long as the coloring component can develop color. It is preferably 1350°C or above, more preferably 1450°C or above, and further preferably 1500°C or above. The upper limit of the calcination temperature is not particularly limited, for example, it is preferably 1600°C or below. It should be noted that the zirconia sintered body of the present invention not only includes a sintered body obtained by sintering the formed zirconia powder under normal pressure and / or without pressure, but also includes a sintered body obtained by densifying it through a high-temperature pressurization treatment such as HIP (Hot Isostatic Pressing) treatment.

[0148] The content of the stabilizer in the zirconia sintered body and the zirconia calcined body of the present invention can be measured by, for example, inductively coupled plasma (ICP: Inductively Coupled Plasma) emission spectrometry, fluorescent X-ray analysis, or the like.

[0149] The zirconia sintered body of the present invention 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 zirconia is at least one of a tetragonal system and a cubic system. The zirconia sintered body may contain both tetragonal and cubic systems. The zirconia sintered body preferably does not substantially contain a monoclinic system. It should be noted that the zirconia obtained by adding a stabilizer to partially stabilize it is called partially stabilized zirconia (PSZ), and the zirconia obtained by fully stabilizing it is called fully stabilized zirconia.

[0150] The present invention includes dental products formed from the aforementioned zirconia sintered body. Examples of such dental products include dental restorations, orthodontic products, and dental implant products. Dental restorations can be used, for example, in zirconia inlays, onlays, laminated veneers, and crowns.

[0151] In the above embodiment, the types and contents of the components may be modified as appropriate, and optional components may be added or deleted. In addition, in the above embodiment, the composition and property values ​​of the coloring liquid may be modified as appropriate and combined.

[0152] The present invention includes various combinations of the above-described configurations within the scope of the technical concept of the present invention as long as the effects of the present invention are exhibited.

[0153] Example

[0154] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0155] [Examples 1-1 to 1-24, 2-1 to 2-18 and Comparative Examples 1-1 to 1-6]

[0156] The colored liquids of the Examples and Comparative Examples were prepared as follows, and their properties were evaluated. The results are shown in Tables 1 to 4.

[0157] [Evaluation Method of Solubility of Organosilicon Compounds in Water]

[0158] After adding 2.985 g and 2.85 g of water having a pH of 7 to 0.015 g and 0.15 g of the organosilicon compound, respectively, the mixture was stirred at 25° C. for 1 hour and visually observed to evaluate the solubility according to the following criteria.

[0159] A: The solubility in water at 25°C is 5% by mass or more.

[0160] B: The solubility in water at 25°C is 0.5% by mass or more and less than 5% by mass.

[0161] C: Solubility in water at 25°C is less than 0.5% by mass.

[0162] [Preparation of coloring liquid]

[0163] The components listed in Tables 1 to 4 were mixed at room temperature in the mass % values ​​listed in the tables to prepare coloring liquids. The organosilicon compounds used are as follows. Their solubility in water was evaluated according to the criteria described below.

[0164] <Silicone Compound>

[0165] KP-120: Made by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone, SP value: 10.0 (cal / cm 3 ) 1 / 2 , Solubility in water: A

[0166] KP-106: Made by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone, SP value: 8.9 (cal / cm 3 ) 1 / 2 , Solubility in water: A

[0167] KP-110: Made by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone, SP value: 8.3 (cal / cm 3 ) 1 / 2 , Solubility in water: B

[0168] KP-104: Made by Shin-Etsu Chemical Co., Ltd., polyol-modified silicone, SP value: 11.6 (cal / cm 3 ) 1 / 2 , Solubility in water: A

[0169] <Alkylsilane Compound>

[0170] KBM-403: 3-Glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: A

[0171] KBM-602: N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Solubility in water: A

[0172] KBM-903: 3-Aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solubility in water: A

[0173] Trimethylsilanol: Made by Shin-Etsu Chemical Co., Ltd., solubility in water: B

[0174] [Evaluation of Storage Stability of Coloring Liquid]

[0175] 12 ml of the prepared coloring liquid was placed in an ES Liquid container (manufactured by Kuraray Noritake Dental Co., Ltd.). After storage at 40°C, 50°C, and 60°C for 60 days, evaluation was performed according to the following criteria, taking into account the actual transportation and storage environments of the coloring liquid.

[0176] ◯: Neither component separation nor gelation of the colored liquid was confirmed by visual observation.

[0177] ×: Component separation of the coloring liquid was visually observed, or gelation of the coloring liquid was visually observed.

[0178] [Manufacturing of zirconia calcined body]

[0179] Next, a method for producing a zirconia calcined body to be coated with the aforementioned coloring liquid will be described.

[0180] First, prepare zirconium oxide powder containing a stabilizer. Add 9.9 mass% (5.5 mol%) of yttrium oxide as a stabilizer to 90.1 mass% of zirconium oxide powder to prepare a mixture. Then, add the mixture to water to prepare a slurry, and wet-grind and mix it using a ball mill until the average particle size becomes less than 0.13 μm. The crushed slurry is dried using a spray dryer, and the resulting powder is calcined at 950°C for 2 hours to prepare a powder (primary powder). It should be noted that the above-mentioned average particle size can be obtained by a laser diffraction scattering method. Specifically, the laser diffraction scattering method can be measured by, for example, a laser diffraction particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation), using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium, and measuring it on a volume basis.

[0181] Water was added to the resulting primary powder to prepare a slurry, which was then wet-milled and mixed using a ball mill until the average particle size was 0.13 μm or less. A binder was added to the milled slurry, which was then dried using a spray dryer to prepare a powder (secondary powder). This secondary powder was used as the raw material powder for the production of the zirconia calcined body described below.

[0182] Next, the method for producing a calcined zirconia body is described. 1.32 g of the raw material powder is placed in a 19 mm diameter mold and subjected to primary press molding for 20 seconds using a single-screw press molding machine at a surface pressure of 57.5 kN. The resulting primary press molding is sintered at 1000°C for 2 hours to produce a calcined zirconia body.

[0183] [Measurement of Chromaticity of Sintered Body]

[0184] The coloring liquid prepared above was applied to the zirconia calcined body produced above using a pen, and then calcined under the calcination conditions described in Tables 1 to 4 to obtain a zirconia sintered body. The obtained zirconia sintered body was ground into a circular plate with a diameter of 15 mm and a thickness of 1.2 mm. The color was measured using a spectrophotometer "Clister AI" manufactured by Olympus Corporation in the measurement mode: 7-band LED light source, white background, based on L * a * b * Color system (JIS Z 8781-4:2013 Color measurement - Part 4: CIE1976L * a * b * The chromaticity of the measured values ​​is shown in Tables 1 to 4. * and b* The average value is used to calculate the chroma C * =((a * ) 2 +(b * ) 2 ) 1 / 2 .

[0185] [Measurement of Transparency of Sintered Body]

[0186] The coloring liquid prepared above was applied to the zirconia calcined body produced above using a pen, and then calcined under the calcination conditions described in Tables 1 to 4 to obtain a sintered body. The obtained sintered body was ground into a circular plate with a diameter of 15 mm and a thickness of 1.2 mm. The lightness (Lw) of the calcined body was measured using a spectrophotometer "Clister AI" manufactured by Olympus Corporation in the measurement mode: 7-band LED light source, white background. * ) and the brightness (Lb) when the chromaticity is measured on a black background using the same test piece and the same measuring device, measuring mode, and light source. * ), the difference between the two (ΔL * =(Lw * )-(Lb * )) as transparency (ΔL * ) (n=3). The average values ​​of the calculated values ​​are shown in Tables 1 to 4. In addition, the rate of change in transparency was calculated using the following formula using a zirconia sintered body (Comparative Example 1-1) not colored with the coloring liquid as a reference.

[0187] Transparency change rate (%) = {(transparency of the sintered body obtained by applying the coloring liquid and calcining - transparency of the uncolored zirconia sintered body) / transparency of the uncolored zirconia sintered body} × 100

[0188] [Evaluation of Shielding Degree of Sintered Body]

[0189] A crown shape was cut from the zirconia calcined body produced above using a dental milling machine (trade name: DWX-51D, manufactured by Roland DG). The coloring liquid prepared above was applied to the inside of the crown shape using a pen. The sintered body was then fired under the firing conditions listed in Tables 1 to 4 to obtain a sintered body. The resulting crown-shaped sintered body was applied to a metal abutment, and the degree of masking was evaluated according to the following criteria.

[0190] ◯: Compared to the sintered body not coated with the coloring liquid, the color of the metal abutment was not visible under visual observation (high degree of obscuration).

[0191] △: The color of the metal abutment was visible through visual observation, but was slightly less visible (the degree of obscuration was slightly higher) than that of the sintered body not coated with the coloring liquid.

[0192] ×: Compared with the sintered body not coated with the coloring liquid, the color of the metal abutment was visually visible or was of the same level (low or no obscuration).

[0193] [Measurement of Biaxial Bending Strength of Sintered Body]

[0194] The prepared coloring liquid was applied to the zirconia calcined body produced above using a pen, and then calcined under the calcination conditions listed in Tables 1-4 to obtain a sintered body with a diameter of 15 mm and a thickness of 1.2 mm. The biaxial flexural strength (n = 3) of the resulting sintered body was measured in accordance with JIS T 6526:2012 using a Shimadzu Corporation universal precision testing machine autoplotter (trade name "AG-I 100 kN") at a crosshead speed of 0.5 mm / min. The average values ​​of the measured values ​​are shown in Tables 1-4. Furthermore, the change in biaxial flexural strength was calculated using the following formula, using a zirconia sintered body not colored with the coloring liquid (Comparative Example 1-1) as a reference.

[0195] Change rate of biaxial bending strength (%) = {(biaxial bending strength of the sintered body obtained by applying the coloring liquid and calcining - biaxial bending strength of the uncolored zirconia sintered body) / biaxial bending strength of the uncolored zirconia sintered body} × 100

[0196]

[0197]

[0198]

[0199]

[0200] Comparative Examples 1-2 and 1-3, which contained inorganic silicon compounds, exhibited poor storage stability, with gelation observed visually during storage. Comparative Example 1-4, which incorporated phosphoric acid, exhibited reduced biaxial bending strength of the zirconia sintered body. Furthermore, Comparative Examples 1-5 and 1-6, which incorporated water-soluble aluminum, showed insufficient masking due to the color of the metal abutment teeth showing through.

[0201] In contrast, Examples 1-1 to 1-24 and 2-1 to 2-18, which contained organosilicon compounds, showed no decrease in the strength of the zirconia sintered bodies, exhibited good storage stability, and demonstrated excellent shielding properties. Furthermore, Examples 1-5 to 1-7, 1-10, 1-11, 1-17 to 1-24, 2-5 to 2-8, 2-10, and 2-12 to 2-18, which contained coloring components, demonstrated good storage stability, excellent shielding properties, and the ability to impart the desired coloring.

[0202] Industrial Applicability

[0203] The dental ceramic coloring liquid of the present invention can suppress the reduction in mechanical strength of sintered dental ceramics, has excellent storage stability, and can impart opacifying properties. Furthermore, when the dental ceramic coloring liquid of the present invention contains a coloring component, it can impart opacifying properties and a desired hue to the dental ceramic. Therefore, it can be suitably used as a coloring liquid for coloring dental ceramics. In particular, the demand for ceramic crowns is increasing, and with the rise in personal aesthetic preferences, the frequency of use of dental ceramic coloring liquids is expected to increase. Therefore, the dental ceramic coloring liquid of the present invention having opacifying properties is useful.

Claims

1. A dental ceramic coloring solution comprising an organosilicon compound, The organosilicon compound is a silicone compound and / or an alkylsilane compound, The silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound, The polyether-modified silicone compound or the polyol-modified silicone compound is a compound represented by the general formula (1), In the formula, each R 1 are the same or different and represent a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R 1 The substituent in is selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group; m is an integer of 1 to 1998; each R 2 The same or different, representing a polyether group or a polyol group, The alkylsilane compound is a compound represented by the following general formula (2): Where R 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent; R 4 represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted aryl group, or a halogen atom, and R 3 and R 4 The alkyl group and R 4 The substituent of the aryl group is selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and a hydroxyl group; 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 It is a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, which may have a substituent, and the alkylene group or the cycloalkylene group may contain -CH2-C6H4-, -S-, -NH-, -NR 6 -, -C(O)-O- or -O- groups, wherein C6H4 represents phenylene, R 5 The type and number of substituents of alkylene and cycloalkylene are the same as R 3 and R 4 The substituents of the alkyl groups are the same; R 6 represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group, or an optionally substituted aryl group, R 6 The type and number of substituents of alkyl, cycloalkyl and aryl groups are related to R 3 and R 4 The substituents of the alkyl groups are the same; 1 represents a hydroxyl group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt which may have a substituent, and Y 1 The types and numbers of substituents of alkoxy, amino and amine salts are similar to those of R 3 and R 4 The substituents of the alkyl groups of B are the same; 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-, wherein C6H4 represents a phenylene group.

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 silicone compound has all R 1 A compound containing a methyl dimethylpolysiloxane group.

4. The coloring liquid according to claim 1 or 2, wherein The silicone compound is liquid at room temperature.

5. The coloring liquid according to claim 1 or 2, wherein The content of the silicone compound is 0.1 to 60% by mass.

6. The coloring liquid according to claim 1 or 2, wherein In the compound represented by the general formula (2), X represents -R 5 -Y 1 or -Y 1 ; Y 1 is a hydroxyl group, an amino group which may have a substituent, an epoxy group, or an amine salt which may have a substituent.

7. The coloring liquid according to claim 6, wherein X stands for -R 5 -Y 1 ; R 5 is a linear or branched alkylene group optionally having a substituent, wherein the alkylene group optionally includes -CH2-C6H4-, -S-, -NH-, -NR 6 -, -C(O)-O- or -O- group, wherein C6H4 represents a phenylene group.

8. The coloring liquid according to claim 1 or 2, wherein The alkylsilane compound is at least one compound selected from 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.

9. The coloring liquid according to claim 1 or 2, wherein The content of the alkylsilane compound is 0.1 to 60% by mass. 10 . The colored liquid according to claim 1 , further comprising a coloring component.

11. The coloring liquid according to claim 10, wherein The coloring component is an ion or a complex.

12. The coloring liquid according to claim 11, wherein The coloring component includes at least one selected from Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb and Er. 13 . The colored liquid according to claim 1 , further comprising water and / or an organic solvent.

14. The coloring liquid according to claim 13, wherein The organic solvent includes at least one selected from alcohols and ketones.

15. The coloring liquid according to claim 13, wherein The organic solvent contains at least one selected from diols and triols.

16. The coloring liquid according to claim 1 or 2, wherein The dental ceramic contains zirconium oxide as a main component, and the main component means that the content of zirconium oxide is 50% by mass or more.

17. A dental ceramic having an organosilicon compound supported on its surface, wherein the organosilicon compound is a silicone compound. The silicone compound is a polyether-modified silicone compound and / or a polyol-modified silicone compound, The polyether-modified silicone compound or the polyol-modified silicone compound is a compound represented by the general formula (1), In the formula, each R 1 are the same or different and represent a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R 1 The substituent in is selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group; m is an integer of 1 to 1998; each R 2 The same or different groups represent polyether groups or polyol groups.

18. The dental ceramic according to claim 17, wherein The organosilicon compound is hydrophilic.

19. The dental ceramic according to claim 17, wherein The silicone compound is a polyether-modified silicone compound and a polyol-modified silicone compound.

20. The dental ceramic according to claim 17 or 18, further carrying a coloring component.

21. The dental ceramic according to claim 20, wherein The coloring component is an ion or a complex.

22. The dental ceramic according to claim 20, wherein The coloring component includes at least one selected from Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb and Er.

23. Dental ceramics, including The surface supports an organic silicon compound, which is an alkylsilane compound, and further supports a coloring component. The alkylsilane compound is a compound represented by the following general formula (2): Where R 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent; R 4 represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted aryl group, or a halogen atom, and R 3 and R 4 The alkyl group and R 4 The substituent of the aryl group is selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and a hydroxyl group; 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 It is a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, which may have a substituent, and the alkylene group or the cycloalkylene group may contain -CH2-C6H4-, -S-, -NH-, -NR 6 -, -C(O)-O- or -O-, wherein C6H4 represents phenylene, R 5 The type and number of substituents of alkylene and cycloalkylene are the same as R 3 and R 4 The substituents of the alkyl groups are the same; R 6 represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group, or an optionally substituted aryl group, R 6 The type and number of substituents of alkyl, cycloalkyl and aryl groups are related to R 3 and R 4 The substituents of the alkyl groups are the same; 1 represents a hydroxyl group, an alkoxy group which may have a substituent, an amino group which may have a substituent, a mercapto group, an epoxy group, a halogen atom, or an amine salt which may have a substituent, and Y 1 The types and numbers of substituents of alkoxy, amino and amine salts are similar to those of R 3 and R 4 The substituents of the alkyl groups of B are the same; 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-, wherein C6H4 represents a phenylene group.

24. The dental ceramic according to claim 23, wherein In the compound represented by the general formula (2), X represents -R 5 -Y 1 or -Y 1 ; Y 1 is a hydroxyl group, an amino group which may have a substituent, an epoxy group, or an amine salt which may have a substituent.

25. The dental ceramic according to claim 23, wherein The coloring component is an ion or a complex.

26. The dental ceramic according to claim 23, wherein The coloring component includes at least one selected from Al, K, Zr, Cr, Fe, Na, V, Y, Gd, La, Yb, Tm, Ni, Mn, Co, Nd, Pr, Cu, Tb and Er.

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