JP7090366B1 - Dental surface smooth composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental surface smooth composition which can be easily applied to the surface of a biological hard tissue or a dental material and can form a cured product having excellent durability, adhesion and aesthetics. The task is to do. SOLUTION: (a) a monomer having 3 or less (meth) acryloyl groups, (b) a monomer having 4 or more (meth) acryloyl groups, (c) a compound containing a plurality of thiol groups, and (c). d) A dental surface smooth composition containing a polymerization initiator, wherein the (d) polymerization initiator is a photopolymerization initiator, with respect to 100% by mass of the dental surface smooth composition. 25 to 90% by mass of the above-mentioned (a) monomer having 3 or less (meth) acryloyl groups, 4 to 65% by mass of the above-mentioned (b) monomer having 4 or more (meth) acryloyl groups, said (c). A dental surface smooth composition containing 0.5 to 15% by mass of a compound containing a plurality of thiol groups and 0.8 to 4.5% by mass of the above-mentioned (d) polymerization initiator. [Selection diagram] None

Description

The present invention relates to a dental surface smooth composition.

In recent dental treatments, the surface of the treated biological hard tissue (tooth) or dental material such as dental filler, crown restoration material, dental prosthesis, etc. is used as the main component of a polymerizable monomer for dentistry. It is coated with a coating material to impart smoothness.

Conventionally, a composition containing a (meth) acrylate-based monomer and a photopolymerization initiator has been used as a dental coating material. By irradiating the composition with light, a radical polymerization chain reaction is started and a polymerization reaction occurs. At this time, oxygen in the air acts as an inhibitor of the polymerization reaction, and the surface of the cured composition is not polymerized. There is a problem that the surface of the cured product lacks smoothness due to the residual monomer of the above, and sufficient hardness cannot be obtained.

Various compositions have been proposed to solve this problem (eg, Patent Documents 1 and 2). Patent Document 1 describes (A) a polyfunctional acrylate, (B) a volatile (meth) acrylate compound, and (C) a (meth) acrylate compound containing a fluoroalkyl group composed of at least one fluorocarbon. (D) A photopolymerizable dental coating composition comprising an acylphosphine oxide-based polymerization initiator is described.
Further, in Patent Document 2, inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified with an alkoxysilane having an unsaturated double bond are mixed with a (meth) acrylate-based polymerizable monomer in a monodispersed state. Described are photopolymerizable dental surface coatings containing up to 70% by weight.

Japanese Unexamined Patent Publication No. 2003-09538 Japanese Unexamined Patent Publication No. 2005-154312

In the compositions of Patent Documents 1 and 2, the influence of polymerization inhibition by oxygen at the time of light irradiation is suppressed, and the surface hardness is improved, but it cannot be said to be sufficient. Further, in the above-mentioned Patent Documents 1 and 2, strain and discoloration during curing are not examined, and there is room for improvement in terms of durability, adhesion, and aesthetics.

The present invention has been made in view of the above circumstances, and is a dental surface that can be easily applied to the surface of a biological hard tissue or a dental material and can form a cured body having excellent durability, adhesion, and aesthetics. An object of the present invention is to provide a smooth composition.

As a result of diligent research to solve the above problems, the present inventors have found that the dental surface smoothing composition shown below can achieve the above object, and have completed the present invention.

That is, the present invention is as follows.

Item 1.
(A) Monomer having 3 or less (meth) acryloyl groups,
(B) Monomer having 4 or more (meth) acryloyl groups,
A dental surface smoothing composition containing (c) a compound containing a plurality of thiol groups and (d) a polymerization initiator.
The (d) polymerization initiator is a photopolymerization initiator.
With respect to 100% by mass of the dental surface smoothing composition
25 to 90% by mass of the above-mentioned (a) monomer having 3 or less (meth) acryloyl groups.
(B) 4 to 65% by mass of the monomer having 4 or more (meth) acryloyl groups.
(C) A dental surface smooth composition containing 0.5 to 15% by mass of a compound containing a plurality of thiol groups and 0.8 to 4.5% by mass of the above (d) polymerization initiator.
Item 2.
Item 1 (a) The monomer having three or less (meth) acryloyl groups is at least one compound selected from the group consisting of methyl methacrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate. The dental surface smoothing composition according to.
Item 3.
Item (b) Item 1 or 2, wherein the monomer having four or more (meth) acryloyl groups is at least one compound selected from the group consisting of dipentaerythritol hexaacrylate and ethoxylated pentaerythritol tetraacrylate. The described dental surface glacier composition.
Item 4.
Item 3. The dental surface smoothing according to any one of Items 1 to 3, wherein the compound (c) containing a plurality of thiol groups is a compound containing two or more mercaptoethylcarbonyl groups or mercaptopropylcarbonyl groups. Composition.
Item 5.
(C) At least one compound selected from the group in which the compound containing a plurality of thiol groups consists of pentaerythritol tetrakis-3-thiopropionate and trimethylolpropanetris (3-mercaptopropionate). The dental surface smoothing composition according to any one of Items 1 to 4.
Item 6.
Item 6. The dental surface smoothing composition according to any one of Items 1 to 5, wherein the polymerization initiator (d) is an acylphosphine oxide-based compound.
Item 7.
At least one compound selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide as the (d) polymerization initiator. The dental surface smoothing composition according to any one of Items 1 to 6.
Item 8.
The dental surface smoothing composition according to any one of Items 1 to 7, further comprising (e) an inorganic filler.
Item 9.
Item 8. The dental surface smoothing composition according to Item 8, wherein the content of the inorganic filler (e) is 40% by mass or less with respect to 100% by mass of the dental surface smoothing composition.
Item 10.
Item 2. The dental surface smoothing composition according to Item 8 or 9, wherein the inorganic filler (e) is silica particles.
Item 11.
Item 2. The dental surface smoothing composition according to any one of Items 1 to 10, wherein the cured dental surface smoothing composition has a pencil hardness of 4H or more.
Item 12.
Item 2. The dental surface smoothing composition according to any one of Items 1 to 10, wherein the spread when 5 μL of the dental surface smoothing composition is dropped onto the evaluation pellets is 10 mm ² to 120 mm ² . ..
Item 13.
Item 1 to 10 in which the color difference (ΔE) of the color tone of the dental surface smoothing composition after being applied on the evaluation pellet and cured with respect to the color tone of the white evaluation pellet is 3.0 or less. The dental surface smoothing composition according to any one of the above.
Item 14.
Item 1 of Items 1 to 10, wherein the amount of curing strain when the dental surface smoothing composition is filled in a silicon mold, covered with a transparent PET film, and then cured is 0.80 mm or less. The dental surface smoothing composition according to the section.

According to the present invention, it is possible to obtain a dental surface smooth composition that can be easily applied to the surface of a biological hard tissue or a dental material and can form a cured product having excellent durability, adhesion and aesthetics. Can be done.

FIG. 1 is a schematic diagram illustrating a test method for coatability. FIG. 2 is a schematic diagram illustrating a test method for the amount of curing strain.

Hereinafter, the present invention will be described in detail.

1. 1. Dental Surface Smooth Composition The dental surface smooth composition of the present invention comprises (a) a monomer having 3 or less (meth) acryloyl groups, and (b) a monomer having 4 or more (meth) acryloyl groups. , (C) A compound containing a plurality of thiol groups, and (d) a polymerization initiator.

The dental surface smoothing composition of the present invention includes a surface smoothing material, a smoothing material, a smoothing composition, a surface smoothing hardening material, a surface smoothing curable composition, a coating material, a coating composition, and a coating material. Alternatively, it can be paraphrased as a coating composition. In addition, the material can be paraphrased as an agent.

Each component to be blended in the dental surface smoothing composition of the present invention will be described below.

(A) Monomer having 3 or less (meth) acryloyl groups The dental surface smoothing composition of the present invention is (a) a monomer having 3 or less (meth) acryloyl groups (hereinafter, "component (a)". In some cases, it contains) as an essential ingredient.
(A) As the monomer having 3 or less (meth) acryloyl groups, a trifunctional or less functional (meth) acrylate-based polymerizable monomer that can be used for dentistry can be used. (A) By containing a monomer having 3 or less (meth) acryloyl groups, the viscosity of the dental surface smooth composition can be adjusted, and the applicability to the surface of the biohard tissue or the dental material (a) Operability) can be improved.

A monomer having 3 or less (meth) acryloyl groups includes a monomer having one acryloyl group or a methacryloyl group in one molecule (monofunctional (meth) acrylate monomer), and two acryloyl groups or methacryloyl groups in one molecule. A monomer having three functions (bifunctional (meth) acrylate monomer) and a monomer having three acryloyl groups or methacryloyl groups in one molecule (trifunctional (meth) acrylate monomer) is included. Here, the functionality can be paraphrased as a functionality, a functional group, or a functional group.

Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) ) Acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, glycerol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) ) Acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, caprolactone-modified dipentaerythritol (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate , 4- (Meta) acryloylmorpholine and the like. Here, n means normal.

Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. ) Acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, glycerol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A glycidyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A glycidyl di (meth) acrylate, 2, 2-Bis (4-methacryloxypropoxyphenyl) propane, 7,7,9-trimethyl-4,13-dioxa-3,14-dioxo-5,12-diazahexadecane-1,16-diol di (meth) acrylate , Neopentyl glycol hydroxypivalic acid ester di (meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, trimethylol ethanedi (meth) acrylate, trimethyl propanidi (meth) acrylate, tripropylene glycol di. (Meta) Acrylate Urethane Di (meth) Acrylate (1,6-bis ((meth) acryloyloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane), 2,2,4-trimethylhexamethylene bis (2-Carbamoyloxyethyl) dimethacrylate, reaction product of 3-chloro-2-hydroxypropyl (meth) acrylate and methylcyclohexanediisocyanate, reaction product of 2-hydroxypropyl (meth) acrylate and methylcyclohexanediisocyanate, Reaction product of 2-hydroxypropyl (meth) acrylate and methylenebis (4-cyclohexyl isocyanate), reaction product of 2-hydroxypropyl (meth) acrylate and trimethylhexamethylene diisocyanate, 2-hydroxyethyl (meth) acrylate Reaction with isophorone diisocyanate Examples thereof include a product, a reaction product of 3-chloro-2-hydroxypropyl (meth) acrylate and isophorone diisocyanate, and the like.

Examples of the trifunctional (meth) acrylate monomer include trimethylolmethanetri (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated tri. Methylolpropane triacrylate, ethoxylated glycerin triacrylate, tris- (2-acryloxyethyl) isocyanurate, bis and tris- (2-acryloxyethyl) isocyanurate, caprolactone-modified tris- (2-acryroxyethyl) isocyanurate. , Pentaerythritol triacrylate and the like.
(A) As the monomer having 3 or less (meth) acryloyl groups, methyl (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like are preferable.

In addition, in this specification, (meth) acrylate represents each of acrylate and methacrylate, and (meth) acryloyl represents each of acryloyl and methacryloyl.

The monomer (a) having three or less (meth) acryloyl groups can be used alone or in combination of two or more as appropriate. Above all, it is preferable to use a mixture of two or more kinds, preferably three kinds of monomers of the component (a). The viscosity can be appropriately adjusted by mixing two or more kinds of monomers having three or less (meth) acryloyl groups.

The content of the monomer having (a) 3 or less (meth) acryloyl groups is usually 25 to 90% by mass, preferably 30 to 80% by mass, based on 100% by mass of the dental surface smoothing composition. More preferably, it is 40 to 70% by mass.

(B) Monomer having 4 or more (meth) acryloyl groups The dental surface smoothing composition of the present invention is (b) a monomer having 4 or more (meth) acryloyl groups (hereinafter, "component (b)". In some cases, it contains) as an essential ingredient.
When the dental surface smoothing composition of the present invention contains a monomer having four or more (meth) acryloyl groups, the applicability (operability) to the surface of the biological hard tissue or the dental material is improved, and the shortness is shortened. Since the curing reaction proceeds over time, a cured product having high hardness can be formed by increasing the crosslink density without being affected by oxygen inhibition during polymerization.

A monomer having 4 or more (meth) acryloyl groups contains 4 or more, preferably 4 to 6, and more preferably 6 acryloyl groups or methacryloyl groups in one molecule. Specifically, a monomer having four or more (meth) acryloyl groups includes a monomer having four acryloyl groups or methacryloyl groups in one molecule (tetrafunctional (meth) acrylate monomer), and an acryloyl group in one molecule. Alternatively, a monomer having 5 methacryloyl groups (pentofunctional (meth) acrylate monomer), a monomer having 6 acryloyl groups or methacryloyl groups in one molecule (six-functional (meth) acrylate monomer), and the like are included.

(B) As the monomer having four or more (meth) acryloyl groups, one type may be used alone, or two or more types may be used in combination.

Examples of the tetrafunctional (meth) acrylate monomer include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol tetraacrylate, and dimethylolpropane tetra (meth) acrylate.
Examples of the pentafunctional (meth) acrylate monomer include dipentaerythritol penta (meth) acrylate.
Examples of the hexafunctional (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate.
(B) Dipentaerythritol hexaacrylate (DPHA) and ethoxylated dipentaerythritol tetraacrylate are preferable as the monomer having four or more (meth) acryloyl groups.

The content of the monomer (b) (meth) acryloyl group having a tetrafunctional group or more is usually 4 to 65% by mass, preferably 10 to 60% by mass with respect to 100% by mass of the dental surface smoothing composition. , More preferably 15 to 50% by mass.

(C) Compound containing a plurality of thiol groups The dental surface smoothing composition of the present invention contains a compound containing a plurality of thiol groups (hereinafter, may be referred to as “component (c)”) as an essential component. contains.
The compound containing a plurality of thiol groups is not particularly limited as long as it is a compound containing two or more thiol groups that function as a chain transfer agent in the polymerization reaction. The number of thiol groups is preferably 3 to 6, more preferably 4 to 6.
The thiol group contained in the component (c) functions as a chain transfer agent in the radical polymerization reaction, and reacts with the growth end of the polymer to stop the growth reaction, and at the same time, the regenerated thienyl radical is used as a monomer. A reaction that reacts and re-grow) occurs. On the other hand, since there is still a thiol residue at the starting end, there is room for polymerization to start from there as well, and cross-linking occurs by a reaction different from the cross-linking structure by the component (b). In addition, the compound containing a plurality of thiol groups has a flexible molecular structure, and by adding this, the stress is relieved by reducing the polymerization shrinkage, and it is possible to suppress the generation of strain during curing. ..
Therefore, by including the compound containing a plurality of thiol groups, the polymerization reactivity of the dental surface smooth composition can be enhanced to improve the hardness, and the strain at the time of curing can be suppressed.

Examples of the compound containing a plurality of thiol groups include a mercaptoethylcarbonyl group (HS- (CH ₂ ) ₂ C (= O)-) or a mercaptopropylcarbonyl group (HS- (CH ₂ ) ₃ C (= O)-). ) Is included in two or more. These compounds can be used alone or in combination of two or more as appropriate.

Examples of the compound containing two or more mercaptoethylcarbonyl groups include ethylenebis (thioglycolate) and pentaerythritol tetrakis-3-thioglycolate.
Examples of compounds containing two or more mercaptopropylcarbonyl groups include pentaerythritol tetrakis-3-thiopropionate (PETP), trimethylolpropanetris (3-mercaptopropionate) (TMMP), and dipentaerythritol hexakis. (3-Mercaptopropionate) and the like.

Among these, (c) pentaerythritol tetrakis-3-thiopropionate (PETP) and trimethylolpropane tris (3-mercaptopropionate) (TMMP) are preferable as compounds containing a plurality of thiol groups. Is.

The content of the compound (c) containing a plurality of thiol groups is usually 0.5 to 15% by mass, preferably 2 to 12% by mass, more preferably with respect to 100% by mass of the dental surface smoothing composition. Is 3 to 10% by mass.

(D) Polymerization Initiator The dental surface smoothing composition of the present invention contains (d) a polymerization initiator (hereinafter, may be referred to as "(d) component") as an essential component. (D) The polymerization initiator is not particularly limited as long as it is a generally used polymerization initiator, and a polymerization initiator used for dental applications is particularly preferable. Generally, different types of polymerization initiators are used depending on the polymerization means of the polymerizable monomer. In the present invention, since the photopolymerization reaction is used as the polymerization means, a photopolymerization initiator is used as the polymerization initiator.

As the photopolymerization initiator, a photopolymerization initiator that reacts with ultraviolet light or visible light to generate radicals can be used. Specifically, examples of the photopolymerization initiator include α-diketones such as diacetyl, acetylbenzoyl, benzyl (diphenylethandione), camphorquinone (CQ), 9,10-phenanthrenequinone, and acenaphthenequinone; benzoin. Benzophenone alkyl ethers such as methyl ether, benzoin ethyl ether, benzoin propyl ether; diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO) Acylphosphine oxide compounds such as 2,4-diethylthioxanthone, thioxanthone compounds such as methylthioxanthone; benzophenone compounds such as benzophenone, p, p'-dimethylaminobenzophenone, p, p'-dimethoxyaminobenzophenone. Can be mentioned. Acylphosphine oxide compounds are preferable as the photopolymerization initiator. Here, p means para. These can be used alone or in combination of two or more as appropriate.

The content of the (d) polymerization initiator is usually 0.8 to 4.5% by mass, preferably 1.0 to 4.3% by mass, based on 100% by mass of the dental surface smoothing composition. , More preferably 1.5 to 4.0% by mass.

(E) Inorganic filler The dental surface smoothing composition of the present invention may further contain an inorganic filler. When the dental surface smoothing composition of the present invention contains an inorganic filler, a cured product having a higher hardness can be obtained.

The inorganic filler is not particularly limited, and is, for example, particles of an oxide such as silicon, tin, titanium, aluminum, cerium (silicon dioxide (silica), tin oxide, titanium oxide, aluminum oxide, cerium oxide, etc.), and Particles of these composite oxides can be mentioned. The inorganic filler may contain one kind or two or more kinds of inorganic fillers. Among them, the preferable inorganic filler is silica particles.

The silica particles are not particularly limited, and examples thereof include spherical or amorphous silica such as colloidal silica, fumed silica, and precipitated silica. Specifically, the silica particles include, for example, Admanano (registered trademark) series such as YC100C, YA050C and YA010C manufactured by Admatex, UFP-30 manufactured by Denka, and NSS-4N and NSS-5N manufactured by Tokuyama. Silfil (registered trademark) series such as, Organo silica sol series such as MEK-ST manufactured by Nissan Chemical Industries, RX50, R974, R812, OX50, OX130, OX200 silica manufactured by Evonik, etc. Can be mentioned. These can be used alone or in combination of two or more as appropriate.

The average particle size of the silica particles is not particularly limited, but is usually 1 to 100 nm, preferably 10 to 80 nm, and more preferably 20 to 70 nm. The average particle diameter means the arithmetic average diameter (volume average diameter) in the particle size distribution measured by the laser diffraction / scattering method.

The shape of the silica particles is not particularly limited, and for example, spherical particles, crushed particles, and the like are used. A cluster of primary particles having these shapes may be used, but a monodisperse is preferable. Further, it may be a combination of different shapes. In the present invention, some treatment (for example, pulverization) may be performed so as to have the above-mentioned shape.

Further, the silica particles may be surface-treated. As the surface treatment method, a known method is adopted and is not particularly limited. The surface treatment agent used for the surface treatment is also not particularly limited.

As the surface treatment agent, a compound usually used as a surface modifier of an inorganic oxide can be used, and for example, 3- (meth) acryloxypropyltrimethoxysilane (3-MPTS), vinyltriethoxysilane. , 3-Aminopropylethoxysilane, 3-chloropropyltrimethoxysilanesilylsilane, silane coupling agents such as vinyltrichlorosilane and the like. Among them, a preferable surface treatment agent is 3- (meth) acryloxylpropyltrimethoxysilane (3-MPTS).

The method for treating the silica particles with the surface treatment agent is not particularly limited, and for example, the silica particles and the surface treatment agent are placed in a solvent such as alcohol for several tens of minutes to about 10 hours, preferably about 1 hour. Examples thereof include a method in which the solvent is removed after heating and recirculating within a range of 5 hours, and the particles are dried under normal pressure or reduced pressure. When it is necessary to promote the hydrolysis of the surface treatment agent, a method of adding water or acidic water such as acetic acid to the solvent at the time of heating and refluxing may be used.

When the inorganic filler is blended, the inorganic filler can be usually added up to 40% by mass with respect to 100% by mass of the dental surface smoothing composition, preferably 5 to 35% by mass, and 10 to 30% by mass. Is more preferable.

(F) Polymerization Accelerator The dental surface smoothing composition of the present invention may further contain (f) a polymerization accelerator. (F) The polymerization accelerator is not particularly limited, and is generally used in combination with a photopolymerization initiator. The polymerization accelerator is not particularly limited, and is, for example, 2- (dimethylamino) ethyl methacrylate (DMAEMA), 2- (dimethylamino) ethyl methacrylate, ethyl methacrylate, 2- (dimethylamino) benzoic acid n. -Butoxyethyl, N, N-dimethyl-p-toluidine, ethyl 4-dimethylaminobenzoate (DMAEB) and the like can be mentioned. These can be used alone or in combination of two or more as appropriate. The (f) polymerization accelerator is a compound different from the above-mentioned (a) monomer having three or less (meth) acryloyl groups.

(F) When the polymerization accelerator is blended, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, and more preferably 0 with respect to 100% by mass of the dental surface smoothing composition. It can be added in a proportion of 1 to 3% by mass.

(G) Optional component The dental surface smoothing composition of the present invention is further, if necessary, a coloring pigment, an emulsion material, or a fluorescent material as long as the effect of the dental surface smoothing composition of the present invention is not impaired. , Opalizing materials, polymerization inhibitors, antioxidants, antibacterial agents, X-ray contrast agents, stabilizers, ultraviolet absorbers, anticoloring agents, silane coupling agents, fluorescent whitening agents, adhesive components, etc. Various additives can be blended. These can be used alone or in combination of two or more as appropriate.

(G) When an arbitrary component is blended, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, and more preferably 0.1 with respect to 100% by mass of the dental surface smoothing composition. It can be added in a proportion of up to 3% by mass.

2. 2. Method for Producing Dental Surface Smooth Composition The dental surface smooth composition material of the present invention comprises the above-mentioned (a) a monomer having 3 or less (meth) acryloyl groups, and (b) 4 or more (meth). It can be produced by blending a monomer having an acryloyl group, (c) a compound containing a plurality of thiol groups, and (d) a polymerization initiator in the above-mentioned specific ratios.

Further, the dental surface smoothing composition of the present invention comprises the above-mentioned (a) a monomer having 3 or less (meth) acryloyl groups, (b) a monomer having 4 or more (meth) acryloyl groups, and (c). It can be produced by blending the above-mentioned (e) inorganic filler with the compound containing a plurality of thiol groups and (d) the polymerization initiator in the above-mentioned specific ratio.

The dental surface smoothing composition of the present invention further comprises (f) a polymerization accelerator, (g) an optional component (for example, a coloring pigment, an emulsion material, a fluorescent material, an opalizing material, and a polymerization inhibitor), if necessary. , Antioxidants, antibacterial agents, X-ray contrast agents, stabilizers, ultraviolet absorbers, discoloration inhibitors, silane coupling agents, fluorescent whitening agents, adhesive components, etc.) can be appropriately blended.

Since the dental surface smoothing composition of the present invention contains a polymerization initiator, care must be taken in its handling, and it is preferable to fill it in a highly airtight bottle or the like and store it in a cool and dark place.

The method for producing a dental surface smoothing composition of the present invention includes a step of taking a predetermined amount of each of the above components in a container, mixing them sufficiently, and dispersing them to obtain a mixture. Further, when air bubbles are mixed in the mixture, a step of kneading the mixture under reduced pressure or vacuum stirring can be provided for the purpose of removing air bubbles. The dental surface smoothing composition thus obtained is in a uniform and bubble-free state.

The order of addition of each of the above components is not particularly limited, and for example, (a) a monomer having 3 or less (meth) acryloyl groups, (b) a monomer having 4 or more (meth) acryloyl groups, and (c). ) A compound containing a plurality of thiol groups and (d) a polymerization initiator can be added simultaneously or sequentially. When a volatile component is used as the component, it is desirable that the order of addition is the last.

Further, if necessary, the above-mentioned (e) inorganic filler, (f) polymerization accelerator, or (g) optional component can be added. The order of addition is not particularly limited. For example, (a) a method comprising a step of adding a monomer having 4 or more (meth) acryloyl groups to a monomer having 3 or less (meth) acryloyl groups; (b) 4 or more. A step of preparing a mixture of a monomer having a (meth) acryloyl group and (e) an inorganic filler, and then a step of adding (a) a monomer having three or less (meth) acryloyl groups to the mixture. (A) A mixture of (e) an inorganic filler and (b) a monomer having four or more (meth) acryloyl groups is added to a monomer having three or less (meth) acryloyl groups. Further, a method including (f) a step of adding a polymerization accelerator and (g) an optional component can be mentioned.

The dental surface smoothing composition of the present invention can be polymerized according to a known photopolymerization method to obtain a cured product.

3. 3. Method for Curing Dental Surface Smoothing Composition The dental surface smoothing composition of the present invention can be polymerized and cured by irradiation with light. The method of polymerizing and curing by light irradiation differs depending on the type of the photopolymerization initiator, and a wavelength of ultraviolet rays can also be used, but the polymerization is cured by irradiating with light at a wavelength of visible light which is usually harmless to the human body. The wavelength of the light is, for example, preferably in the range of 250 to 700 nm, more preferably 300 to 500 nm, still more preferably 380 to 420 nm.

The light source in the wavelength range is not particularly limited, and for example, light such as an LED lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a laser, a fluorescent lamp, and sunlight can be used.

The irradiation time of the light varies depending on the thickness, transparency, color tone and amount of light of the irradiation light of the dental prosthesis obtained from the dental surface smooth composition, but is generally determined appropriately according to the desired polymerization time. good. Light irradiation is preferably performed for about 5 to 3 minutes, more preferably 10 to 120 seconds, and even more preferably 20 to 60 seconds.

The dental surface smooth composition includes not only the state before curing but also the meaning of the cured body (cured product or cured film) after curing obtained by irradiating the dental surface smooth composition with light. .. Since it is currently impossible or nearly impractical to determine the structure of this cured product completely, the product-by-process claim describes the cured product.

The cured product of the dental surface smoothing composition of the present invention after polymerization curing is excellent in durability. Specifically, the pencil hardness of the surface of the dental surface smooth composition applied and cured on the evaluation pellets is 4H or more, preferably 6H or more, and more preferably 8H or more. Considering that there is a problem in abrasion resistance and the pencil hardness of the dental acrylic resin material mainly used for temporary (short-term) applications is about H to 4H, the dental surface smooth composition It is considered that the pencil hardness of the cured product needs to be 4H or more. It can be said that the larger the pencil hardness is, the less scratches are made on the surface, the longer the gloss is maintained, and the more durable the material is.

The dental surface smoothing composition of the present invention is easy to apply to the surface of a biological hard tissue or a dental material, and is excellent in applicability (operability). Specifically, the spread (area) when 5 μL of the dental surface smoothing composition is dropped onto the evaluation pellets is in the range of 10 mm ² to 120 mm ² . Within the above range, it spreads moderately at the time of coating, so that it is excellent in coatability, and the film to be formed has an appropriate thickness, and no handwriting remains after curing, so that it is excellent in smoothness.

The dental surface smoothing composition of the present invention has little discoloration due to photocuring. Specifically, the color difference (ΔE) of the color tone of the dental surface smooth composition after being applied and cured on the evaluation pellet is small with respect to the color tone of the white evaluation pellet. The color difference (ΔE) can be calculated by the following formula. Note that Δ means delta.
Equation: ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
ΔL ^* = L ₁ ^* -L ₂ ^*
Δa ^* = a ₁ ^* -a ₂ ^*
Δb ^* = b ₁ ^* -b ₂ ^*
here,
L ₁ ^* : Brightness of the dental surface smooth composition after curing a ₁ ^* , b ₁ ^* : Chromaticity of the dental surface smooth composition after curing L ₂ ^* : Brightness of the evaluation pellets a ₂ ^* , b ₂ ^* : The chromaticity of the evaluation pellets.

When the dental surface smoothing composition of the present invention was uniformly applied to the surface of white evaluation pellets so as to have a thickness of 20 to 30 μm and cured, the color difference (ΔE) calculated by the above formula was 3.0. Hereinafter, it is preferably 2.5 or less, and more preferably 2.0 or less. The dental surface smooth composition is required not to affect the color tone of the hard tissue to be applied or the dental material, but if ΔE is 3.0 or less, it cures when visually observed. Since the color before and after curing is close to transparent and it is difficult to recognize the change in color, it can be said that the influence on the color tone of the biological hard tissue or the dental material is small.
Here, the value of the color difference (ΔE) changes depending on the thickness of the composition applied to the surface of the evaluation pellets and the color tone of the evaluation pellets. For example, if the thickness of the composition to be applied is reduced or the chromaticity (redness or yellowness) of the evaluation pellet is increased, the color difference (ΔE) becomes smaller.
The dental surface smooth composition is generally not white, but is applied to the surface of a slightly yellowish ivory-colored (tooth-colored) material with a thickness of 5 to 20 μm. As a method for evaluating the color difference performed in the examples, the conditions considered to be the strictest were set assuming the actual use of the dental surface smoothing composition.

The dental surface smoothing composition of the present invention has a small strain during curing. Specifically, the amount of curing strain when the dental surface smoothing composition is filled in a silicon mold of a specific size, covered with a transparent PET film, and then cured is preferably 0.80 mm or less. It is 0.60 mm or less, more preferably 0.40 mm or less. When the amount of curing strain is 0.80 mm or less, peeling or cracking is less likely to occur even when the thickness of the cured product is increased by overcoating the dental surface smoothing composition clinically.

4. Applications The dental surface smoothing composition of the present invention is applied to the surface of a biological hard tissue or a dental material such as a dental filler, a crown restoration material, a dental prosthesis, etc., and is used for dentistry to give a gloss. It is suitably used as a coating material, particularly as a dental surface lubricant.

The biological hard tissue to be applied is not particularly limited, and examples thereof include teeth (enamel or dentin). These biological hard tissues are mainly composed of inorganic components such as hydroxyapatite and proteins such as collagen.

Examples of the dental filler to be applied include composite resins for dental filling, examples of the crown restoration material include inlays, onlays, crowns, bridges, and the like, and examples of the dental prosthesis include dentures. The resin material used for these is not particularly limited, and for example, a dental resin obtained by curing a (meth) acrylate-based polymerizable monomer containing inorganic particles as a reinforcing material, and other dental resins (made of polyester). , Polyamide, polycarbonate, etc.) and the like.

The dental surface smoothing composition of the present invention is not only used for dentistry, but also for filling and repairing recesses of articles; filling and repairing materials for holes in articles (for example, filling and repairing materials for cracks, scratches, holes, etc. in articles). It can also be used as a surface lubricant for articles, a convex forming material for articles; a cured product (cured material) for serving articles, and a coating material for nails and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited to these examples.

The raw materials used in Examples and Comparative Examples are shown below.

[(A) Monomer having 3 or less (meth) acryloyl groups]
(A-1) MMA: Methyl Methacrylate, (a-2) TPGDA: Tripropylene Glycol Diacrylate, (a-3) TMPTA: Trimethylolpropane Triacrylate [(b) 4 or more (meth) acryloyl groups Monomer to have]
(B-1) DPHA: dipentaerythritol hexaacrylate ・ (b-2) ATM-4E: ethoxylated pentaerythritol tetraacrylate [(c) a compound containing a plurality of thiol groups]
・ (C-1) PETP: Pentaerythritol tetrakis-3-thiopropionate ・ (c-2) TMMP: Trimethylolpropanetris (3-mercaptopropionate)
[(D) Polymerization Initiator]
(D-1) TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide ・ (d-2) BAPO: Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide [(e) Inorganic filler]
-Silica particles (average particle diameter 50 nm)

(Example 1)
(A-1) component 21.2 parts by mass, (a-2) component 2.9 parts by mass, (a-3) component 4.8 parts by mass, (b-1) component 62.5 parts by mass, (c) -1) 4.8 parts by mass of the component and 3.8 parts by mass of the component (d-1) were mixed under shading to obtain a dental surface smooth composition.

(Examples 2 to 10 and 13 to 16)
Each dental surface smooth composition was produced by the same method as in Example 1 except that the blending ratios shown in Table 1, Table 2 or Table 4 below were used.

(Example 11)
29.2 parts by mass of (e) component was added to 13.6 parts by mass of (b-1) component and mixed, and 36.9 parts by mass of (a-1) component was added to the obtained mixture. -2) 4.9 parts by mass of the component, 8.8 parts by mass of the (a-3) component, 3.9 parts by mass of the (c-1) component, and 2.7 parts by mass of the (d-1) component. It was added and mixed under shading to give a dental surface smooth composition.

(Example 12)
A dental surface smooth composition was produced by the same method as in Example 11 except that the blending ratios shown in Table 3 below were used.

(Comparative Examples 1 to 11)
Each comparative composition was produced by the same method as in Example 1 except that the blending ratios shown in Table 1, Table 2 or Table 4 below were used.

Evaluation of Dental Surface Smooth Composition The pencil hardness, coatability, color difference, glossiness, and hardening of the dental surface smooth composition obtained in each of the above Examples and the comparative composition obtained in each Comparative Example were obtained. The amount of strain was measured by the following method.

[Pencil hardness]
Pencil hardness was measured according to JIS K 5600-5-4: 1999.
A hard resin for crown (YAMAKIN, Luna Wing (registered trademark) Enamel E3) is filled in a mold (diameter 15 mm, thickness 1.0 mm), and a photopolymerizer (YAMAKIN, LED cure master) is used. It was cured by irradiating it with LED light having a wavelength of 375 to 495 nm for 180 seconds. The coated surface was polished using P1000 water-resistant abrasive paper. After polishing, it was washed in ethanol for 10 minutes using an ultrasonic cleaner and then dried to prepare pellets for evaluation. The dental surface smoothing composition is uniformly applied to the surface of the evaluation pellet, and is irradiated with LED light having a wavelength of 375 to 495 nm for 60 seconds using a photopolymerization device (LED Cure Master manufactured by YAMAKIN) for testing. A sample was prepared. The pencil lead was cut with a cutter so that it had a smooth columnar shape and the exposed part of the lead was 5 to 6 mm. In order to flatten the tip of the pencil lead, the pencil was vertically applied to the polishing paper of P1000 and moved back and forth to polish (the above operation was repeated for each test). The pencil was pressed against the coating film at 45 ± 1.0 degrees and a load of 750 ± 10 g, moved at a speed of 0.5 to 1.0 mm, and moved at a distance of at least 7 mm. It was carried out up to 10 hours, and the presence or absence of indentations was visually confirmed. The hardness of the hardest pencil that did not cause scratches was taken as the pencil hardness of the test sample (n = 2). When the pencil hardness was 4H or more, it was evaluated as "◯", and when it was 3H or less, it was evaluated as "x".

[Applicability]
FIG. 1 is a schematic diagram illustrating a coatability test. Hereinafter, the test method of the coatability test will be described with reference to FIG.
A hard resin for crown (YAMAKIN, Luna Wing (registered trademark) Enamel E3) is filled in a mold (diameter 15 mm x thickness 1.0 mm), and a photopolymerizer (YAMAKIN, LED cure master) is used. It was cured by irradiating it with LED light having a wavelength of 375 to 495 nm for 180 seconds. The coated surface was polished using P1000 water-resistant abrasive paper. After polishing, it was washed in ethanol for 10 minutes using an ultrasonic cleaner and then dried to prepare pellets for evaluation ((1) in FIG. 1). After 5 μL of the dental surface smoothing composition was dropped onto the surface of the evaluation pellet with a micropipette ((2) in FIG. 1), the area of the dental surface smoothing composition when it spread to the maximum and stopped spreading was determined. Measured with a microscope (VHX (registered trademark) -660 manufactured by KEYENCE CORPORATION) (n = 2) ((3) in FIG. 1).
When the area was 10 to 120 mm ² , it was evaluated as “◯”, and when it was less than 10 mm ² and exceeded 120 mm ² , it was evaluated as “x”.

[Color difference (ΔE)]
A hard resin for crown (YAMAKIN, Luna Wing (registered trademark) Invisible Opaque IvO) is filled in a mold (diameter 15 mm x thickness 1.0 mm), and a photopolymerization device (YAMAKIN, LED cure master) is used. Then, LED light having a wavelength of 375 to 495 nm was irradiated for 180 seconds to cure the mixture, and white pellets were prepared. The coated surface was polished using P1000 water-resistant abrasive paper. After polishing, it was washed in ethanol for 10 minutes using an ultrasonic cleaner and then dried to prepare white evaluation pellets. The dental surface smoothing composition is uniformly applied to the surface of the evaluation pellet so as to have a thickness of 20 to 30 μm, and LED light having a wavelength of 375 to 495 nm is used using a photopolymerization device “(LED Cure Master, manufactured by YAMAKIN)). For 60 seconds, the color difference (ΔE) of the color tone of the dental surface smooth composition after being applied on the evaluation pellet and cured with respect to the color tone of the white evaluation pellet with a colorimeter. Calculated (n = 3).
When the color difference (ΔE) was 3.0 or less, it was evaluated as “◯”, and when it exceeded 3.0, it was evaluated as “x”.
The color difference (ΔE) of the dental surface smooth composition is derived from the component (d) among the components constituting the dental surface smooth composition, and the cause is that the component itself is colored, and , May be colored by photopolymerization reaction. Therefore, the color difference (ΔE) was measured for the compositions of Examples 13 to 16 and Comparative Examples 6 to 11 in which the content of the component (d) was changed from 0.5 parts by mass to 10 parts by weight. The results are shown in Table 4.
Further, in the compositions of Examples 1 to 12 and Comparative Examples 1 to 5 in which the color difference (ΔE) was not measured, the component (d) was 1 to 3.8 parts by mass, so that the color difference (ΔE) was obtained. Is expected to be 3.0 or less.

[Glossiness]
A hard resin for crown (YAMAKIN, Luna Wing (registered trademark) Invisible Opaque IvO) is filled in a mold (diameter 15 mm x thickness 1.0 mm), and a photopolymerization device (YAMAKIN, LED cure master) is used. The white pellets were prepared by irradiating with LED light of 375 to 495 nm for 180 seconds and curing. The coated surface was polished using P1000 water-resistant abrasive paper. After polishing, it was washed in ethanol for 10 minutes using an ultrasonic cleaner and then dried. The dental surface smoothing composition is uniformly applied to the pellet surface so as to have a thickness of 20 to 30 μm, and LED light having a wavelength of 375 to 495 nm is emitted for 60 seconds using a photopolymerization device (LED Cure Master manufactured by YAMAKIN). Irradiation was performed to prepare a sample for evaluation. The surface coated with the dental surface smoothing composition of the evaluation sample was visually observed by three people with normal color vision under a fluorescent lamp (n = 3), and evaluation was performed in the following three stages.
〇: Glossy △: Glossy, but handwriting remains and is not smooth ×: No gloss or hardening

[Hardening strain amount]
FIG. 2 is a schematic diagram illustrating a test for the amount of curing strain. Hereinafter, a test method for the amount of curing strain will be described with reference to FIG.
As shown in FIG. 2, the dental surface smoothing composition of the present invention is dropped and filled in a silicon mold (diameter 15 mm × depth 1.0 mm) ((1) in FIG. 2) having an open upper surface (FIG. 2). 2 (2)), cover with a transparent PET film so that the upper surface of the dental surface smooth composition is flat ((3) in Fig. 2), and a photopolymerizer (LED Cure Master manufactured by YAMAKIN). Was irradiated with LED light having a wavelength of 375 to 495 nm for 60 seconds ((4) in FIG. 2) to prepare a cured sample ((5) in FIG. 2).
The total thickness of the cured sample after light irradiation was measured four times in 45 degree increments using a digital caliper (ABS Digimatic (registered trademark) caliper manufactured by Mitutoyo Co., Ltd.) (FIG. 2 (6)). From the average value of the four measured values and the thickness (1.0 mm) of the composition before curing, the amount of deformation (curing strain amount) was calculated by the following formula.
Formula: [Hardening strain amount (mm)] =
[Thickness of composition after curing (mm)]-[Thickness of composition before curing (1.0 mm)]
When the amount of curing strain was less than 0.80 mm, it was evaluated as "◯", and when it was 0.80 mm or more, it was evaluated as "x" (cracks may occur).

<Result>
From the test results in Tables 1 to 4, the dental surface smoothing compositions of Examples 1 to 16 were obtained with good evaluation. That is, the dental surface smoothing compositions of Examples 1 to 16 are excellent in coatability and have excellent adhesion because the amount of hardening strain is less than 0.80 mm. Further, the cured product of the surface smoothing composition of Examples 1 to 16 has excellent durability because the pencil hardness is 4H or more, is glossy, and has a color difference (ΔE) of 3.0 or less. Therefore, it has excellent aesthetics.
The comparative composition of Comparative Example 1 had poor coatability because the component (a) was small. Since the comparative composition of Comparative Example 2 did not contain the component (b), the pencil hardness was as low as 2H, and the coatability was also poor. In the curing strain amount test of Comparative Example 2, since the thickness of the sample was 1.0 mm, the curing did not proceed sufficiently and the sample could not be prepared. The comparative composition of Comparative Example 3 did not contain the component (c) and did not cure due to the small amount of the component (d), so that the pencil hardness test could not be performed. On the other hand, a sample used for the curing strain amount test could be prepared and the test could be carried out. This is because in the curing strain amount test, when a sample is prepared, the polymerization is polymerized by irradiating it with light while the sample is covered with a transparent PET film, so that the polymerization inhibition due to oxygen is suppressed and the polymerization curing progresses sufficiently. It is probable that it was done. In the comparative composition of Comparative Example 5, the pencil hardness was as low as 2H because the amount of the component (c) was large. In the comparative composition of Comparative Example 6, the pencil hardness was as low as 2H because the blending amount of the component (d) was small. In the comparative compositions of Comparative Examples 7 to 10, the color difference (ΔE) was larger than 3 because the amount of the component (d) was large. Since the comparative composition of Comparative Example 11 did not contain the component (c) and contained a large amount of the component (d), the amount of curing strain was large and the color difference (ΔE) was larger than 3.

Claims (8)

(A) Monomer having 3 or less (meth) acryloyl groups,
(B) Monomer having 4 or more (meth) acryloyl groups,
A dental surface smoothing composition containing (c) a compound containing a plurality of thiol groups and (d) a polymerization initiator.
The (d) polymerization initiator is a photopolymerization initiator.
With respect to 100% by mass of the dental surface smoothing composition
25 to 90% by mass of the above-mentioned (a) monomer having 3 or less (meth) acryloyl groups.
(B) 4 to 65% by mass of the monomer having 4 or more (meth) acryloyl groups.
(C) A dental surface smooth composition containing 0.5 to 15% by mass of a compound containing a plurality of thiol groups and 0.8 to 4.5% by mass of the above (d) polymerization initiator. The dental surface smoothing composition according to claim 1, wherein the compound (c) containing a plurality of thiol groups is a compound containing two or more mercaptoethylcarbonyl groups or mercaptopropylcarbonyl groups. (C) At least one compound selected from the group in which the compound containing a plurality of thiol groups consists of pentaerythritol tetrakis-3-thiopropionate and trimethylolpropanetris (3-mercaptopropionate). The dental surface smoothing composition according to claim 1 or 2. The dental surface smoothing composition according to any one of claims 1 to 3, wherein the polymerization initiator (d) is an acylphosphine oxide-based compound. At least one compound selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide as the (d) polymerization initiator. The dental surface smoothing composition according to any one of claims 1 to 4. The dental surface smoothing composition according to any one of claims 1 to 5, further comprising (e) an inorganic filler. The dental surface smoothing composition according to claim 6, wherein the content of the inorganic filler (e) is 40% by mass or less with respect to 100% by mass of the dental surface smoothing composition. The dental surface smoothing composition according to claim 6 or 7, wherein the inorganic filler (e) is silica particles.

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