JP7049106B2 - How to make a dental impression type - Google Patents

Description

The present invention relates to a method for manufacturing a dental impression type, a method for manufacturing a dental model using the obtained dental impression type, and a dental impression type made of a specific material.

Dental prostheses and occlusal splints used in dental treatment may be manufactured using dental models that have a shape that corresponds to the shape of the patient's dental tissue. Conventionally, such a dental model is made by applying an impression material made of silicone, agar, alginate, etc. to the dental tissue such as teeth in the oral cavity of a patient to manufacture a dental impression type, and then this dental impression type. It was manufactured by filling a model material such as plaster. However, the method of applying the impression material to the patient has a problem that the burden on the patient is large.

As a method for solving such a problem, a method using 3D digital data can be considered. In this method, 3D digital data such as dental tissue in the oral cavity is acquired by taking a picture of the oral cavity with a camera, and then the model material is milled based on the 3D digital data, or a 3D printer or the like. A target dental model can be manufactured by manufacturing a dental impression mold by the laminated modeling method according to the above method and then filling the dental impression mold with a model material such as plaster. As related to the latter method, for example, in Patent Document 1, when manufacturing an orthodontic appliance, digital data representing at least a part of a patient's dental tissue is acquired and the digital data is used. A method of forming a negative mold, manufacturing a dental model from the negative mold, and manufacturing a target orthodontic appliance using the dental model is described.

Special Table 2010-54087 Gazette

When manufacturing a dental model using a conventional dental impression mold, the dental impression mold is filled with a model material such as plaster to form a dental model, and then the dental impression mold is taken out. Was difficult. In addition, it may be necessary to prepare multiple dental models with the same shape, but the conventional dental impression type is the same because the dental impression type is easily damaged when the dental model is taken out. It was difficult to obtain multiple dental models with shapes.

Therefore, the present invention can easily manufacture a dental impression type that can easily take out a dental model and easily obtain a plurality of dental models having the same shape without imposing an excessive burden on the patient. It is an object of the present invention to provide a method for producing a dental impression type that can be used. Further, according to the present invention, a dental model using the dental impression type obtained by the manufacturing method can be easily taken out and a plurality of dental models having the same shape can be easily obtained. It is an object of the present invention to provide a manufacturing method and a dental impression type in which a dental model can be easily taken out and a plurality of dental models having the same shape can be easily obtained.

As a result of diligent studies to achieve the above object, the present inventors have selected a material to be used when manufacturing a dental impression type using 3D digital data such as dental tissue, and the like is obtained for dentistry. By setting the flexural modulus of the material constituting the impression type within a specific range, the dental impression type can be easily taken out and a plurality of dental models having the same shape can be easily obtained. Was found to be able to be easily produced without imposing an undue burden on the patient, and further studies were conducted based on the findings to complete the present invention.

That is, the present invention relates to the following [1] to [17].
[1] A step (1) of acquiring digital data representing at least a part of the dental tissue, and a step of forming a dental impression type having a shape corresponding to the outer shape of the at least a part using the digital data (1). A method for manufacturing a dental impression type including 2), wherein the flexural modulus of the material constituting the dental impression type is 5 to 300 N / mm ² .
[2] The manufacturing method according to [1], wherein the material constituting the dental impression mold has a tensile strength of 5 to 40 MPa.
[3] The production method according to [1] or [2], wherein the material constituting the dental impression mold has a tear strength of 5 to 50 kN / m.
[4] The production method according to any one of [1] to [3], wherein the dental impression type includes a portion corresponding to the labial tooth surface, and the thickness of the portion is 0.3 to 45 mm.
[5] The production method according to any one of [1] to [4], wherein the dental impression type includes a portion corresponding to the lingual tooth surface, and the thickness of the portion is 0.1 to 45 mm.
[6] The production according to any one of [1] to [5], wherein the dental impression type includes a portion corresponding to an occlusal surface and / or an incisal surface, and the thickness of the portion is 0.1 to 45 mm. Method.
[7] The production method according to any one of [1] to [6], which comprises a tooth whose at least a part thereof is paired with each other.
[8] The manufacturing method according to [7], wherein the relative position of each portion corresponding to the outer shape of the facing tooth is within the range of the relative position that the facing tooth can obtain.
[9] The relative positions that the opposing teeth can take are within the ranges of the sagittal condyle angle of 5 to 60 °, the lateral condyle angle of 1 to 20 °, and the immediate side shift of 0.1 to 4 mm. The manufacturing method according to [8], which is a relative position that can be obtained by jaw movement.
[10] The manufacturing method according to any one of [1] to [9], wherein the step (2) is performed by a laminated molding method.
[11] A method for manufacturing a dental model, which comprises a step of filling a dental impression mold obtained by the manufacturing method according to any one of [1] to [10] with a model material.
[12] The manufacturing method according to [11], wherein the model material is gypsum.
[13] The manufacturing method according to [11] or [12], wherein a plurality of dental models are manufactured using the same dental impression mold.
[14] A dental impression type having a shape corresponding to the outer shape of at least a part of the dental tissue, and having a flexural modulus of 5 to 300 N / mm ² of the constituent material.
[15] The dental impression type according to [14], which comprises teeth at least partially facing each other.
[16] The dental impression type according to [15], wherein the relative position of each portion corresponding to the outer shape of the facing tooth is within the range of the relative position that the facing tooth can take.
[17] The relative positions that the opposing teeth can take are within the ranges of a sagittal condyle angle of 5 to 60 °, a lateral condyle angle of 1 to 20 °, and an immediate side shift of 0.1 to 4 mm. The dental impression type according to [16], which is a relative position that can be obtained by jaw movement.

According to the present invention, a dental impression type that can easily take out a dental model and easily obtain a plurality of dental models having the same shape can be easily obtained without imposing an excessive burden on the patient. A method of manufacturing a dental impression type that can be manufactured is provided. Further, according to the present invention, a dental model using the dental impression type obtained by the manufacturing method can be easily taken out and a plurality of dental models having the same shape can be easily obtained for dentistry. Provided are a method for manufacturing a model and a dental impression type in which a dental model can be easily taken out and a plurality of dental models having the same shape can be easily obtained.

Hereinafter, the present invention will be described in detail. In the present specification, the upper limit value and the lower limit value of the numerical range (content of each component, value calculated from each component, each physical property, etc.) can be appropriately combined.
[Manufacturing method of dental impression type]
The dental impression type manufacturing method of the present invention has a step (1) of acquiring digital data representing at least a part of the tooth system tissue, and a shape corresponding to the outer shape of the at least part using the digital data. The step (2) of forming a dental impression type is included. The flexural modulus of the material constituting the dental impression type is 5 to 300 N / mm ² . By the manufacturing method of the dental impression type, the dental impression type that can easily take out the dental model and easily obtain a plurality of dental models having the same shape imposes an excessive burden on the patient. It can be easily manufactured without any need.

<< Process (1) >>
In step (1), digital data (typically 3D digital data) representing at least a part of the tooth system tissue is acquired. Examples of the dental tissue for which digital data is acquired include the entire oral tissue including teeth, maxillary dental arch, lower dental arch, one or more teeth, and the like. It may be only one or, if possible, two or more of them (eg, both maxillary and mandibular arches). Digital data may be acquired in an open state in which the maxillary dental arch and the lower dental arch are not in contact with each other, in a closed state in which they are in contact with each other, or in an open state and a closed state, respectively. Digital data may be acquired in.

The method for acquiring the above digital data is not particularly limited. For example, a method for acquiring digital data from the patient's dental tissue, a method for obtaining an impression type from the patient's dental tissue, and a method for acquiring digital data from this impression type. , A method of acquiring digital data from this dental model after obtaining a dental model corresponding to the patient's dental tissue. Among these, a method of acquiring digital data from the patient's dental tissue is preferable because it is possible to more easily manufacture a dental model that is closer to the shape of the patient's dental tissue.

Specific methods for acquiring digital data from the dental tissue of a patient include, for example, a direct intraoral optical measurement method, a pattern projection method, a method using an intraoral scanner such as an intraoral camera, and a method using X-rays. , Non-contact method that does not substantially contact the dental tissue such as a method using CT scan such as cone beam CT scan; contact method using an intraoral contact probe and the like. Among these, the non-contact method is preferable because the burden on the patient can be further reduced, the method using a CT scan and the method using an intraoral scanner are more preferable, and digital data can be acquired without powder. , Oral scanners are more preferred.

The obtained digital data is taken into CAD (Computer Aided Design) software as master data (basic data), processed as necessary, and then used for forming a dental impression type in step (2). be able to. By acquiring digital data representing at least a part of the dental tissue in step (1), it can be transferred or saved using e-mail, FTP (File Transfer Protocol) server, cloud service, or the like. be able to. The obtained digital data may be converted into various file formats (for example, STL format) as needed.

In the step (2) described later, all of the obtained digital data may be used, but only a part of the obtained digital data may be used. For example, among the obtained digital data, the target dental impression type may be used. Only the part corresponding to can be used. To use only a part of the obtained digital data, for example, a range line may be determined on CAD software to specify a range of necessary digital data. As an example of the range, the buccal side is up to the position corresponding to the gingival transition, the palate side is not defined, and the throat side is up to the transition to soft tissue. Within such a range, the oral cavity can be evenly included. The range of the digital data may be specified before the design of the dental impression type shape described later in the description of the step (2), or may be performed after the design.

<< Process (2) >>
In the step (2), the digital data acquired in the step (1) is used to form a dental impression type having a shape corresponding to the outer shape of at least a part of the tooth system tissue. Examples of the shape corresponding to the outer shape of at least a part of the tooth system tissue include a concave shape corresponding to the outer shape of at least a part of the tooth system tissue (such as the shape of a tooth). The shape corresponding to the outer shape of at least a part of the tooth system tissue may correspond to all the outer shapes of the tooth system tissue based on the digital data used in the step (2), but one of them. It may correspond only to a part. For example, as will be described later, when digital data is processed (such as processing to eliminate concave parts such as defective parts and scraped parts in the tooth system tissue), the dental impression type manufactured is the part that has not been processed. It suffices to have at least a shape corresponding to the outer shape of the dental tissue based on digital data.

In forming the dental impression type, it is preferable to design the shape of the dental impression type in advance by using the digital data acquired in the step (1).

When the target dental impression type includes a portion corresponding to the labial tooth surface (the wall portion in the dental impression type facing the labial tooth surface), the portion (wall portion) from the viewpoint of shape stability and the like. The thickness of the above is preferably 0.3 mm or more, more preferably 1 mm or more, further preferably 2 mm or more, preferably 45 mm or less, and more preferably 20 mm or less. It is more preferably 10 mm or less.

When the target dental impression type includes a portion corresponding to the lingual tooth surface (wall portion in the dental impression type facing the lingual tooth surface), the portion (wall portion) from the viewpoint of shape stability and the like. The thickness of the above is preferably 0.1 mm or more, more preferably 0.5 mm or more, further preferably 1 mm or more, preferably 45 mm or less, and preferably 20 mm or less. It is more preferably 10 mm or less, and even more preferably 10 mm or less.

When the target dental impression type includes a portion corresponding to the occlusal surface and / or the incisal surface (the bottom of the dental impression type facing the occlusal surface and / or the incisal surface), from the viewpoint of shape stability and the like. The thickness of the portion (bottom) is preferably 0.1 mm or more, more preferably 1 mm or more, further preferably 2 mm or more, and preferably 45 mm or less, preferably 20 mm or less. More preferably, it is more preferably 15 mm or less.

Further, in designing the shape of the dental impression type, at least a part of the digital data may be processed so that the dental impression type having a desired shape can be obtained. Examples of the processing include processing to reduce the size of the concave portion, processing to increase the size of the concave portion, and processing to eliminate the concave portion in the concave portion such as a defective portion or a scraped portion in the tooth system tissue. And so on. Further, the shape may be designed so as to newly provide a concave portion that does not originally exist in the tooth system tissue.

In the present invention, at least a part of the tooth system tissue for which digital data is acquired may include teeth facing each other (maxillary teeth and facing lower jaw teeth). In this case, in the manufactured dental impression type, the relative position of each part corresponding to the outer shape of the facing tooth can be taken in the living body of the patient (subject). By keeping it within the range of (relative position), it is easy to create a dental prosthesis with good occlusion and a dental model that can give an occlusal splint with excellent static stability and low pronunciation inhibition when placed in the oral cavity. It is possible to easily manufacture a dental impression type that can be manufactured.

Regarding the range of relative positions where the facing teeth can be obtained, the sagittal condyle angle is preferably 5 ° or more, more preferably 30 ° or more, and more preferably 60 ° or less. It is preferably 40 ° or less, and more preferably 40 ° or less. The lateral condyle path angle is preferably 1 ° or more, more preferably 4 ° or more, more preferably 20 ° or less, and even more preferably 10 ° or less. The immediate side shift is preferably 0.1 mm or more, more preferably 1 mm or more, preferably 4 mm or less, and more preferably 3 mm or less.

In the dental impression mold to be manufactured, for example, in order to make the relative position of each part corresponding to the outer shape of the facing tooth within the range of the relative position that the facing tooth can take, for example. In step (1), digital data on the labial side of the dental tissue is mainly acquired in a closed state where the upper and lower dental arches are in contact with each other, and the upper and lower dental arches are combined. Digital data of the upper and lower dental arches are acquired in a non-contact open state, and these digital data are synthesized on CAD software to stabilize the upper and lower dental arches. The occlusal position may be specified, and the relative position may be defined from the occlusal position. In defining the relative position from the stable occlusal position, if a virtual digital articulator is further coupled to the digital data synthesized on CAD software, the assumed jaw movement can be easily grasped. In the manufactured dental impression mold, it is easy to make the relative position of each part corresponding to the outer shape of the facing tooth within the range of the desired relative position that the facing tooth can obtain. become.

A specific method for forming a dental impression mold having a shape corresponding to the outer shape of at least a part of the dental tissue using the digital data is the flexural modulus of the material constituting the obtained dental impression mold. There is no particular limitation as long as the method can be within the range described later. For example, a method of milling a dental impression type forming material may be adopted, but a desired dental impression type can be more easily used. It is preferable to adopt the laminated molding method because it can be obtained.

The specific method of the laminated modeling method is not particularly limited as long as the flexural modulus of the material constituting the obtained dental impression mold can be within the range described later. For example, stereolithography is performed. Method; Fused deposition modeling method (FDM method) in which molten resins are laminated; a liquefied material (which may contain a binder or a material having a desired color) is sprayed and laminated. An inkjet method that repeats the above can be mentioned. Further, a method of injecting molten wax may be adopted. Among these, the stereolithography method is preferable because it is possible to more easily manufacture a dental model that is closer to the shape of the patient's dental tissue.

As an optical three-dimensional modeling method, a method of sintering or thermally melting a powder (thermoplastic resin powder, etc.) that can be sintered or thermally melted by optical energy is used (powder lamination modeling method). However, since it is not necessary to use a support material separately and it is possible to more easily manufacture a dental model that is closer to the shape of the patient's dental tissue, it is a liquid material that can be cured by optical energy. It is preferable to adopt a method of sequentially forming each layer having a desired shape by curing the layers with optical energy. Examples of the above-mentioned optical energy include those using an active energy ray, and the optical energy can be imparted by irradiation with the active energy ray.

The type of active energy ray is not particularly limited, and examples thereof include ultraviolet rays, visible rays, infrared rays, electron beams, X-rays, radiation, and high frequencies. Among these, ultraviolet rays or visible light are preferable, ultraviolet rays or visible light having a wavelength of 300 to 450 nm is more preferable, and ultraviolet rays or visible light having a wavelength of 300 to 400 nm are further preferable. Examples of the light source of the active energy ray include various lasers (for example, semiconductor-excited solid-state laser, Ar laser, He-Cd laser, LED laser, etc.), halogen lamps, xenon lamps, metal halide lamps, LEDs, and various mercury lamps (high-pressure mercury lamps, etc.). Ultra-high pressure mercury lamp, low pressure mercury lamp, etc.), fluorescent lamp, etc., and laser is preferable. If a laser is used as a light source, the energy level can be increased and the molding time can be shortened, and a dental impression type with high molding accuracy can be obtained by utilizing the good light collecting property.

When irradiating the active energy rays, a method of irradiating the active energy rays focused in dots such as a laser by a line drawing method may be adopted, or a liquid crystal shutter, a digital micromirror shutter (DMD), etc. may be adopted. A method of irradiating an active energy ray through a planar drawing mask formed by arranging a plurality of small light shutters may be adopted.

As a specific method for sequentially forming each layer having a desired shape by using a liquid material that can be cured by optical energy and curing it with optical energy, for example, a free liquid level method is used. The regulated liquid level method is preferable because it is possible to more easily manufacture a dental model that is closer to the shape of the patient's dental tissue.

In the free liquid level method, the layer is locally hardened by irradiating the liquid material with active energy rays from the upper side of the container containing the liquid material to sequentially form a dental impression type one by one. In this process, a liquid material for forming the next layer on the hardened layer by precipitating one layer of the hardened layer formed near the liquid level of the liquid material contained in the container into the liquid material. Is arranged using a recorder or the like as necessary, and the operation of irradiating the arranged liquid material with active energy rays is repeated.

On the other hand, in the regulated liquid level method, the layer is locally hardened by irradiating the liquid material with active energy rays from the lower side of the container containing the liquid material through the bottom surface of the container, and the dental impression type is sequentially formed layer by layer. It will form. In this process, the cured layer is raised by one layer, and a liquid material for forming the next layer is flowed between the lower surface of the cured layer and the bottom surface of the container, and the liquid material is activated by the flowing liquid material. Repeat the operation of irradiating the energy ray.

In both the free liquid level method and the regulated liquid level method, the desired shape is obtained by irradiating the active energy ray according to the slice data of each layer based on the digital data corresponding to the target dental impression type 3D shape. It is possible to manufacture a dental impression mold having.

As the container used in the regulated liquid level method, a container in which at least a part of the bottom surface is optically transparent can be used. The entire bottom surface of the container may be formed of an active energy ray permeable material, or the peripheral portion of the bottom surface is formed of a material that does not transmit the active energy ray and is surrounded by the peripheral portion. May be formed from an active energy ray permeable material, and the area of the optically transparent portion on the bottom surface of the container can be determined according to the size of the desired dental impression type and the like. Examples of the active energy ray-permeable material include transparent glass and transparent plastic.

The liquid material that can be cured by the above-mentioned optical energy is not particularly limited, and examples thereof include a composition containing a polymerizable monomer and a photopolymerization initiator, a photocurable resin, and the like, and the obtained dental impression type can be obtained. Since each physical property such as the bending elasticity of the constituent material can be easily set within the range described later, the composition containing the polymerizable monomer and the photopolymerization initiator (hereinafter referred to as "modeling composition"). It may be referred to).

[Polymerizable monomer]
-Compounds (I)-(III)
The type of the polymerizable monomer contained in the modeling composition is not particularly limited, but each physical property such as the flexural modulus of the material constituting the obtained dental impression mold can be easily set within the range described later. Select from the group consisting of the compound (I) represented by the following formula (I), the compound (II) represented by the following formula (II), and the compound (III) represented by the following formula (III). It is preferable to contain at least one of these.

In the above formula (I), R ¹ is a hydrogen atom or a methyl group, a is 1 or 2, A ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and b is 3 It is an integer of up to 6, c is an integer of 3 to 14, and d is 2 or 3.

In formula (II) above, R ² and R ³ are independently hydrogen atoms or methyl groups, e is 1 or 2, and A ² is a divalent or trivalent unsubstituted or substituted hydrocarbon. It is a hydrogen group, f is an integer of 4 to 20, and g is 2 or 3.

In the above formula (III), R ⁴ and R ⁵ are independently hydrogen atoms or methyl groups, A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and h is 4. It is an integer of ~ 20, and j is 2 or 3.

In the above formula (I) relating to the compound (I), R ¹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable. a is 1 or 2, preferably 1. b is an integer of 3 to 6, and is preferably an integer of 4 to 6 from the viewpoint of stability of compound (I), ease of manufacture, and the like, and more preferably 5.

In the above formula (I), c is an integer of 3 to 14, preferably an integer of 3 to 10, and more preferably an integer of 3 to 6. When c is not more than the above upper limit, it is possible to suppress an excessive increase in the viscosity of the modeling composition, and the strength of the obtained dental impression type is also improved. Further, when c is at least the above lower limit, the flexibility and shock absorption of the obtained dental impression type are improved.

In the above formula (I), d is 2 or 3, preferably 2. When d is 2, the flexibility of the obtained dental impression type is more likely to be improved as compared with the case where d is 3.

In the above formula (I), A ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms. It is preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms, and more preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 13 carbon atoms. It is more preferably a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include a linear or branched alkylene group and an alkaneylene group. Examples of the alkylene group include hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group and hexa. Examples thereof include a decamethylene group, a heptadecamethylene group, an octadecamethylene group, a nonadecamethylene group, and an eikosamethylene group. Examples of the alkenylene group include a 1-hexenylene group, a 2-hexenylene group, a 3-hexenylene group and the like.

Examples of the alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group. Examples of the cycloalkylene group include a cyclohexylene group, a methylcyclohexylene group, a dimethylcyclohexylene group, a cycloheptylene group, a cyclooctylene group and the like. Examples of the cycloalkenylene group include a cyclohexenylene group, a cycloheptenylene group, a cyclooctenylene group, a cyclononenylene group, a cyclodecenylene group and the like.

Examples of the aromatic hydrocarbon group include an arylene group. Examples of the arylene group include a phenylene group, a tolylen group, a methylphenylene group, a xylylene group, a naphthylene group, an anthrasenylene group, a phenanthrylene group, a biphenylene group, a fluorene group and the like.

These hydrocarbon groups may be isomers, if any. Further, the hydrocarbon group may be a group in which two or more kinds selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined, for example, with an alkylene group. A combination with a cycloalkylene group; a combination of an alkylene group and an arylene group; a combination of a cycloalkylene group and an arylene group; a combination of an alkylene group, a cycloalkylene group and an arylene group may be used.

Examples of the substituent that the hydrocarbon group may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom); hydroxy group; amino group; linear or linear group having 1 to 12 carbon atoms. Examples thereof include a branched alkyl group; a linear or branched alkoxy group having 1 to 12 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; and an aryl group having 6 to 14 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert. -Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- Examples thereof include an undecyl group and an n-dodecyl group.

Examples of the linear or branched alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-pentyloxy group, and n-. Examples thereof include a hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-decyloxy group and an n-dodecyloxy group.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group and a cyclotetra. Examples thereof include a decyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, a cycloicosyl group and the like.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, an ethylphenyl group and an isopropyl group. Examples thereof include a phenyl group and a tetramethylphenyl group.
If there is an isomer, these substituents may be the isomer.

The number of substituents contained in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and even more preferably 1 to 4. Is particularly preferred. A ¹ may have one kind of substituent or may have two or more kinds of substituents.

As will be described later, compound (I) is preferably produced using a diisocyanate compound or a triisocyanate compound represented by the formula: A ¹ − (NCO) _d (A ¹ and d have the same meanings as described above). From this point of view, A ¹ is preferably a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or the triisocyanate compound used for producing the compound (I).

Preferred specific examples of A ¹ include, for example, an isophorondiyl group, a tolylen group, a 4,4'-diphenylmethanediyl group, a naphthylene group, a xylylene group, a phenylene group, and a 3,3'-dichloro-4,4'-diphenylmethanediyl. Examples thereof include a group, a toluylene group, a hexamethylene group, a 4,4'-dicyclohexylmethanediyl group, a hydrogenated xylylene group, a triphenylene methanetriyl group, a tetramethylxylene group, and a hydrided 4,4'-diphenylmethanediyl group. ..

As the compound (I), R ¹ is a hydrogen atom, a is 1, b is an integer of 4 to 6, c is an integer of 3 to 14, d is 2 or 3, and A. It is preferred that ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms; R ¹ is a hydrogen atom, a is 1, b is 5 and c. Is an integer of 3 to 10, d is 2 or 3, and A ¹ is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms; R ¹ Is a hydrogen atom, a is 1, b is 5, c is an integer of 3 to 6, d is 2, and A ¹ is a divalent or trivalent non-valent with 6 to 13 carbon atoms. Substituted or substituted hydrocarbon groups are more preferred.

The method for producing the compound (I) is not particularly limited, but the mono (meth) acrylic acid ester of ethylene glycol represented by the following formula (i) can be obtained more efficiently. A step (step (a)) of reacting a di (meth) acrylic acid ester of glycerin with a lactone represented by the following formula (ii) to produce a lactone adduct represented by the following formula (iii), and. , The step of reacting the lactone adduct with the diisocyanate compound or triisocyanate compound represented by the above formula: A ¹ − (NCO) _d (A ¹ and d have the same meanings as above) (step (b)). ) Can be preferably adopted.

In the above formula (i), R ¹ and a have the same meaning as described above.

In the above formula (ii), b has the same meaning as above.

In the above formula (iii), R ¹ , a, b and c have the same meanings as described above.

In the step (a), it is preferable to use a catalyst because the lactone adduct can be efficiently obtained. Examples of the catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); cationic catalysts; anionic catalysts (eg, tin (Sn), titanium (eg, tin (Sn), titanium). Ti), aluminum (Al), antimony (Sb), germanium (Ge), zirconium (Zr), alkyl metals for zinc (Zn), etc.); metal oxides, halides, carboxylates, alkoxides, etc. Can be mentioned. The reaction temperature in the step (a) can be, for example, 100 to 150 ° C.

In the step (b), it is preferable to use a urethanization catalyst because the target compound (I) can be efficiently obtained. Examples of the urethanization catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); tertiary amine catalysts (eg, triethylenediamine, triethanolamine, etc.). , Pentamethyldiethylenetriamine, triethylamine, tributylamine, pyridine, 4-N, N-dimethylaminopyridine, 4-pyrrolidinopyridine, etc.) and the like. Further, the step (b) is preferably performed in the presence of a polymerization inhibitor. As the polymerization inhibitor, the same polymerization inhibitor as described later, which can be used as a stabilizer in the modeling composition, can be used. The reaction temperature in the step (b) can be, for example, 40 to 90 ° C.

Preferred specific examples of the diisocyanate compound or triisocyanate compound represented by the above formula: A ¹ − (NCO) _d include, for example, isophorone diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthylene diisocyanate, and xyli. Ranged isocyanate, Phenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate , Tetramethylxylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate and the like. These diisocyanate compounds or triisocyanate compounds may be used alone or in combination of two or more. Among these, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate are more preferable because the flexibility and fracture resistance of the obtained dental impression type are improved.

In the above formula (II) relating to compound (II), R ² and R ³ are independently hydrogen atoms or methyl groups, respectively. R ² is preferably a hydrogen atom. Further, R ³ is preferably a methyl group. e is 1 or 2, preferably 1. f is an integer of 4 to 20, preferably an integer of 5 to 14, and more preferably an integer of 6 to 10. When f is not more than the above upper limit, it is possible to suppress an excessive increase in the viscosity of the modeling composition, and the strength of the obtained dental impression type is also improved. Further, when f is at least the above lower limit, the flexibility and shock absorption of the obtained dental impression type are improved.

In the above formula (II), g is 2 or 3, preferably 2. When g is 2, the flexibility of the obtained dental impression type is more likely to be improved as compared with the case where g is 3.

In the above formula (II), A ² is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms. It is preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms, and more preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 13 carbon atoms. It is more preferably a hydrocarbon group. The description of A ² is the same as that of A ¹ in compound (I), and duplicate description is omitted here.

As described later, compound (II) is preferably produced using a diisocyanate compound or a triisocyanate compound represented by the formula: A ^2- (NCO) _g (A ² and g have the same meanings as described above). From this point of view, A ² is preferably a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or the triisocyanate compound used for producing the compound (II). The preferred embodiment of A ² is the same as the preferred embodiment of A ¹ in compound (I), and redundant description will be omitted here.

As the compound (II), R ² is a hydrogen atom, R ³ is a methyl group, e is 1, f is an integer of 4 to 20, g is 2 or 3, and A ² is. It is preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms; R ² is a hydrogen atom, R ³ is a methyl group, e is 1 and f. Is an integer of 5 to 14, g is 2 or 3, and A ² is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms; R ² Is a hydrogen atom, R ³ is a methyl group, e is 1, f is an integer of 6 to 10, g is 2, and A ² is divalent or trivalent with 6 to 13 carbon atoms. It is more preferably an unsubstituted or substituted hydrocarbon group of.

The method for producing the compound (II) is not particularly limited, but since the compound (II) can be obtained more efficiently, the ethylene glycol mono (meth) acrylic acid ester represented by the following formula (iv) or Di (meth) acrylic acid ester of glycerin and ethylene oxide represented by the following formula (v) (when R ³ is a hydrogen atom in the following formula (v)) or propylene oxide (R ³ in the following formula (v)) (When it is a methyl group) to produce an ethylene oxide and / or propylene oxide adduct represented by the following formula (vi) (step (c)), and with the ethylene oxide and / or propylene oxide adduct. A method comprising a step (step (d)) of reacting with a diisocyanate compound or a triisocyanate compound represented by the above formula: A ^2- (NCO) _g (A ² and g have the same meanings as described above) is preferable. Can be adopted.

In formula (iv) above, R ² and e have the same meaning as above.

In the above formula (v), R ³ has the same meaning as above.

In the above formula (vi), R ² , R ³ , e and f have the same meanings as described above.

In step (c), it is preferable to use a catalyst because ethylene oxide and / or propylene oxide adduct can be efficiently obtained. Examples of the catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); cationic catalysts; anionic catalysts (eg, tin (Sn), titanium (eg, tin (Sn), titanium). Ti), aluminum (Al), antimony (Sb), germanium (Ge), zirconium (Zr), alkyl metals for zinc (Zn), etc.); metal oxides, halides, carboxylates, alkoxides, etc. Can be mentioned. The reaction temperature in the step (c) can be, for example, 100 to 150 ° C.

In the step (d), it is preferable to use a urethanization catalyst because the target compound (II) can be efficiently obtained. Examples of the urethanization catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); tertiary amine catalysts (eg, triethylenediamine, triethanolamine, etc.). , Pentamethyldiethylenetriamine, triethylamine, tributylamine, pyridine, 4-N, N-dimethylaminopyridine, 4-pyrrolidinopyridine, etc.) and the like. Further, the step (d) is preferably performed in the presence of a polymerization inhibitor. As the polymerization inhibitor, the same polymerization inhibitor as described later, which can be used as a stabilizer in the modeling composition, can be used. The reaction temperature in the step (d) can be, for example, 40 to 90 ° C.

Preferred specific examples of the diisocyanate compound or triisocyanate compound represented by the above formula: A ^2- (NCO) _g include, for example, isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, and xyli. Ranged isocyanate, Phenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate , Tetramethylxylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate and the like. These diisocyanate compounds or triisocyanate compounds may be used alone or in combination of two or more. Among these, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate are more preferable because the flexibility and fracture resistance of the obtained dental impression type are improved.

In the above formula (III) according to the compound (III), R ⁴ and R ⁵ are independently hydrogen atoms or methyl groups, respectively. R ⁴ is preferably a hydrogen atom. Further, R ⁵ is preferably a methyl group. h is an integer of 4 to 20, preferably an integer of 5 to 14, and more preferably an integer of 6 to 10. When h is not more than the above upper limit, it is possible to suppress an excessive increase in the viscosity of the modeling composition, and the strength of the obtained dental impression type is also improved. Further, when h is at least the above lower limit, the flexibility and shock absorption of the obtained dental impression type are improved.

In the above formula (III), j is 2 or 3, preferably 2. When j is 2, the flexibility of the obtained dental impression type is more likely to be improved as compared with the case where j is 3.

In the above formula (III), A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms. It is preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms, and more preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 13 carbon atoms. It is more preferably a hydrocarbon group. The description of A ³ is the same as that of A ¹ in compound (I), and duplicate description is omitted here.

As described later, compound (III) is preferably produced using a diisocyanate compound or a triisocyanate compound represented by the formula: A ^3- (NCO) _j (A ³ and j have the same meanings as described above). From this point of view, A ³ is preferably a divalent or trivalent residue excluding the isocyanate group of the diisocyanate compound or the triisocyanate compound used for producing the compound (III). The preferred embodiment of A ³ is the same as the preferred embodiment of A ¹ in compound (I), and redundant description will be omitted here.

As the compound (III), R ⁴ is a hydrogen atom, R ⁵ is a hydrogen atom or a methyl group, h is an integer of 4 to 20, j is 2 or 3, and A ³ has 6 carbon atoms. It is preferably a divalent or trivalent unsubstituted or substituted hydrocarbon group of ~ 20; R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and h is an integer of 5-14. More preferably, j is 2 or 3 and A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 14 carbon atoms; R ⁴ is a hydrogen atom and R ⁵ is. Further are methyl groups, h is an integer of 6 to 10, j is 2, and A ³ is a divalent or trivalent unsubstituted or substituted hydrocarbon group having 6 to 13 carbon atoms. preferable.

The method for producing the compound (III) is not particularly limited, but since the compound (III) can be obtained more efficiently, (meth) acrylic acid and ethylene oxide represented by the following formula (vii) (the following formula). Ethylene oxide and / or propylene represented by the following formula (viii) by reacting (when R ⁵ is a hydrogen atom in (vii)) or propylene oxide (when R ⁵ is a methyl group in the following formula (vii)). The step of producing the oxide adduct (step (e)) and the ethylene oxide and / or propylene oxide adduct described above and the above formula: A ^3- (NCO) _j (A ³ and j have the same meanings as above). A method including a step of reacting with the diisocyanate compound or the triisocyanate compound represented by (step (f)) can be preferably adopted.

In the above formula (vii), R ⁵ has the same meaning as above.

In the above formula (viii), R ⁴ , R ⁵ and h have the same meanings as described above.

In the step (e), it is preferable to use a catalyst because ethylene oxide and / or a propylene oxide adduct can be efficiently obtained. Examples of the catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); cationic catalysts; anionic catalysts (eg, tin (Sn), titanium (eg, tin (Sn), titanium). Ti), aluminum (Al), antimony (Sb), germanium (Ge), zirconium (Zr), alkyl metals for zinc (Zn), etc.); metal oxides, halides, carboxylates, alkoxides, etc. Can be mentioned. The reaction temperature in the step (e) can be, for example, 100 to 150 ° C.

In the step (f), it is preferable to use a urethanization catalyst because the target compound (II) can be efficiently obtained. Examples of the urethanization catalyst include organic tin catalysts such as dibutyltin compounds (eg, di-n-butyltin dilauryrate, dibutyltin diacetate, dibutyltin maleate, etc.); tertiary amine catalysts (eg, triethylenediamine, triethanolamine, etc.). , Pentamethyldiethylenetriamine, triethylamine, tributylamine, pyridine, 4-N, N-dimethylaminopyridine, 4-pyrrolidinopyridine, etc.) and the like. Further, the step (f) is preferably performed in the presence of a polymerization inhibitor. As the polymerization inhibitor, the same polymerization inhibitor as described later, which can be used as a stabilizer in the modeling composition, can be used. The reaction temperature in the step (f) can be, for example, 40 to 90 ° C.

Preferred specific examples of the diisocyanate compound or triisocyanate compound represented by the above formula: A ^3- (NCO) _j include, for example, isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, and xyli. Ranged isocyanate, Phenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate , Tetramethylxylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate and the like. These diisocyanate compounds or triisocyanate compounds may be used alone or in combination of two or more. Among these, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate are more preferable because the flexibility and fracture resistance of the obtained dental impression type are improved.

The polymerizable monomer contained in the modeling composition may contain only one of compound (I), compound (II) and compound (III), or may contain two or more of them. good. For example, the modeling composition may contain compound (I) and at least one of compound (II) and compound (III).

The content of at least one selected from the group consisting of compound (I), compound (II) and compound (III) in the polymerizable monomer is 10 because the desired dental impression type can be easily obtained. It is preferably 1% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. The upper limit of the content is not particularly limited, but the content may be, for example, 99% by mass or less, 95% by mass or less, and further 90% by mass or less.

-The polymerizable monomer contained in the (meth) acrylamide modeling composition is a compound (IV) represented by the following formula (IV) and the following formula because the desired dental impression type can be easily obtained. It is preferable to contain at least one (meth) acrylamide selected from the group consisting of the compound (V) represented by (V), and the group consisting of the above-mentioned compound (I), compound (II) and compound (III). It is more preferable to include the (meth) acrylamide together with at least one selected from the above.

In the above formula (IV), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ and R ⁸ are independent hydrogen atoms or unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, respectively, and R ⁷ and R ⁸ are not directly coupled to each other.

In the above formula (V), R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is an unsubstituted or substituted alkylene group having 1 to 8 carbon atoms, and R ¹¹ , R ¹² and R ¹³ are independent of each other. It is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, R ¹² and R ¹³ are not directly bonded to each other, and R ¹¹ and R ¹² are not directly bonded to each other. R ¹¹ and R ¹³ are not directly coupled to each other.

In the above formula (IV), R ⁶ is a hydrogen atom or a methyl group. It has good miscibility with at least one selected from the group consisting of compound (I), compound (II) and compound (III), and has excellent curability and surface smoothness in the obtained dental impression type. R ⁶ is preferably a hydrogen atom.

In the above formula (IV), R ⁷ and R ⁸ are independently substituted or substituted alkyl groups having a hydrogen atom or 1 to 8 carbon atoms. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. Further, R ⁷ and R ⁸ are one of hydrogen atoms or an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, and the other is an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms. It is preferable that one of them is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, and the other is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. More preferably, one is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, and the other is an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms. ..
R ⁷ and R ⁸ are not directly coupled to each other. As a result, a rigid and bulky annular structure is not formed, the mobility of the molecular chain in the modeling composition is improved, and a dental impression type having desired physical properties can be easily obtained.

The above-mentioned unsubstituted or substituted alkyl group having 1 to 8 carbon atoms may be linear or branched, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n. -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group. And so on.

As the substituent which may be possessed by the above-mentioned unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, the substituent which may be possessed by the hydrocarbon group represented by A ¹ of compound (I) is used. It can be the same as the one described above, and duplicate description is omitted here.

The number of substituents of the above-mentioned unsubstituted or substituted alkyl group having 1 to 8 carbon atoms is preferably 1 to 10, more preferably 1 to 8, and 1 to 6. It is more preferable to have one, and it is particularly preferable to have one to four. The alkyl group may have one kind of substituent or may have two or more kinds of substituents.

Specific examples of the compound (IV) include, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, and N-isopropyl (. Meta) Acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-hexyl (meth) acrylamide, N, N-di-n-octyl (meth) acrylamide, N, N- Examples thereof include di (2-ethylhexyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-di (2-hydroxyethyl) (meth) acrylamide and the like. These (meth) acrylamides may be used alone or in combination of two or more. Among these, it has good compatibility with at least one selected from the group consisting of compound (I), compound (II) and compound (III), and is excellent in curability and surface smoothness in the obtained dental impression type. Therefore, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N- Di-n-butyl (meth) acrylamide and N- (2-hydroxyethyl) (meth) acrylamide are preferred, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and N-isopropyl (meth) acrylamide. ) Acrylamide, N- (2-hydroxyethyl) (meth) acrylamide is more preferred, and N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide are even more preferred. , N, N-diethylacrylamide is particularly preferred.

In the above formula (V), R ⁹ is a hydrogen atom or a methyl group. It has good miscibility with at least one selected from the group consisting of compound (I), compound (II) and compound (III), and has excellent curability and surface smoothness in the obtained dental impression type. R ⁹ is preferably a hydrogen atom.

In the above formula (V), R ¹⁰ is an unsubstituted or substituted alkylene group having 1 to 8 carbon atoms. The alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

The above-mentioned unsubstituted or substituted alkylene group having 1 to 8 carbon atoms may be linear or branched, and may be, for example, a methylene group, an ethylene group, a trimethylene group, an n-propylene group or an isopropi. Examples thereof include a lidene group, a tetramethylene group, an isobutylidene group, a sec-butylidene group, a pentamethylene group, a hexamethylene group, a heptamethylene group and an octamethylene group.

The substituent which may be contained in the above-mentioned unsubstituted or substituted alkylene group having 1 to 8 carbon atoms is the above-mentioned substituent which may be contained in the hydrocarbon group represented by A ¹ of compound (I). It can be the same as the one used above, and duplicate explanations will be omitted here.

The number of substituents of the above-mentioned unsubstituted or substituted alkylene group having 1 to 8 carbon atoms is preferably 1 to 10, more preferably 1 to 8, and 1 to 6. It is more preferable to have one, and it is particularly preferable to have one to four. The alkylene group may have one kind of substituent or may have two or more kinds of substituents.

In the above formula (V), R ¹¹ , R ¹² and R ¹³ are independently substituted or substituted alkyl groups having a hydrogen atom or 1 to 8 carbon atoms. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. Further, in R ¹¹ , R ¹² and R ¹³ , any one or two are hydrogen atoms or unsubstituted or substituted alkyl groups having 1 to 5 carbon atoms, and the rest are unsubstituted or substituted or substituted having 1 to 5 carbon atoms. It is preferably a substituted alkyl group, one or two of which is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, and the rest being an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. More preferably, it is a substituted alkyl group, one or two of which are hydrogen atoms or unsubstituted or substituted alkyl groups of 1 to 3 carbon atoms, and the rest of which are unsubstituted or substituted of 1 to 3 carbon atoms. Alternatively, it is more preferably a substituted alkyl group.
R ¹² and R ¹³ are not directly bound to each other, R ¹¹ and R ¹² are not directly bound to each other, and R ¹¹ and R ¹³ are not directly bound to each other. As a result, a rigid and bulky annular structure is not formed, the mobility of the molecular chain in the modeling composition is improved, and a dental impression type having desired physical properties can be easily obtained.

The above-mentioned unsubstituted or substituted alkyl group having 1 to 8 carbon atoms is the same as that of the unsubstituted or substituted alkyl group having 1 to 8 carbon atoms represented by R ⁷ and R ⁸ in compound (IV). This can be done, and duplicate explanations are omitted here.

Specific examples of the compound (V) include, for example, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-Dibutylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N- Dibutylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N, N-dipropylaminobutyl (meth) acrylamide, N, N-dibutylamino Examples include butyl (meth) acrylamide. These (meth) acrylamides may be used alone or in combination of two or more. Among these, it has good compatibility with at least one selected from the group consisting of compound (I), compound (II) and compound (III), and is excellent in curability and surface smoothness in the obtained dental impression type. Therefore, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide are preferred, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, It is preferable to N-dimethylaminopropyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide, and is preferable to N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide and N. , N-diethylaminopropylacrylamide is more preferred, and N, N-dimethylaminopropylacrylamide is particularly preferred.

The content of at least one (meth) acrylamide selected from the group consisting of compound (IV) and compound (V) in the polymerizable monomer is 1 because the desired dental impression type can be easily obtained. It is preferably 5% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 80% by mass or less, and 60% by mass or less. Is more preferable, and 40% by mass or less is further preferable.

-Fluorine-containing (meth) acrylic acid ester The polymerizable monomer contained in the modeling composition may contain a fluorine-containing (meth) acrylic acid ester for the purpose of color resistance and the like. In this case, the above It is preferable to include the fluorine-containing (meth) acrylic acid ester together with at least one selected from the group consisting of the compound (I), the compound (II) and the compound (III). Specific examples of such a fluorine-containing (meth) acrylic acid ester include, for example, 2,2,2-trifluoroethyl (meth) acrylate and 2,2,3,3,3-pentafluoropropyl (meth) acrylate. , 2- (Perfluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl- 2-Hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meta) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, etc. Can be mentioned. Among these, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) are excellent in color resistance. ) Acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate is preferable. More preferably, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate.

The content of the fluorine-containing (meth) acrylic acid ester in the polymerizable monomer is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass from the viewpoint of curability or the like. The above is more preferable, and it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.

The polymerizable monomer contained in the modeling composition is at least one selected from the group consisting of compound (I), compound (II) and compound (III), and the group consisting of compound (IV) and compound (V). The main component may be at least one (meth) acrylamide selected from the above, and any one or more of the fluorine-containing (meth) acrylic acid esters. In this case, the polymerizable monomer is selected from at least one selected from the group consisting of compound (I), compound (II) and compound (III), and selected from the group consisting of compound (IV) and compound (V). The content of at least one (meth) acrylamide and other polymerizable monomers other than the fluorine-containing (meth) acrylic acid ester is preferably 10% by mass or less, preferably 5% by mass or less. More preferably, it is more preferably 1% by mass or less, and it may be 0.1% by mass or less, and further preferably 0.01% by mass or less.

The total content of all the polymerizable monomers in the modeling composition is preferably 10% by mass or more, preferably 30% by mass or more, because the desired dental impression type can be easily obtained. More preferably, it is more preferably 50% by mass or more. The upper limit of the content is not particularly limited, but the content may be, for example, 99.9% by mass or less, 99.5% by mass or less, and further 99% by mass or less.

[Photopolymerization initiator]
As the photopolymerization initiator contained in the modeling composition, it can be appropriately selected from the photopolymerization initiators used in the general industry, and among them, the photopolymerization initiator used for dental applications is preferable. Can be used.

Specific photopolymerization initiators include, for example, (bis) acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, and coumarins. , Anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds and the like. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination. Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and α-diketones. As a result, it is possible to more efficiently produce a dental impression type having an excellent photocurability in both the ultraviolet region (including the near-ultraviolet region) and the visible light region and having a desired shape by an optical three-dimensional modeling method. In particular, various lasers such as Ar laser and He-Cd laser; any light source such as halogen lamp, xenon lamp, metal halide lamp, LED, various mercury lamp, fluorescent lamp, etc. can be used to perform sufficient optical three-dimensional modeling. Can be done.

Among the (bis) acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commonly known as "TPO"), 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi -(2,6-dimethylphenyl) phosphonate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Examples include the ammonium salt of phosphine oxide.

Among the above (bis) acylphosphin oxides, examples of the bisacylphosphin oxides include bis (2,6-dichlorobenzoyl) phenylphosphin oxide and bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl. Phosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples thereof include phenylphosphine oxide and bis (2,3,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide. Further, the compounds described in JP-A-2000-159621 can also be used.

Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxides, sodium salts of 2,4,6-trimethylbenzoylphenylphosphine oxides are preferred.

Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphtenquinone and the like. .. Among these, camphorquinone is particularly preferable when a light source in the visible light region is used.

The content of the photopolymerization initiator in the modeling composition depends on the type of the photopolymerization initiator used, but from the viewpoint of the efficiency of optical three-dimensional modeling, it may be 0.01% by mass or more. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and 20% by mass or less. It is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[Polymerization accelerator]
The modeling composition may further contain a polymerization accelerator for the purpose of improving curability and the like. Examples of the polymerization accelerator include ethyl 4- (N, N-dimethylamino) benzoate, methyl 4- (N, N-dimethylamino) benzoate, and n 4- (N, N-dimethylamino) benzoate. -Butoxyethyl, 4- (N, N-dimethylamino) benzoate 2- (methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) butyl benzoate, etc. Can be mentioned. Among these, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate and 4- (N, N) benzoate are more excellent in curability. -At least one selected from the group consisting of (dimethylamino) benzophenone is preferred.

The content of the polymerization accelerator in the molding composition depends on the type of the polymerization accelerator used, but is preferably 0.01% by mass or more, preferably 0.05% by mass, from the viewpoint of curability and the like. % Or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and preferably 20% by mass or less, preferably 10% by mass. It is more preferably less than or equal to, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[Filler]
The modeling composition may further contain a filler for purposes such as adjusting the paste properties and improving the strength of the obtained dental impression mold. Examples of the filler include an organic filler, an inorganic filler, and an organic-inorganic composite filler. One type of filler may be used alone, or two or more types may be used in combination.

Examples of the material of the organic filler include polymethyl methacrylate, ethyl polymethacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethylmethacrylate, crosslinked polyethyl methacrylate, polyester, polyamide, and polycarbonate. Polyphenylene ether, polyoxymethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene Examples include copolymers. These may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.

Examples of the material of the inorganic filler include quartz, silica, alumina, silica-titania, silica-titania-valium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, and strontium glass. Glass ceramic, aluminosilicate glass, bariumboroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calciumfluoroaluminosilicate glass, strontiumfluoroaluminosilicate glass, bariumfluoroaluminosilicate glass, strontium calciumfluoroaluminosilicate glass, etc. Can be mentioned. These may be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and for example, an amorphous filler or a spherical filler can be appropriately selected and used.

The content of the filler in the modeling composition is preferably 0.1% by mass or more, preferably 1% by mass or more, because it is easier to obtain a dental impression type having desired physical properties. Is more preferable, 5% by mass or more is further preferable, 10% by mass or more is particularly preferable, 85% by mass or less is preferable, 70% by mass or less is more preferable, and 50 is more preferable. It is more preferably mass% or less.

[Polymer]
The modeling composition may further contain a polymer for the purpose of improving its fluidity and the flexibility of the obtained dental impression type. Examples of the polymer include natural rubber, synthetic polyisoprene rubber, liquid polyisoprene rubber or its hydrogen additive, polybutadiene rubber, liquid polybutadiene rubber or its hydrogen additive, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, and the like. Examples thereof include acrylic rubber, isoprene-isobutylene rubber, acrylonitrile-butadiene rubber, and styrene-based elastomer. Examples of the styrene-based elastomer include polystyrene-polyisoprene-polystyrene block copolymers, polystyrene-polybutadiene-polystyrene block copolymers, and poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) block copolymer weights. Examples thereof include coalescing, poly (p-methylstyrene) -polybutadiene-poly (p-methylstyrene) block copolymers, or hydrogenated products thereof. One type of polymer may be used alone, or two or more types may be used in combination.

The content of the polymer in the modeling composition is preferably 0.1% by mass or more, preferably 1% by mass or more, because it is easier to obtain a dental impression type having desired physical properties. More preferably, it is more preferably 5% by mass or more, particularly preferably 10% by mass or more, more preferably 85% by mass or less, still more preferably 70% by mass or less. It is more preferably 50% by mass or less.

[Softener]
The modeling composition may further contain a softening agent. Examples of the softener include petroleum-based softeners such as paraffin-based process oils, naphthen-based process oils, and aromatic process oils; vegetable oil-based softeners such as paraffin, peanut oil, and rosin. One type of softener may be used alone, or two or more types may be used in combination.

The content of the softening agent in the modeling composition is preferably 0.1% by mass or more, preferably 1% by mass or more, because it is easier to obtain a dental impression type having desired physical properties. More preferably, it is more preferably 5% by mass or more, particularly preferably 10% by mass or more, more preferably 85% by mass or less, still more preferably 70% by mass or less. It is more preferably 50% by mass or less.

[Stabilizer]
The modeling composition may further contain a stabilizer for purposes such as suppressing deterioration and adjusting curability. As the stabilizer, a known stabilizer can be used, and examples thereof include a polymerization inhibitor, an ultraviolet absorber, and an antioxidant. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, and 2,6-di-t-butylphenol. , 3,5-Di-t-butyl-4-hydroxytoluene (commonly known as "BHT") and the like. One type of stabilizer may be used alone, or two or more types may be used in combination.

The content of the stabilizer in the modeling composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more. Further, it is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

[Other additives]
The modeling composition may further contain additives other than those described above. As the other additive, a known additive can be used, and examples thereof include pigments, dyes, organic solvents, and thickeners. As the other additives, one type may be used alone, or two or more types may be used in combination.

The content of the other additives in the modeling composition is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 5% by mass or less.

The model obtained by the above-mentioned laminated modeling method may be used as it is as a dental impression type, or may be post-cured by irradiation with active energy rays or heat to obtain mechanical properties, shape stability, etc. It may be used as a dental impression type after improving.

《Dental impression type》
In the method for manufacturing a dental impression mold of the present invention, it is necessary that the flexural modulus of the material constituting the dental impression mold is 5 to 300 N / mm ² . This provides a dental impression type in which a dental model can be easily taken out and a plurality of dental models having the same shape can be easily obtained. From such a viewpoint, the flexural modulus is preferably 10 N / mm ² or more, more preferably 30 N / mm ² or more, further preferably 50 N / mm ² or more, and further preferably 200 N / mm 2. It is preferably / mm ² or less, and more preferably 100 N / mm ² or less. The flexural modulus can be obtained by a three-point bending test, and specifically, can be obtained by the method described later in the examples. Here, as the test piece used for measuring the flexural modulus, a test piece obtained from a dental impression mold can be used, but a test piece made of the same material as the material constituting the dental impression mold. May be prepared separately and measured using it.

The dental impression type obtained by the production method of the present invention preferably has a total light transmittance of 4 to 95% per 1 mm of the material constituting the dental impression type. Conventionally, when a dental model is manufactured using a dental impression mold, it is assumed that proper filling is not performed due to air or the like being mixed when filling the dental impression mold with a model material such as plaster. However, it was difficult to notice this until the dental model was removed from the dental impression type after the model material was cured, and there were problems such as wasting materials and time. Since the total light transmittance per 1 mm of the constituent material is within the above range, it is easy to grasp the filling state when filling the model material, and the dental impression that the dental model can be efficiently manufactured. It becomes a mold. From such a viewpoint, the total light transmittance is more preferably 10% or more, further preferably 20% or more, particularly preferably 30% or more, 40% or more, 50% or more. Further, it may be 60% or more, more preferably 90% or less, still more preferably 85% or less. The total light transmittance can be determined by a haze meter (D65 light source) by applying the provisions of JIS K7361-1: 1997 mutatis mutandis. Here, as the test piece used for measuring the total light transmittance, a test piece obtained from a dental impression type can be used, but a test made of the same material as the material constituting the dental impression type. Pieces may be prepared separately and used for measurement.

The dental impression type obtained by the production method of the present invention preferably has a tensile strength of 5 to 40 MPa of the material constituting the dental impression type. This results in a dental impression type with better shape stability. From such a viewpoint, the tensile strength is more preferably 7.5 MPa or more, further preferably 10 MPa or more, and even more preferably 20 MPa or less. Further, the dental impression type obtained by the manufacturing method of the present invention preferably has a tensile elongation (elongation at the time of cutting) of 30 to 300% of the material constituting the dental impression type. This makes it easier to take out the dental model and manufacture multiple dental models. From such a viewpoint, the tensile elongation is more preferably 50% or more, further preferably 60% or more, and further preferably 200% or less.
The tensile strength and tensile elongation can be obtained by applying the provisions of JIS K6251: 2017 mutatis mutandis, and specifically, can be obtained by the method described later in the examples. Here, as the test piece used for measuring the tensile strength and the tensile elongation, those obtained from the dental impression mold can be used, but the same material as the material constituting the dental impression mold can be used. A test piece made of the above may be separately prepared and used for measurement.

The dental impression type obtained by the production method of the present invention preferably has a tear strength of 5 to 50 kN / m as a constituent material. This results in a dental impression type with better shape stability. From such a viewpoint, the tear strength is more preferably 10 kN / m or more, further preferably 20 kN / m or more, particularly preferably 25 kN / m or more, and 40 kN / m. The following is more preferable. The tear strength can be determined by applying the provisions of JIS K6252-1: 2015 mutatis mutandis, and specifically, can be determined by the method described later in the examples. Here, as the test piece used for measuring the tear strength, a test piece obtained from a dental impression type can be used, but a test piece made of the same material as the material constituting the dental impression type. May be prepared separately and measured using it.

Preferred embodiments of the dental impression type manufacturing method of the present invention including the steps (1) and (2) are shown below.
That is, in the embodiment, first, the condition in the oral cavity of the patient is confirmed, and digital data of the dental tissue including the teeth to be paired is acquired by using an intraoral scanner or the like. At this time, the digital data on the labial side of the dental tissue is mainly acquired in the closed state where the upper and lower dental arches are in contact with each other, and the upper and lower dental arches are in contact with each other. Obtain digital data for the maxillary and mandibular arches with no openings. It should be noted that the patient's dental tissue may be ground before the digital data is acquired. Next, the digital data is taken into the CAD software, a virtual digital articulator is coupled on the CAD software, the occlusal position where the maxillary and mandibular arches are stable is specified, and the occlusal position is used. The dental impression mold is designed so that the relative position of each part corresponding to the outer shape of the facing tooth in the manufactured dental impression mold is within the range of the relative position that the facing tooth can take. Then, the range of the dental impression type actually manufactured is defined on the CAD software, and the thickness of the portion corresponding to the labial tooth surface, the thickness of the portion corresponding to the lingual tooth surface, the occlusal surface and / or the incisal surface are further defined. Specify the thickness of the part corresponding to. Next, the designed digital data is converted into the STL format, and the desired dental impression type is manufactured using the optical three-dimensional modeling device.

[Manufacturing method of dental model]
The method for manufacturing a dental model of the present invention includes a step of filling a model material into the dental impression mold obtained by the above-described method for manufacturing a dental impression mold of the present invention. According to the method for manufacturing the dental model, the dental model can be easily taken out and a plurality of dental models having the same shape can be easily obtained.

The model material used is not particularly limited, and a material suitable for the target dental model can be appropriately selected. Examples of the model material include gypsum, phosphate-based materials, and resin materials. As the gypsum, for example, a gypsum having a water mixture ratio of 0.05 to 75% ([mass of water] / [mass of solid content]) is preferable, and a linear expansion coefficient during curing is 0.01 to 3%. Is preferable. Examples of the phosphate-based material include those containing silica, ammonium phosphate, alumina and magnesia and kneaded with an aqueous medium such as water or colloidal silica aqueous dispersion. The mixing ratio of the phosphate-based material is preferably 0.01 to 50% ([mass of aqueous medium] / [mass of solid content]). Examples of the resin material include a photocurable resin material (for example, one that cures with light having a wavelength of 250 to 600 nm), an immediate room temperature polymerization type resin material that cures in a room temperature environment, and a thermosetting resin material such as an epoxy resin (for example). , Those that polymerize at 40 to 115 ° C., etc.), wax materials (for example, those having a melting point of 40 to 115 ° C., etc.) and the like. Among these, gypsum is preferable because it is possible to manufacture a dental model more efficiently and it is easy to use.

In manufacturing a dental model, a plurality of dental models may be manufactured using the same dental impression type. It may be necessary to prepare multiple dental models of the same shape, but by manufacturing multiple dental models using the same dental impression type, a dental model of the same shape can be obtained. Easy to get rid of. In particular, when the flexural modulus of the material constituting the dental impression mold is within the above range, it becomes easy to manufacture a plurality of dental models using the same dental impression mold.

The dental model may be manufactured by filling the dental impression mold in a batch with the model material, or may be filled in a plurality of times. In particular, when using a dental impression type having a shape corresponding to the outer shape of the facing tooth, the model material is filled in the tooth on one side and cured, and then the model material is applied to the tooth on the other side. By filling and curing, the desired dental model can be manufactured.

[Dental impression type]
The present invention includes a dental impression type having a shape corresponding to the outer shape of at least a part of the tooth system tissue and having a flexural modulus of the constituent material of 5 to 300 N / mm ² . According to the dental impression type, the dental model can be easily taken out and a plurality of dental models having the same shape can be easily obtained. The dental impression mold can be manufactured, for example, by the above-mentioned manufacturing method of the dental impression mold of the present invention. Other explanations about the dental impression type can be the same as the above-mentioned explanations in the method for manufacturing the dental impression type, and duplicate explanations are omitted here.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Each measurement or evaluation method adopted in the following examples is shown below.

(1) Flexural modulus The flexural modulus of the material constituting the dental impression mold is 40 mm × 4 mm × 3 mm produced by the same optical modeling apparatus as in each example using the modeling composition used in each example. It was obtained by performing a three-point bending test under the conditions of a distance between fulcrums of 30 mm and a bending distance of 3 mm using an autograph manufactured by Shimadzu Corporation using the rectangular test piece of.

(2) Total light transmittance The total light transmittance per 1 mm of the material constituting the dental impression mold was prepared by the same optical modeling apparatus as in each example using the modeling composition used in each example. Using a disk-shaped test piece having a diameter of 22 mm and a thickness of 1 mm, the measurement was performed by a haze meter (D65 light source) in accordance with the provisions of JIS K7361-1: 1997.

(3) Tensile strength and tensile elongation The tensile strength and tensile elongation of the materials constituting the dental impression mold are the same as those of each embodiment using the modeling composition used in each example. A test piece having the same dimensions as the dumbbell-shaped No. 8 test piece described in JIS K6251: 2017 was made from the sheet (thickness 2 mm) manufactured by Shimadzu Corporation using a punching blade. It was obtained by conducting a tensile test at a test speed of 500 mm / min by applying the above JIS K6251: 2017 provisions mutatis mutandis.

(4) Tear strength The tear strength of the material constituting the dental impression mold is a sheet (thickness 2 mm) produced by the same stereolithography apparatus as in each example using the modeling composition used in each example. A test piece having the same dimensions as the trauser-shaped test piece described in JIS K6252-1: 2015 was manufactured using a punching blade, and using this test piece, the above JIS K6252 was manufactured by Shimadzu Corporation. -1: Obtained by performing a tensile test at a test speed of 500 mm / min by applying the provisions of 2015 mutatis mutandis.

The contents of each component used in the following examples are shown below.
[Polymerizable monomer]
-Compound (I-1)
In the above formula (I), R ¹ = hydrogen atom, A ¹ = isophorone group (residue obtained by removing two isocyanate groups from isophorone diisocyanate) obtained by reacting a caprolactone adduct of 2-hydroxyethyl acrylate with isophorone diisocyanate. ), A = 1, b = 5, c = 6, and d = 2.
-Compound (III-1)
In the above formula (III), which is obtained by reacting the propylene oxide adduct of acrylic acid with isophorone diisocyanate, R ⁴ = hydrogen atom, R ⁵ = methyl group, A ³ = isophorone group (two isocyanate groups from isophorone diisocyanate). Residues excluded), h = 10, and j = 2.
・ DEAA
N, N-diethylacrylamide [Photopolymerization Initiator]
・ TPO
2,4,6-trimethylbenzoyldiphenylphosphine oxide [stabilizer]
・ BHT
3,5-di-t-butyl-4-hydroxytoluene

[Example 1]
(1) Using a non-contact intraoral scanner (“TRIOS3 Oral Scanner”, manufactured by 3Shape), 3D digital data of the entire maxilla, mandible, and labial tooth system tissue in the closed state were acquired. .. In addition, for the subjects, using a facebow, data on each range of lateral condyle angle, sagittal condyle angle, and immediate side shift that can be obtained during jaw movement were acquired. These data were imported into CAD software (manufactured by EXOCAD). Next, on the CAD software, the occlusal position where the maxillary and mandibular arch was stable was specified, and the dental impression type was designed so as to match the position. The specific design is as follows. The obtained digital data was combined with a virtual digital articulator on CAD software. The obtained digital data was converted into STL format and output.

(design)
For the maxillary dental arch, the position of the labial tooth system tissue in the range between the distal parts of both canines was defined as a line connecting both points 5 mm from the cervical line of both canines toward the root of the gum. .. However, the upper lip zonule was made to pass a point 2 mm from the cervical line of the middle incisor toward the base of the gingiva so as to avoid that part. The position of the labial tooth system tissue on the distal side of both canines in the direction of the gingival root is 3 mm from the molar cervical line to the gingival root, and from the above-mentioned both canine cervical lines to the gingival root. I tried to shift as much as possible from both points of 5 mm. The thickness of the portion corresponding to the labial tooth system tissue (including the portion corresponding to the labial tooth surface) was 2.5 mm.
Further, as the position of the lingual tooth system tissue in the direction of the gingival root, a position of 0.8 mm from the cervical line toward the gingival root was set. The thickness of the portion corresponding to the lingual tooth system tissue (including the portion corresponding to the lingual tooth surface) was 1 mm.
Further, the thickness of the portion corresponding to the occlusal surface and the incisal surface (distance between the maxillary dental arch and the mandibular dental arch) was set to 2 mm.

On the other hand, for the mandibular dental arch, the position of the labial tooth system tissue in the range between the distal parts of both canines in the direction of the gingival root is a line connecting both points 2 mm from the cervical line of both canines toward the gingival root. And said. However, the lower lip zonule was made to pass a point 1 mm from the central incisor cervical line toward the root of the gingiva so as to avoid that part. The position of the labial tooth system tissue on the distal side of both canines in the direction of the gingival root is 1.5 mm from the molar cervical line to the gingival root, and the above-mentioned two canine gingival lines to the gingival root. I tried to move as much as possible from both points of 2 mm in the direction. The thickness of the portion corresponding to the labial tooth system tissue (including the portion corresponding to the labial tooth surface) was 2.5 mm.
Further, as the position of the lingual tooth system tissue in the direction of the gingival root, a position of 1.5 mm from the cervical line toward the gingival root was set. The thickness of the portion corresponding to the lingual tooth system tissue (including the portion corresponding to the lingual tooth surface) was 1.5 mm.

(2) Next, using the output digital data, the relative position of each part corresponding to the outer shape of the facing tooth is set by the stereolithography device (“DigitalWax” 028J +, manufactured by DWS). A dental impression type within the range of possible relative positions (sagittal condyle angle 33 °, lateral condyle angle 5 °, and immediate side shift 3 mm) was manufactured by stereolithography. The modeling composition used at this time includes 50 parts by mass of compound (I-1), 20 parts by mass of compound (III-1), 30 parts by mass of DEAA, 2 parts by mass of TPO, and BHT. A mixture of 0.05 parts by mass was used. Table 1 shows the physical characteristics of the materials constituting the obtained dental impression type.

(3) The obtained dental impression mold was used, and the model material was filled on one of the jaw sides. As a model material, dental anhydrite ("Noritake Super Rock Ex", manufactured by Kuraray Noritake Dental Co., Ltd.) is kneaded at a mixing ratio ([mass of water] / [mass of solids]) of 20%. Using. It was visually confirmed from the outside of the dental impression type that there was no air bubble entrainment or other filling defects during filling. After the model material was cured, the dental impression mold was bent and the dental impression mold was taken out without destroying the dental impression mold. Subsequently, a dental model was similarly prepared and taken out for the other jaw side. It was confirmed that the obtained dental model had excellent surface reproducibility and had little error with the intraoral data. The dental model could reproduce the oral environment of the patient by attaching it to the articulator.
In addition, another dental model was further produced in the same manner as above by using the dental impression type used above again.

[Example 2]
(1) In the design of (1) of Example 1, digital data was converted into STL format and output in the same manner as in Example 1 except for the following.

(design)
For the maxillary dental arch, the position of the labial tooth system tissue in the range between the distal parts of both canines was defined as a line connecting both points 5 mm from the cervical line of both canines toward the root of the gum. .. However, the upper lip zonule was made to pass a point 2 mm from the cervical line of the middle incisor toward the base of the gingiva so as to avoid that part. The position of the labial tooth system tissue on the distal side of both canines in the direction of the gingival root is 4 mm from the molar cervical line to the gingival root, and from the above-mentioned both canine gingival lines to the gingival root. I tried to shift as much as possible from both points of 5 mm. The thickness of the portion corresponding to the labial tooth system tissue (including the portion corresponding to the labial tooth surface) was 8 mm.
Further, as the position of the lingual tooth system tissue in the direction of the gingival root, a position of 5 mm from the cervical line toward the gingival root was set. The thickness of the portion corresponding to the lingual tooth system tissue (including the portion corresponding to the lingual tooth surface) was 5 mm.
Further, the thickness of the portion corresponding to the occlusal surface and the incisal surface (distance between the maxillary dental arch and the mandibular dental arch) was set to 15 mm.

On the other hand, for the mandibular dental arch, the position of the labial tooth system tissue in the range between the distal parts of both canines in the direction of the gingival root is a line connecting both points 3 mm from the cervical line of both canines toward the gingival root. And said. However, the lower lip zonule was made to pass 2.5 mm from the central incisor cervical line toward the root of the gingiva so as to avoid that part. The position of the labial tooth system tissue on the distal side of both canines in the direction of the gingival root is 2 mm from the molar cervical line to the gingival root, and from the above-mentioned both canine gingival lines to the gingival root. I tried to move as much as possible from both points of 3 mm. The thickness of the portion corresponding to the labial tooth system tissue (including the portion corresponding to the labial tooth surface) was 5 mm.
Further, as the position of the lingual tooth system tissue in the direction of the gingival root, a position of 5 mm from the cervical line toward the gingival root was set. The thickness of the portion corresponding to the lingual tooth system tissue (including the portion corresponding to the lingual tooth surface) was 5 mm.

(2) Next, using the output digital data, the relative position of each part corresponding to the outer shape of the facing tooth is set by the stereolithography device (“DigitalWax” 028J +, manufactured by DWS). A dental impression type within the range of possible relative positions (sagittal condyle angle 30 °, lateral condyle angle 7 °, and immediate side shift 3 mm) was manufactured by stereolithography. The modeling composition used at this time was a mixture of compound (III-1) in an amount of 85 parts by mass, DEAA in an amount of 15 parts by mass, TPO in an amount of 1 part by mass, and BHT in an amount of 0.05 parts by mass. Was used. Table 1 shows the physical characteristics of the materials constituting the obtained dental impression type.

(3) The obtained dental impression mold was used, and the model material was filled on one of the jaw sides. The model material is a phosphate-based fireproof model material (“Noribest”, manufactured by Kuraray Noritake Dental Co., Ltd.) kneaded at a water mixing ratio ([mass of aqueous medium] / [mass of solid content]) of 20%. Was used. It was visually confirmed from the outside of the dental impression type that there was no air bubble entrainment or other filling defects during filling. After the model material was cured, the dental impression mold was bent and the dental impression mold was taken out without destroying the dental impression mold. Subsequently, a dental model was similarly prepared and taken out for the other jaw side. It was confirmed that the obtained dental model had excellent surface reproducibility and had little error with the intraoral data. The dental model could reproduce the oral environment of the patient by attaching it to the articulator.
In addition, the dental impression type used above is used again, and as a model material, dental anhydrite ("Noritake Super Rock Ex", manufactured by Kuraray Noritake Dental Co., Ltd.) is mixed with water ratio ([mass of water] / [ Mass of solid content]) Another dental model was further prepared in the same manner as above except that the one kneaded at 20% was used.

Claims (17)

A step (1) of acquiring digital data representing at least a part of the tooth system tissue and a step (2) of forming a dental impression type having a shape corresponding to the outer shape of the at least part using the digital data. A method for manufacturing a dental impression type including, wherein the flexural modulus of the material constituting the dental impression type is 30 N / mm ² or more and 300 N / mm ² or less . The manufacturing method according to claim 1, wherein the material constituting the dental impression mold has a tensile strength of 5 to 40 MPa. The manufacturing method according to claim 1 or 2, wherein the material constituting the dental impression mold has a tear strength of 5 to 50 kN / m. The manufacturing method according to any one of claims 1 to 3, wherein the dental impression type includes a portion corresponding to the labial tooth surface, and the thickness of the portion is 0.3 to 45 mm. The manufacturing method according to any one of claims 1 to 4, wherein the dental impression type includes a portion corresponding to the lingual tooth surface, and the thickness of the portion is 0.1 to 45 mm. The production method according to any one of claims 1 to 5, wherein the dental impression type includes a portion corresponding to an occlusal surface and / or an incisal surface, and the thickness of the portion is 0.1 to 45 mm. The production method according to any one of claims 1 to 6, wherein the manufacturing method comprises a tooth in which at least a part thereof is paired. The manufacturing method according to claim 7, wherein the relative positions of the respective parts corresponding to the outer shapes of the facing teeth are within the range of the relative positions that the facing teeth can obtain. The relative positions that the opposing teeth can take are in the range of sagittal condyle angle 5 to 60 °, lateral condyle angle 1 to 20 °, and immediate side shift 0.1 to 4 mm. The manufacturing method according to claim 8, which is a possible relative position. The manufacturing method according to any one of claims 1 to 9, wherein the step (2) is performed by a laminated molding method. A method for manufacturing a dental model, which comprises a step of filling a model material in a dental impression mold obtained by the manufacturing method according to any one of claims 1 to 10. The manufacturing method according to claim 11, wherein the model material is gypsum. The manufacturing method according to claim 11 or 12, wherein a plurality of dental models are manufactured using the same dental impression mold. It is a dental impression type having a shape corresponding to the outer shape of at least a part of the tooth system tissue, and the flexural modulus of the constituent material is 30 N / mm ² or more and 300 N / mm ² or less (however, the dental impression type is used. The constituent materials are excluding silicone) , dental impression type. The dental impression type according to claim 14, wherein the dental impression type includes at least a portion of the teeth facing each other. The dental impression type according to claim 15, wherein the relative position of each portion corresponding to the outer shape of the facing tooth is within the range of the relative position that the facing tooth can take. The relative positions that the opposing teeth can take are in the range of sagittal condyle angle 5 to 60 °, lateral condyle angle 1 to 20 °, and immediate side shift 0.1 to 4 mm. The dental impression type according to claim 16, which is a possible relative position.