JP2011225526A - Portion pack type polymerizable support base construction material for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable support base construction material for dental use which has excellent operability on the construction of a support base such as dischargeability and shaping performances, and which also can form a support base in which a cured material exhibits satisfactory mechanical strength.SOLUTION: The portion pack type polymerizable support base construction material comprises a first paste (A) and a second paste (B), and both pastes include a (meth)acrylate monomer (a), at least either of the pastes includes inorganic particles (b) with the average particle size of 0.5 to 10 μm surface-treated with a specified silane coupling agent (m1), inorganic particles (c) with the average particle size of 0.01 to 0.1 μm surface-treated with a specified silane coupling agent (m2) and inorganic particles (d) with the average particle size of 0.005 to 0.1 μm not subjected to surface treatment, either paste comprises an oxidizing agent (e), and the other paste includes a reducing agent (f), respectively.

Description

  The present invention relates to a packaging type dental abutment building material. More specifically, the present invention relates to a packaging-type dental polymerizable abutment building material that has good operability when building an abutment and can form an abutment with excellent mechanical strength after polymerization.

  In recent years, a polymerizable composition containing a polymerizable monomer, a filler, a polymerization initiator and the like has been widely used as a restorative material in dental clinics. When the dental polymerizable composition is classified according to the type of polymerization initiator, that is, the polymerization method, it is classified into a photopolymerization type composition, a chemical polymerization type composition, and a dual cure type composition that is cured by photopolymerization and chemical polymerization. Divided. Further, when the dental polymerizable composition is classified according to the packaging form, it can be classified into a 1 paste type and a 2 paste type.

  A photopolymerizable composition using a photopolymerization initiator is a one-paste type. In recent years, due to significant advances in light irradiators, photopolymerizable compositions have become widely used in dental practice. However, the photopolymerization type composition cannot be used for repaired parts where irradiation light does not reach, such as the lower bottom part in the root canal and the inner surface side of the repair material.

  The chemical polymerization type composition and the dual cure type composition using a redox initiator consisting of an oxidizing agent and a reducing agent as a polymerization initiator should be packaged separately in order to ensure storage stability. Is preferred. For this reason, it is usually a two-paste type.

  The chemical polymerization composition is polymerized by reacting an oxidizing agent and a reducing agent by kneading two kinds of pastes using a tool such as a spatula or a kneading stick. The chemical polymerization composition has an advantage that it can be used even in a repaired part where the irradiation light does not reach, but it has a drawback that it is difficult to adjust the polymerization curing time.

  The dual cure type composition is a dental polymerizable composition that has been developed to solve the above-mentioned problems of the chemical polymerization type composition. In the dual cure type composition, a portion where the irradiation light does not reach is cured by a redox initiator, and a portion where the irradiation light reaches is cured in a short time by a photopolymerization initiator whose polymerization curing time can be easily adjusted. The dual-cure composition is also used as an abutment-building material for repairing a root canal site where a root canal is formed by taking out the pulp of the root site when the progress of touching is significant.

  In such an abutment construction material, the following are mainly listed as required physical properties. The two pastes are easily kneaded and can be filled without difficulty to the root canal bottom, have an appropriate shapeability so that they do not sag when built, and have sufficient strength to withstand occlusion after curing.

  From this point of view, Patent Document 1 discloses an increase in viscosity due to the filling of inorganic particles by blending dental particles with inorganic particles having a particle diameter of 0.1 μm or less that have been surface-treated with a silane coupling agent having a long alkyl chain. Attempts have been made to improve mechanical strength while mitigating. Further, Patent Document 1 describes that the mechanical strength is further improved when inorganic particles having a particle diameter of 0.1 μm to 100 μm, preferably surface-treated with a silane coupling agent, are further blended.

  In Patent Document 2, inorganic particles having an average particle size of 1.0 to 5.0 μm surface-treated with a silane coupling agent having a long alkyl chain and an average particle size of 0.01 having been surface-treated with a silane coupling agent having a short alkyl chain are disclosed. An example is described in which formability and strength are balanced by blending ˜0.10 μm inorganic particles into a dental curable composition.

  Patent Document 3 discloses that inorganic particles having an average particle size of 0.7 to 10 μm and an average particle size of 0.001 to 0.050 μm, which are preferably surface-treated with a silane coupling agent. An example is described in which the particles are blended into a packaging type dental polymerizable abutment building material to balance dischargeability, shapeability and strength.

JP-A-2-134307 International Publication No. 2008/093596 Pamphlet International Publication No. 2006/030645 Pamphlet

  However, although patent document 1 describes the improvement effect of the mechanical strength of the dental restorative material, there is no description regarding operability such as dischargeability and shaping. When the present inventors examined, it turned out that the dental restoration material of patent document 1 has room for improvement in a shaping property. The dental curable composition of Patent Document 2 having a good balance of formability and strength, and the dental polymerizable abutment building material of Patent Document 3 having a good balance of dischargeability, shapeability and strength are also shaped. It turns out that there is room for improvement in sex.

  Therefore, the present invention is a dental polymerizable abutment building material that is excellent in operability at the time of abutment construction such as dischargeability and shaping, and that can form an abutment in which a cured product exhibits good mechanical strength. The purpose is to provide.

The present invention includes a first paste (A) and a second paste (B),
Both pastes both contain (meth) acrylate monomer (a), and at least one of the pastes is surface-treated with a silane coupling agent (m1) represented by the following formula (I) Inorganic particles (b) having a diameter of 0.5 to 10 μm, inorganic particles (c) having an average particle diameter of 0.01 to 0.1 μm and surface-treated with a silane coupling agent (m2) represented by the following formula (II) And inorganic particles (d) having an average particle diameter of 0.005 to 0.1 μm that have not been surface-treated, one of the pastes containing the oxidizing agent (e) and the other paste containing the reducing agent (f). Each is a wrapping-type dental polymerizable abutment building material.

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is an oxygen atom or a sulfur atom, and p is 2 or 3, q is an integer of 8-13.)

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrolyzable group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, X ² is an oxygen atom or a sulfur atom, and s is 2 or 3, t is an integer of 1-13.)

  In the abutment building material of the present invention, the (meth) acrylate monomer (a) is an aromatic (meth) acrylate monomer (a-1) having a hydroxyl group or an aromatic (meta) having no hydroxyl group. ) Acrylate monomer (a-2) and aliphatic (meth) acrylate monomer (a-3), and the (meth) acrylate monomer (a-1) and (meth) acrylate monomer (A-2) and (meth) acrylate monomer (a-3) are contained in one or both of the first paste (A) and the second paste (B), respectively. Is preferred.

  The abutment building material of the present invention has a surface treatment with a silane coupling agent (m3) represented by the following formula (III), and an average particle size of 0.5 to 40 μm. It is preferable to further contain 10 μm inorganic particles (g).

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrolyzable group, R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms, X ³ is an oxygen atom or a sulfur atom, and v is 2 or 3, w is an integer of 1-7.)

  The abutment building material of the present invention preferably further contains a photopolymerization initiator (h).

  An example of a preferable composition of the abutment building material of the present invention is that hydroxyl groups are contained in 100 parts by weight of the (meth) acrylate monomer (a) contained in the first paste (A) and the second paste (B). 1 to 25 parts by weight of aromatic (meth) acrylate monomer (a-1), 20 to 75 parts by weight of aromatic (meth) acrylate monomer (a-2) having no hydroxyl group, and aliphatic ( 20 to 75 parts by weight of the (meth) acrylate monomer (a-3), and 50 to 750 parts by weight of the inorganic particles (b) with respect to 100 parts by weight of the (meth) acrylate monomer (a), Inorganic particles (c) 5-50 parts by weight, inorganic particles (d) 1-25 parts by weight, oxidizing agent (e) 0.1-20 parts by weight, reducing agent (f) 0.1-20 parts by weight, inorganic particles (G) 0 to 250 parts by weight, and photopolymerization initiator (h) 0.05 to 10 parts by weight And composed.

  The abutment building material of the present invention has both high dischargeability before curing and shapeability, and is excellent in operability when building the abutment. Moreover, the hardened | cured material of the abutment building material of this invention is excellent in mechanical strength.

  The abutment building material of the present invention has an average particle diameter of 0.5 to 10 μm which is surface-treated with a (meth) acrylate monomer (a) and a silane coupling agent (m1) represented by the above formula (I). Inorganic particles (b), inorganic particles (c) having an average particle diameter of 0.01 to 0.1 μm, surface-treated with the silane coupling agent (m2) represented by the above formula (II), average not having been surface-treated The inorganic particles (d) having a particle size of 0.005 to 0.1 μm, the oxidizing agent (e), and the reducing agent (f) are essential components, and these components are configured as a package type divided into at least two pastes. It has a special feature. First, each component of the abutment building material of the present invention will be described.

(Meth) acrylate monomer (a)
The (meth) acrylate monomer (a) is used in the abutment building material of the present invention as a component that enables polymerization and curing. The (meth) acrylate monomer (a) is contained in both the first paste (A) and the second paste (B). In the present specification, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acryloyl” means acryloyl and / or methacryloyl.

  In the present invention, the (meth) acrylate monomer (a) is an aromatic (meth) acrylate monomer having a hydroxyl group (a-1) or an aromatic (meth) acrylate monomer having no hydroxyl group (a- 2) and aliphatic (meth) acrylate monomers (a-3). The (meth) acrylate monomer (a-1), (meth) acrylate monomer (a-2), and (meth) acrylate monomer (a-3) are the same as the first paste (A) and It is contained in either one or both of the second paste (B).

  The aromatic (meth) acrylate monomer (a-1) having a hydroxyl group is not particularly limited as long as it is a (meth) acrylate monomer having an aromatic ring and a hydroxyl group, and the number of aromatic rings and the number of hydroxyl groups are independent from each other. It is only necessary to have at least one functional group. Examples of such a compound include a (meth) acrylate monomer having a bisphenol A skeleton and a hydroxyl group, and more specifically 2,2-bis [4- (3- (meth) acryloyloxy). ) -2-Hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- [2,3- Di (meth) acryloyloxypropoxy] phenyl] propane (common name “Bis3”), 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- (meth) acryloyloxy Diethoxyphenyl] propane, 2- [4-[(meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4 (Meth) acryloyloxytriethoxyphenyl] propane, 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- (meth) acryloyloxydipropoxyphenyl] propane and the like These can be used alone or in combination of two or more. Among these, Bis-GMA is preferable because it is more excellent in strength when used as an abutment building material.

  The aromatic (meth) acrylate monomer (a-2) having no hydroxyl group is not particularly limited as long as it is an (meth) acrylate monomer having an aromatic ring and no hydroxyl group, and at least one As long as it has an aromatic ring. Examples of such a compound include a (meth) acrylate monomer having a bisphenol A skeleton and no hydroxyl group, and more specifically 2,2-bis ((meth) acryloyloxyphenyl) propane. 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyl) Oxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acrylic Royloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) Examples include propane and 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane. In addition, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate or the like can be used. Among these, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane is preferable because the operability of the obtained abutment building material and the strength of the cured product thereof are more excellent. Among 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, a compound having an average addition mole number of ethoxy groups of 2.6 (commonly referred to as “D-2.6E”) is preferable. .

  The aliphatic (meth) acrylate monomer (a-3) is not particularly limited as long as it is a (meth) acrylate monomer having no aromatic ring, and may or may not have a hydroxyl group. Good. Examples include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3- Methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as “UDMA”), trimethylolpropane tri ( Acrylate), trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N -(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxy Methyl-4-oxyheptane, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate. Among these, glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 because it is superior in the operability of the obtained abutment building material and the strength of the cured product thereof. , 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate and 1,2-bis (3 -Methacryloyloxy-2-hydroxypropoxy) ethane is preferred.

  About the ratio of said (meth) acrylate monomer (a-1), (meth) acrylate monomer (a-2), and (meth) acrylate monomer (a-3), the abutment building material obtained From the viewpoint of the operability of the resin and the strength of the cured product, when the total amount of the (meth) acrylate monomer (a) is 100 parts by weight, the (meth) acrylate monomer (a-1) is 1 to 25 weights. Parts, (meth) acrylate monomer (a-2) 20 to 75 parts by weight, (meth) acrylate monomer (a-3) 20 to 75 parts by weight, (meth) acrylate monomer (A-1) 5 to 20 parts by weight, (meth) acrylate monomer (a-2) 25 to 70 parts by weight, (meth) acrylate monomer (a-3) 25 to 70 parts by weight More preferred. In the present specification, the “total amount of (meth) acrylate monomer (a)” means (meth) acrylate contained in the entire abutment building material (usually paste (A) and paste (B)). It means the total amount of monomers.

Inorganic particles (b)
In the present invention, the inorganic particles (b) are essential for increasing the strength of the abutment building material. The inorganic particles (b) in the present invention are inorganic particles having an average particle diameter of 0.5 to 10 μm, which have been surface-treated with the silane coupling agent (m1) represented by the above formula (I). The inorganic particles (b) are contained in one or both of the first paste (A) and the second paste (B).

  There is no restriction | limiting in particular in the shape of an inorganic particle (b), An indefinite shape, spherical shape or substantially spherical shape may be sufficient.

  Examples of the inorganic particles serving as the core filler to be surface-treated in the inorganic particles (b) include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, and borosilicate. Acid glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontiumboroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoro Examples thereof include particles such as aluminosilicate glass and strontium calcium fluoroaluminosilicate glass. These can be used alone or in admixture of two or more.

In the present invention, in order to increase the filling amount of the inorganic particles (b) and improve the strength of the cured product while suppressing an increase in the viscosity of the paste, the inorganic particles are added when the inorganic particles (b) are blended. The surface is treated with a silane coupling agent (m1) represented by the formula (I). In the above formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrolyzable group, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, X ¹ represents an oxygen atom or a sulfur atom, p Is 2 or 3, q is an integer of 8-13.

Examples of the hydrolyzable group represented by R ² include an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group, a chlorine atom, and an isocyanate group. Among these, an alkoxy group is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a vinyl group, an allyl group, and a methylvinyl group. , Propenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, phenyl group and the like. Of these, a methyl group and an ethyl group are preferable.

X ¹ is preferably an oxygen atom.

  Specific examples of the silane coupling agent (m1) represented by the above formula (I) include 8-methacryloyloxyoctyltrimethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 11 -Methacryloyloxyundecyltrimethoxysilane, 11-methacryloyloxyundecyldichloromethylsilane, 11-methacryloyloxyundecyltrichlorosilane, 11-methacryloyloxyundecylchlorodimethoxysilane, 12-methacryloyloxidedecyltrimethoxysilane, 13- A methacryloyloxy tridecyl trimethoxysilane etc. are mentioned, These can be used individually or in mixture of 2 or more types. Among these, since the paste can be reduced in viscosity while dispersing more inorganic particles, 8-methacryloyloxyoctyltrimethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane 11-methacryloyloxyundecyltrimethoxysilane is preferred, and 11-methacryloyloxyundecyltrimethoxysilane is particularly preferred.

  In this invention, in order to adjust the fluidity | liquidity of an abutment building material, you may surface-treat together with well-known surface treatment compounds other than the said silane coupling agent (m1) as needed. Examples of such surface treatment compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and the like. The content of the silane coupling agent (m1) is preferably 60% by weight or more, more preferably in the surface treatment agent (the silane coupling agent (m1) and the surface treatment compound) from the viewpoint of not impairing the effects of the present invention. 80% by weight or more, more preferably 100% by weight.

  As a surface treatment method using a surface treatment agent, a known method can be used without particular limitation. For example, a method of spray-adding the surface treatment agent with vigorous stirring of the inorganic particles, a method of removing the solvent after dispersing or dissolving the inorganic particles and the surface treatment agent in an appropriate solvent, or the above in an aqueous solution There is a method of removing water after hydrolyzing the hydrolyzable group of the surface treatment agent with an acid catalyst to convert it to a silanol group, attaching the surface treatment agent to the surface of the inorganic particles in the aqueous solution, etc. Also in this method, by heating normally in the range of 50-150 degreeC, reaction of an inorganic particle surface and the said surface treating agent can be completed, and surface treatment can be performed.

  The amount of treatment with the silane coupling agent (m1) in the inorganic particles (b) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the core filler before the treatment. .

  The average particle diameter of the inorganic particles (b) is 0.5 to 10 μm and 0.75 to 7.5 μm from the viewpoint of the operability of the obtained abutment building material and the strength of the cured product. preferable. In the present invention, the average particle size of the inorganic particles can be determined by a laser diffraction scattering method. Specifically, for example, it can be measured using a laser diffraction type particle size distribution measuring apparatus (eg, SALD-2100: manufactured by Shimadzu Corporation). In addition, about the particle | grains with an average particle diameter of 100 nm or less, an electron micrograph of particle | grains can be measured and an average particle diameter can also be calculated | required as an average value of the particle diameter of 100 particles selected at random. When the particles are non-spherical, the particle diameter is defined as an arithmetic average of the longest and shortest lengths of the particles.

  The blending amount of the inorganic particles (b) is 50 to 50 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylate monomer (a), from the viewpoint of the operability of the obtained abutment building material and the strength of the cured product. 750 parts by weight is preferable, and 100 to 400 parts by weight is more preferable.

Inorganic particles (c)
In the present invention, the inorganic particles (c) are essential in order to suppress the change in fluidity of the abutment building material. The inorganic particles (c) in the present invention are inorganic particles having an average particle diameter of 0.01 to 0.1 μm, which has been surface-treated with the silane coupling agent (m2) represented by the above formula (II). The inorganic particles (c) are contained in one or both of the first paste (A) and the second paste (B).

  There is no restriction | limiting in particular in the shape of an inorganic particle (c), An indefinite shape, spherical shape or substantially spherical shape may be sufficient.

  Examples of the inorganic particles serving as the core filler to be surface-treated in the inorganic particles (c) include quartz, silica, alumina, silica-titania, silica-alumina, borosilicate glass, soda glass, glass ceramic, aluminosilicate glass, and fluoro. Examples of the particles include aluminosilicate glass and calcium fluoroaluminosilicate glass. These can be used alone or in admixture of two or more.

The inorganic particles (c) are surface-treated with a silane coupling agent (m2) represented by the above formula (II). In the above formula (II), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrolyzable group, R ⁶ represents a hydrocarbon group having 1 to ⁶ carbon atoms, X ² represents an oxygen atom or a sulfur atom, and s Is 2 or 3, and t is an integer of 1-13.

The hydrolyzable group represented by R ⁵ is the same as the hydrolyzable group represented by R ² . The hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ is the same as the hydrocarbon group having 1 to 6 carbon atoms represented by R ³ . X ² is preferably an oxygen atom. t is preferably an integer of 1 to 6.

  Specific examples of the silane coupling agent (m2) include those listed as specific examples of the silane coupling agent (m1), methacryloyloxymethyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, and 3-methacryloyloxypropyl. Examples include trimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, 6-methacryloyloxyhexyltrimethoxysilane, 7-methacryloyloxyheptyltrimethoxysilane, and the like. A mixture of seeds or more can be used. Among these, 3-methacryloyloxypropyltrimethoxysilane is preferred from the viewpoint of easy availability and the ability to disperse more inorganic particles.

  As long as the effects of the present invention are not impaired, surface treatment may be performed by using a known surface treatment compound other than the silane coupling agent (m2). Examples of the surface treatment compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-aminopropyltrimethoxysilane.

  A known method can be used for the surface treatment without any particular limitation.

  The treatment amount of the inorganic particles (c) with the silane coupling agent (m2) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the core filler before the treatment. .

  The average particle diameter of the inorganic particles (c) is 0.01 to 0.1 μm and 0.02 to 0.06 μm from the viewpoint of the operability of the obtained abutment building material and the strength of the cured product. It is preferable.

  The blending amount of the inorganic particles (c) is 5 to 5 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylate monomer (a) from the viewpoints of the operability of the obtained abutment building material and the strength of the cured product. 50 parts by weight is preferable, and 7.5 to 25 parts by weight is more preferable.

Inorganic particles (d)
Conventionally, by using together two kinds of inorganic particles having different particle diameters treated with a silane coupling agent, the discharge property, the shapeability and the strength of the cured product have been improved in a balanced manner. However, the abutment building material of the present invention further contains inorganic particles (d) having an average particle diameter of 0.005 to 0.1 μm which are not surface-treated as an essential component. With this inorganic particle (d), the formability of the abutment building material can be further improved. The inorganic particles (d) are contained in one or both of the first paste (A) and the second paste (B).

  In the present invention, “non-surface-treated inorganic particles” means “treatment with a surface treatment agent (compound that binds to the surface of inorganic particles; eg, silane coupling agent, titanate coupling agent, fatty acid, surfactant, etc.). It means “inorganic particles that have not been treated”.

  The shape of the inorganic particles (d) is not particularly limited, and may be indefinite, spherical or substantially spherical.

  Examples of the inorganic particles (d) include particles of quartz, silica, alumina, silica-titania, silica-alumina, sulfite, hydroxide salt, and the like. These can be used alone or in admixture of two or more.

  The average particle diameter of the inorganic particles (d) is 0.005 to 0.1 μm, preferably 0.01 to 0.02 μm, from the viewpoint of the formability of the obtained abutment building material.

  The blending amount of the inorganic particles (d) is from 1 to 100 parts by weight with respect to the total amount of the (meth) acrylate monomer (a) from the viewpoint of the operability of the obtained abutment building material and the strength of the cured product. 25 parts by weight is preferable, and 2.5 to 20 parts by weight is more preferable.

Inorganic particles (g)
In the present invention, it is advantageous to blend inorganic particles (g) in order to further improve the operability of the abutment building material and the strength of the cured product. The inorganic particles (g) in the present invention are surface-treated with a silane coupling agent (m3) represented by the above formula (III) and have an average particle size of 0.5 to 40 μm. It is an inorganic particle of 10 μm. The inorganic particles (g) are contained in one or both of the first paste (A) and the second paste (B).

  There is no restriction | limiting in particular in the shape of an inorganic particle (g), An indefinite shape, spherical shape or substantially spherical shape may be sufficient.

  Examples of the inorganic particles serving as the core filler to be surface-treated in the inorganic particles (g) include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass. , Soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate Examples thereof include particles such as glass and strontium calcium fluoroaluminosilicate glass. These can be used alone or in admixture of two or more.

The inorganic particles (g) are surface-treated with a silane coupling agent (m3) represented by the above formula (III). In the above formula (III), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrolyzable group, R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms, X ³ is an oxygen atom or a sulfur atom, and v Is 2 or 3, and w is an integer of 1-7.

The hydrolyzable group represented by R ⁸ is the same as the hydrolyzable group represented by R ² . The hydrocarbon group having 1 to 6 carbon atoms represented by R ⁹ is the same as the hydrocarbon group having 1 to 6 carbon atoms represented by R ³ . X ³ is preferably an oxygen atom.

  Specific examples of the silane coupling agent (m3) include methacryloyloxymethyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, and 5-methacryloyl. Examples thereof include oxypentyltrimethoxysilane, 6-methacryloyloxyhexyltrimethoxysilane, and 7-methacryloyloxyheptyltrimethoxysilane, and these can be used alone or in combination of two or more. Among these, 3-methacryloyloxypropyltrimethoxysilane is preferred from the viewpoint of easy availability and the ability to disperse more inorganic particles.

  As long as the effects of the present invention are not impaired, the surface treatment may be performed using a known surface treatment compound other than the silane coupling agent (m3). Examples of the surface treatment compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-aminopropyltrimethoxysilane.

  A known method can be used for the surface treatment without any particular limitation.

  The treatment amount of the inorganic particles (g) with the silane coupling agent (m3) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the core filler before the treatment. .

  Inorganic particles (g) have a particle diameter in the range of 0.1 to 40 μm and an average particle diameter of 0.5 to 0.5 from the viewpoints of the operability of the obtained abutment building material and the strength of the cured product. 10 μm. The particle diameter is preferably in the range of 0.5 to 30 μm, and the average particle diameter is preferably 1.5 to 10 μm. In addition, that the particle diameter is in the range of 0.1 to 40 μm means that the minimum particle diameter of the particles is 0.1 μm or more and the maximum particle diameter is 40 μm or less.

  The blending amount of the inorganic particles (g) is 250 weights with respect to 100 parts by weight of the total amount of the (meth) acrylate monomer (a) from the viewpoints of the operability of the resulting abutment construction material and the strength of the cured product. Parts by weight or less, more preferably 50 to 200 parts by weight.

  The abutment building material of the present invention is blended with a redox initiator that is a combination of an oxidizing agent (e) and a reducing agent (f) as a chemical polymerization initiator. From the viewpoint of storage stability, the oxidant (e) is contained in one of the first paste (A) and the second paste (B), and the reducing agent (f) is the other (oxidant (e ) Is contained in the paste).

Oxidizing agent (e)
Examples of the oxidizing agent (e) include organic peroxides, azo compounds, and inorganic peroxides. Examples of the organic peroxide include diacyl peroxides, peroxyesters, peroxycarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide, and the like. Specific examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, t-butyl peroxy-2-ethylhexanoate, and the like. Specific examples of peroxycarbonates include t-butyl peroxyisopropyl carbonate. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, and the like. Specific examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1- Bis (t-hexylperoxy) cyclohexane and the like can be mentioned. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Examples of the azo compound include azobisisobutyronitrile and azobisisobutylvaleronitrile. Examples of inorganic peroxides include sodium persulfate, potassium persulfate, aluminum persulfate, and ammonium persulfate.

Reducing agent (f)
Examples of the reducing agent (f) include aromatic amines, thioureas, ascorbic acid and the like that do not have an electron withdrawing group in the aromatic ring. The oxidizing agent (e) and the reducing agent (f) are also collectively referred to as a chemical polymerization initiator in the present invention.

  As an aromatic amine having no electron withdrawing group in the aromatic ring, the hydrogen atom of the aromatic ring of the aromatic amine is not substituted with an electron withdrawing group such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group. Specific examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N- Bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N , N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2 Hydroxyethyl) -3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p- Toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline and the like can be mentioned. As for the aromatic amine which does not have an electron withdrawing group in the aromatic ring mentioned above, one kind may be used alone or plural kinds may be used in combination.

  Examples of thioureas include thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea. , Triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like. Any of the above-described thioureas may be used alone or in combination.

  If the blending amount of the oxidizing agent (e) and the reducing agent (f) is too small, the curing speed is too slow and the adhesive strength may decrease. If it is too large, the curing time is too fast and the working time is secured. It may not be possible. Therefore, the blending amount of the oxidizing agent (e) is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylate monomer (a). preferable. Moreover, 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of (meth) acrylate monomer (a), and, as for the compounding quantity of a reducing agent (f), 0.5-5 weight part is more. preferable.

Photopolymerization initiator (h)
One preferred embodiment of the abutment building material of the present invention is a dual cure type abutment building material. At this time, a photopolymerization initiator (h) is blended in order to impart photocurability to the abutment building material. The photopolymerization initiator (h) is contained in one or both of the first paste (A) and the second paste (B). Examples of the photopolymerization initiator (h) include (bis) acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds And α-aminoketone compounds. Specific examples thereof include those described in the pamphlet of International Publication No. 2008/089777.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, and α-diketones. As a result, an abutment construction material having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

  Although the compounding quantity of a photoinitiator (f) is not specifically limited, From a photocurable viewpoint, 0.05-10 weight part is with respect to 100 weight part of total amounts of a (meth) acrylate monomer (a). Preferably, 0.10-3 weight part is more preferable.

  The abutment construction material of the present invention can contain a polymerization accelerator for the purpose of adjusting the polymerization rate. Examples of such a polymerization accelerator include aliphatic amines, aromatic tertiary amines having an electron withdrawing group, sulfinic acid and / or salts thereof, sulfur-containing reducing inorganic compounds, and nitrogen-containing reducing inorganic compounds. , Borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, and the like.

  Moreover, a well-known additive can be mix | blended with the abutment building material of this invention in the range which does not reduce a performance. Examples of such additives include polymerization inhibitors, organic fillers, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners, and the like.

  Examples of the polymerization inhibitor include 2,6-dibutylhydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, and 2,6-t-butylphenol. The content of the polymerization inhibitor is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of the (meth) acrylate monomer (a).

  Organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, and chloroprene rubber. , Nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and other organic fillers. It can be used as a mixture of the above. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.

  As an example of a suitable composition of the abutment building material of the present invention, an aromatic (meth) acrylate monomer having a hydroxyl group (a-1) in a total amount of 100 parts by weight of the (meth) acrylate monomer (a) ) 1 to 25 parts by weight, 20 to 75 parts by weight of an aromatic (meth) acrylate monomer (a-2) having no hydroxyl group, and 20 to 75 aliphatic (meth) acrylate monomer (a-3). 50 parts by weight of inorganic particles (b), 5 to 50 parts by weight of inorganic particles (c), and inorganic particles with respect to 100 parts by weight of the total amount of (meth) acrylate monomer (a). (D) 1 to 25 parts by weight, oxidizing agent (e) 0.1 to 20 parts by weight, reducing agent (f) 0.1 to 20 parts by weight, inorganic particles (g) 0 to 250 parts by weight, and initiation of photopolymerization 0.05 to 10 parts by weight of the agent (h) is contained.

  A 1st paste (A) and a 2nd paste (B) can be prepared by mixing said component according to a well-known method using a stirrer, a kneader, a disperser etc., for example.

  As described above, the abutment building material of the present invention has a form in which the first paste (A) and the second paste (B) are packaged (that is, stored in another container or packaging). It is a material for use in abutment construction. The first paste (A) and the second paste (B) are packaged so that they do not come into contact with each other, but at the time of building the abutment, an appropriate amount of both pastes is taken out from the container or packaging, respectively. Used. The form of the container or packaging for storing each paste is not necessarily limited, but in consideration of ease of taking out, a form such as a syringe or tube is preferable. Furthermore, considering the convenience in the abutment building operation, a pair of cylindrical storage containers arranged in parallel, a mixer mounted on the front end side of these storage containers, and the rear end side of each storage container A form in which both pastes are separately filled in each storage container of a kneading apparatus comprising an extruder formed by connecting and fixing a pair of cylindrical extrusion members fitted to each storage container is particularly preferable. In consideration of long-term storage stability, it is preferable to use a container or packaging having good light-shielding properties and sealing properties so that the paste is shielded from ambient light and oxygen.

  The mixing weight ratio of the first paste (A) and the second paste (B) is preferably 1: 5 to 5: 1 in terms of curability of the obtained abutment construction material and operation margin time. : 2 to 2: 1 is more preferable, and about 1: 1 is most preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by these Examples. The abbreviations used below are as follows.

[(Meth) acrylate monomer (a)]
Bis-GMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane D-2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane NPG: Neo Pentyl glycol dimethacrylate # 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane 3G: triethylene glycol dimethacrylate

[Inorganic particles (b)]
Inorganic particles (b-1) to (b-3) are obtained according to the following production method. In addition, in the following manufacturing methods, room temperature shows 25 degreeC.

Inorganic particles (b-1): 11-methacryloyloxyundecyltrimethoxysilane-treated barium glass powder Barium glass (“Raysorb E-3000” manufactured by ESTEC Co., Ltd.) is pulverized with a vibration ball mill to obtain amorphous barium glass fine powder. It was. 100 g of the obtained barium glass powder, 2.0 g of 11-methacryloyloxyundecyltrimethoxysilane (2.0 parts by weight with respect to 100 parts by weight of the core filler) and 200 mL of toluene were placed in a 500 mL single-necked eggplant flask, and 2 at room temperature. Stir for hours. Subsequently, toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours, and further vacuum drying at 90 ° C. for 3 hours to obtain 11-methacryloyloxyundecyltrimethoxysilane-treated barium glass powder [inorganic particles (b- 1)] was obtained. It was 2.5 micrometers when the average particle diameter of the inorganic particle (b-1) was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu make, type "SALD-2100").

Inorganic particles (b-2): 8-methacryloyloxyoctyltrimethoxysilane-treated barium glass powder 11-methacryloyloxyundecyltrimethoxysilane was changed to 8-methacryloyloxyoctyltrimethoxysilane, and grinding with a vibrating ball mill was shortened In the same manner as in the inorganic particles (b-1), 8-methacryloyloxyoctyltrimethoxysilane-treated barium glass powder [inorganic particles (b-2)] was obtained. It was 4.2 micrometers when the average particle diameter of the inorganic particle (b-2) was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu make, model "SALD-2100").

Inorganic particles (b-3): 13-methacryloyloxytridecyltrimethoxysilane-treated barium glass powder 11-methacryloyloxyundecyltrimethoxysilane was changed to 13-methacryloyloxytridecyltrimethoxysilane, pulverization by a vibration ball mill Was treated in the same manner as the inorganic particles (b-1) except that 13-methacryloyloxytridecyltrimethoxysilane-treated barium glass powder [inorganic particles (b-3)] was obtained. It was 1.6 micrometers when the average particle diameter of the inorganic particle (b-3) was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation model "SALD-2100").

[Inorganic particles (c)]
Inorganic particles (c-1) to (c-2) are obtained according to the following production method.

Inorganic particles (c-1): 11-methacryloyloxyundecyltrimethoxysilane-treated colloidal silica powder Barium glass (“Raysorb E-3000” manufactured by ESTEC) was changed to colloidal silica (“Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.) In the same manner as the inorganic particles (b-1) except that the pulverization with a vibration ball mill was not performed, 11-methacryloyloxyundecyltrimethoxysilane-treated colloidal silica powder [inorganic particles (c-1)] Obtained. It was 0.04 micrometer when the average particle diameter of the inorganic particle (c-1) was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation model "SALD-2100").

Inorganic particles (c-2): 3-methacryloyloxypropyltrimethoxysilane-treated colloidal silica powder Barium glass (“Raysorb E-3000” manufactured by Estec) colloidal silica (“Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.), and 11− 3-methacryloyloxy was treated in the same manner as the inorganic particles (b-1) except that methacryloyloxyundecyltrimethoxysilane was changed to 3-methacryloyloxypropyltrimethoxysilane and pulverization by a vibration ball mill was not performed. Propyltrimethoxysilane-treated colloidal silica powder [inorganic particles (c-2)] was obtained. It was 0.02 micrometer when the average particle diameter of the inorganic particle (c-2) was measured using the laser diffraction type particle size distribution measuring apparatus (made by Shimadzu Corporation, model "SALD-2100").

[Inorganic particles (d)]
Inorganic particles (d-1): Alumina powder (“Aluminum Oxide C” manufactured by Nippon Aerosil Co., Ltd., average particle size 0.02 μm)
Inorganic particles (d-2): colloidal silica (“Aerosil 130” manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 0.02 μm)

[Inorganic particles (g)]
The inorganic particles (g) are obtained according to the following production method.

Inorganic particles (g-1): 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder Barium glass (“Raysorb E-3000” manufactured by STEC Co.) was dispersed in water in a constant temperature bath maintained at 30 ° C. After allowing to stand for a period of time, unprecipitated dispersed particles in the supernatant were removed to obtain precipitated inorganic particles. Subsequently, treatment was performed in the same manner as the inorganic particles (b-1) except that 11-methacryloyloxyundecyltrimethoxysilane was changed to 3-methacryloyloxypropyltrimethoxysilane and pulverization with a vibration ball mill was not performed. 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder [inorganic particles (g-1)] was obtained. When the average particle diameter of the inorganic particles (g-1) was measured in the same manner as the inorganic particles (b-1), the particle diameter was in the range of 0.7 to 27 μm, and the average particle diameter was 4.5 μm.

Inorganic particles (g-2): 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder Inorganic particles (b-1) except that 11-methacryloyloxyundecyltrimethoxysilane was changed to 3-methacryloyloxypropyltrimethoxysilane In the same manner as above, 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder [inorganic particles (g-2)] was obtained. When the average particle diameter of the inorganic particles (g-2) was measured in the same manner as the inorganic particles (b-1), the particle diameter was in the range of 0.1 to 27 μm, and the average particle diameter was 2.5 μm.

[Inorganic particles (i)]
Inorganic particles (i): silica powder (“KE-P250” manufactured by Nippon Shokubai Co., Ltd., particle size range 0.15-26 μm, average particle size 2.5 μm)

[Chemical polymerization initiator: oxidizing agent (e)]
BPO: Benzoyl peroxide

[Chemical polymerization initiator: reducing agent (f)]
DEPT: N, N-di (2-hydroxyethyl) -p-toluidine

[Photoinitiator (h)]
CQ: dl-camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Polymerization accelerator]
PDE: 4-N, N-dimethylaminobenzoic acid ethyl ester

[Polymerization inhibitor]
BHT: 2,6-di-t-butyl-4-methylphenol MEHQ: p-hydroquinone monomethyl ether

Examples 1-8 and Comparative Examples 1-6 (Preparation of abutment building materials)
The raw materials shown in Tables 1 to 3 were mixed at room temperature (25 ° C.) to prepare A paste and B paste, and the characteristics were examined according to the methods of Test Examples 1 to 5 below. The results are shown in Tables 1-3.

Test example 1 Discharge force (discharge property)
For the measurement of the discharge force, a storage container made of polyolefin resin in which a pair of cylinders of the same type are arranged in parallel (total internal volume 10 ml, manufactured by Mixpack, product code “SDL 010-01-50”), An extruding device (Mixpak Co., Ltd.) connected and fixed to a mixer mounted on the front end side of these storage containers and a pair of cylindrical push-out members fitted in the respective storage containers from the rear end side of each storage container And a product code “PLH 010-01-46”). By pushing the pushing member, an equal amount of paste inside the cylindrical container is collected. The mixer is bent at an angle of 60 degrees attached to the mixing section (mixed pack, product code “ML 2.5-08-D”) having eight stirring blades (elements) and the mixing section. And a plastic discharge section (product code “IOR 209-20”, manufactured by Mixpack Co., Ltd.), and the container is made of an environmental light-impermeable member.

  After the A paste and B paste are stored separately in each storage container, a pair of extrusion members are inserted into the pair of storage containers, and the paste in each storage container is extruded into the mixing section of the mixer, and mixed. The kneaded product produced by kneading the two pastes in the part was discharged from the discharge part. The discharge force (force required to extrude the paste from the storage container to the mixer) at this time was measured using a universal testing machine (manufactured by Shimadzu Corporation, product code “AGI-100”). The storage container was set up vertically, the crosshead equipped with a jig for compressive strength test was lowered at 4 mm / min, and the paste was discharged while applying a load, and the maximum load at that time was defined as the discharge force. The discharge force was measured at 25 ° C. When the discharge force is 100 N or less, discharge is easy and discharge is good, and discharge is possible at 100 N to 150 N, but discharge is poor, and discharge is impossible at 150 N or more.

Test Example 2 Sagging (Shaping)
A circle with a diameter of 4 mm is drawn in advance on a 30 mm × 30 mm square glass plate, and 0.03 g of the kneaded product is discharged into the circle using the kneading device used in the above-described discharge force evaluation. The glass plate was set up vertically in a 35 ° C. incubator, and allowed to stand for 3 minutes in that state, and the moving distance of the kneaded product from the circle was measured to obtain the drooping distance (mm). The smaller the sag distance, the less likely it will sag and the better the shapeability, so it is suitable for abutment construction materials.

Test Example 3 Shape of ejected material (Shaping property)
A circle with a diameter of 4 mm is drawn in advance on a 30 mm × 30 mm square glass plate, and 0.03 g of the kneaded product is discharged into the circle using the kneading device used in the above-described discharge force evaluation. The glass plate was placed horizontally in a 35 ° C. incubator, left in that state for 30 seconds, and the shape of the kneaded product was visually observed, and the shape of the discharged product was evaluated according to the following evaluation criteria. In addition, 2-4 was set as the pass.
1: A hemispherical shape is not formed, and the discharged shape is maintained.
2: The ejected shape remains slightly while forming a hemispherical shape.
3: A hemisphere is formed and the shape is maintained as it is.
4: A hemispherical shape is formed, but the height is lowered.
5: A hemisphere is not formed.

Test Example 4 Bending test (strength of photocured product)
Using the kneading device used in the above discharge force evaluation, after filling into a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), the top and bottom are pressed with a slide glass, and a dental visible light irradiator Morita, Jetlight 3000) was cured by irradiating both sides with light at 5 points on one side for 20 seconds per point. The obtained cured product is removed from the mold, deburred, stored in water at 37 ° C. for 24 hours, and then the distance between fulcrums using a universal testing machine (product code “AGI-100” manufactured by Shimadzu Corporation). The bending strength was measured at 20 mm and a crosshead speed of 1 mm / min. The bending strength was 130 MPa or more.

Test Example 5 Bending test (strength of chemically cured product)
The test was conducted in the same manner as in Test Example 4 except that the sample was immersed in water at 37 ° C. for 1 hour without being irradiated with light and cured. A bending strength of 120 MPa or more was considered acceptable.

  From the results of Tables 1 to 3, in the abutment building materials of Examples 1 to 8 which are the abutment building materials of the present invention, discharge performance of 100 N or less is obtained, the sagging distance is 0 or 0.5 mm, and the discharge The shape of the object was also good. Moreover, in the abutment building material of Examples 1-8, the intensity | strength of photocured material was 130 Mpa or more, and the intensity | strength of chemical-cured material was 120 Mpa or more. Therefore, according to the abutment building material of the present invention, it can be seen that an abutment building material having excellent dischargeability and formability and excellent strength of the cured product can be obtained.

  The package-type dental polymerizable abutment building material of the present invention is suitably used in the field of dentistry when forming an abutment.

Claims (5)

Including a first paste (A) and a second paste (B),
Both pastes both contain (meth) acrylate monomer (a), and at least one of the pastes is surface-treated with a silane coupling agent (m1) represented by the following formula (I) Inorganic particles (b) having a diameter of 0.5 to 10 μm, inorganic particles (c) having an average particle diameter of 0.01 to 0.1 μm and surface-treated with a silane coupling agent (m2) represented by the following formula (II) And inorganic particles (d) having an average particle diameter of 0.005 to 0.1 μm that have not been surface-treated, one of the pastes containing the oxidizing agent (e) and the other paste containing the reducing agent (f). Packaged dental polymerizable abutment building materials each containing.

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is an oxygen atom or a sulfur atom, and p is 2 or 3, q is an integer of 8-13.)

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrolyzable group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, X ² is an oxygen atom or a sulfur atom, and s is 2 or 3, t is an integer of 1-13.)   The (meth) acrylate monomer (a) is an aromatic (meth) acrylate monomer (a-1) having a hydroxyl group, an aromatic (meth) acrylate monomer (a-2) having no hydroxyl group And an aliphatic (meth) acrylate monomer (a-3), the (meth) acrylate monomer (a-1), (meth) acrylate monomer (a-2), and (meth) The package-type dentistry according to claim 1, wherein the acrylate monomer (a-3) is contained in one or both of the first paste (A) and the second paste (B). Polymerizable abutment building materials. Further, inorganic particles (g) having an average particle diameter of 0.5 to 10 μm and having a particle diameter in the range of 0.1 to 40 μm, which has been surface-treated with a silane coupling agent (m3) represented by the following formula (III) 3. The packaging type dental polymerizable abutment building material according to claim 1 or 2 which is contained.

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrolyzable group, R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms, X ³ is an oxygen atom or a sulfur atom, and v is 2 or 3, w is an integer of 1-7.)   The package-type dental polymerizable abutment building material according to any one of claims 1 to 3, further comprising a photopolymerization initiator (h). In 100 parts by weight of the (meth) acrylate monomer (a) contained in the first paste (A) and the second paste (B), an aromatic (meth) acrylate monomer having a hydroxyl group (a-1 ) 1 to 25 parts by weight, 20 to 75 parts by weight of an aromatic (meth) acrylate monomer (a-2) having no hydroxyl group, and 20 to 75 aliphatic (meth) acrylate monomer (a-3). Containing 50 parts by weight of inorganic particles (b), 5 to 50 parts by weight of inorganic particles (c), and inorganic particles (100 parts by weight) with respect to 100 parts by weight of the (meth) acrylate monomer (a). d) 1 to 25 parts by weight, oxidizing agent (e) 0.1 to 20 parts by weight, reducing agent (f) 0.1 to 20 parts by weight, silane coupling agent (m3) represented by the following formula (III) The average particle size is 0.5 to 0.5 when the particle size is in the range of 0.1 to 40 μm. 2. The packaging-type dental polymerizable abutment according to claim 1, comprising 0 to 250 parts by weight of 0 μm inorganic particles (g) and 0.05 to 10 parts by weight of a photopolymerization initiator (h). material.

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrolyzable group, R ⁹ is a hydrocarbon group having 1 to 6 carbon atoms, X ³ is an oxygen atom or a sulfur atom, and v is 2 or 3, w is an integer of 1-7.)