JP5890220B2 - Dental temporary cement composition - Google Patents

Description

  The present invention relates to a one-step dental temporary cement composition suitable for a dental temporary cement, especially an implant temporary cement.

  In dental treatment, new technologies are being developed every day, and accordingly, development of new dental materials is required.

  For example, in recent years, in dental treatment, treatment by implant placement has become widespread for patients whose teeth have been lost due to elderly age or the like. The implant is composed of an artificial root portion and an upper crown portion directly embedded in the jawbone, and a tooth base portion called an abutment that connects the artificial root portion and the crown portion, and these are used by bonding them together. Temporary cement may be used for this adhesion, but since the implant may be removed for maintenance such as cleaning, the adhesive part needs to be pierce. For this reason, temporary cements are required to have excellent adhesiveness while having appropriate adhesiveness to materials such as metals and ceramics used for implants. Temporary cement is often used after being filled into a syringe-like container (syringe container) and discharged from the container. However, it is easy to discharge, but excess cement after the crown portion is attached does not drip. It is required to have such a shapeable property and excellent operability. In addition, there is a tissue called periodontal ligament in the tooth root of a living body, and the impact due to occlusion is absorbed by this tissue, and the propagation to the jawbone is mitigated. However, since there is no periodontal ligament in the implant treatment part and the impact propagates to the jawbone, it is required to reduce the impact caused by occlusion in the artificial tooth root.

  On the other hand, as an adhesive dental composition in which the cured product has flexibility, Patent Documents 1 and 2 disclose a number average molecular weight composed of an aromatic vinyl monomer as a dental composition suitable for a denture base rebase material and the like. Discloses a dental composition containing a thermoplastic elastomer having a thermoplastic polymer block of 3,000 or more and an elastomer polymer block of at least one block; a (meth) acrylic monomer; and a polymerization initiator . Patent Document 3 discloses a polymer block A mainly containing a styrene unit having an alkyl group having 1 to 8 carbon atoms, a conjugated diene compound unit, and a conjugated diene compound as a dental composition suitable for temporary cement for implants and the like. An alkylstyrene block copolymer comprising a hydrogenated unit and a polymer block B mainly comprising at least one monomer unit selected from the group consisting of isobutylene units; a polymerizable monomer; and a polymerization initiator A dental polymerizable composition is disclosed.

JP-A-10-139613 Japanese Patent Laid-Open No. 10-182329 International Publication No. 2011/048801

  The dental compositions of Patent Documents 1 and 2 assume a denture base rebase material and the like, and there is no description about temporary cement use. The hard segment of the elastomer is a polymer block of various compounds such as styrene, various substituted styrenes, vinyl naphthalene, and the soft segment is a polymer of various compounds such as isoprene, isobutylene, butadiene, and butyl acrylate. The block can be used, and the dischargeability and shapeability of the composition and the vibration damping property of the cured product have not been studied. Furthermore, the dental compositions of Patent Documents 1 and 2 are used as a two-step mold in which a primer is first applied to a denture base and then applied, and thus requires a plurality of operation steps. There was a problem in operability.

  The dental composition of Patent Document 3 is suitable for temporary cements for implants and the like, but as a hard segment of elastomer, a polymer block of substituted styrene (alkyl styrene) is used, and as a soft segment, butadiene, It is said that polymer blocks of various compounds such as isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene can be used, and the dischargeability of the composition and its curing There has been no study on the vibration control of things.

  Therefore, as described above, the temporary cement for an implant has good dischargeability and formability of the composition, adhesion to metals and ceramics, and flexibility and vibration damping of the cured product, and is simple in one step. As a result, it has been found that a temporary cement for an implant that can be used in a single step has not been found.

  Therefore, the present invention is suitable for temporary cement for implants, and is excellent in dischargeability and formability of the composition, adhesion to metals and ceramics, flexibility and vibration damping property of the cured product, and does not require a primer. An object is to provide a one-step temporary cement composition.

The present invention that has achieved the above object includes a polymer block A mainly containing styrene units, and a polymer block B mainly containing at least one monomer unit selected from the group consisting of isoprene units and hydrogenated isoprene units. A styrene block copolymer (a) having a total amount of 1,2-bond units and 3,4-bond units in the polymer block B of 40 mol% or more, (meth) acrylate polymerizable monomer (B) and a polymerization initiator (c),
A one-step dental temporary composition in which the content of the styrenic block copolymer (a) is 2.5 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylate polymerizable monomer (b). It is a cemented cement composition.

  The polymerization initiator (c) of the one-step dental temporary cement composition of the present invention is preferably a chemical polymerization initiator (c-1).

  The one-step dental temporary cement composition of the present invention preferably further contains a polymerization accelerator (d).

  In the one-step type dental temporary cement composition of the present invention, the filler (e) is further added to a total amount of 100 parts by weight of the styrene block copolymer (a) and the (meth) acrylate polymerizable monomer (b). It is preferable to contain 1-250 weight part with respect to this.

  In a preferred embodiment, the one-step dental temporary cement composition of the present invention is a first material containing a chemical polymerization initiator (c-1) and a second material containing a polymerization accelerator (d). Packaged in

  The one-step dental temporary cement composition of the present invention is preferably for an implant.

  The present invention is also a dental temporary cement in which the one-step dental temporary cement composition is stored in a syringe container.

  The one-step dental temporary cement composition of the present invention is excellent in operability because both dischargeability and shaping are compatible. In addition, it exhibits good adhesion suitable for temporary attachment to metals and ceramics used for implants. The cured product of the one-step dental temporary cement composition of the present invention is excellent in flexibility. Furthermore, tan δ around 37 ° C. obtained by dynamic viscoelasticity measurement is high, and the vibration damping property when used as a temporary cement in the oral cavity is excellent. The one-step dental temporary cement composition of the present invention can be used without using a primer. Therefore, the 1-step type dental temporary cement composition of the present invention can be suitably used as a temporary cement for implants.

  The one-step dental temporary cement composition of the present invention is at least selected from the group consisting of a polymer block A mainly containing styrene units, isoprene units and hydrogenated isoprene units (units hydrogenated to isoprene units). And a polymer block B mainly containing one monomer unit, and the total amount of 1,2-bond units and 3,4-bond units in the polymer block B is 40 mol% or more. The blend (a), the (meth) acrylate polymerizable monomer (b), and the polymerization initiator (c) are contained as essential components.

Styrenic block copolymer (a)
The styrenic block copolymer (a) used in the one-step type temporary dental cement composition of the present invention comprises a polymer block A mainly containing styrene units, an isoprene unit and a hydrogenated isoprene unit. And a polymer block B mainly containing at least one selected monomer unit. The total amount of 1,2-bond units and 3,4-bond units in the polymer block B is 40 mol% or more.

  In the present invention, “mainly contains” means that the total monomer units (repeating units) of the polymer block include the corresponding monomer units in an amount of 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. It means that.

  Polystyrene is less compatible with polyisoprene and hydrogenated polyisoprene than substituted polystyrene such as poly (α-methylstyrene) and poly (p-methylstyrene). Therefore, in the styrenic block copolymer (a) used in the present invention, the polymer A mainly containing styrene units and the polymer block B containing isoprene units and / or hydrogenated isoprene units are easily phase-separated. For this reason, the polymer block B, which is a segment having a low glass transition temperature, is hardly inhibited by the polymer block A, which is a segment having a high glass transition temperature, and the body temperature of the human body (37 ° C.) in the cured product of the composition. ) It can exist in a state of high mobility at a temperature around, and as a result, the vibration damping property at around 37 ° C. of the cured product of the composition containing the styrenic block copolymer (a) becomes high. Further, when the polymer block B mainly contains at least one monomer unit selected from isoprene units and hydrogenated isoprene units, the dischargeability of the composition containing the styrene block copolymer (a) is improved. .

  The polymer block A may contain other monomer units as required in addition to the styrene units. Examples of other monomers include butadiene and isoprene. The bonding form of the styrene unit and the other monomer units in the polymer block A may be any form such as random, block, alternating, and tapered.

  The polymer block B may contain other monomer units in addition to the isoprene unit and the hydrogenated isoprene unit as long as the object and effect of the present invention are not hindered. Examples of other monomer units include structural units derived from styrene, p-methylstyrene, butadiene, and the like. Two or more of these units may be contained. There is no particular limitation on the form of bonding with the isoprene unit, hydrogenated isoprene unit, and other monomer units in the polymer block B, and it is random, tapered, completely alternating, partially block-like, block-like, or two of them. It may be a combination of more than one species.

  The total amount of 1,2-bond units and 3,4-bond units of isoprene units and hydrogenated isoprene units in all monomer units of polymer block B is the discharge of the one-step dental temporary cement composition 40 mol% or more, preferably 40 to 90 mol%, more preferably 42.5 to 75 mol%, more preferably 45 to 60 mol. % Is more preferable.

  The hydrogenated isoprene unit is usually introduced by producing a styrene block copolymer (a) containing an isoprene unit and hydrogenating it. When the polymer block B contains a hydrogenated isoprene unit, the content of the hydrogenated isoprene unit relative to the total of the isoprene unit and the hydrogenated isoprene unit is not particularly limited. The ratio of the hydrogenated isoprene unit to the total of the isoprene unit and the hydrogenated isoprene unit can be determined by iodine value measurement, infrared spectroscopy measurement, NMR measurement, or the like.

  As long as the polymer block A and the polymer block B are bonded to the styrenic block copolymer (a), the bonding type is not limited, and is linear, branched, radial, or 2 thereof. Any combination of two or more may be used. Among them, it is preferable that the bond form of the polymer block A and the polymer block B is a linear form, for example, when the polymer block A is represented by A and the polymer block B is represented by B. In addition, a diblock copolymer represented by A-B, a triblock copolymer represented by A-B-A, a tetra-block copolymer represented by A-B-A-B, A-B-A- Examples thereof include a pentablock copolymer represented by B-A. Among them, the diblock copolymer (A-B) and the triblock copolymer (A-B-A) are easy to produce the styrenic block copolymer (a), and the cured product of the composition. It is preferably used from the viewpoint of flexibility.

The content of the polymer block A in the styrenic block copolymer (a) is within the range of 5 to 50% by weight from the viewpoint of the flexibility of the cured product obtained from the one-step type dental temporary cement composition. It is preferable that it is within a range of 10 to 40% by weight. The content of the polymer block A in the styrenic block copolymer (a) can be determined by, for example, the ¹ H-NMR measurement.

  In addition, the styrenic block copolymer (a) has a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular end unless the purpose of the present invention is impaired. You may have 1 type, or 2 or more types of group. Further, as the styrene block copolymer (a), the above-described styrene block copolymer (a) having a functional group and a styrene block copolymer (a) having no functional group are mixed and used. May be.

  The weight average molecular weight of the styrenic block copolymer (a) is preferably in the range of 10,000 to 500,000, more preferably in the range of 30,000 to 400,000. When the weight average molecular weight of the styrenic block copolymer (a) is less than 10,000, the mechanical strength of the cured product obtained from the one-step dental temporary cement composition may be reduced. If it exceeds 500,000, the cured product of the one-step dental temporary cement composition may be inferior in flexibility. In addition, a weight average molecular weight here means the weight average molecular weight of polystyrene conversion calculated | required by a gel permeation chromatography (GPC) measurement.

  The weight average molecular weight of the polymer block A in the styrenic block copolymer (a) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000. The weight average molecular weight of the polymer block B in the styrenic block copolymer (a) is preferably 10,000 to 450,000, more preferably 20,000 to 250,000.

  The molecular weight distribution (weight average molecular weight / number average molecular weight: Mw / Mn) of the styrenic block copolymer (a) of the present invention is easy to obtain an appropriate viscosity and formability of the composition and a high flexibility of the cured product. Therefore, it is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, and still more preferably 1.0 to 1.3. The styrene block copolymer (a) having such a molecular weight distribution can be obtained by a living anion polymerization method.

  As a suitable example of the manufacturing method by the living anion polymerization method of a styrene-type block copolymer (a), an alkyl lithium compound etc. is used as an initiator in an organic solvent inert to polymerization reaction, such as n-hexane and a cyclohexane. And a method of sequentially polymerizing styrene and isoprene to form a block copolymer.

  In order to produce a styrene block copolymer (a) containing a hydrogenated isoprene unit, the styrene block copolymer obtained by the above living anion polymerization method is used, for example, with a saturated hydrocarbon solvent such as cyclohexane. Among them, hydrogenation catalysts such as Ziegler-type catalysts composed of combinations of organometallic compounds composed of Group 9 and 10 metals such as nickel and cobalt and organoaluminum compounds such as triethylaluminum and triisobutylaluminum, or organolithium compounds In general, hydrogenation may be performed under the conditions of a reaction temperature of 20 to 100 ° C. and a hydrogen pressure of 0.1 to 10 MPa.

  The one-step dental temporary cement composition containing the styrenic block copolymer (a) of the present invention has a high tan δ around 37 ° C. obtained by measuring the dynamic viscoelasticity of the cured product. Excellent vibration damping when used for temporary cement. Such tan δ can be measured by a dynamic viscoelasticity measuring device, and the larger the value of tan δ, the better the vibration damping property, and the more the impact caused by occlusion can be absorbed. The tan δ at 37 ° C. of the composition obtained by dynamic viscoelasticity measurement is preferably 0.01 or more, and more preferably 0.1 or more.

(Meth) acrylate polymerizable monomer (b)
As the (meth) acrylate polymerizable monomer (b) in the present invention, there are a monofunctional monomer having one (meth) acryloyl group and a polyfunctional monomer having a plurality of (meth) acryloyl groups. Illustrated. The (meth) acrylate polymerizable monomer (b) may be used alone or in combination of two or more.

  Examples of monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy Hexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl ( (Meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3 -(Meth) acryloyloxypropyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, (meth) acrylamide and the like. These may be used alone or in combination of two or more. Among these, n-hexyl (meth) acrylate, cyclohexyl (meta) are preferred because they are miscible with the styrenic block copolymer (a) and have excellent flexibility in the cured product of the one-step dental temporary cement composition. ) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and cetyl (meth) acrylate are preferred.

  Examples of the polyfunctional monomer include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, and trifunctional or higher functional polymerizable monomers. It is done.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxy) Phenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2 -(4- (meth) acryloyloxyditriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane is preferable in terms of excellent miscibility with the styrenic block copolymer (a) and the cured product strength of the composition. Among them, a compound having an average addition mole number of ethoxy groups of 2.6 (common name “D2.6E”) is preferable.

  Examples of aliphatic compound-based bifunctional polymerizable monomers 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, 1,3-butanediol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-ethyl-1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- Decanediol (Meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as “UDMA”), etc. Can be mentioned. Among these, triethylene glycol di (meth) acrylate, 2-ethyl-1,6-hexanediol diene is preferable in that it is miscible with the styrenic block copolymer (a) and is easy to handle the resulting composition. (Meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1,10-decanol di (meth) acrylate are preferred.

  Examples of trifunctional or higher polymerizable monomers include trimethylolpropane tri (meth) 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-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like. Among these, trimethylolpropane tri (meth) acrylate is preferable because it is excellent in miscibility with the styrene-based block copolymer (a).

  The monofunctional monomer and polyfunctional monomer described above do not contain an acidic group, but the one-step dental temporary cement composition of the present invention adjusts the adhesive strength to the prosthesis. Therefore, an acidic group-containing polymerizable monomer may be included as the (meth) acrylate-based polymerizable monomer (b). Such an acidic group-containing polymerizable monomer has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and ( Examples thereof include a radical polymerizable monomer having at least one (meth) acryloyl group.

  Examples of the polymerizable monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyldi Hydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxy Octyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) actyl Royloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate, Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- ( (Meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloylo Sidedecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen Examples thereof include phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. These may be used alone or in combination of two or more.

  The above (meth) acrylate polymerizable monomer (b) may be used alone, but from the viewpoint of flexibility of the cured product of the one-step dental temporary cement composition, bifunctional polymerization It is preferable to use a monomer and a monofunctional monomer in combination, and the ratio in the case of using them together is not particularly limited, but the total amount of the (meth) acrylate polymerizable monomer (b) is 100% by weight. The amount of the bifunctional polymerizable monomer is preferably 1 to 75% by weight, more preferably 2.5 to 50% by weight, and 5 to 25% by weight. Is more preferable. When the blending amount of the bifunctional polymerizable monomer is 75% by weight or less, the toughness of the cured product of the one-step type temporary dental cement composition is increased and is difficult to break. In the present specification, the “total amount of (meth) acrylate polymerizable monomer (b)” means the total amount of (meth) acrylate polymerizable monomer contained in the entire composition. For example, when the composition of the present invention takes a two-material form, it means a sum of weights of (meth) acrylate polymerizable monomers contained in each material.

  The amount of the acidic group-containing polymerizable monomer is not particularly limited, but may be 5% by weight or less when the total amount of the (meth) acrylate polymerizable monomer (b) is 100% by weight. Preferably, it is 1% by weight or less. When the blending amount of the acidic group-containing polymerizable monomer is 5% by weight or less, appropriate temporary attachment properties are maintained.

  About the usage-amount of a styrene-type block copolymer (a) and a (meth) acrylate type polymerizable monomer (b), with respect to 100 weight part of the total amount of a (meth) acrylate type polymerizable monomer (b), Styrenic block copolymer (a) is preferably 2.5 to 100 parts by weight, more preferably 5 to 75 parts by weight, and most preferably 5 to 60 parts by weight.

Polymerization initiator (c)
The polymerization initiator (c) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental use are preferably used. In particular, the chemical polymerization initiator (c-1) and the photopolymerization initiator (c-2) are used alone or in appropriate combination of two or more.

  Of the polymerization initiator (c) used in the present invention, an organic peroxide is preferably used as the chemical polymerization initiator (c-1). The organic peroxide used for a chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

  Examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

  Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1, 1,3,3-tetramethylbutyl hydroperoxide and the like.

  Examples of the diacyl peroxide used as the chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.

  Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  Examples of the peroxyketal used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, etc. Can be mentioned.

  Peroxyesters used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.

  Examples of the peroxydicarbonate used as the chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples include peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

  Among these organic peroxides, diacyl peroxide is preferably used from the overall balance of safety, storage stability and radical generating ability, and benzoyl peroxide is particularly preferably used among them.

  As the photopolymerization initiator (c-2), (bis) acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds And α-aminoketone compounds.

  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, a composition 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.

  Examples of the (bis) acylphosphine oxides used as the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, and bis (2,4,6). -Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of the α-diketone used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′- Examples thereof include oxybenzyl and acenaphthenequinone. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Although the compounding quantity of the polymerization initiator (c) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, the total amount of (meth) acrylate type | system | group polymerizable monomer (b) is 100 weight. It is preferable that 0.001-30 weight part of polymerization initiators (c) are contained with respect to parts. When the blending amount of the polymerization initiator (c) is less than 0.001 part by weight, the polymerization may not proceed sufficiently and may cause stickiness, more preferably 0.05 part by weight or more, and even more preferably 0. .1 part by weight or more. On the other hand, when the blending amount of the polymerization initiator (c) exceeds 30 parts by weight, if the polymerization performance of the polymerization initiator itself is low, it may cause precipitation from the composition. Parts or less, more preferably 15 parts by weight or less, and most preferably 10 parts by weight or less.

  The one-step dental temporary cement composition of the present invention contains the styrene block copolymer (a), a (meth) acrylate polymerizable monomer (b), and a polymerization initiator (c). As long as it is not particularly limited, it can be easily produced by methods known to those skilled in the art.

Polymerization accelerator (d)
The one-step dental temporary cement composition of the present invention preferably contains a polymerization accelerator (d). Examples of the polymerization accelerator (d) include amines, sulfinic acid and salts thereof, sulfites, bisulfites, aldehydes, thiourea compounds, organophosphorus compounds, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, A tin compound, a vanadium compound, a halogen compound thiol compound, etc. are mentioned.

  Examples of amines used as the polymerization accelerator (d) include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; diisopropylamine, dibutylamine, N-methylethanolamine and the like. Secondary aliphatic amines; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine Dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, triethanolamine Tertiary aliphatic amines such as butylamine; 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, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethyl Aminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4 -Aromatic amines such as butyl dimethylaminobenzoate. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of the thiourea compound used as the polymerization accelerator (d) include 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-. Diethylthiourea, N, N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthio Examples include urea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like.

  Although the compounding quantity of the polymerization accelerator (d) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, the total amount of (meth) acrylate type | system | group polymerizable monomer (b) is 100 weight. It is preferable to contain 0.001-30 weight part of polymerization accelerators (d) with respect to parts. When the blending amount of the polymerization accelerator (d) is less than 0.001 part by weight, the polymerization may not proceed sufficiently and may cause stickiness, more preferably 0.05 part by weight or more, and even more preferably 0. .1 part by weight or more. On the other hand, when the blending amount of the polymerization accelerator (d) exceeds 30 parts by weight, if the polymerization performance of the polymerization initiator itself is low, it may cause precipitation from the composition. Part or less, more preferably 10 parts by weight or less.

  In the present invention, the chemical polymerization initiator (c-1) and the polymerization accelerator (d) may be combined to form a redox polymerization initiator. At this time, from the viewpoint of storage stability, the chemical polymerization initiator (c-1) and the polymerization accelerator (d) are separately packaged and stored. Accordingly, the one-step dental temporary cement composition is provided as including at least a first material containing a chemical polymerization initiator (c-1) and a second material containing a polymerization accelerator (d). Preferably, it is provided as a two-material type kit comprising the first material and the second material, and more preferably in a two-paste type form in which the two materials are both in the form of a paste. Provided as a kit to be used. When used in the form of a two-paste type, each paste is stored in a state where the pastes are isolated from each other, and the two pastes are kneaded immediately before use to advance chemical polymerization, and further contains a photopolymerization initiator. In some cases, it is preferable to cure by proceeding chemical polymerization and photopolymerization.

Filler (e)
The one-step dental temporary cement composition of the present invention includes a filler (e) for adjusting the paste properties of the temporary cement composition before curing and for imparting X-ray contrast properties to the cured product. ) Can be further blended. Examples of such fillers include organic fillers, inorganic fillers, and organic-inorganic composite fillers.

  Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyester, polyamide, polycarbonate, and 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 copolymer A polymer etc. are mentioned, These can be used individually or in mixture of 2 or more types. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.

  Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramic. , Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. . These can also be used individually or in mixture of 2 or more types. The shape of the inorganic filler is not particularly limited, and an amorphous filler and a spherical filler can be appropriately selected and used.

  In order to adjust the miscibility with the (meth) acrylate polymerizable monomer (b), the inorganic filler is used after being previously surface-treated with a known surface treatment agent such as a silane coupling agent as necessary. May be. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

  As the surface treatment method, a known method can be used without any particular limitation. For example, the surface treatment agent is spray-added while vigorously stirring the inorganic filler, the inorganic filler and the surface treatment into an appropriate solvent, and the like. After dispersing or dissolving the agent, remove the solvent, or hydrolyze the alkoxy group of the surface treatment agent with an acid catalyst in an aqueous solution to convert it to a silanol group, and adhere to the surface of the inorganic filler in the aqueous solution In any method, heating is usually performed in the range of 50 to 150 ° C. to complete the reaction between the surface of the inorganic filler and the surface treatment agent. It can be carried out.

  The organic-inorganic composite filler is obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, forming a paste, polymerizing, and pulverizing. As the organic-inorganic composite filler, for example, a TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.

  The average particle size of the filler (e) is preferably 0.001 to 50 μm, and preferably 0.001 to 10 μm, from the viewpoint of the handleability of the composition obtained and the mechanical strength of the cured product. More preferred. In the present specification, the average particle diameter of the filler can be measured by any method known to those skilled in the art, and can be easily measured by, for example, a laser diffraction type particle size distribution measuring apparatus described in the following examples.

  Although the compounding quantity of a filler (e) is not specifically limited, From a viewpoint of the handleability of the composition obtained, and the softness | flexibility of the hardened | cured material, a styrene-type block copolymer (a) and a (meth) acrylate type polymerizable monomer The amount is preferably 1 to 250 parts by weight, more preferably 1 to 100 parts by weight based on 100 parts by weight of the total amount of the body (b).

  The one-step dental temporary cement composition of the present invention includes other polymers such as natural rubber and synthetic polymers for the purpose of modifying flexibility, fluidity and the like within the scope of the present invention. Isoprene rubber, liquid polyisoprene rubber and hydrogenated product thereof, polybutadiene rubber, liquid polybutadiene rubber and hydrogenated product thereof, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, isoprene-isobutylene rubber, acrylonitrile-butadiene rubber Styrene-based elastomers such as polystyrene-polybutadiene-polystyrene block copolymers or hydrogenated products thereof can be added.

  The one-step dental temporary cement composition of the present invention can contain a softener as necessary. Examples of the softener include petroleum softeners such as paraffinic, naphthenic and aromatic process oils, and vegetable oil softeners such as paraffin and rosin. These softeners can be used alone or in admixture of two or more. The content of the softening agent is not particularly limited as long as the gist of the present invention is not impaired. Usually, the total amount of the styrene block copolymer (a) and the (meth) acrylate polymerizable monomer (b) is 100. It is 300 parts by weight or less, preferably 100 parts by weight or less with respect to parts by weight.

  Moreover, a well-known additive can be mix | blended with the 1-step type dental temporary cement composition of this invention in the range which does not reduce performance. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners and the like.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene and the like can be mentioned. The content of the polymerization inhibitor is preferably 0.001 to 1.0 part by weight with respect to 100 parts by weight of the total amount of the styrene block copolymer (a) and the (meth) acrylate polymerizable monomer (b). .

  The one-step dental temporary cement composition of the present invention is excellent in operability because both dischargeability and shaping are compatible. Moreover, the adhesiveness which is not too high and not too low to the extent that it can be temporarily attached with respect to the metal and ceramics used for an implant is shown. Furthermore, the cured product of the one-step dental temporary cement composition of the present invention is excellent in flexibility. In addition, it has excellent vibration damping properties around 37 ° C. The one-step dental temporary cement composition of the present invention can be used without using a primer. Therefore, the one-step type dental temporary cement composition of the present invention can be suitably used as a dental temporary cement that makes use of such advantages, and can be optimally used as a temporary cement for an implant.

  An example of the suitable structure of the temporary cement for implants is shown. The temporary cement for an implant is 2.5 to 100 parts by weight of a styrenic block copolymer (a), 100% by weight of a polymerization initiator (100% by weight of the total amount of the (meth) acrylate polymerizable monomer (b)). c) 0.05 to 15 parts by weight, polymerization accelerator (d) 0.05 to 20 parts by weight, and styrene block copolymer (a) and (meth) acrylate polymerizable monomer (b 1) to 250 parts by weight of filler (e) with respect to 100 parts by weight of the total amount of)), and styrene block copolymer (100 parts by weight of (meth) acrylate polymerizable monomer (b)). 5) to 75 parts by weight of a), 0.1 to 10 parts by weight of the polymerization initiator (c), 0.1 to 10 parts by weight of the polymerization accelerator (d), and a styrenic block copolymer (a) And the total amount of the (meth) acrylate polymerizable monomer (b) More preferably contains the filler (e) 1 to 100 parts by weight per 00 parts by weight.

  The one-step dental temporary cement composition of the present invention can be stored in a syringe container to obtain a dental temporary cement in a product form. When the one-step type dental temporary cement composition is a two-material type, for example, each material is stored in two syringe containers connected in parallel to form a dental temporary cement in a product form. The syringe container may further include a mixer such as a mixing tip at its tip.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.

In the following reference examples, the weight average molecular weights of sampled polymers (polymers forming blocks) and styrene block copolymers (final polymers) were measured by gel permeation chromatography (hereinafter referred to as GPC). From polystyrene conversion. The apparatus and conditions used for GPC measurement are as follows.
[GPC measurement equipment and conditions]
-Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: tetrahydrofuran Eluent flow rate: 1.0 ml / min Detection method: differential refractive index (RI)
UV absorption rate

Moreover, in the following reference examples, the constituent ratio of each polymer block in the styrene block copolymer was determined by ¹ H-NMR measurement. ^The apparatus and conditions used for ¹ H-NMR measurement are as follows.
^[1 apparatus and conditions H-NMR measurement]
・ Device: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform

  The styrenic block copolymer used in this example was produced as follows.

Reference Example 1 Production of Styrenic Block Copolymer (a) -1 In a pressure vessel equipped with a nitrogen-substituted stirrer, 5000 g of cyclohexane and 13.0 ml of sec-butyllithium (11 wt%, cyclohexane solution) were added, and this solution To this was added 157 g of styrene over 30 minutes and polymerized at 50 ° C. for 30 minutes. The weight average molecular weight of polystyrene analyzed by GPC was 10,000. Next, 15 g of tetrahydrofuran was added, 1220 g of isoprene was added over 60 minutes, polymerized at 40 ° C. for 30 minutes, 157 g of styrene was further added over 30 minutes, polymerized at 40 ° C. for 30 minutes, and polystyrene-poly A reaction mixture containing an isoprene-polystyrene triblock copolymer (hereinafter referred to as a block copolymer (a) -1) was obtained. The number average molecular weight of the obtained block copolymer (a) -1 was 127,000, the weight average molecular weight was 130000, and the styrene content measured by ¹ H-NMR was 20% by weight. The total of 1,2-bond units and 3,4-bond units in the polyisoprene block was 55 mol%.

Reference Example 2 Production of Styrenic Block Copolymer (a) -2 In the polymerization reaction solution obtained in Reference Example 1, a Ziegler hydrogenation catalyst formed from nickel octylate and triethylaluminum was placed in a hydrogen atmosphere. And hydrogenation reaction of polystyrene-polyisoprene-polystyrene triblock copolymer by performing hydrogenation reaction at a hydrogen pressure of 0.8 MPa and 80 ° C. for 5 hours [hereinafter referred to as block copolymer (a) -2]]. As a result of GPC measurement of the obtained block copolymer (a) -2, the main components were Mt (peak top of average molecular weight) = 120,000, Mn (number average molecular weight) = 1115,000, Mw (weight average molecular weight) = 18000, It was a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer having Mw / Mn = 1.02, and the hydrogenation rate of isoprene block B measured by ¹ H-NMR was 90%.

Reference Example 3 Production of Styrenic Block Copolymer (a) -3 In a pressure vessel equipped with a stirrer purged with nitrogen, 5000 g of cyclohexane and 15.6 ml of sec-butyllithium (11 wt%, cyclohexane solution) were added, and this solution To this was added 235 g of styrene over 30 minutes and polymerized at 50 ° C. for 30 minutes. The weight average molecular weight of polystyrene analyzed by GPC was 8,500. Next, 13 g of tetrahydrofuran was added, 1070 g of isoprene was added over 60 minutes, polymerized at 50 ° C. for 30 minutes, 235 g of styrene was further added over 30 minutes, polymerized at 50 ° C. for 30 minutes, and polystyrene-poly A reaction mixed solution containing an isoprene-polystyrene triblock copolymer (hereinafter referred to as a block copolymer (a) -3) was obtained. The number average molecular weight of the obtained block copolymer (a) -3 was 85000, the weight average molecular weight was 87000, and the styrene content measured by ¹ H-NMR was 30% by weight. The total of 1,2-bond units and 3,4-bond units in the polyisoprene block was 42 mol%.

Reference Example 4 Production of Styrenic Block Copolymer (a) -4 In a pressure vessel equipped with a stirrer purged with nitrogen, 5000 g of cyclohexane and 13.0 ml of sec-butyllithium (11 wt%, cyclohexane solution) were added, and this solution 157 g of styrene was added over 30 minutes to polymerize at 50 ° C. for 30 minutes, then 15 g of tetrahydrofuran was added, and then 1220 kg of a mixture of 90/10 isoprene / butadiene mixture ratio (volume ratio) was added over 60 minutes. Then, after polymerizing at 40 ° C. for 30 minutes, 157 g of styrene was further added over 30 minutes, polymerized at 40 ° C. for 30 minutes, and a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer (hereinafter referred to as this). A reaction mixture containing a block copolymer (a) -4) was obtained. The number average molecular weight of the obtained block copolymer (a) -4 was 127,000, the weight average molecular weight was 130000, and the styrene content measured by ¹ H-NMR was 20% by weight. The total of 1,2-bond units and 3,4-bond units in the poly (isoprene / butadiene) block was 50 mol%.

Reference Example 5 Production of Styrenic Block Copolymer 1 In a pressure vessel equipped with a nitrogen-substituted stirrer, 5000 g of cyclohexane and 13.0 ml of sec-butyl lithium (11 wt%, cyclohexane solution) were added, and 157 g of styrene was added to this solution. It added over 30 minutes and superposed | polymerized at 50 degreeC for 30 minutes. The weight average molecular weight of polystyrene analyzed by GPC was 10,000. Next, 15 g of tetrahydrofuran was added, 1220 g of butadiene was added over 60 minutes, polymerized at 40 ° C. for 30 minutes, 157 g of styrene was further added over 30 minutes, polymerized at 40 ° C. for 30 minutes, and polystyrene-polybutadiene. A reaction mixture containing polystyrene triblock copolymer (hereinafter referred to as block copolymer 1) was obtained. The number average molecular weight of the obtained block copolymer 1 was 127,000, the weight average molecular weight was 130000, and the styrene content measured by ¹ H-NMR was 20% by weight. The 1,2-bond unit in the polybutadiene block was 55 mol%.

Reference Example 6 Production of Styrenic Block Copolymer 2 In a pressure vessel equipped with a stirrer substituted with nitrogen, 5000 g of cyclohexane and 13.0 ml of sec-butyl lithium (11 wt%, cyclohexane solution) were added, and 157 g of styrene was added to this solution. Add over 30 minutes and polymerize at 50 ° C. for 30 minutes, then add 5 g of tetrahydrofuran, add 1220 g of isoprene over 60 minutes and polymerize at 40 ° C. for 30 minutes, then add 157 g of styrene over 30 minutes. In addition, polymerization was carried out at 40 ° C. for 30 minutes to obtain a reaction mixture containing a polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as block copolymer 2). The number average molecular weight of the obtained block copolymer 2 was 127,000, the weight average molecular weight was 130000, and the styrene content measured by ¹ H-NMR was 20% by weight. The total of 1,2-bond units and 3,4-bond units in the polyisoprene block was 30 mol%.

  Next, components of the dental temporary cement compositions of Examples and Comparative Examples are described below together with abbreviations.

[(Meth) acrylate-based polymerizable monomer (b)]
DD: 1,10-decanediol dimethacrylate D2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane EHMA: 2-ethylhexyl methacrylate MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Chemical polymerization initiator (c-1)]
BPO: Benzoyl peroxide

[Photopolymerization initiator (c-2)]
CQ: camphorquinone BAPO: bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Polymerization accelerator (d)]
DEPT: N, N-di (2-hydroxyethyl) -p-toluidine PDE: N, N-dimethylaminobenzoic acid ethyl ester

[Filler (e)]
Fillers (e) -1 and (e) -2 are obtained according to the following production method.

Filler (e) -1: 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder Barium glass (“E-3000” manufactured by ESTEC) was pulverized with a vibration ball mill to obtain barium glass powder. 100 g of the obtained barium glass powder, 0.5 g of 3-methacryloyloxypropyltrimethoxysilane, and 200 ml of toluene were placed in a 500 ml one-necked eggplant flask and stirred at room temperature for 2 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 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder (filler (e) -1 ) It was 2.4 micrometers when the average particle diameter of the filler (e) -1 was measured using the laser diffraction type particle size distribution measuring apparatus (made by Shimadzu Corporation, model "SALD-2100").

Filler (e) -2: 3-methacryloyloxypropyltrimethoxysilane-treated colloidal silica powder 100 g of colloidal silica powder (“Aerosil OX50” manufactured by Nippon Aerosil Co., Ltd.), 0.5 g of 3-methacryloyloxypropyltrimethoxysilane and 200 ml of toluene 500 ml And stirred at room temperature for 2 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, and 3-methacryloyloxypropyltrimethoxysilane-treated colloidal silica powder (filler (e) -2 ) It was 0.04 micrometer when the average particle diameter of the filler (e) -2 was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu make, model "SALD-2100").

[Polymerization inhibitor]
BHT: 3,5-di-tert-butyl-4-hydroxytoluene

Examples 1-7 and Comparative Examples 1-4
The raw materials shown in Table 1 and Table 2 were mixed at room temperature (25 ° C.) to prepare A paste and B paste, and dental temporary cement compositions of Examples and Comparative Examples were obtained. The dischargeability, shapeability, adhesion to metals and ceramics, bending elastic modulus of the cured product of the composition, and tan δ at 37 ° C. were measured or evaluated as follows.

Test Example 1 Dischargeability (Discharge force):
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 5 ml, manufactured by Mixpack, product code “SDL 005-01-SI”), 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 “PED 005-01-SI”). By pushing the pushing member, an equal amount of paste inside the cylindrical container is collected. The mixer used was a mixing chip (product code “ML 2.5-08-S” manufactured by Mixpack Co., Ltd.) having eight stirring blades (elements).

  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 ejection force is 40 N or less, ejection is easy and the ejection performance is good, and ejection is possible at 40 N to 60 N, but ejection is poor, and ejection is impossible at 60 N or more.

Test Example 2 Shapeability:
A circle with a diameter of 3 mm is drawn on a dental kneaded paper of 59 mm long and 83 mm wide, 0.3 g of a dental temporary cement composition is placed in the circle, and it stands vertically in a 35 ° C. incubator. Then, the dental temporary cement composition was moved for 3 minutes from the circle. This test was performed three times, and the average value of the three measurement values was defined as the sagging distance (mm). It shows that a dental temporary cement composition flows easily, so that drooping distance is large. Those having a sagging distance of 3 mm or more in this test have no formability and poor operability.

Test Example 3 Flexural modulus:
It evaluated by the bending test based on ISO4049. That is, the dental temporary cement composition prepared in the above example was filled in a SUS mold (length 2 mm × thickness 2 mm × length 25 mm), and the top and bottom were pressed with a slide glass, and a constant temperature water bath at 37 ° C. The dental temporary cement composition was cured by immersion in The obtained cured product was subjected to a bending test at a crosshead speed of 2 mm / min using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-100kNI), and the bending elastic modulus was measured. In order to ensure excellent flexibility, the flexural modulus is preferably 500 MPa or less.

Test Example 4 Adhesiveness to Metal # 1000 Silicon Carbide Paper (Nippon Kenshi) under running water on a piece of titanium 10 mm long and 5 mm thick (manufactured by Matsukaze Co., Ltd., titanium 100, titanium content 99.5% or more) After polishing to obtain a smooth surface, water on the surface was blown off with a dental air syringe.

  A 150 μm-thick adhesive tape having a round hole with a diameter of 5 mm was applied to the smooth surface of the titanium piece to define the adhesion area. Next, the dental temporary adhering cement composition is filled into the round hole, and the excess portion overflowing from the round hole is removed with a razor so that the surface becomes smooth, and then left in a room at 25 ° C. for 1 hour. The dental temporary cement composition was cured. With respect to the hardened | cured material which left the unpolymerized layer of the obtained dental temporary cement composition, stainless steel cylindrical rods (diameter 7mm, using Kuraray Medical Co., Ltd., Panavia 21) were used. One end face (circular cross section) having a length of 2.5 cm) was bonded. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. A total of five samples for adhesion test were prepared, and all the samples immersed in distilled water were stored in a thermostat kept at 37 ° C. for 24 hours.

  The tensile bond strength of the above sample for the adhesion test was measured with a universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-100kNI) at a crosshead speed of 2 mm / min, and the average value was taken as the tensile bond strength. When the adhesive strength is less than 0.5 MPa, the adhesive force is too low, causing dropout, and when it is greater than 5 MPa, the adhesive strength is too strong to obtain temporary attachment.

Test Example 5 Adhesiveness with Ceramics Tested in the same manner as in Test Example 4 except that the titanium 100 of Test Example 4 was replaced with a ceramic piece (Vitaseley, manufactured by VITA).

Test Example 6 Adhesiveness with zirconia The test was conducted in the same manner as in Test Example 4 except that the titanium 100 of Test Example 4 was replaced with a zirconia piece (Delzply, Cercon).

Test Example 7 tan δ:
A cured product of a temporary dental cement composition is placed on a rheometer (manufactured by TA Instruments Japan Co., Ltd., AR2000), a parallel plate having a diameter of 20 mm is used, and a shear rate of 100 Hz is set in a range of 0 to 60 ° C. Tan δ was measured by rotating in a certain direction at a frequency. When the value of tan δ at 37 ° C. in this measurement is 0.01 or less, the vibration damping property is small.

  From the results in Table 1, the dental temporary cement composition of the example containing the styrenic block copolymer corresponding to the styrenic block copolymer (a) is suitable for ejection and shaping, and before curing. It can be seen that the operability is excellent. Moreover, it turns out that it has the adhesiveness suitable for temporary attachment with respect to titanium and ceramics. Further, it can be seen that the cured product has a low flexural modulus and is excellent in flexibility. It can also be seen that the cured product has a large tan δ value at 37 ° C. and is excellent in vibration damping properties. On the other hand, from the results shown in Table 2, the dental temporary cement composition of Comparative Example not containing a styrene block copolymer or a styrene block copolymer not corresponding to the styrene block copolymer (a) is contained. It can be seen that the dental temporary cement composition of the comparative example cannot simultaneously satisfy all the properties of discharge property, formability, adhesion to titanium and ceramics, flexural modulus, and tan δ value at 37 ° C. From the above, it can be seen that the dental temporary cement composition of the present invention is particularly suitable for temporary cement for implants.

  The one-step dental temporary cement composition of the present invention can be suitably used as a temporary cement for implants among dental temporary cements.

Claims (8)

A polymer block A styrene units (excluding substituted styrenes) including 90 wt% or more, the polymer block B comprising at least one monomer units 90 wt% or more selected from the group consisting of isoprene units and hydrogenated isoprene units A styrene block copolymer (a) in which the total amount of 1,2-bond units and 3,4-bond units in the polymer block B is 40 mol% or more, (meth) acrylate polymerizability Containing a monomer (b) and a polymerization initiator (c);
A one-step dental temporary composition in which the content of the styrenic block copolymer (a) is 2.5 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylate polymerizable monomer (b). Cementation composition.   The one-step dental temporary cement composition according to claim 1, wherein the polymerization initiator (c) is a chemical polymerization initiator (c-1).   The one-step dental temporary cement composition according to claim 1 or 2, further comprising a polymerization accelerator (d).   The filler (e) is further contained in an amount of 1 to 250 parts by weight based on 100 parts by weight of the total amount of the styrene block copolymer (a) and the (meth) acrylate polymerizable monomer (b). The one-step type temporary dental cement composition according to any one of the above.   1 step of any one of Claims 1-4 currently packaged by the 1st material containing a chemical-polymerization initiator (c-1) and the 2nd material containing a polymerization accelerator (d). Type dental temporary cement composition. The molecular weight distribution (Mw / Mn) of the styrenic block copolymer (a) is 1.0 to 1.5. The one-step dental temporary cement composition according to any one of claims 1 to 5. object. The one-step dental temporary cement composition according to any one of claims 1 to 6 , which is used for an implant. A dental temporary cement in which the one-step dental temporary cement composition according to any one of claims 1 to 7 is housed in a syringe container.