JP5539763B2 - Silicone impression material composition for medical and dental use - Google Patents

Description

The present invention relates to a one-part composition comprising a medical / dental silicone impression material in which at least one reactive component is encapsulated in micro / nano form.

In the medical / dental field, alginic acid-based impression materials and silicone-based impression materials are used for taking impressions of living hard tissues and the like. For example, in the case of an alginate impression material, an ion exchange reaction between powdered sodium alginate and multivalent ions such as calcium ions is performed in the presence of water and cured to obtain an impression. Further, in the silicone impression material, for example, a) addition curable compound such as vinyl group-containing organopolysiloxane, b) organopolysiloxane crosslinking agent containing SiH group, c) noble metal-containing catalyst such as hydrosilylated platinum-containing catalyst, d) Two or more kinds of pastes in a combination that does not react with each other among fillers such as silica and calcium carbonate are prepared in advance, and the addition reaction is started and cured by mixing them at the clinical site. Gaining. In other words, all medical / dental impression materials currently in clinical use require a mixing step.

JP2007-191722 Special table 2004-529135 Special table 2003-507350

As described above, in the current form in which the mixing process is essential at the clinical site, mixing by an expert is required. Moreover, the complicated mixing container cleaning work is also necessary. Furthermore, industrial waste discharge of a large amount of mixing containers including mixing chips is performed every day. These have a great influence on environmental problems such as global warming. That is, in medical / dental silicone impression materials, a large amount of plastics is used and disposed of only to isolate reactive substances.

As a result of intensive studies to solve this problem, the inventors have found that the composition can coexist stably by micro-nanoencapsulating one of the noble metal catalyst and / or the reactive substance. Furthermore, as an alternative method to the mixing step, a method of breaking micro / nanocapsules by ultrasonic waves, shock waves and electromagnetic waves was adopted. As a result, we developed an innovative medical and dental silicone impression material that does not require a mixing process by skilled workers.

The medical / dental silicone impression material provided by the present invention eliminates the need for a complicated and skillful mixing operation, and makes it possible to provide a uniform and uniform mixed silicone impression material. In addition, a large amount of plastic waste that was used solely for the isolation of reactive substances was brought to a minimum.

Preferred embodiments of the present invention are: (1) an addition polymerizable compound containing a vinyl group-containing organopolysiloxane, (2) a crosslinkable compound containing an organopolysiloxane having at least two SiH bonds in one molecule, (3 ) At least one of the three species of noble metal-containing catalyst capable of catalyzing the hydroxylation reaction is microencapsulated to form a coexistent form. Furthermore, 10 mass%-90 mass% in these compositions are occupied with fillers, such as a silica and a calcium carbonate. These fillers are added for the purpose of minimizing polymerization shrinkage.

The vinyl group-containing organopolysiloxane is the siloxane polymer shown in FIG. The organopolysiloxane having at least two SiH bonds in one molecule is the siloxane polymer shown in FIG. Further, examples of the noble metal-containing catalyst capable of catalyzing the hydroxylation reaction include a calsette type platinum catalyst.

U.S. Pat.No. 3,715,334 U.S. Pat.No. 3,775,452 U.S. Pat.No. 3,814,730

Micro / nanocapsule production methods include submerged drying method, coacervation method, interfacial polymerization method, suspension polymerization method (bead polymerization method), in situ polymerization method, submerged cured coating method, melt dispersion cooling method, inorganic There are wall encapsulating method, inter-droplet uniting method, etc., and the manufacturing method by inter-droplet uniting method and interfacial polymerization method will be described below, but the present invention is based on medical / microencapsulation of reactive substances. Since the liquefaction of the dental silicone impression material is characteristic, it is not limited at all by the description of these synthesis methods.

In the method of coalescence between droplets, it is possible to easily synthesize by adjusting emulsions having greatly different particle sizes and mixing the emulsions. That is, a primary emulsion having an average particle size of about 100 μm is prepared by dispersing a vinyl group-containing organopolysiloxane containing a noble metal-containing catalyst in a continuous aqueous phase containing an appropriate amount of a surfactant. If necessary, a dispersion stabilizer such as silica may be added. Next, a secondary emulsion having an average particle diameter of about 1 μm is prepared by dispersing a crosslinkable compound containing an organopolysiloxane having at least two SiH bonds in one molecule in some water phase containing an appropriate amount of a surfactant. By adding this secondary emulsion to the primary emulsion, a coalescence reaction is caused at the interface of the primary emulsion to synthesize noble metal-containing catalyst microcapsules. The film formed is a polysiloxane cross-linked cured product equivalent to the final product. It is also possible to obtain nanocapsules by adjusting the primary and secondary emulsion particle sizes.
In the in situ polymerization method, a primary O / W emulsion is prepared by adding an appropriate amount of a surfactant to a vinyl group-containing organopolysiloxane containing a noble metal-containing catalyst and dispersing it in water. The primary O / W emulsion is dispersed in a radical polymerizable monomer containing an appropriate amount of a surfactant and a radical polymerization initiator to prepare a [(O / W) / O] composite emulsion. The [[(O / W) / O] / W] composite emulsion is prepared by dispersing the obtained [(O / W) / O] composite emulsion in water again. If necessary, a dispersion stabilizer such as silica may be added. The composite emulsion is radical polymerized to synthesize noble metal-containing catalyst microcapsules.

The surfactant may be at least one kind of amphiphilic substance, such as an anionic monomer, a cationic monomer, a nonionic monomer, an anionic polymer, a cationic polymer, Nonionic polymers and the like can be mentioned. Specifically, alkylbenzene sulfonates such as sodium benzenesulfonate and sodium dodecylbenzenesulfonate, polyoxyethylene sulfate, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, poly (meth) Acrylic acid, polyvinyl alcohol, hexaethylcellulose, methylcellulose, carboxymethylcellulose, kaizen, gum arabic, lecithin, gelatin, funnel oil, silicone surfactant, clay mineral and the like can be mentioned.

The dispersion stabilizer may be any substance that does not dissolve in the continuous layer and the polymerizable monomer. For example, silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, calcium carbonate, barium carbonate, carbonate At least one selected from magnesium, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate and the like is selected.

Examples of radically polymerizable monomers that are incompatible with water include styrene, methylstyrene, ethylstyrene, chloromethylstyrene, t-butoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, methoxypolyethylene glycol di (meth) acrylate, glycidyl di (meth) acrylate, diethylaminoethyl (meth) acrylate Vinyl acetate, vinyl propionate, vinyl butyrate and the like.

The method for producing micro / nanocapsules and the impression material composition according to the present invention will be described in detail, but the present invention is not limited to these descriptions.

Example 1
Vinyl group-containing organopolysiloxane (DMS-V22, GELEST, Inc., 5% by weight of platinum complex (SIP6830.3, GELEST, Inc., USA)
USA) 3g surfactant (Silwet L-77, Union
Carbide Corp., USA) O / W emulsion ¹ (average particle size 100 μm) was prepared by homogenizing with 30 g of distilled water in the presence of 300 ppm and 3 g of calcium carbonate. In addition, methylhydrosiloxane oil (HMS301,
GELEST, Inc., USA) 0.5g surfactant (Silwet L-77,
Union Carbide Corp., USA) O / W emulsion ² (average particle size 1 μm) was prepared by homogenizing with 3 g of distilled water in the presence of 3000 ppm. Next, by adding O / W emulsion ² while stirring O / W emulsion ¹ , droplets coalesce to form polysiloxane (shell) at the interface, and microencapsulation of platinum complex-containing silicone oil (core) Went. In addition, emulsion adjustment etc. were all performed at 23 degreeC.

Example 2
Vinyl group-containing organopolysiloxane (DMS-V31, GELEST, Inc., containing 20 w% platinum complex (SIP6830.3, GELEST, Inc., USA)
USA) 3g surfactant (Silwet L-77, Union
Carbide Corp., USA) O / W emulsion ¹ (average particle size 1 μm) was prepared by homogenizing with 10 g of distilled water in the presence of 3000 ppm. This O / W emulsion ¹ was converted into a platinum complex (SIP6830.3, GELEST, Inc.,
(USA) 1w% and Nikomulus WO (Nikko Chemicals, Japan) 1wt% vinyl group-containing organopolysiloxane (DMS-V31, GELEST, Inc.,
USA) was dispersed in 30 g to prepare [(O / W) / O] emulsion ² (average particle size 100 μm). In addition, methylhydrosiloxane oil (HMS301,
GELEST, Inc., USA) 0.5g surfactant (Silwet L-77,
Union Carbide Corp., USA) O / W emulsion ³ (average particle size 1 μm) was prepared by homogenizing with 3 g of distilled water in the presence of 3000 ppm. Next, while stirring [(O / W) / O] Emulsion ² , O / W Emulsion ³ is added to coalesce the droplets to form a polysiloxane (shell) at the interface, containing a platinum complex suspended in water Silicon oil (core) was microencapsulated. In addition, emulsion adjustment etc. were all performed at 23 degreeC.

Example 3
Vinyl group-containing organopolysiloxane (DMS-V31, containing 20 w% platinum complex (SIP6830.3, GELEST, Inc., USA) and 1 wt% carbon microcoil
GELEST, Inc., USA) 3g surfactant (Silwet L-77,
Union Carbide Corp., USA) O / W emulsion ¹ (average particle size 1 μm) was prepared by homogenizing with 10 g of distilled water in the presence of 3000 ppm. This O / W emulsion ¹ was converted into a platinum complex (SIP6830.3, GELEST, Inc.,
(USA) 1w% and Nikomulus WO (Nikko Chemicals, Japan) 1wt% vinyl group-containing organopolysiloxane (DMS-V31, GELEST, Inc.,
USA) was dispersed in 30 g to prepare [(O / W) / O] emulsion ² (average particle size 100 μm). In addition, methylhydrosiloxane oil (HMS301,
GELEST, Inc., USA) 0.5g surfactant (Silwet L-77,
Union Carbide Corp., USA) O / W emulsion ³ (average particle size 1 μm) was prepared by homogenizing with 3 g of distilled water in the presence of 3000 ppm. Next, while stirring [(O / W) / O] Emulsion ² , O / W Emulsion ³ is added to coalesce the droplets to form a polysiloxane (shell) at the interface, containing a platinum complex suspended in water Silicon oil (core) was microencapsulated. In addition, emulsion adjustment etc. were all performed at 23 degreeC.

Example 4
Vinyl group-containing organopolysiloxane (DMS-V31, GELEST, Inc., containing 20 w% platinum complex (SIP6830.3, GELEST, Inc., USA)
USA) 3g surfactant (Silwet L-77, Union
Carbide Corp., USA) O / W emulsion ¹ (average particle size 1 μm) was prepared by homogenizing with 10 g of distilled water in the presence of 3000 ppm. This O / W emulsion ¹ was diphenyl (2,4,6-trimethylbenzoyl) -phosphine
[(O / W) / O] emulsion dispersed in 30 g of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) containing 1 w% oxide (ALDRICH, USA) and 1 wt% Nicomulus WO (Nikko Chemicals, Japan) ² (average particle size 100 μm) was adjusted. Next, [(O / W) / O] emulsion ² was added to a surfactant (Silwet L-77, Union
(Carbide Corp., USA) After being dispersed in 300 g of distilled water containing 300 ppm, microcapsulation of a silicone oil (core) containing platinum complex suspended in water was performed by irradiating LED light with a wavelength of 400 nm. In addition, emulsion adjustment etc. were all performed at 23 degreeC.

Example 5
Vinyl group-containing organopolysiloxane (DMS-V31, GELEST, Inc., containing 20 w% platinum complex (SIP6830.3, GELEST, Inc., USA)
USA) 3g surfactant (Silwet L-77, Union
Carbide Corp., USA) O / W emulsion ¹ (average particle size 1 μm) was prepared by homogenizing with 10 g of distilled water in the presence of 3000 ppm. This O / W emulsion ¹ was diphenyl (2,4,6-trimethylbenzoyl) -phosphine
oxide (ALDRICH, USA) 1w%, ferrite (FE-3.5SI-4.5CR-V1,
[(O / W) / O] emulsion dispersed in 30 g of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) containing 5% by weight (EPSON ATMIX CORPORATION, JAPAN) and 1% by weight of Nikomulus WO (Nikko Chemicals, Japan) ² (average particle size 100 μm) was adjusted. Next, [(O / W) / O] emulsion ² was added to a surfactant (Silwet L-77, Union
(Carbide Corp., USA) After being dispersed in 300 g of distilled water containing 300 ppm, microcapsulation of a silicone oil (core) containing platinum complex suspended in water was performed by irradiating LED light with a wavelength of 400 nm. In addition, emulsion adjustment etc. were all performed at 23 degreeC.

Preparation of one-part silicone curable composition Using the platinum complex-containing microcapsules obtained in Example 1-5, a one-part silicone curable composition was prepared in a mortar. The amount of microcapsules added was adjusted so that the effective platinum complex concentration was 0.1 wt%. Table 1 shows the preparation compositions of Preparation Example 1-5 and Comparative Example 1.

One-part silicone curable composition storage stability test results The storage stability of the one-part silicone curable composition prepared with the composition shown in Table 1 was evaluated. Storage conditions were as follows: 30 g of a sample was filled in a 50 ml glass sample bottle, sealed, and stored in a thermostat at 50 ° C., and the viscosity change was visually observed. The test results are listed in Table 2. As a test result, the one-part silicone curable composition using Examples 1 to 5 was stable with no change in viscosity observed even at 50 ° C. for 30 days. In Comparative Example 1, the addition reaction started from the preparation of the one-part silicone curable composition, the viscosity increased, and curing was achieved in about 3 minutes.

Table 3 shows the curing test results of the one-part silicone curable composition curing test result adjustment example 1-5. As a test result, it was confirmed that the addition polymerization reaction was quickly started by irradiating with ultrasonic waves or microwaves.

Currently, in the medical / dental field, two-component (two-paste) silicone impression materials are used for taking impressions of living hard tissues and the like. That is, a) addition curable compound such as vinyl group-containing organopolysiloxane, b) organopolysiloxane crosslinking agent containing SiH group, c) noble metal-containing catalyst such as hydrosilylated platinum-containing catalyst, d) silica, calcium carbonate, etc. Among these fillers, two or more kinds of pastes are preliminarily adjusted in a combination that does not react with each other, and the addition reaction is started and cured by mixing them at the clinical site, thereby obtaining an impression. Therefore, all medical / dental impression materials currently in clinical use require a mixing step. However, according to the present invention, these reactive substances can coexist, and a one-paste type silicone impression material can be adjusted. This eliminates the need for complicated operations such as mixing, resulting in a large gain in the medical field. Furthermore, plastic waste can be greatly reduced, and the environmental load can be reduced.

Vinyl group-containing organopolysiloxane Organopolysiloxane with Si-H bond

Claims (2)

(1) an addition polymerizable compound containing a vinyl group-containing organopolysiloxane,
(2) a crosslinkable compound containing an organopolysiloxane having at least two SiH bonds in one molecule;
(3) Noble metal-containing catalyst
A medical and dental silicone impression material composition comprising:
At least one of (1) to (3) including (3) is microencapsulated,
Containing water inside the micro-nanocapsule,
A silicone impression material composition for medical / dental use, wherein a curing reaction is initiated by irradiation with microwaves. The medical / dental silicone impression material composition according to claim 1, further comprising a carbon microcoil inside the micro / nanocapsule.