JPS59122410A - Dental cement composition - Google Patents

Abstract

PURPOSE:A dental cement composition for adjusting easily curing speed, obtained by blending a carboxyl group-containing polymer and or a phosphoric acid group or phosphonic acid group-containing polymer with a metallic salt of an inorganic acid besides a reactive metal oxide. CONSTITUTION:(A) (i) A carboxyl group-containing polymer such as a monopolymer or copolymer of acrylic acid and/or (ii) a phosphoric acid group- and/ or phosphonic acid group-containing polymer such as a monopolymer or copolymer of vinyl phosphate or vinyl phosphonate are blended with (B) a reactive metal oxide such as zinc oxide, magnesium oxide, bismuth oxide, clacium oxide, etc., and (C) a metallic salt of an inorganic acid preferably selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, condensed phosphoric acid, and boric acid, preferably a metallic salt selected from I -IV groups of periodic table, to give a dental cement composition capable of adjusting curing time properly, consisting of at least three components.

Description

[Detailed description of the invention] The present invention relates to dental cement compositions.

In detail, (I) (a) polymers containing carboxylic acid groups and/or (1 → polymers containing phosphoric acid groups and/or phosphonic acid groups, (11) reactive metal oxides and (110 inorganic acid) This is a dental cement composition consisting of at least three components (1) of metal salts.Incidentally, the phosphoric acid group is a releasing group or a group derived therefrom.The polymer belonging to the above (11) is a carboxyl M group or a group derived from a phosphoric acid group. It is a general term that includes homopolymers of monotactic bodies having phosphoric acid groups and/or bosphonic acid groups and copolymers having the monotactic bodies as the main component.

Conventionally, dental cement hardening products (e.g., λ) are prepared by mixing and kneading a liquid component of a polymer containing carboxylic acid groups, typically an acrylic acid polymer, and a reactive powder component containing zinc oxide as the main component. It was created by When manufacturing dental cement, hardening speed is an important factor when mixing these powder components and liquid components.

The hardening speed represents the hardening speed when mixing and kneading both the above-mentioned liquid component and powder component, which are raw materials for dental cement, and usually hardens from the start of mixing until a certain hardness is achieved. (referred to as curing time).

If this curing time was too short, the surgeon could not create a completely cured product because there was less time for kneading.If the curing time was too long, proper physical properties would not be expressed or time would be wasted. I don't like it. Therefore, controlling the hardening speed is very important, and there has been a demand for cement components that harden in a suitable hardening time.

The present inventors have conducted intensive research to solve the above technical problems. As a result, it was discovered that the hardening speed of dental cement made from a specific polymer as one of its raw materials could be adjusted by the simple means of adding a metal salt of an inorganic acid. It was completed.

That is, the present invention provides (1) (a) a polymer having carboxylic acid groups and/or (b) a polymer containing a phosphoric acid group and/or a phosphonic acid group, (11) a reactive metal oxide and a GID inorganic It is a dental cement composition consisting of six components, including a small number of metal salts of acids.

The polymer shown in (i) K used in the present invention is (a) a polymer containing a carboxylic acid group, and/or (b) a polymer containing a phosphoric acid group and/or
Or a polymer containing phosphonic acid groups. As the polymer containing a carboxylic acid group, those known as raw materials for dental cement can be used, and a representative example thereof is an acrylic acid homopolymer or copolymer. Further, polymers containing phosphoric acid groups or phosphonic acid groups can also be used as dental cement without any particular limitation. For example, a homopolymer or copolymer of general vinyl phosphonate or vinylphosphonic acid is suitably used. The method for producing these polymers is not particularly limited in the present invention, and ordinary polymerization methods may be employed as appropriate. Comonomers preferably used to synthesize the above copolymer are acrylic acid, methacrylic acid, and itaconic acid.

One or more of salts having carboxylic acid groups such as maleic acid and fumaric acid, or metal salts thereof, and hydrocarbon esters consisting of alkyl groups having 1 to 10 carbon atoms. These monomers can also be used as copolymerizable monomers with monomers containing phosphoric acid or phosphonic acid, such as vinyl phosphate and vinylphosphonic acid.

The copolymerizable monomer in this case can be used in a wide range of contents, preferably in a range of 20 to 80 mol%. The polymerization is usually carried out using water as a solvent and a radical initiator such as ammonium persulfate. The molecular weight of the polymer thus synthesized is preferably in the range of (5) 5,000 to 100,000. Further, the polymer is generally used as an aqueous solution component with a concentration of 40 to 60% by weight.

Furthermore, the reactive metal oxide used in the present invention is not particularly limited and may be any of those known as cement powder components commonly used in dentistry. Examples of materials that are generally preferably used include zinc oxide, magnesium oxide, and bismuth oxide.

Calcium oxide, etc., used alone or in combination. Most commonly, a powder containing 80 to 95% by weight of zinc oxide as the above-mentioned powder component and further containing small amounts of magnesium oxide, bismuth oxide, calcium oxide, silica, alumina, etc. is preferably used. The mixture of the above-mentioned metal oxides is preferably calcined at 1200 to 1400 DEG C. and ground in a ball mill to obtain an average particle size of 5 to 15 .mu.m.

The greatest feature of the present invention is that in addition to the polymer or liquid component shown in (1) above and the reactive gold(6) group oxide shown in (11) or powder component, metal salts of inorganic acids such as sulfuric acid,
Nitric acid, hydrochloric acid, phosphoric acid, condensed phosphoric acid.

The purpose is to contain a metal salt derived from an inorganic acid such as boric acid. It is a completely unexpected phenomenon that the curing rate of the cement composition can be adjusted by incorporating the above-mentioned metal salt into the cement composition. Moreover, the fact that the curing rate can be adjusted by such easy means has a very large impact on the industry.

The metal salt of the inorganic acid that can be used in the present invention is not particularly limited and may be any known metal salt of the inorganic acid. Generally, metal salts derived from inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, condensed phosphoric acid, and boric acid are preferably used. One or more metal salts of the inorganic acid may be used without particular limitation. These metal salts can be classified into those that exhibit two effects when included in the dental cement composition. For example, there are those that have a curing accelerating effect and those that have a curing retarding effect. Examples of metal salts that accelerate curing include sulfates, nitrates, and hydrochlorides, and those that retard curing include phosphates, condensed phosphates, borates, and the like. The reason and mechanism of this effect are not clear, but it is thought that a variety of factors overlap in a complex manner. Furthermore, the effect of accelerating or retarding curing differs depending on the type of metal ion, and cannot be determined by anion alone. Furthermore, the solubility of these metal salts in water or acids is a factor that greatly affects changes in the curing rate. In general, the lower the solubility, the smaller the change in curing speed.
The greater the solubility, the greater the change in curing rate. Therefore, it is possible to control the curing speed by using a small amount of highly soluble materials. The solubility of the metal salt preferably used in the present invention in 100 f of drainage water is 0.
Metal salts having a solubility in an aqueous solution of an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid with a pH of 0.5 or more and 100 or more are preferably used.

The metal salt of an inorganic acid used in the present invention is not particularly limited as long as it has the above properties. As the metal, those selected from the group consisting of Group 1, Group GN, and Group Ⅰ of the periodic table are particularly preferred.

Representative examples of the metal salts of inorganic acids preferably used in the present invention are listed below. That is, as metal salts of inorganic acids that accelerate curing, (1) sodium sulfate, potassium sulfate,
Cerium sulfate.

Zinc sulfate, aluminum sulfate, or hydrates thereof, (
2) Sodium chloride, potassium chloride.

Hydrates of calcium chloride, aluminum chloride or chloride, (
3) Sodium nitrate, potassium nitrate.

These include zinc nitrate, aluminum nitrate, or hydrates thereof. Typical examples of metal salts of inorganic acids that delay curing include (1) IJ oxide.

Disodium hydrogen phosphate, sodium dihydrogen phosphate 5, trisodium phosphate, macer phosphate (9) gnesium, zinc phosphate, sodium pyrophosphate, sodium tripolyphosphate, or hydrates thereof, (2) boron Sodium chloride, sodium tetraborate), or its hydration behavior.

Of course, these metal salts of inorganic acids may be used alone,
Two or more types may be mixed and used. Moreover, metal salts of various inorganic acids can be appropriately employed without being limited to these.

By adding a metal salt of an inorganic acid used in the present invention to either the powder component or the liquid component, it is possible to adjust the hardening speed of the dental cement. The amount of the metal salt of the inorganic acid to be added can be determined as appropriate depending on the type of the metal salt, and if the curing rate changes significantly, it can be adjusted by adding a small amount. 0.01~ for normal powder or liquid components
It is appropriate to add in an amount of 10% by weight.

As described above, a powder or liquid component to which an appropriate amount of the metal salt of the inorganic acid is added is mixed with the powder or liquid component shown in (1) or (ii) above.

(lO) By kneading, it is possible to obtain a hardened cement body with an appropriate hardening time.

The present invention makes it possible to improve physical properties by the simple means of adding metal salts, thereby providing a cement that is easier to handle than ever before.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, the measurement method of curing time in the examples is A I
) A S (American Dental Association Standards) Muro 1 was used.

That is, the sample was kneaded in a constant silver chamber at 23°C and 50X humidity, and 2 minutes after the start of kneading, the sample was placed in a tI1m tank at 67°C and 100% humidity, and the curing time was measured using a Gilmore needle (hereinafter simply referred to as Gilmore needle). (called Dharma).

Example 1 Acrylic acid 1oor, ammonium persulfate 2.4M',
Water 160m to 200F in advance? It was added dropwise at 90°C using a -F funnel into a flask containing water, the addition was stopped after 2 hours, and the reaction was carried out for 2 hours under the same width. I got it. This was prepared as a liquid component at #7 of bo weight tx.

Separately, mix 90v of bent lead oxide, 1-8f of magne oxide, and 2ri of calcium fluoride, and heat in an electric furnace at 1500C, 5
At 1411 t, after calcination, rJ: - It was crushed for 4 hours in Lumil to obtain a powder with an average particle size of 7μ.To this powder ior, O-005u+nl of various metal salts listed in Table 1 were added and mixed and crushed. (The powder component was added to the cement powder component in Step 7. The powder/liquid was mixed at a ratio of 1.7 to make Sansol. [7] The setting time was measured using a Gilmore needle.) The results were The number of votes in Table 1 was 0. The curing time was 5 minutes and 60 seconds with and without addition of the metal salts shown in Table 1.

Table 1 (13) Example 2 Acrylic acid BOW, vinylphosphonic acid 60V, water is
oy, add 3 vol of ammonium persulfate to 1 liter of water from the dropping funnel.
50f was added dropwise to a container containing 6v of ammonium persulfate, and the dropping was completed in 2 hours at 9FIC, and the polymerization reaction was continued for an additional 4 hours to synthesize a polymer. This polymer was prepared as a cement liquid component at a degree of 52 times.

As the cement powder component, the zinc oxide powder used in Example 1 was used. 10f of this powder [0,000 moles of various metal salts shown in Table 2 were added, mixed and pulverized, and the powder obtained was mixed with the cement component. Measurements were carried out in the same manner as in Example 1. The results are shown in Iri Table 2.

(14) Table 2 patent applicant Tokuyama Todatsu Co., Ltd. (15) 69-

Claims (3)

[Claims] (1)(1)(a) Polymer containing carboxylic acid group and/or
or (b) a polymer containing a phosphoric acid group and/or a phosphonic acid group; a dental cement composition comprising at least three components: (II) a reactive metal infusion and a metal salt of a 610 inorganic acid. (2) The composition according to claim (1), wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, condensed phosphoric acid, and boric acid. (3) The composition according to claim (1), wherein the metal salt is at least one metal salt selected from the group consisting of Groups 1, 2, 2, and 3 of the periodic table. thing.