JPS645003B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to improvements in dental cement used for bonding, root canal filling, denture lining, etc. Conventionally, the above-mentioned dental cements include zinc phosphate cement, silicate cement, carboxylate cement, glass ionomer, etc., and eugenol cement has been used as a dental cement for temporary sealing. Among these, zinc phosphate cement is
It is composed of a composition based on zinc oxide and a composition based on phosphoric acid, and because the reaction form is to create salt, shrinkage inevitably occurs, poor sealing properties at filling and adhesive interfaces, and poor adhesive strength. 1~5Kg/ ^cm2
The drawback was that it was only a small size. Silicate cement is composed of a composition mainly composed of aluminosilicate glass and a composition mainly composed of phosphoric acid, and its adhesive strength is 7 to 20 kg/cm ² , which is quite good, but the reaction form is gel-like. Since this is due to the formation, some shrinkage still occurs, and there is a drawback that sealing properties are poor when filling. Carboxylate cement is composed of a composition whose main ingredient is zinc oxide and a composition whose main ingredient is polyacrylic acid.Since the polyacrylic acid plays the majority of the role in curing, the cured product is slightly Shrink.
This results in insufficient sealing properties at the adhesive interface, especially when filling. However, the adhesive strength is 25~35Kg/
^cm2 , so it is widely used. Glass ionomer is composed of a composition based on aluminosilicate glass and a composition based on polyacrylic acid, and has an adhesive strength of 38 to 48 kg/ ^cm2 , which is the highest among conventional products. Since polyacrylic acid is used, it has the drawbacks of extremely large shrinkage and poor sealing properties at the adhesive interface. Also, in order to minimize shrinkage, it is necessary to increase the amount of the composition whose main ingredient is aluminosilicate glass, but this means that the amount of polyacrylic acid used during use must be relatively reduced, resulting in considerable hard kneading. However, it had the disadvantage of poor workability during kneading and filling. It is mainly used as a restorative material because it has good margin sealing properties. As mentioned above, some conventional products have high adhesive strength, but all of them have large shrinkage and poor sealing properties, making them particularly unsuitable for filling. If you try to make it smaller, workability during kneading and treatment will deteriorate,
There was also the inconvenience of having to hold down the bonded and filled portions until the curing was completed. On the other hand, conventional eugenol cement is composed of a composition based on zinc oxide and a composition based on eugenol liquid, and although it has the advantage of not causing large shrinkage during chelate formation during curing, it has strong adhesive strength. Since the weight is small at 1 to 5 Kg/cm ² and the sealing properties are not sufficiently good, they were not used for bonding, but were mainly used for temporary sealing. Strength, sealing properties, and workability are required properties for dental cement used for bonding, filling, lining, etc., but if only one of these properties is outstanding, it is not enough to make an excellent dental cement. Rather, it is preferable that these characteristics be balanced with few defects. The present invention aims to improve the above-mentioned drawbacks of the conventional products, especially the sealing properties, and to provide a dental cement composition having a well-balanced combination of strength, sealing properties, and workability. In particular, the present invention focuses on the fact that conventional dental eugenol cement does not shrink, and by improving its strength and sealing properties, it provides a dental cement composition that has the above three properties. . Therefore, the gist of the present invention is to use a base material: Calcium Zinc Hydroxide Hydrate.
A composition whose main ingredients are Hydrate, Ca [Zn(OH) ₃ ] _{2.2H 2} O) and rosin, and which contains gallic acid, salicylic acid, or hydroxyapatite alone or simultaneously with gallic acid and hydroxyapatite as a sequestering property improver. Eugenol agent: A composition containing clove oil and rosin as main ingredients and glacial acetic acid as a curing accelerator. Consisting of two agents, the above base and eugenol agent,
A dental cement composition characterized in that at least one of the base and the eugenol agent contains olive oil. In the dental cement composition of the present invention, the base is usually in powder form and does not contain olive oil, and the eugenol agent that is kneaded with the base during use is liquid and contains olive oil, but in special cases, the base may be in the form of a paste. When making a paste, add olive oil and knead it. Correspondingly, Eugenol usually does not contain olive oil and has a high proportion of rosin to form a paste. The present invention will be explained in more detail below. First, regarding the powder base, the calcium zinc hydroxide hydrate used as the main ingredient is a hydrate of ursium and zinc, and X-ray diffraction reveals that the structural formula is Ca
[Zn(OH) ₃ ] It has been confirmed that it is _{2.2H 2} O. Another main ingredient is rosin, and natural rosin and synthetic rosin are used. There are four types of sequestrant improvers: gallic acid, salicylic acid or hydroxyapatite used alone, and gallic acid and hydroxyapatite used simultaneously. Hereinafter, the preferred blending ratio of the base when the above-mentioned four types of sealing property improvers are blended into the base will be explained. (1) When gallic acid is used as a sequestering property improver, it is produced by mixing and pulverizing 45-70% by weight of calcium zinc hydroxide hydrate, 20-35% by weight of rosin and 1-30% by weight of gallic acid. If the rosin content is less than 20% by weight, setting will be delayed, and if it exceeds 35% by weight, setting will be accelerated too much, resulting in poor workability. If calcium zinc hydroxide hydrate is less than 45% by weight, unreacted substances such as clove oil, rosin, hardening accelerator, etc. will increase, resulting in poor curing, and if it exceeds 70% by weight, workability will deteriorate. If the amount of gallic acid is less than 1% by weight, high strength will not be obtained and the sealing properties after curing will be poor, and if it exceeds 30% by weight, setting will be delayed. (2) When using salicylic acid as a sequestering property improver: 60-70% by weight of calcium zinc hydroxide hydrate, 30-35% by weight of rosin.
It is produced by mixing and pulverizing 1 to 10% by weight of salicylic acid. Here, if the rosin content is less than 30% by weight, setting will be delayed, and if it exceeds 35% by weight, setting will be accelerated too much, resulting in poor workability.
If calcium zinc hydroxide hydrate is less than 60% by weight, unreacted substances will increase, resulting in poor curing, and if it exceeds 70% by weight, workability will deteriorate. When the salicylic acid content is less than 1% by weight, high strength cannot be obtained and the sealing properties are poor after curing, and when the content exceeds 10% by weight, curing will be poor. (3) When gallic acid and hydroxyapatite are used simultaneously as sequestrant improvers Calcium zinc hydroxide
It is produced by mixing and pulverizing 15-55% by weight of hydrate, 7-27% by weight of rosin, 2-9% by weight of gallic acid and 10-75% by weight of hydroxyapatite. If the rosin content is less than 7% by weight, setting will be delayed, and if it exceeds 27% by weight, setting will be accelerated too much, resulting in poor workability. calcium zinc
Hydroxide hydrate 15% by weight
If it is less than 55% by weight, unreacted substances will increase, resulting in poor curing, and if it exceeds 55% by weight, workability will deteriorate. If the amount of gallic acid is less than 2% by weight, high strength cannot be obtained and the sealing properties after curing will be poor, and if it exceeds 9% by weight, curing will be poor. If hydroxyapatite is less than 10% by weight, the effect of maintaining high strength over a long period of time will be reduced, and if it exceeds 75% by weight, workability will deteriorate. In addition, when gallic acid and hydroxyapatite are used together, as seen in the sample of Example 3 in Table 2, there is a characteristic of maintaining high strength over a long period of wood age. (4) When using hydroxyapatite as a sequestrant improver Calcium zinc hydroxide
It is produced by mixing and pulverizing 33-60% by weight of hydrate, 15-30% by weight of rosin and 10-50% by weight of hydroxyapatite. Rosin is 15% by weight here.
If it is less than 30% by weight, setting will be delayed, and if it exceeds 30% by weight, setting will be accelerated too much, resulting in poor workability. If calcium zinc hydroxide hydrate is less than 33% by weight, there will be a large amount of unreacted substances, resulting in poor curing, and if it exceeds 60% by weight, workability will deteriorate. If the amount of hydroxyapatite is less than 10% by weight, high strength cannot be obtained and the sealing properties will be poor after curing, and if it exceeds 50% by weight, workability will be poor. Next, a suitable formulation of the liquid eugenol agent to be reacted with the above-mentioned base will be explained. The formulation of the eugenol agent is common to all formulations of the above bases. That is, it is prepared by mixing and dissolving 65-75% by weight of clove oil, 3-5% by weight of olive oil, 20-30% by weight of rosin, and 1-15% by weight of glacial acetic acid as a hardening accelerator. If the clove oil is less than 65% by weight, the workability is poor, and if it exceeds 75% by weight, the stickiness is too high and the workability is poor. If the olive oil content is less than 3% by weight, workability is poor, and if it exceeds 5% by weight, curing failure will occur. If the rosin content is less than 20% by weight, setting will be delayed, and if it exceeds 30% by weight, setting will be accelerated too much, resulting in poor workability. Furthermore, adding the appropriate amount of glacial acetic acid as a hardening accelerator has the effect of improving workability for a certain period of time after kneading, shortening the time from the beginning of stiffness to hardening, and making the rise of the hardening curve steeper. If the amount added is less than 1% by weight, the effect will be small, and if the amount exceeds 15% by weight, workability will deteriorate. The above describes the formulation when the base is in powder form and the Eugenol agent is in liquid form. However, when both the base and Eugenol agent are used as a paste, it is 3 to 15% by weight based on the above powdered base. Add olive oil and mix to make a paste. On the other hand, Eugenol agents usually do not use olive oil and have an increased blending ratio of rosin, with clove oil at 60-70% by weight and rosin at 30-30% by weight.
40% by weight and 2 to 5% by weight of glacial acetic acid are mixed and kneaded to form a paste. In this case, if the amount of olive oil is less than 3% by weight, it will not become paste-like, and if it is more than 15% by weight, poor curing will occur. In addition, if clove oil is less than 60% by weight, workability is poor;
If the value exceeds , the stickiness will be too high and workability will be poor. If the rosin is less than 30% by weight, setting will be delayed, and if it exceeds 40% by weight, setting will be accelerated too much, resulting in stiffness and poor workability.
Furthermore, when glacial acetic acid is added in the above-mentioned appropriate amount, it has the effect of improving workability for a certain period of time after kneading, shortening the time from the beginning of stiffness to hardening, and making the rise of the hardening curve steeper. When using the base as a paste, the minimum amount of olive oil necessary for making the paste may be added to the base, and the remainder may be added to the eugenol agent. As mentioned above, the dental cement composition of the present invention has extremely good reactivity between the base and the eugenol agent, and is particularly easy to work with from kneading to filling the affected area or applying adhesive. After being bonded, it hardens rapidly, does not shrink after hardening, has excellent sealing properties, and has improved strength properties. This applies to all embodiments in which the base is in powder form and the eugenol agent is in liquid form, and in the case where both the base and eugenol agent are pastes. The reason why such effects occur is that the plate-like diamond-shaped crystals of calcium zinc hydroxide hydrate form a chelate by covering themselves with tempura when forming a chelate with the eugenol agent. Secondly, it can be seen from the results of X-ray diffraction that the presence of gallic acid, salicylic acid or hydroxyapatite promotes the crystallization and maintains the chelation stably for a long period of time. That is, it is thought that this is because the above-mentioned complete chelation occurs instantly after a certain period of time after kneading the base and the eugenol agent, and then this chelation is maintained for a long period of time. As a result, as shown in Experiment 1 below, the sealing properties were significantly improved compared to conventional products. Regarding the strength properties, as shown in Experiment 2 below, while the adhesive strength of conventional Eugenol cement is 1 to 5 kg/cm ² , the adhesive strength of the present invention differs slightly depending on the type of hardening accelerator, but the adhesive strength of the above (1) For case 24.5~31Kg/ ^cm2 , for (2) 10~18
Kg/cm ² , (3) 26~31Kg/cm ² (4) 14~24
Kg/cm ² , which has significantly improved. This value is equivalent to or higher than conventional zinc phosphate cement, silicate cement or carboxylate cement. In addition, the setting time is extremely short, 4.5 to 5.5 minutes, from mixing to curing after filling or adhering to the affected tooth in the oral cavity, making it suitable for use as a dental cement. The present invention will be explained in more detail with reference to Examples below.
These Examples are merely illustrative of embodiments of the present invention, and the present invention is not limited thereto. Example 1 Base: rosin 30g, calcium zinc hydroxide hydrate 60g, gallic acid 10g
After mixing well, crush and pass through a 200 mesh sieve to obtain the product. Eugenol agent: clove oil 68.5g, rosin 25.2g, olive oil 3.9g
Take 2.4 g of glacial acetic acid and mix well to dissolve and prepare the product. Example 2 Base: 32 g of rosin, 63 g of calcium zinc hydroxide hydrate, 5 g of salicylic acid
After mixing well, grind and pass through a 200 mesh sieve to obtain a product. Eugenol agent: Same as Example 1 Example 3 Base: rosin 21g, calcium zinc hydroxide hydrate 42g, gallic acid 7
Take 30 g of hydroxyapatite, mix well, crush, and pass through a 200 mesh sieve to obtain a product. Eugenol agent: Same as Example 1 Example 4 Base: Take 17 g of rosin, 33 g of calcium zinc hydroxide hydrate, and 50 g of hydroxyapatite, mix well, and then crush and pass through a 200 mesh sieve to obtain a product. Eugenol agent: Same as Example 1 Example 5 Base: rosin 26.4g, calcium zinc hydroxide hydrate 52.8g, gallic acid
Mix 88g with 12g of olive oil to form a uniform paste and use it as a product. Eugenol agent: Add 60 g of clove oil, 37 g of rosin, and 3 g of glacial acetic acid, mix and dissolve well, and make a paste. Experiment 1 Eugenol cement of the present invention obtained in Examples 1 to 5 above and commercially available zinc phosphate cement (Company A), silicate cement (Company B) as comparative examples,
Carboxylate cement (Company C), glass ionomer (Company D), Eugenol cement (Company E)
The following experiment was conducted on the following, and the results of the experiment are shown in Table 1. A glass tube with an inner diameter of 5 mm is cut into 5 cm lengths, and a 5 mm length area of the inner surface at the lower end of the tube is polished with a diamond point to make it rough. In the case of , mix 1g of base and 0.2g of eugenol agent) and harden.
It was filled with muddy cement that had been mixed for 30 seconds and left to harden completely for 10 minutes (commercially available products were mixed according to the specified formulation). The glass tube thus filled was filled with anhydrous copper sulfate powder to a height of about 70% of its total length, and the upper end of the glass tube was closed with dental temporary stoppers and then fixed to a wooden frame. Ten such samples were prepared for each type of cement, and the lower end of each tube was immersed in hot water at 37°C. Observation was continued for 50 days, and the number of tubes in which the copper sulfate turned blue due to water passage was determined every day.

【table】

Claims (1)

[Claims] 1 Base: Calcium Zinc Hydroxide Hydrate
A composition whose main ingredients are Hydrate, Ca [Zn(OH) ₃ ] ₂ ·2H ₂ O) and rosin, and which contains gallic acid, salicylic acid, or hydroxyapatite alone or together as a sequestering property improver. Eugenol agent: A composition containing clove oil and rosin as main ingredients and glacial acetic acid as a curing accelerator. Consisting of two agents, the above base and eugenol agent,
A dental cement composition characterized in that at least one of the base and the eugenol agent contains olive oil. 2. In claim 1, the base material is calcium zinc hydroxide hydrate based on the total amount of the base material.
Hydroxide Hydrate, Ca [Zn(OH) ₃ ] ₂・2H ₂ O)
1. A dental cement composition comprising 45-70% by weight of rosin, 20-35% by weight of rosin, and 1-30% by weight of gallic acid. 3. In claim 1, the base material is calcium zinc hydroxide hydrate based on the total amount of base material.
Hydroxide Hydrate, Ca [Zn(OH) ₃ ] ₂・2H ₂ O)
1. A dental cement composition comprising 60-70% by weight of rosin, 30-35% by weight of rosin, and 1-10% by weight of salicylic acid. 4 In claim 1, the base material is calcium zinc hydroxide hydrate (calcium zinc hydroxide hydrate) based on the total amount of base material.
Hydroxide Hydrate, Ca [Zn(OH) ₃ ] ₂・2H ₂ O)
15-55% by weight, rosin 7-27% by weight, gallic acid 2
A dental cement composition comprising ~9% by weight of hydroxyapatite and 10-75% by weight of hydroxyapatite. 5 In claim 1, the base material is calcium zinc hydroxide hydrate based on the total amount of the base material.
Hydroxide Hydrate, Ca [Zn(OH) ₃ ] ₂・2H ₂ O)
1. A dental cement composition comprising 33 to 60% by weight of rosin, 15 to 30% by weight of rosin, and 10 to 50% by weight of hydroxyapatite. 6. In any of claims 1 to 5, the eugenol agent contains 65 to 75% by weight of clove oil and 3 to 5% of olive oil based on the total amount of eugenol agent.
1. A dental cement composition comprising 20 to 30% by weight of rosin and 1 to 15% by weight of glacial acetic acid. 7. In any one of claims 1 to 5, the base is a paste composition containing 3 to 15% by weight of olive oil, and the eugenol agent is in a proportion of 3 to 15% by weight based on the total amount of the eugenol agent. Clove oil 60~
70% by weight, 30-40% by weight of rosin and 2-5% of glacial acetic acid
A dental cement composition characterized in that it is a paste-like composition consisting of % by weight.