JPH07101819A - Dental resin composition having sustained releasability of fluorine ion - Google Patents

Abstract

PURPOSE:To obtain a dental resin composition enabling sustained release of fluorine ion in the oral cavity over a long period by using at least one kind of compound selected from cyclic phosphazene compound, a polymer and a copolymer containing the compound as a recurring unit. CONSTITUTION:This dental resin composition contains at least one kind of compound selected from a cyclic phosphazene compound having a constituent unit of the formula (at least one of R<1> and R<2> in the cyclic phosphazene compound is F and the others are group having polymerizable double bond) and a polymer and copolymer containing the compound as a recurring unit. This composition stably exhibits the caries-preventing effect and dentine-strengthening effect of fluorine. The composition can be used widely as a resin for local denture base, its rebase or relining agent, a hard resin for crown, a filling resin, a caries-preventing sealant, an adhesive for orthodontic bracket, a bonding cement, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoride ion sustained-release dental resin composition capable of gradually releasing fluoride ions in the oral cavity over a long period of time.
More specifically, the present invention relates to a resin composition for stably exhibiting a caries food preventive effect and a tooth strengthening effect by fluorine over a long period of time, and such a composition is a resin for a local denture base and its rebase. Alternatively, it is widely used as a relining material, a hard resin for crowns, a resin for filling, a sealant for preventing edible foods, an adhesive for orthodontic brackets, and cement for attachment.

[0002]

2. Description of the Related Art The use of an aqueous solution of an inorganic fluoride as a tooth surface coating agent for preventing dental caries is known. By using an aqueous solution of these inorganic fluorides, a large amount of fluoride ions are temporarily incorporated into the enamel, but since the incorporated fluoride ions are eluted into saliva in the oral cavity in a relatively short time, the solution Need to be applied repeatedly,
There is a problem that it is extremely complicated to use.

Attempts have also been made to mix an inorganic fluoride such as sodium fluoride with a monomer such as bisphenol A glycidyl methacrylate, which is a raw material for adhesives. In this case also, fluoride ions are eluted into the oral cavity in a short time. At the same time, there is a problem that the mechanical strength of the resin is greatly reduced due to an increase in water absorption.

Further, it is known that a glass ionomer cement composition in which an inorganic fluoride is contained in glass also exhibits a caries food preventive effect, but like the above, fluoride ions are eluted in a short time and the durability is improved. There is a problem of poor sex.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems, and an object thereof is to provide a dental resin composition capable of gradually releasing fluoride ions over a long period of time. Is.

[0006]

The dental resin composition of the present invention has the following chemical formula:

[0007]

[Chemical 2] (R ¹ and R ² are at least one F in the cyclic phosphazene compound described below, and the rest are the same or different groups having a polymerizable double bond)

The gist of the present invention is to contain at least one selected from the group consisting of a cyclic phosphazene compound having a structural unit represented by the following, a polymer and a copolymer having the compound as a repeating unit.

[0009]

The cyclic phosphazene compound used in the present invention may be any one having a structural unit represented by the above chemical formula, and examples thereof include a 6-membered ring compound and an 8-membered ring compound. In the formula, at least one of R ¹ and R ² in the formed cyclic phosphazene compound is F, and the rest are the same or different groups having a polymerizable double bond. Therefore, R ¹ and R ² should not be limitedly interpreted as having an absolute meaning. The group having a polymerizable double bond is preferably 2- (meth) acryloyloxymethoxy group, 2- (meth) acryloyloxyethoxy group, 2- (meth) acryloyloxypropoxy group, 2
-(Meth) acryloyloxybutoxy group and other (meth)
It is an acryloyloxyalkyl group, more preferably a 2- (meth) acryloyloxyethoxy group.

As an example of such a cyclic phosphazene compound
And preferably P₃ N₃ (F)_n [O (CH₂ )₂ CO
O (CH₃ ) C = CH₂ ]_6-n (N is 1 to 5)
Some integer) 6-membered ring compound or P_Four N_Four (F)_m [O
(CH₂ )₂ COO (CH₃) C = CH₂ ]_8-m (M
Is an 8-membered ring compound of any one of 1 to 7)
To be These compounds are, for example, P₃ N₃ F₆ 6 members
Ring compound or P_Four N_Four F ₈ The 8-membered ring compound of
Obtained by reacting with cythyl methacrylate
Be done. This reaction method is not particularly limited, and known methods can be used.
For example, in an organic solvent such as benzene or toluene,
Dehydrofluorinating agents such as pyridine and triethylamine
5 to 60 at about 50 ° C. with the above reaction substance using an organic base
It is obtained by reacting for a time.

Next, the polymer used in the present invention is obtained by radical polymerization of the above-mentioned polymerizable cyclic phosphazene compound in the presence or absence of a solvent. The polymerization method at this time is not particularly limited, and examples thereof include a method of polymerizing using a polymerization initiator, a method of polymerizing with ultraviolet rays and visible rays, and a method of polymerizing by heating.

Among these, examples of the polymerization initiator when the polymerization initiator is used include peroxides such as benzoyl peroxide; and azo compounds such as azobisisobutyronitrile. At this time, it is also effective to use a redox catalyst in which a tertiary amine compound such as dimethyl-p-toluidine, a ferrous salt, etc. are used in combination, if necessary. Among these, the peroxide-tertiary amine-based initiator is particularly preferable, and the content thereof is 0.1 to 2% with respect to the composition of the present invention.
It is preferably 0% by weight.

In the case of polymerizing with ultraviolet light and visible light, a photosensitizer such as camphorquinone, dibenzoyl, 2-methacryloxyethylene-p-dimethylaminobenzoate is used, and a tertiary amine compound or ferrous iron is used. A salt or the like may be used in combination, and the preferable content of these photosensitizers is
It is 0.05 to 7.0% by weight with respect to the composition of the present invention.
When polymerizing by heating, the polymerization temperature is 60 to 1.
It is preferably 40 ° C.

Further, the copolymer used in the present invention is
It can be obtained by copolymerizing two or more different compounds of the above cyclic phosphazene compounds or by copolymerizing the above cyclic phosphazene compounds with other different polymerizable monomers. Such a polymerizable monomer may be either monofunctional or polyfunctional, and examples thereof include methyl (meth) acrylate; hydroxymethyl (meth) acrylate, hydroxyethyl (meth).
Hydroxyalkyl (meth) acrylates such as acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; ethylene glycol di (meth) acrylate; di- or tri- or tetraethylene glycol di (meth) acrylate; di (methacryloxyethyl) ) Trimethylhexamethylene diurethane [generally abbreviated as UDMA]; 2,2-bis (4-methacryloethoxyphenyl) propane (Bis
-MEPP) and other phenyl group-containing dimethacrylates; vinyl acetate, vinyl butyrate, vinyl stearate and other carboxylic acid vinyl esters; fumaric acid, maleic acid, itaconic acid and other ethylenically unsaturated dicarboxylic acids, and the like. Is hydroxyethyl methacrylate. The content of these polymerizable monomers, the viscosity,
Although it varies depending on the curing time and the desired physical properties, it is usually preferable to use 0.1 to 10 times the amount of the cyclic phosphazene compound with respect to 100 parts by weight.

In the dental resin composition of the present invention, the above cyclic phosphazene compounds, polymers and copolymers may be used alone or in admixture of two or more. When the cyclic phosphazene compound is used alone, it is preferably contained in an amount of 1 to 100% by weight, more preferably 5 to 80% by weight, based on the entire composition. When two or more kinds of the above-mentioned polymers or copolymers or the above-mentioned cyclic phosphazene compounds, polymers and / or copolymers are mixed and used, they are blended so as to be 0.1 to 100% by weight based on the whole composition. Is preferable, and more preferably 2 to 80% by weight. These contents are appropriately changed depending on the purpose of use, for example, when it is necessary to release a large amount of fluorine ions,
A large amount of cyclic phosphazene compounds, polymers and / or copolymers having a large amount of fluorine moieties are contained.

As described above, the composition of the present invention contains a fluorine atom and a moiety having a polymerizable group in the same molecule. Therefore, when this is used in a dental resin or the like, the fluorine atom-bonded portion is gradually hydrolyzed by the water in saliva and H
As a result of F being released, fluorine ions are eluted. The elution amount of this fluorine ion becomes more remarkable as the number of fluorine atoms increases. Further, the fluorine atom-bonded portion becomes P-OH after HF is released and is stabilized, and the polymerizable portion is polymerized to increase the mechanical strength of the resin. In the above cyclic phosphazene compound, when R ¹ and R ² are all F, not only is the water resistance lowered, but the polymerizable group is lost, which is not practical. The composition of the present invention contains the above-mentioned components as essential components, but when the cyclic phosphazene compound is used alone, the above-mentioned polymerization initiator is further used in combination.

Further, in the composition of the present invention, a filler is used in order to improve hardness and abrasion resistance, and to reduce shrinkage and thermal expansion coefficient during polymerization. As such an example, for example, an inorganic filler such as silica, talc, alumina, apatite, glass beads, colloidal silica, barium silicate, and silicon carbide having a particle size of 30 μm or less which is surface-treated with silane and titanate compounds; polymethyl (meth) acrylate And the like organic fillers. The content of these is preferably 0.5 to 8 times the amount of the cyclic phosphazene compound. Alternatively, the cyclic phosphazene compound used in the present invention may be preliminarily polymerized to obtain a cured product, which may be crushed and used as an organic filler.

When the composition of the present invention is used in the clinical field, the packaging form of the composition is two packaging forms of a combination of paste and paste or a combination of liquid agent and powder. That is, one of these is blended with a peroxide as a polymerization initiator, the other is blended with a tertiary amine compound as a polymerization accelerator, and both are mixed at a ratio of 1: 1 to 5 for about 1 minute. Just mix.

When the composition of the present invention is used as an adhesive or a coalescing agent, the composition is dissolved in an organic solvent such as ethanol, and this is divided into two parts to form two packaging forms.
That is, in the same manner as described above, one may be blended with a peroxide and the other with a tertiary amine compound, and these may be mixed at a ratio of 1: 1 to 3 and kneaded for about 1 minute.

1 when the composition of the present invention is a photopolymerization type
The composition is packaged, and the composition is mixed with the photosensitizer, the filler, the other polymerizable monomer and the like as described above to form a paste, which is then put in a light-shielding bottle. These are treated in the same manner as conventional methods and used in the clinical field such as local denture base resin, rebase or relining material thereof, hard resin for crowns, resin for filling, sealant for preventing dental caries and the like. Hereinafter, the present invention will be described in more detail with reference to examples, but these are for showing representative examples, and are not intended to limit the present invention.

[0021]

【Example】

(Production Examples 1 to 7) As shown in Table 1, P ₃ N ₃ F ₆ (hereinafter, abbreviated as 3PNF) or P ₄ N ₄ F ₈ (hereinafter,
4PNF) and 2-hydroxyethylmethacrylate (hereinafter abbreviated as HEMA) were reacted at various molar ratios to prepare cyclic phosphazene compounds of Production Examples 1 to 7. In the cyclic phosphazene compounds shown in the table, unsubstituted F is abbreviated as (F), and hydrogen-dissociated HEMA residue is abbreviated as (O-EMA).

[0022]

[Table 1]

(Example 1) Liquid (A) and powder (B) shown below were mixed at a ratio of 40:60, and 3 × 3 × 35 m
After being filled in a mould-made Teflon mold, the mixture was cured at room temperature for 5 to 8 minutes to prepare a powder-liquid type (2 packaging form) composition of the present invention. In the following description, what is simply shown as “part” means “part by weight”. A: Cyclic phosphazene compound of Preparation Example 30 30 parts Methyl methacrylate 30 parts Dimethyl-p-toluidine 0.4 parts B: Polymethyl methacrylate (PMMA, molecular weight about 400,000, 60 μm) 100 parts Benzoyl peroxide 0.3 parts

Example 2 Example 1 was repeated except that the cyclic phosphazene compound of Production Example 1 was replaced with the compound of Production Example 2.
A powder-liquid type composition was obtained in the same manner as in. Example 3 A powder-liquid type composition was obtained in the same manner as in Example 1 except that the cyclic phosphazene compound of Production Example 1 was replaced with the compound of Production Example 3.

Example 4 Example 1 was repeated except that the cyclic phosphazene compound of Production Example 1 was replaced with the compound of Production Example 4.
A powder-liquid type composition was obtained in the same manner as in. Example 5 A powder-liquid type composition was obtained in the same manner as in Example 1 except that the cyclic phosphazene compound of Production Example 1 was replaced with the compound of Production Example 6.

Example 6 The following paste-like photopolymerization type composition was prepared and filled in a Teflon mold having a size of 3 × 3 × 35 mm.
Using 20 to 520 nm, Dentacolor XS, Kurttur Co., Ltd., curing and polymerization was performed by irradiating light from the upper and lower surfaces for 3 minutes in total for 6 minutes in total. After curing, each polymer was polished with water resistant abrasive paper (No. 1000). Cyclic phosphazene compound of Production Example 5 14 parts Di (methacryloxyethyl) trimethyl hexamethylene diurethane (UDMA) 20 parts PMMA 65 parts Silica (Aerogel R972, manufactured by Tegusa) 1 part Camphaquinone 0.30 as a photosensitizer Parts dibenzoyl 0.15 parts 2-methacryloxyethylene-p-dimethylaminobenzoate 1.40 parts (the content of the photosensitizer is the amount based on the total amount of the cyclic phosphazene compound of Production Example 5 and UDMA).

Example 7 Example 6 except that the cyclic phosphazene compound of Production Example 5 was replaced with the compound of Production Example 7.
A composition of Example 7 was prepared in the same manner as in. Example 8 A composition of Example 8 was produced in the same manner as in Example 6 except that the cyclic phosphazene compound of Production Example 5 was replaced with the compound of Production Example 1.

Comparative Example 0.28 part of NaF in place of the cyclic phosphazene compound of Production Example 5 (amount of fluorine corresponding to the fluorine content of the cyclic phosphazene compound of Production Example 5)
A composition of Comparative Example was prepared in the same manner as in Example 13, except that 33.72 parts of UDMA was used instead of 20 parts of UDMA.

(Experimental Example 1) When the compositions of Examples 1 to 8 and Comparative Example were immersed in 5 ml of distilled water, the elution amount of fluorine ions was measured daily. The elution amount of fluorine ions was measured as follows. First, measure each composition 3 ×
The composition was molded into a size of 3 × 35 mm, and the composition was immersed in 5 pieces each (total surface area: 21.9 cm ² ) in 5 ml of distilled water. After immersion 1
On the day, the composition was taken out and the amount of fluorine ions eluted in distilled water was measured. Fluoride ion was measured using a composite type fluoride ion electrode (96-09, manufactured by Orion Co., Ltd.) and expressed in units of ppm / cm ² · day. next,
5 ml of fresh distilled water was added to the composition, and the elution amount on the 10th day after immersion was measured in the same manner. In the same manner, the elution amounts on the 30th and 60th days after immersion were measured. The results are shown in Table 2.

[0030]

[Table 2]

The amounts of fluorine ions eluted into water on days 1, 10, 30 and 60 after immersion were as follows: Example 1 → 2 → 3 (when 3 PNF was used) and Example 4 → 5 (when using 4PNF),
Further, in the case of a photopolymerization type composition, the composition of Example 6 → 7
It was found that the elution amount of fluorine ions increased as the number of moles of fluorine increased, as is clear by comparing (when PNF was used).

Further, the effect of sustained release of fluorine ions in the composition of the present invention becomes clear by comparing Example 6 and Comparative Example in which the content of fluorine ions is the same. That is, in Example 6, the elution amount of fluorine ions was small on the 1st and 10th days after the immersion, and the degree thereof was almost constant even on the 60th day after the immersion, whereas in the comparative example, it was 1% after the immersion.
A large amount of fluoride ions were eluted on the day, but it was almost halved on the 10th day, and decreased to about 1/60 on the 60th day after immersion.

As described above, when the composition of Comparative Example was used, it was difficult to stably elute the fluorine ions for a long period of time because a large amount of fluorine ions were eluted in a short period of time. It was found that with the composition of the present invention, it is possible to gradually release a substantially constant amount of fluoride ions over a long period of time.

(Examples 9 to 19) As shown in Table 3, the mixing ratio of the cyclic phosphazene compound of Production Example 1 and UDMA was variously changed, and the amount of the compound and UDMA was changed to that of Example 6. The photopolymerization type compositions of Examples 9 to 19 were prepared by mixing the same amount of the photosensitizer having the same composition. When these polymers were immersed in distilled water for 7 days, the elution amount of fluorine ions was measured in the same manner as in Experimental Example 1. The results are shown in Table 3.

[0035]

[Table 3]

As is apparent from the table, the elution amount of fluorine ions can be increased by increasing the ratio of the cyclic phosphazene compound. Therefore, it was found that the elution amount of fluorine ions can be adjusted by arbitrarily changing the content of the cyclic phosphazene compound.

[0037]

Since the dental resin composition of the present invention is constituted as described above, when the composition is immersed in water, not only is the fluoride ion gradually released for a long period of time, but The elution amount is kept almost constant. Furthermore, by optionally changing the compounding amount of the cyclic phosphazene compound, the polymer and / or the copolymer,
The elution amount of fluoride ions can be adjusted. As described above, the composition of the present invention can gradually release fluoride ions in the oral cavity over a long period of time, so that it has an excellent effect of preventing caries food and can easily strengthen the tooth structure.

Claims (1)

[Claims] 1. The following chemical formula: (Wherein R ¹ and R ² are at least one F in the cyclic phosphazene compound described below, and the rest are the same or different groups each having a polymerizable double bond). A dental resin composition comprising at least one selected from the group consisting of a formula phosphazene compound, a polymer having the compound as a repeating unit, and a copolymer.