JP3452613B2 - Fluoride ion sustained release dental resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
That can gradually release sulfur over a long period of time
The present invention relates to an ion-releasing dental resin composition.
In detail, the effect of fluorine on preventing caries and strengthening teeth
Resin composition for stably exerting the effect over a long period of time
Such a composition is intended for a local denture base
Resin, its rebase or relining material, hard for crown
Resin, resin for filling, sealant for cormorant prevention, straightening
Widely used as adhesives for mounting brackets and cement for luting.
Used for range. [0002] 2. Description of the Related Art An aqueous solution of an inorganic fluoride is used for preventing tooth erosion.
It is known to use as a tooth surface coating agent. These inorganic
By using an aqueous solution of fluoride, a large amount of
Fluorine ions are incorporated into enamel,
Fluoride ions in the saliva in the oral cavity in a relatively short time
To elute, it is necessary to repeatedly apply the solution,
There is a problem that it is extremely complicated in use. In addition, inorganic fluorides such as sodium fluoride
Of bisphenol A glycidylme as an adhesive material
Attempts have been made to mix it with monomers such as tacrylate.
However, also in this case, fluoride ions dissolve in the oral cavity in a short time.
As well as the water absorption increases,
There is a problem that the degree is greatly reduced. Further, an inorganic fluoride is contained in the glass.
Glass ionomer cement composition also has an anticortic effect
It is known to exert, but in a short time as described above
Fluoride ions are eluted and the durability is poor
There is a title. [0005] SUMMARY OF THE INVENTION The present invention solves the above problems.
The purpose is to solve
Dental dental material that can gradually release
It is to provide a gin composition. [0006] DISCLOSURE OF THE INVENTION Dental resin set of the present invention
The product has the following chemical formula [0007] Embedded image (R¹ , R^Two Represents an odor in the cyclic phosphazene compound described below.
And at least one is F and the rest are the same or different
Is a group having a polymerizable double bond) A cyclic phosphor having a structural unit represented by the formula:
A Zen compound, a polymer having the compound as a repeating unit,
At least one selected from the group consisting of
Is essential. [0009] The cyclic phosphazene compound used in the present invention
Has a structural unit represented by the above chemical formula.
And a six-membered ring compound, an eight-membered ring compound, and the like.
Can be In the formula, R¹ , R^Two Is the cyclic phos
In the phazene compound, at least one is F.
The remainder is the same or different and has a polymerizable double bond.
It is. Therefore R¹ , R^Two Has absolute meaning
Should not be construed as limited. Having the above polymerizable double bond
Is preferably 2- (meth) acryloyloxy
Methoxy group, 2- (meth) acryloyloxyethoxy
Group, 2- (meth) acryloyloxypropoxy group, 2
-(Meth) such as (meth) acryloyloxybutoxy group
Acryloyloxyalkyl group, more preferably
2- (meth) acryloyloxyethoxy group. As an example of such a cyclic phosphazene compound,
And preferably P_Three N_Three (F)_n [O (CH_Two )_Two CO
O (CH_Three ) C = CH_Two ]_6-n (N is 1 to 5
6-membered ring compound or P_Four N_Four (F)_m [O
(CH_Two )_Two COO (CH_Three) C = CH_Two ]_8-m (M
Is an integer of 1 to 7).
Can be These compounds are, for example, P_Three N_Three F₆ 6 members
Ring compound or P_Four N_Four F ₈ With an 8-membered ring compound
Obtained by reacting with ethyl methacrylate.
It is. The reaction method is not particularly limited, and a known method can be used.
For example, in an organic solvent such as benzene and toluene,
Pyridine, triethylamine, etc. as dehydrofluorinating agents
Using an organic base, the above reactants at about 50 ° C. at 5 to 60
It is obtained by reacting for hours. Next, the polymer used in the present invention is as described above.
The polymerizable cyclic phosphazene compound is dissolved in the presence or absence of a solvent.
It is obtained by radical polymerization in the presence. This
The polymerization method at this time is not particularly limited.
Polymerization method using initiator, UV and visible light
And a method of polymerizing by heating.
It is. In the case where a polymerization initiator is used,
As the initiator, for example, a peroxide such as benzoyl peroxide
Azo compounds such as azobisisobutyronitrile
Can be At this time, if necessary, dimethyl-p-toluidine
Redo with tertiary amine compounds such as thiol or ferrous salts
It is also effective to use a water-based catalyst. Among these
Particularly preferred are peroxide-tertiary amine initiators.
And the content is 0.1 to 2.
It is preferably 0% by weight. When polymerizing with ultraviolet light and visible light
Includes camphorquinone, dibenzoyl, 2-methacryloyl
Light such as xylene-p-dimethylaminobenzoate
A sensitizer is used to remove tertiary amine compounds, ferrous salts, etc.
May be used in combination, the preferred content of these photosensitizers,
It is 0.05 to 7.0% by weight based on the composition of the present invention.
When polymerizing by heating, the polymerization temperature is 60 to 1
Preferably it is 40 ° C. Further, the copolymer used in the present invention is:
Compounds of two or more different cyclic phosphazene compounds
The compound is copolymerized or the cyclic phosphazene
The compound can be copolymerized with other different polymerizable monomers.
And obtained by Such polymerizable monomers are monofunctional
Or polyfunctional, such as
For example, methyl (meth) acrylate;
Chill (meth) acrylate, hydroxyethyl (meth)
Acrylate, hydroxypropyl (meth) acrylate
Hydro, such as hydroxybutyl (meth) acrylate
Xyalkyl (meth) acrylate; ethylene glycol
Rudi (meth) acrylate; di- or tri- or tetra-ethyl
Lenglycol di (meth) acrylate; di (methacrylic)
Roxyethyl) trimethylhexamethylene diurethane
[Generally abbreviated as UDMA]; 2,2-bis
(4-methacryloethoxyphenyl) propane (Bis
Dimethacrylate having a phenyl group such as -MEPP)
G; vinyl acetate, vinyl butyrate, vinyl stearate, etc.
Carboxylic acid vinyl ester; fumaric acid, maleic acid, a
Examples include ethylenically unsaturated dicarboxylic acids such as taconic acid.
And preferably hydroxyethyl methacrylate.
I can do it. The content of these polymerizable monomers, viscosity,
Varies depending on curing time and desired physical properties
100 parts by weight of the cyclic phosphazene compound
It is preferable to use 0.1 to 10 times the amount. [0015] The dental resin composition of the present invention comprises the above cyclic resin
Phosphazene compounds, polymers and copolymers
These may be used alone or as a mixture of two or more. Cyclic e
When a sphazene compound is used alone,
It is preferably contained so as to be 1 to 100% by weight.
More preferably, it is 5 to 80% by weight. Ma
The polymer or copolymer, or the cyclic compound
Phosphazene compounds, polymers and / or copolymers
When two or more types are used in combination, the total composition
Preferably, it is blended to be 0.1 to 100% by weight.
More preferably, it is 2 to 80% by weight. this
Their contents may be changed as appropriate depending on the purpose of use.
For example, if a large amount of fluoride ion needs to be released,
Cyclic phosphazene compounds, polymers and fluorine-rich compounds
And / or a large amount of copolymer. As described above, the composition of the present invention comprises
Contains a fluorine atom and a portion having a polymerizable group.
You. Therefore, when this is used for dental resin, etc.
The fluorine atom bond is gradually hydrolyzed by the moisture of H
As a result of the release of F, fluorine ions are eluted.
You. The amount of fluorine ions eluted is
The more noticeable it becomes. Further, the fluorine atom bond
After the release of HF, the combined portion becomes P-OH and is stabilized.
At the same time as the polymerizable portion polymerizes,
The mechanical strength of the component increases. The above cyclic phosphase
In the compound, R¹ , R^Two Are all F
Not only reduces water resistance, but also eliminates polymerizable groups.
Not practical. The composition of the present invention requires the above components.
Contains cyclic phosphazene compound alone
When used in, the above polymerization initiator is used in combination
Used. Further, the composition of the present invention has a hardness and abrasion resistance.
Improves abrasion and reduces shrinkage and thermal expansion coefficient during polymerization.
Fillers are used in a mixture to reduce the amount. Like that
A good example is the surface with silane and titanate compounds
Silica, talc, aluminum with a particle size of 30 μm or less
Na, apatite, glass beads, colloidal silica,
Inorganic fillers such as barium ioate and silicon carbide; polymethyl
Organic fillers such as
You. These contents are determined according to the cyclic phosphazene compound.
The amount is preferably 0.5 to 8 times. Alternatively,
The previously used cyclic phosphazene compound is polymerized in advance.
After obtaining a cured product, it is pulverized into an organic filler.
It is also possible to use. When the composition of the present invention is used in the clinical field,
Means that the packaging form of the composition is a paste-paste combination
Or a two-package combination of liquid and powder. sand
That is, one of these is provided with a peroxide as a polymerization initiator.
And, on the other hand, a tertiary amine compound as a polymerization accelerator.
Mix, mix both at a ratio of 1: 1 to 5 and knead for about 1 minute
You just have to add them. Further, the composition of the present invention may be used as an adhesive or a coalescent.
When the composition is used as a
It is dissolved in an organic solvent and is divided into two equal parts to form two packages.
That is, as described above, one is a peroxide and the other is a peroxide.
Tertiary amine compounds are blended, and these are added in a ratio of
The mixture may be mixed and kneaded for about 1 minute. When the composition of the present invention is of the photopolymerization type, 1
In the form of a package, the composition may contain a photosensitizer,
Color and other polymerizable monomers into a paste
After that, put in a light-shielding bottle. These are similar to the traditional methods
Processed, local denture base resin, its rebase or lira
Inning material, hard resin for crown, resin for filling, cormorant
Used in clinical fields such as protective sealants. Below
The present invention will be described in more detail with reference to examples,
This is for the purpose of showing a typical example, and the
Not to the effect. [0021] 【Example】 (Production Examples 1 to 7) As shown in Table 1, P_Three N_Three F₆ (After
Below, abbreviated as 3PNF) or P_Four N_FourF₈ (Less than,
4PNF) and 2-hydroxyethylmethac
Related (hereinafter abbreviated as HEMA) in various moles
And reacted with each other to form the cyclic phosphazene compound of Production Examples 1 to 7.
A product was made. The cyclic phosphazene compounds listed in the table
Then, the unsubstituted F is replaced with (F), and the HEMA residue from which hydrogen has been eliminated.
The group is abbreviated as (O-EMA). [0022] [Table 1](Example 1) Liquid (A) and powder shown below
(B) at a ratio of 40:60 and 3 × 3 × 35 m
m for 5 to 8 minutes after filling in a Teflon mold
By curing, the powder-liquid type of the present invention (2-package type)
A composition of the present invention was prepared. In the following description,
What is shown as "part" means "part by weight". A: 30 parts of cyclic phosphazene compound of Production Example 1 30 parts of methyl methacrylate 0.4 parts of dimethyl-p-toluidine B: Polymethyl methacrylate (PMMA, molecular weight about 400,000, 60 μm) 100 parts Benzoyl peroxide 0.3 parts Example 2 The cyclic phosphazene of Production Example 1
Example 1 except that the compound was changed to the compound of Preparation Example 2
In the same manner as in the above, a powder-liquid type composition was obtained. Example 3 Production of cyclic phosphazene compound of Production Example 1
As in Example 1 except that the compound of Example 3 was replaced
A powder-liquid type composition was obtained. Example 4 Cyclic phosphazene of Production Example 1
Example 1 except that the compound was changed to the compound of Preparation Example 4
In the same manner as in the above, a powder-liquid type composition was obtained. Example 5 Production of cyclic phosphazene compound of Production Example 1
As in Example 1 except that the compound of Example 6 was replaced
A powder-liquid type composition was obtained. Example 6 The following paste-like photopolymerization
A 3 × 3 × 35 mm Tef was prepared.
After filling in a mold made of Ron, a visible light polymerization device (wavelength 3
20-520nm, Dentacolor XS, Krutour
) For 3 minutes each from the upper and lower surfaces for a total of 6 minutes
It was cured and polymerized by irradiation. After curing, each polymer
Was polished with water-resistant abrasive paper (No. 1000).           14 parts of the cyclic phosphazene compound of Production Example 5           Di (methacryloxyethyl) trimethyl           Hexamethylene diurethane (UDA) 20 parts           PMMA 65 parts           Silica (Aegirsil R972, manufactured by Tegusa) 1 part           As photosensitizer             Camphaquinone 0.30 parts             0.15 parts of dibenzoyl             2-methacryloxyethylene-             1.40 parts of p-dimethylaminobenzoate (The content of the photosensitizer is the cyclic phosphazene of Production Example 5
The amount is based on the sum of the compound and UDMA) Example 7 The cyclic phosphazene of Production Example 5
Example 6 except that the compound was changed to the compound of Preparation Example 7
In the same manner as in Example 7, a composition of Example 7 was produced. Example 8 Production of cyclic phosphazene compound of Production Example 5
Same as Example 6 except that the compound of Example 1 was replaced
The composition of Example 8 was produced. Comparative Example Cyclic phosphazene of Production Example 5
0.28 parts of NaF instead of the compound (cyclic
The amount of fluorine corresponding to the fluorine content of the sphazene compound)
Used, 33.72 parts UDMA instead of 20 parts
Except for this, the composition of Comparative Example was prepared in the same manner as in Example 13.
Made. (Experimental Example 1) Set of Examples 1 to 8 and Comparative Example
Of fluorine ion when the product is immersed in 5 ml of distilled water
The elution amount was measured daily. Measurement of fluoride ion elution amount
The determination was performed as follows. First, each composition is measured in 3 ×
The composition was molded into 3 × 35 mm, and each of the compositions was divided into 5 pieces (total surface area).
21.9cm^Two ) Dipped in 5 ml of distilled water. After immersion 1
Fluoride eluted in distilled water on the day after taking out the composition
The amount of ions was measured. Complex type measurement of fluorine ion
Using a fluorine ion electrode (96-09, manufactured by Orion)
And perform ppm / cm^Two -Expressed in day units. next,
Add 5 ml of fresh distilled water to the composition and 10 days after immersion
The amount of eye elution was measured in the same manner. After that, in the same way,
The elution amount on days 30 and 60 was measured. That
Table 2 shows the results. [0030] [Table 2] On days 1, 10, 30, and 60 after immersion
The amount of fluoride ion eluted into water depends on the composition of the powder-liquid type.
In the case of a product, the example 1 → 2 → 3 (3PNF
Case) and Example 4 → 5 (when 4PNF is used)
In the case of a photopolymerization type composition, Examples 6 → 7 (4
As is clear from comparison with the case of using PNF),
As the number of moles of fluorine increases, the elution amount of fluorine ions also increases
Was found to increase. In the composition of the present invention, the fluorine ion
The sustained release effect of
It becomes clear when the example 6 is compared with the comparative example. That is,
In Example 6, fluorine ions at 1 and 10 days after immersion
Is small, and the extent is 60 days after immersion.
However, in the comparative example, it is almost constant even after the immersion.
On the day, a large amount of fluoride ions elute, but on the 10th day
Is almost halved and reduced to about 1/60 on the 60th day after immersion
A little. Thus, when the composition of the comparative example was used,
Is long term because a large amount of fluoride ions elute in a short time
It was difficult to stably elute fluoride ions over the interval
On the other hand, in the composition of the present invention,
It is possible to release a certain amount of fluoride ions slowly.
I understood. (Examples 9 to 19) Production examples as shown in Table 3
The mixing ratio between the cyclic phosphazene compound of No. 1 and UDMA
To the total amount of the compound and UDMA,
By mixing the same amount of a photosensitizer having the same composition as in Example 6,
To prepare photopolymerizable compositions of Examples 9 to 19.
Was. When these polymers are immersed in distilled water for 7 days,
The amount of fluoride ion eluted in the same manner as in Experimental Example 1.
It was measured. Table 3 shows the results. [0035] [Table 3] As is clear from the table, the cyclic phosphazene conversion
Elution of fluorine ions by increasing the proportion of compound
The amount can be increased. Therefore, the cyclic phosphase
By changing the content of the
It is clear that the elution amount of nitrogen ions can be adjusted
Was. [0037] The dental resin composition of the present invention has been described above.
When the composition is immersed in water,
Fluoride ions are gradually released over a long period of time
Not only that, the elution amount is kept almost constant. Further
The above cyclic phosphazene compound, polymer and / or
By arbitrarily changing the blending amount of the copolymer,
The elution amount of fluorine ions can be adjusted. Like this
The composition of the present invention provides a long-term
As it can be released gradually over a period of time, it has an anti-corrosive effect
It is excellent in fruits and can easily reinforce the tooth quality.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-132409 (JP, A) JP-A-2-135237 (JP, A) JP-A-62-26287 (JP, A) JP-A-62-287 JP-A-2-129210 (JP, A) JP-A-61-47406 (JP, A) JP-A-60-38307 (JP, A) JP-A-1-167337 (JP, A) JP-A-2-247192 (JP, A) JP-T-63-502344 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 6/00-6/10

Claims (1)

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