JPH0633295B2 - Monomer composite composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel dental monomer composite composition, and more specifically, the monomer is a composite material controlled at a molecular level, Since it has multi-functionality, its polymerized cured product not only obtains high mechanical properties that could not be expected from conventional monomers, but also wear resistance,
Shows low thermal expansion and water resistance. Further, the present invention has adhesiveness to tooth substance and metal, and its application field is excellent in durability as a dental resin material, especially a denture base, a dental filling material, a crown restorative material, an adhesive and a bonding material. Not only can a practical resin material be provided, but the above-mentioned characteristics are to provide a monomer composite composition that can be applied in the general industry.

There is no conventional technology.

[Problems to be solved by the invention]

Conventionally used dental monomers are those of methylmethacrylate type, and a few percent benzoyl peroxide or benzoyl peroxide and a tertiary amine are added to this, and a transparent polymer is obtained when polymerized by heating and at room temperature. It is relatively widely used as a denture base, a filling material, a crown restorative material, and a resin tooth because it is obtained, is relatively inexpensive, and is easy to operate.

However, the physical properties of the polymer (polymethylmethacrylate) obtained from this monomer are much higher than those of other dental materials used for the same purpose, such as metal, amalgam, porcelain and cement. Is inferior in terms of. That is, polymethylmethacrylate not only has inferior mechanical properties, but also has large polymerization shrinkage, coefficient of thermal expansion and water absorption, low abrasion resistance, and is relatively easily colored. It is difficult to use a material having such physical properties in a severe environment where there is a large temperature difference in the oral cavity and under constant humidity.

As measures for improving the above-mentioned various drawbacks, conventionally, methyl methacrylate (MMA) is mixed with glass fiber or the like, or as a filler, quartz having a particle size of 20 μm or less, alumina, apatite, glass beads, colloidal silica, nitriding, etc. In addition, a composite resin in which an inorganic filler such as silicon carbide is mechanically mixed is partially used.
On the other hand, as another monomer for MMA, 2,2-bis [4-
(2-Hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), di (methacryloxyethyl) trimethylhexamethylenediurethane (UD
(MA) and the like are mechanically mixed in a large amount to improve the physical properties. On the other hand, MMA is mechanically mixed with Bis-GMA and 2-hydroxy-3- (β-naphthoxy) propylmethacrylate (HNPM) for the purpose of adhering to dentin and metal to form a bonding material for dental restoration or Attempts have been made to use it as an adhesive.

However, in all of the known monomers described above, as is well known, since the molecular main chain is composed of a carbon-carbon homo bond, the bond energy is not only small as compared with the hetero bond, but also the bending energy is small. The nature is great. In other words,
The polymer obtained by polymerizing these monomers has many drawbacks as described above. On the other hand, a polymer obtained by mechanically mixing an inorganic filler with these monomers has a hardness,
Although the thermal expansion coefficient and the polymerization shrinkage are considerably improved, the polymer becomes brittle, the bond between the resin matrix and the core of the inorganic filler is insufficient, and the hardness of the resin and the filler is large. Since they are different, the matrix first wears down during use, the filler is isolated and falls off, greatly reducing the wear resistance,
As a result of the increased water absorption, the restoration is colored and discolored. On the other hand, the adhesive force sharply decreases due to water absorption, and the purpose cannot be achieved.

That is, no matter how skillfully the various conventional monomers are mixed, and even if a large amount of various fillers are mixed with these monomers, it is impossible to drastically solve the above drawbacks. it is obvious.

Therefore, it has been earnestly desired to develop a material having a high degree of durability without impairing the characteristics of the polymer material such as aesthetics, good operability and low cost.

[Means for solving problems]

The present inventors have synthesized and studied various novel monomers in order to drastically solve the above-mentioned fatal defects of the dental resin. As a result, phosphorus nitride having a hetero bond as the central skeleton of the monomer (M is 3 or 4), that is, a monomer composite composition in which a cyclic 3 or tetramer is a main chain and a group having various functions controlled at the molecular level is bonded to the main chain is suitable for this purpose. The inventors of the present invention have found out that, and have reached the present invention.

That is, a compound having a skeleton and a main chain composed of a nitrogen-phosphorus hetero bond, particularly a cyclic compound, is well known in the art.
Compared with a compound consisting of a carbon-carbon homo bond, its binding energy is large, its thermal decomposition point is high, the rotation of the molecule is low, and it is rigid. It is called a semi-inorganic compound.

As can be understood from these things, the polymer obtained by polymerizing the monomer composed of the compound shows high mechanical properties, and both the polymerization shrinkage and the thermal expansion coefficient are small, and the specific gravity is It has excellent characteristics as a dental material such as large size and abrasion resistance, and is highly practical.

The phosphorus nitride compound that can be used in the present invention has a general formula (Wherein m is 3 or 4), and has X and Y in the molecule, the X and Y are bonded to the constituent phosphorus atoms, the number of X and Y in the molecule is larger than O, A cyclic compound in which the number of (X + Y) per unit is 2, and X is (N is 2 to 8), which is selected from the group that is oxy-bonded with phosphorus, and Y is a group other than X and can be selected from the group consisting of a group in which the oxygen of the hydroxyl group of the hydroxyl-containing compound is oxy-bonded to phosphorus. Is more preferably a monomer composite composition characterized in that the oxygen of the hydroxyl group of the hydroxyl group-containing compound selected from the hydroxyl group-containing fluoride and the hydroxyl group-containing saturated carboxylic acid compound is a group oxy-bonded with phosphorus. .

In the above formula, when Y is a group other than X and is a hydroxyl group-containing compound, X is
Although the composition ratio of Y and Y varies depending on the purpose of use such as denture base, filling material, crown restoration, adhesion and attachment, X is 17 mol% or more, preferably 33 mol% or more in the cyclic trimer. , Y is 67 mol% or less, and in the cyclic tetramer, X is 12.
5 mol% or more, preferably 25 mol% or more, and Y is 7
It is characterized by comprising 5 mol% or less.

The methacrylate ester X used in the production of the monomer composite composition of the present invention may be any hydroxyl group-containing alkyl methacrylate ester.
Hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 7-hydroxyheptyl methacrylate and 8-hydroxyoctyl methacrylate are suitable, and preferably 2-hydroxyethyl. Methacrylate.

On the other hand, Y may be a hydroxyl group-containing compound other than the above-mentioned hydroxy methacrylate, but in order to improve the water resistance, abrasion resistance, reduction of water absorption and discoloration resistance of the polymer, Y is required.
The _{Z (CF 2) nCH 2 O-} ( are n 1 to 4, Z is hydrogen or fluorine) is appropriate and (CF ₃₎ fluoride represented by ₂ CHO-. As the fluoride, 2,2,2-trifluoroethanol; 2,2,3,3,3,3-pentafluoro 1-propanol; 2,2,3,3,4,4,4,4-
Heptafluoro-1-butanol; 2.2, 3.3-tetrafluoro-1-propanol; 2.2, 3.3, 4.3
4,5,5-octafluoro-1-pentanol and 1
-1, 1, 3, 3, 3-hexafluoro-2-propanol and the like.

On the other hand, when the purpose of use of the monomer composite composition of the present invention is to improve adhesiveness and flexibility, Y
A saturated carboxylic acid compound _{-O (CH 2) nCOOH (n} = 1~15), and carbocyclic carboxylic acid compound _{-OC 6 H 4 (CH 2)} nCOO
H (n = 0, 1 and _{2), - OC 6 H 3} (COOH) 2
And _{-OC 6 H 3 (R) COOH} (R = OH and OC
H ₃ ), etc., for example, as the saturated carboxylic acid compound, hydroxyacetic acid, 4-hydroxybutyric acid, β-hydroxypropionic acid, 12-hydroxydecanoic acid, 16-hydroxyhexadecanic acid, etc. As the carbocyclic carboxylic acid, P-hydroxybenzoic acid, P-hydroxyphenylacetic acid, P-hydroxyphenylpropionic acid, 4-hydroxyphthalic acid, 2.3-dihydroxybenzoic acid,
2,4-dihydroxy decanamic acid, 4-hydroxy 3-methoxybenzoic acid and the like are included.

Further, the monomer composite composition may be a mixture containing two or more kinds of fluoride and carboxylic acid compound depending on the purpose of use.

The production of the composition can be accomplished by using phosphorus oxynitride [NP (Cl ₂ )] ₃ and ₄ as starting materials and substituting the chlorine with the above hydroxyl group-containing compound. In order to accelerate the reaction, a target product can be obtained in a short time by adding a tertiary amine during the reaction.

Examples of the tertiary amines include trimethylamine,
Triethylamine, triisopropylamine, tri-n-
Propylamine, tri-n-butylamine, pyrividine,
A tertiary amine containing diamine such as N.N.N-tetramethylethylenediamine is used, or preferably,
It is pyridine. At this time, pyridine is preferably used in an amount 3 to 5 times the theoretical amount generated as pyridine hydrochloride.

On the other hand, the solvent needs to be a solvent containing no water,
Any solvent may be used as long as it dissolves phosphorus oxynitride and the hydroxyl group-containing compound according to the present invention, but generally usable solvents are benzene, chloroform, cyclohexane, methylene chloride, toluene, xylene, ether,
Hexane, tetrahydrofuran and the like. Benzene or benzene and a mixture thereof are preferably used, and the amount thereof is preferably 4 to 10 times the weight of phosphorus oxynitride.

The temperature and time at the time of reaction vary depending on whether the reactivity with the hydroxyl group-containing compound that replaces chlorine is good or not and the final desired target composition, but are generally in the range of 25 to 90 ° C.,
The time is in the range of 1 to 180 hours, and naturally, the lower the temperature, the longer the reaction is required.

The procedure for producing the monomer composite composition is, for example, in the case where the final desired composition is one in which the carboxylic acid and the fluorinated compound are each replaced with two chlorines and the remaining chlorine is replaced with a hydroxyalkyl methacrylate. A predetermined amount of phosphorus oxynitride is reacted with a theoretical amount of a carboxylic acid compound corresponding to two chlorines, and then a fluorine compound is reacted in the same manner, and then a theoretical amount of hydroxyalkyl methacrylate corresponding to the remaining chlorine is reacted. A method of reacting a smaller excess amount is suitable. In this case, if the hydroxyalkyl methacrylate is replaced in advance before being replaced with another compound, a part of the hydroxymethacrylate is polymerized, and not only the viscosity of the target composition is increased, but also unsubstituted chlorine is replaced by the target compound. Trace amount remains inside, not suitable.

On the other hand, the target product is purified by neutralizing and washing with hydrochloric acid, potassium carbonate and an aqueous solution of sodium chloride, dehydrating and then removing the solvent.

In order to polymerize and cure the composition of the present invention at room temperature, a general peroxide-tertiary amine-based polymerization initiator is used. At this time, the amount of the peroxide and the amine used is preferably 0.1 to 5.0 parts with respect to 100 parts by weight (hereinafter abbreviated as parts) of the total weight of the monomer composite composition. Also,
When polymerizing with ultraviolet light and visible light, 0.05 to 5.0 parts of dibenzoyl, benzoin methyl ether, benzoin ethyl ether, P-chlorobenzophenone, benzoyl peroxide or camphorquinone and amines are blended as a photosensitizer. By doing so, both are practically used clinically. Further, the composition is easily polymerized by heating, and the temperature at this time is preferably in the range of 60 to 140 ° C. In addition, a general peroxide and a tertiary amine-based polymerization initiator alone or in combination thereof are added in an amount of 0.1 to 3.0 parts based on 100 parts by weight of the present composition. Polymerize at 60-80 ° C for 5-30 minutes. It is also possible to pulverize a polymer obtained by such a method and apply it as an organic filler.

Further, other polymerizable monomers that may be used in admixture with the composition may be monofunctional or polyfunctional, such as methyl acrylate, methacrylate, hydroxyethyl acrylate and methacrylate, ethylene glycol. These include mediacrylate and methacrylate, di- or tri- and tetraethylene glycol diacrylate and methacrylate, glycidyl acrylate and methacrylate, UDMA, Bis-MEPP and the like. As the vinyl ester of carboxylic acid, vinyl acetate, vinyl butyrate, vinyl stearate, ethylenically unsaturated dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, etc. may be mixed and used.

When the above compound is mixed with the monomer composite composition, the mixing amount is changed depending on the viscosity, the curing time and the desired physical properties, but is usually 2 to 80 parts by weight with respect to 100 parts by weight of the composition of the present invention. Department is applicable.

On the other hand, in order to improve wear resistance, hardness, polymerization shrinkage and thermal expansion coefficient by the composition, quartz, quartz having a particle size of 20 μm or less, which is surface-treated with silane and titanate compounds,
An inorganic filler such as talc, alumina, apatite, glass beads, colloidal silica, barium silicate, nitriding and silicon carbide, or an organic filler such as polymethylmethacrylate can be mixed and used. The amount of the mixture is preferably 0.1 to 8 times the amount of the composition.
Further, a curing agent, a polymerization inhibitor, a colorant, an antioxidant, an ultraviolet absorber and the like are used in the above mixture as required.

For clinical use, the above mixture should be packaged in two forms, one paste or solution containing the above general peroxide, and the other paste or powder containing the amine-based polymerization accelerator. Then, the paste and the paste and the solution and the powder are kneaded for about 1 minute, respectively.

When the composition is used as an adhesive for a filler, the composition is dissolved in an organic solvent such as ethanol, chloroform, or ether to a concentration of 5 to 40 parts by weight. Was divided into two parts to form two packaging forms, one of which was mixed with a peroxide and the other of which was mixed with an amine-based polymerization accelerator, and both were mixed and immediately etched with phosphoric acid. When applied to the surface of the tooth substance and the solvent is removed by evaporation, a strong adhesive layer is formed and it can be used as a filler adhesive. Furthermore, in the case of the photopolymerization type, one packaging form is used, and the composition is mixed with a photosensitizer, a filler, etc. to form a paste, and a thickness of 4 is applied to the tooth cavity.
It is filled in mm and is used as a filling material, and as a photopolymerization type crown restorative material and denture base material in the same manner as in the conventional method.

[Action]

Since the composition of the present invention contains groups having various functions controlled at the molecular level in the same molecule, its action is arbitrarily changed depending on the purpose of use to provide a material imparting desired high functionality. There is a point to gain. That is, since the raw material for producing the composition is a trimer and tetramer of cyclic phosphorus oxynitride, it contains 6 and 8 chlorines, respectively, and these chlorines are substituted with an arbitrary hydroxyl group-containing compound. Get, but
The polymer obtained by substituting all of 6 and 8 chlorines with alkyl methacrylate can obtain very large compressive strength and hardness, but on the other hand, the bending strength is small, and further, the water resistance and abrasion resistance are deteriorated. Therefore, in order to improve the bending strength, it is a good idea to use an alkyl methacrylate having a long carbon chain, but other properties are not improved, and when immersed in water for a long time, the water absorption increases, The drawback is that the mechanical properties are reduced.

The best way to solve these difficulties is achieved by the monomer composite composition in which 1 to 6 of chlorine is substituted by using various fluorides according to the present invention. That is, by replacing the fluoride, fluorine in the fluoride acts as a hydrophobic group, not only to prevent water absorption of the polymer,
At the same time, since it lowers the friction coefficient of the polymer, it has the effect of significantly reducing the amount of wear due to the antagonist teeth.
It is useful as a crown restorative material and filling material.

On the other hand, in order to produce a monomer composite composition that adheres to tooth substance and metal, a composition in which various carboxylic acid compounds according to the present invention are substituted with 1 to 4 chlorine is suitable.

It is well known that the action of the carboxylic acid compound is that the carboxyl group exerts an adhesive force by chelating with calcium of the tooth substance and an oxide on the metal surface. However, as the number of substitutions of the carboxylic acid compound increases, the adhesive strength temporarily increases, but when immersed in water for a long time, the adhesive strength decreases, and the water absorption increases and the mechanical properties increase. Is reduced.

Measures to prevent this decrease in adhesive strength can be achieved by the above-mentioned fluoride. That is, at the same time that an adhesive force is obtained with a carboxylic acid compound that is a hydrophilic group, water absorption is prevented by a fluoride having a hydrophobic group, and a large adhesive force can be maintained. In this case, it is necessary that the hydrophilic group-containing group and the hydrophobic group-containing group are well balanced.

After all, the function of the monomer composite composition of the present invention is to improve the mechanical strength of the polymer by using cyclic phosphorus nitride as a skeleton and a main component, and by binding an alkyl methacrylate as a polymerization curable group thereto. At the same time, by combining a fluoride and a carboxylic acid compound in the same molecule, at the same time imparting water resistance and abrasion resistance, and further, having a good durability and multi-functionality that can obtain a large adhesive force. Therefore, the clinical practice of the monomer composite composition is to simplify the conventional operation method.

EXAMPLES Next, the present invention will be described more specifically with reference to Examples.

(1) A typical monomer composite composition was obtained as follows.
(Reference example and Examples 1-4).

Reference Example 1 34.7 g (0.1 mol) of phosphorus dichloride nitride trimer was added to 21
Dehydrated benzene 350m in a 3-necked flask
Then, 190 g of pyridine was added, and purified 2-hydroxyethyl methacrylate 8 with stirring under ice cooling.
5.8 g (0.66 mol) was added dropwise over 1 hour, then
After reacting at 60 ° C. for 60 hours, ice-cooling was performed to remove pyridine hydrochloride, and in order to remove excess pyridine,
The organic layer was washed with 2N hydrochloric acid and then twice with a 5% solution of potassium carbonate and sodium chloride, respectively, and then dehydrated with anhydrous magnesium sulfate.
Next, benzene was removed under reduced pressure to obtain an oily target product 7
6 g (yield about 90%) was obtained. Specific gravity 1.33, viscosity 16 poise, refractive index 1.520 at 20 ° C.

Example 1 The amounts of phosphorus dichloride / nitride trimer, benzene and pyridine were the same as in Reference Example 1, and 200 g (0.2 mol) of 2.2.2-trifluoroethanol was added to this solution to give 8
After reacting at 0 ° C. for 5 hours, the mixture was cooled, and further, 57.2 g (0.44 mol) of 2-hydroxyethyl methacrylate was added.
l) was added and reacted at 60 ° C. for 50 hours, and then Reference Example 1
58.4 g of the target product (yield about 70
%)Obtained. Specific gravity 1.40, viscosity 9 poise, refractive index at 20 ° C 1.473.

Example 2 46.4 g (0.1 mol) of phosphorus dichloride nitride tetramer was added to 21
450m of dehydrated benzene in a 3-necked flask
Then, 316 g of pyridine was added, and then 12-hydroxydecanoic acid 4 dissolved in 200 m of ether was added.
After adding 3.3 g (0.2 mol) and reacting at 40 ° C. for 10 hours, 2-hydroxyethyl methacrylate 8 was added.
5.1 g (0.66 mol) was added, and the mixture was reacted at 60 ° C. for 50 hours. Purification was carried out in the same manner as in Reference Example 1, and the desired product 117
g (yield about 85%) was obtained. Specific gravity 1.36, viscosity 24 poise, refractive index 1.441 at 20 ° C.

Example 3 Phosphorus dichloride nitride tetramer, benzene and pyridine were the same as in Example 2, and tetrahydrofuran 20 was added to this solution.
After adding 33.2 g (0.2 mol) of P-hydroxyphenylpropionic acid dissolved in 0 m and reacting at 50 ° C. for 5 hours, 2,2,2-trifluoroethanol 2 was added.
0.0 g (0.2 mol) was added and reacted at 50 ° C. for 10 hours. Next, 57.3 g (0.44 mol) of 2-hydroxyethyl methacrylate was added to this solution, and 6 more
The reaction was carried out at 0 ° C for 50 hours. Purification was carried out in the same manner as in Reference Example 1 to obtain 101 g of the desired product (yield 80%). Specific gravity 1.4
1, viscosity 92 poise, refractive index at 20 ° C. 1.460.

Example 4 The amounts of phosphorus dichloride nitride tetramer, benzene and pyridine were the same as in Example 2, and cyclohexane 2 was added to this solution.
After adding 49.8 g (0.3 mol) of P-hydroxyphenylpropionic acid dissolved in 00 m and reacting at 50 ° C. for 5 hours, 2,2,3,3,3,3-pentafluoro 1
-Add 46.4 g (0.2 mol) of pentanol and add 50
The reaction was carried out at 0 ° C for 10 hours. Next, 61.4 g (0.33 mol) of 6-hydroxyhexyl methacrylate was added to this solution.
Was added, and the mixture was further reacted at 60 ° C. for 50 hours. Purification was carried out in the same manner as in Reference Example 1, with 117 g of the desired product (yield about 70%).
Got Specific gravity 1.34, viscosity 110 poise, refractive index 1.420 at 20 ° C.

These objects are all 1R (Hitachi 295 type, KBr
The characteristic absorption of each of them was measured using a plate or a tablet, and NMR (JNM-F × 100, FT-NMR100) was used.
Mhz, acetone D ₆ , TMS), ¹ H and ¹³ C
Was measured, and it was confirmed that each of them was the target product.

(2) Polymerization and curing method and use Table 1 shows the main physical properties of the dental filling material.
Reference Example 2 and Examples 5 to 7 Reference Example 2 100 parts by weight of the monomer obtained in Reference Example 1 (hereinafter abbreviated as "part") was divided into two parts, and 50 parts of one of them was benzoyl peroxide (hereinafter abbreviated as "BPO"). ) Add 0.25 part and add 5 of the other
0.4 part of NN-dimethylparatoluidine (hereinafter abbreviated as DMPT) was added to 0 part, and both were mixed to cure in 2 minutes.

Polymerization shrinkage is 7.0%, thermal expansion coefficient is 46.5 × 10 ^-6 /
The temperature was 0 ° C (20 → 80 ° C). The amount of wear by the toothbrush showed a small value of 1/10 or less of PMMA.

Example 5 A solution prepared by adding 0.6 parts of BPO to 100 parts of the monomer composite composition obtained in Example 1 was designated as A, while 100 parts of quartz (10 μm) whose surface was silanized was treated with paratolyldiethanolamine. The powder added 7 parts is B, and A / B is 30 /
The mixture was kneaded at a ratio of 70 to obtain a filler. The curing time was 2 minutes. The amount of wear by the toothbrush was about 1/30 of PMMA.

Example 6 20 parts of the composition obtained in Example 1 was mixed with 10 parts of triethylene glycol dimethacrylate, 70 parts of silicon nitride (1 μm) whose surface was silanized, and 0.6 parts of BPO to prepare a paste A, Separately, Bis-GMA (30 parts), surface-silane-treated silicon nitride (70 parts) and DMPT (0.7 parts) were mixed to prepare paste B, and A / B was kneaded at a ratio of 50/50. The curing time was 3 minutes and 30 seconds.

Example 7 To 50 parts of the composition obtained in Example 2 was added 10 parts of triethylene glycol dimethacrylate, and this was divided into two parts. One part was mixed with 0.7 part of BPO and 70 parts of silane-treated quartz. To prepare a paste A, and to the other one, 0.7 part of paratolyl diethanolamine and 70 parts of surface-treated quartz are mixed to prepare a paste B, and A / B is 50 /
Kneaded at a ratio of 50. The curing time was 4 minutes.

A hard resin for crown restoration was prepared. The main physical properties are shown in Table 1. Reference Example 3 and Example 8 Reference Example 3 A solution of 100 parts of the composition obtained in Reference Example 1 and a powder of technical resin (manufactured by Sankin Industry Co., Ltd., BPO; 0.3%, PMMA powder) were used. The mixture was kneaded at a liquid / powder ratio of 70/100 and polymerized at 140 ° C. under 4 atmospheres.

Example 8 A hard resin was produced under the same conditions as in Reference Example 3 except that 100 parts of the composition obtained in Example 1 was used as a solution.

The reference example 3 and the example 8 can be applied to the denture base.

An adhesive and a binder were prepared. The main physical properties are shown in Table 1 (Example 9).

Example 9 A liquid obtained by adding 80 parts of ethyl alcohol to 20 parts of the composition obtained in Example 2 was divided into two, and 50 parts of one of them was added with BPO;
Solution A was prepared by blending 2 parts, and 0.4 part of paratolyl diethanolamine was blended with 50 parts of the other solution B.
Was prepared and mixed at an A / B ratio of 50/50 to prepare a dentin adhesive.

Example 10 Using 10 parts of the composition obtained in Example 3, 1 part of maleic acid was added thereto, 79 parts of ethyl alcohol and 10 parts of ether were further mixed, and the resulting mixture was divided into two parts. A tooth adhesive was prepared with.

Example 11 To 100 parts of the composition obtained in Example 3, 1.0 part of BPO was added to prepare a solution A, and separately, semen powder carlon (manufactured by Sankin Industry Co., Ltd., zinc oxide powder) was added to paratolyl diethanolamine. 0.8 part was added to prepare powder B, which was kneaded at an A / B ratio of 40/60 to prepare a binder.

Example 12 An adhesive was produced on 10 parts of the composition obtained in Example 4 in the same manner as in Example 9 below.

Example 13 A bonding material was produced on 100 parts of the composition obtained in Example 4 in the same manner as in Example 11. The composition obtained in Example 4 can be applied to the denture base in the same manner as in Reference Example 1.

Method of measuring physical properties (1) Polymerization shrinkage was determined by the specific gravity method.

(2) The viscosity was measured at 20 ° C. using a viscometer manufactured by Lyon.

(3) The refractive index was measured at 20 ° C. using an Abbe refractometer.

(4) The compressive strength was measured with a crosshead of 2 mm / min after immersing a sample of 4φ × 5 mm in 37 ° C. for 24 hours.

(5) Bending strength is 25 × 2 × 2m according to ISO4049
The measurement was carried out at a crosshead speed of 1 mm / min with a fulcrum distance of 20 mm as a sample of m.

(6) The hardness was measured with a Knoop hardness meter under a load of 100 g.

(7) The water absorption rate is 15φ x 0.5mm, and it is 7 ℃ at 37 ℃.
After soaking for a day, the weight increase relative to the original weight was divided by the surface area and displayed.

(8) The adhesive strength was measured by using the front labial surface of a fresh bovine tooth on one side of the adherend, polishing the surface with emery paper, # 600 to expose the ivory surface, and applying a phosphorus of 50% concentration on the surface. It was etched with an acid solution for 30 seconds, washed with water, and then air-dried with nitrogen gas. The other adherend was stainless steel, and the surface thereof was polished with # 400. Adhesion area is 5φmm and the film thickness is 45μm using spacers.
After applying the sample mud to both adherend surfaces, load 2
After adding kg and holding for 13 minutes, the load was removed, and then the pieces were immersed in water at 37 ° C. for 7 days, and then the adhesive strength was measured at a crosshead speed of 10 mm / minute.

Effects of the Invention Various physical properties of the dental material using the monomer composite composition of the present invention are compared with Reference Examples used for the same purpose, as is clear from Examples 5 to 13 in Table 1. All of its physical properties show excellent results and are highly practical.

That is, when the monomer composite composition of the present invention and the composite obtained in Examples 1 to 2 were used as a filler, the water absorption amount in Reference Example 2 was large, but 2 mol of the fluoride of Example 5 was used. When it was contained, the water absorption amount decreased to about 1/4 and other properties were improved. On the other hand, in Example 7 containing a carboxyl group, the adhesive property was exhibited, the bending strength was increased, and the effect of the composite composition was remarkably exhibited.

On the other hand, in Reference Example 3 in which a hard resin was produced, the mechanical strength was higher than that in Example 8, but the water absorption amount was small in Example 8 containing a fluoride.

In the case of the adhesives and the binders of Examples 9 to 13, the adhesive strength is high, and particularly in the case of containing the carboxyl group, the fluoride and the methacryl group of Example 11, the mechanical strength and the adhesive strength. Was relatively large and the water absorption was small. Similarly, in Example 12, the water absorption was the smallest and the adhesive strength was large. Obviously, these things cannot be achieved unless the monomer composite composition of the present invention is used.

That is, it is clear that the mechanical strength is obtained by the cyclic structure of phosphating nitridation and the hetero bond, the decrease in water absorption is due to the effect of fluoride, and the adhesive strength is due to the effect of the carboxyl group, The fact that no decrease in adhesion and mechanical strength was observed even after immersion in water is due to the synergistic effect of the hydrophobic group fluoride.

Claims (10)

[Claims] 1. A general formula as a basic skeleton (Wherein m is 3 or 4), a group selected from the substituent X and the substituent Y is bonded to the phosphorus atom,
Substituent X in the molecule is selected from phosphorus and oxy-bonded groups of the formula _{CH 2 = C (CH 3)} CO 2 (CH 2) n-O- ( wherein n is 2-8),
The substituent Y in the molecule is a group in which the oxygen of the hydroxyl group of the hydroxyl group-containing compound selected from the hydroxyl group-containing fluoride and the hydroxyl group-containing saturated carboxylic acid compound is oxy-bonded with phosphorus, and the number of X and Y in the molecule is from 0 Large, (X
Cyclic phosphorus nitride 3 characterized in that the number of + Y) is 2
Or the monomer composite composition of 4. 2. X is CH ₂ : C (CH ₃ ) CO ₂ (CH ₂ ) n.
The composition according to claim 1, which is O- (n is 2 to 8). 3. The composition according to claim 1, wherein Y is Z (CF ₂ ) nCH ₂ O—, n is 1 to 4, and Z is hydrogen or fluorine. 4. The composition according to claim 1, wherein Y is (CF ₃ ) ₂ CHO-. 5. Y is --O (CH ₂ ) nCOOH, and n
The composition according to claim 1, wherein is 1 to 15. 6. The composition according to claim 1, wherein Y is —OC ₆ H ₄ (CH ₂ ) nCOOH and n is 0, 1 or 2. 7. The composition according to claim 1, wherein Y is —OC ₆ H ₃ (COOH) ₂ . 8. Y is --OC ₆ H ₃ (R) COOH and R is O.
The composition of claim 1 which is H or OCH ₃ . 9. A cyclic trimer, wherein X is 17 mol% or more, and Y
The composition according to claim 1, which comprises 83 mol% or less of the oxy-bonded group according to any one of claims 3 to 8. 10. A cyclic tetramer, wherein X is 12.5 mol% or more and Y is an oxy-bonded group according to any one of claims 3 to 8 of 87.5 mol% or less. A composition according to claim 1 consisting of: