JPH0418866B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a filler for human hard tissue containing a phosphate ester derivative and/or a polymer produced from the derivative. The filling material of the present invention has excellent mechanical properties (strength, elastic modulus, etc.), handling properties, etc., and is used for repairing hard tissues of the human body such as bones and teeth, and exhibits remarkable effects particularly in dental treatment. Therefore, although the following description will focus on dental use, these descriptions are not intended to limit the scope of application of the filler of the present invention. Various dental filling materials have been known as filling materials for partially missing teeth in dental treatment, but among them, so-called composite filling resins made of polymerizable monomers and inorganic fillers have excellent strength, aesthetics, Because of its excellent operability, it is widely used for the restoration of anterior teeth, and recently, its use for the restoration of deciduous molars is also being considered. However, since considerable occlusal pressure is applied to molar teeth, it is necessary to further improve the strength (compressive strength, bending strength, etc.) in order to use it for molar restoration. Therefore, there has been a demand for the development of high-strength composite filled resins. For example, methods for making inorganic fillers finer are known, but there is still room for improvement in polymer compounds. Examples of polymerizable monomers that provide such high-strength resins include those disclosed in U.S. Patent No.
No. 3066112 and No. 3179623 Compound represented by (diglycidyl dimethacrylate derivative of bisphenol A: hereinafter referred to as bisGMA)
is proposed. This monomer occupies the mainstream of composite filled resins, and even recently bisGMA
Very few polymerizable monomers have been developed. However, bis-GMA has the disadvantage that it has an extremely high viscosity and is difficult to handle unless a suitable reactive diluent such as methyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc. is added. Because of its low moisture resistance, it absorbs a large amount of water and has the problem of reducing the strength after curing, which has a very serious negative effect on the curing of BisGMA. Another fundamental problem is that all of the above-mentioned reactive diluents are low-molecular-weight compounds, have a high degree of penetration into dental pulp tissue, and have the drawback of being highly irritating to patients. Therefore, we need a product with a lower viscosity than Bis-GMA, in other words, one that allows the amount of reactive diluent added to be as small as possible, making it unnecessary if possible, and one with good crosslinking properties that improves strength after polymerization and biological There has come to be a demand for something with excellent compatibility. The present inventors have developed a filler that has these characteristics, particularly excellent strength (compression, bending, etc.) and hardness, low water absorption, appropriate viscosity during kneading, and excellent compatibility with living organisms. The present invention was completed through research to develop a new filler. That is, the filler of the present invention has the general formula (In the formula, R is alkenyl, acryloyloxy,
lower alkyl or aryl having one or more groups selected from the group consisting of methacryloyloxy, where lower alkyl denotes a group optionally further substituted with halogen, or one of R is of the formula -M [where M means alkyl or aryl, and these are aryl, halogen,
Alkyl, alkoxy, hydroxy and (wherein R has the same meaning as above), and the substituent is further substituted with one or more halogen and/or aryl. may be done,
The latter aryl is further (in the formula, R means a group substituted with a group represented by [optionally substituted with a group represented by the above)], and The main component is a polymerizable phosphoric acid ester derivative in which one or two groups of the formula (R in the formula have the same meaning as above) are present in one molecule, and if necessary, a molecule different from the main component. A filler for human hard tissue containing a polymerizable monomer having at least two polymerizable double bonds, an inorganic filler, and/or a curing catalyst. In addition, among the compounds serving as the main components above, R is of the formula -M
A compound not substituted with a group represented by the formula -M will be referred to as a compound (), and a compound in which one R is replaced with a group represented by the formula -M will be referred to as a compound (). The above compounds () and () are produced according to the following reaction formula. The reaction is divided into two types: compound () is produced according to reaction A, and compound () is produced according to reaction B. reaction A reaction B [In the formula, R and M are the same as above] In these reactions, if a mixture is used as the compound represented by R-OH, target substances having different R's can be obtained. When carrying out reaction B, the starting compound () is selected depending on the type of substituent present in the target compound. A more detailed explanation of the groups represented by R and M in the above general formula is as follows. R means lower alkyl or aryl having one or more groups selected from the group consisting of alkenyl, acryloyloxy, and methacryloyloxy, such as allyl, acryloyloxy, lower alkyl, methacryloyloxy, and lower alkyl, which are polymerizable 2 In addition to groups having one double bond,
Examples include groups having two or more polymerizable double bonds, such as diacryloyloxy lower alkyl and trimethacryloyloxy lower alkyl, and the vinyl group contained therein imparts polymerizability to the target compound. In addition to allyl, examples of alkenyl include vinyl, isopropenyl, and the like. Examples of the lower alkyl in R include alkyl having 1 to 6 carbon atoms (hereinafter referred to as the lower alkyl) such as methyl, ethyl, propyl, butyl, tertiary butyl, pentyl, and hexyl. Alkyl may be further substituted with halogen (hereinafter referred to as halogen) such as fluorine, chlorine, bromine and iodine, or hydroxy. Examples of the aryl include phenyl, xylyl, tolyl, biphenyl, anthryl, phenanthryl, etc. (hereinafter referred to as the above-mentioned aryl), and the aryl is the above-mentioned lower alkyl; methoxy, ethoxy, propoxy,
It may be substituted with lower alkoxy (hereinafter referred to as the lower alkoxy) such as isopropoxy, butoxy, tertiary butoxy, pentoxy, hexyloxy, etc., or the above halogen. M represents alkyl or aryl, but these may have specific substituents, and when expressing the -OM group including these substituents, it is roughly expressed as -OM=-OR ¹ -R ² - R ³ -R ⁴ [In the formula, R ¹ represents a first substituent, R ² represents a second substituent R 3 represents a third substituent, ^{R 4 represents} a fourth substituent, and R ² , R ³ and R ⁴ represent The presence of each substituent shown is optional. R ¹ is a group that replaces the hydrogen of the hydroxyl group of orthophosphoric acid, R ² is the hydrogen of R ¹ , R ³ is the hydrogen of R ² , R ⁴ is the group of R ³
This is a group that replaces each hydrogen in . M is at least
The present invention includes various cases in which the side chain has a side chain represented by R ¹ and has no substituents after R ² to cases in which up to R ⁴ are substituted. still
The number of substituents for R ² , R ³ and R ⁴ is not limited to one. R ¹ means alkyl or aryl, and alkyl includes, in addition to the above-mentioned lower alkyl, alkyl having a larger number of carbon atoms and unsaturated hydrocarbons. Moreover, the above-mentioned aryl is exemplified as the aryl. Next, the second substituent represented by R ² includes alkenyl; acryloyloxy; methacryloyloxy; the above aryl; the above halogen; the above lower alkyl; the above lower alkoxy; hydroxy; The groups represented by are exemplified. In addition, R ² is alkenyl,
When it is either acryloyloxy or methacryloyloxy, ^-OR1 -- ^R2 and -OR may mean the same group. The third substituent represented by R ³ is exemplified by the above-mentioned aryl or the above-mentioned halogen. The fourth substituent of R ⁴ is alkenyl, acryloyloxy, methacryloyloxy or The groups represented by are exemplified. R in R ⁴ is the same as R mentioned above. Next, the above process for producing compound () or () will be explained. Regarding reaction A, ie, the synthesis of the compound of general formula (): The reaction proceeds by dissolving the compound () together with a base in a reaction medium and reacting with phosphorus oxyhalide under anhydrous conditions at low temperature. As the solvent, a solvent that does not adversely affect the reaction, such as methylene chloride or chloroform, is preferred. As the base, a tertiary amine such as trialkylamine or pyridine is preferable, and as an inorganic base, a weak base such as carbonate is preferable. The reaction temperature is preferably 0 to 10°C. After the reaction is completed, water is added and the mixture is isolated and purified according to a conventional method to obtain the compound (). Next, regarding reaction B, that is, the synthesis reaction of compound (): The reaction is divided into two steps: first, compound () is reacted with phosphorus oxyhalide under anhydrous conditions. Although phosphorus oxyhalide also serves as a reaction solvent, the above-mentioned solvents may be used in combination depending on the case. Although the reaction temperature is not particularly limited, the reaction is carried out under normal heating or heating. As a result of the reaction, phosphoryl dichloride represented by the compound () is obtained. Next, the compound () dissolved in the solvent is reacted with the alcoholic compound represented by the compound () under anhydrous conditions and in the presence of a base. The reaction is carried out in the same solvent as above at a reaction temperature of about 0°C. After the reaction is completed, the mixture is washed with hydrochloric acid, potassium hydroxide, etc., dried, and the solvent is distilled off to obtain the compound (). The starting material () in the above reaction is an alcoholic compound having a polymerizable double bond as R, and the following are exemplified. _CH2 =CH− _CH2 −OH _CH2 =CH _{− COOCH2CH2OH} On the other hand, among the compounds (), non-polymerizable compounds having a hydroxyl group include: Examples of the polymerizable compound having a hydroxyl group include: etc. are exemplified. Various target compounds can be produced by selecting possible combinations from the above-mentioned compound groups as starting material compounds ()(). The target compound () or () thus obtained is a monomer having polymerizability, and exhibits polymerizability due to the vinyl group in R or M. When using the above compound as a filler, it is mixed with another polymerizable monomer different from these if necessary, and preferably with a curing catalyst (benzoyl peroxide, etc.) and a reaction accelerator (amines) to form the filler. A product is formed, and if necessary, an inorganic filler (such as quartz powder) is added, and the material is filled into, for example, a defective tooth and hardened. Depending on the size and shape of the application area, it is often better not to add an inorganic filler. The application of such a filling material is not limited to teeth as described above, but can be applied to any hard tissue of the human body. Next, the characteristics of the filler of the present invention will be explained. For example, dental fillings such as those mentioned above,
Durability is required to withstand long-term use after application, and if these are insufficient, the filling will easily break. However, since the filler of the present invention has excellent tensile, bending, and compressive strengths and elastic modulus after polymerization, it exhibits excellent durability against various stresses received in the oral cavity, and also has excellent wear resistance and Due to its excellent hardness, the filling surface will not be damaged or worn away. Furthermore, since it absorbs less water and has a lower coefficient of thermal expansion, it exhibits stable durability even under the temperature and humidity conditions in the oral cavity. Furthermore, since the curing time of this filler is short, there is little burden on the patient. In addition, the gelation time is appropriate and workability during kneading is not impaired, so there is no need to incorporate a low-molecular reactive diluent, and there is no problem of strength loss due to moisture absorption after curing and no irritation to the dental pulp. There is also an advantage. As described above, the composition of the present invention not only has high utility value as a dental filling material, but also exhibits good properties as a filler for other hard tissues of the human body, and can be applied to a wide range of fields. Next, a manufacturing example of the present invention will be shown. Production Example 1 In a methylene chloride solution containing 2-hydroxyethyl acrylate (39 g) and pyridine (36 g), while dropping phosphorus oxychloride (16 g),
The mixture was stirred and reacted at 10°C for 2 hours. After the reaction is complete,
The mixture was added to ice water, washed successively with 5% hydrochloric acid, 5% aqueous potassium hydroxide solution, and water, and then dried over sodium sulfate. The solvent was distilled off under reduced pressure to synthesize a phosphate compound (34.5 g) as a colorless and transparent oil. (CH ₂ = CHCOOCH ₂ CH ₂ O) ₃ P = O IR: ν _nax , cm ^-1 2900, 1720, 1630, 1365, 1160, 970 NMR (CDCl ₃ ): δ 6.35 (m, 3H×3, vinyl protons ) 4.25 (m 4H x 3, -CH ₂ CH ₂ -) Production Example 2 In the same manner as Production Example 1, 2-hydroxyethyl methacrylate (34.8 g) and pyridine (36 g)
Phosphorous oxychloride (16
g) and treated in the same manner as in Production Example 1 to synthesize a phosphate compound (41.0 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1365, 1160, 980 NMR (CDCl ₃ ): δ 6.10 (bs, 1H x 3, vinyl proton) 5.55 (m, 1H x 3, vinyl proton) 4.30 ( m, 4H x 3, -CH ₂ CH ₂ -) 1.90 (d, 3H x 3, vinyl CH ₃ ) Production Example 3 In the same manner as Production Example 1, 2-hydroxypropyl methacrylate (34.8 g) and pyridine (36
A phosphate compound (30.5 g) was synthesized by reacting phosphorus oxychloride (16 g) in a methylene chloride solution containing g) and treating in the same manner as in Production Example 1. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1375, 1160, 1000 NMR (CDCl ₃ ): δ 6.10 (bs, 1H x 3, vinyl proton) 5.55 (m, 1H x 3, vinyl proton) 4.85 ( m, 1H x 3, -CH ₂ CH CH ₃ ) 4.15 (m, 2H x 3, - CH ₂ CHCH ₃ ) 1.90 (d, 3H x 3, vinyl CH ₃ ) 1.30 (m, 3H x 3, -CH ₂ CH CH ₃ ) Production Example 4 In the same manner as Production Example 1, phosphorus oxychloride (16 g) was reacted in a methylene chloride solution containing 2-chloro-3-hydroxypropyl methacrylate (45 g) and pyridine (36 g), A phosphate compound (48.5 g) was synthesized by the same treatment as in Production Example 1. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1370, 1160, 1000, 760 NMR (CDCl ₃ ): δ 6.10 (bs, 1H×3, vinyl proton) 5.50 (m, 1H×3, vinyl proton) 4.20 (m, 4H×3, − CH ₂ CH (Cl) CH ₂ ) 3.65 (m, 1H×3, −CH ₂ CH (Cl) CH ₂ ) 1.90 (d, 3H×3, vinyl CH ₃ ) Production example 5 In the same manner as in Production Example 1, phosphorus oxychloride (16 g) was reacted in a methylene chloride solution containing allyl alcohol (17.4 g) and pyridine (36 g), and by treatment in the same manner as in Production Example 1. , a phosphate compound (17.0g) was synthesized. (CH ₂ = CHCH ₂ O) ₃ = P = O IR: ν _nax , cm ^-1 2900, 1630, 1365, 1160, 980 NMR (CDCl ₃ ): δ 5.60 (bs, 2H×3, vinyl protons) 4.10 ( bs, 1H x 3, vinyl proton) 3.50 (t, 2H x 3, -CH ₂ -) Production example 6 Phenol (120g), phosphorus oxychloride (180g)
and calcium chloride (25g) at 150°C.
It was heated for 5 hours. After the reaction was completed, excess phosphorus oxychloride was distilled off under reduced pressure to obtain the following phosphoryl dichloride (221 g). This product (211 g) was dissolved in methylene chloride (300 ml) and added dropwise to a solution of 2-hydroxyethyl methacrylate (240 g) and pyridine (160 g) in methylene chloride (400 ml) at 0°C, followed by stirring for 5 hours. After the reaction was completed, the mixture was washed with 5% hydrochloric acid, 5% aqueous potassium hydroxide solution and water in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure to synthesize a colorless transparent oily phosphate compound (350 g). IR: ν _nax , cm ^-1 2900, 1720, 1630, 1600, 1365, 1160, 960 NMR (CDCl ₃ ): δ 7.35 (s, 5H×1, arom. protons) 6.10 (bs, 1H×2, vinyl protons) ) 5.50 (m, 1H x 2, vinyl proton) 4.25 (m, 4H x 2, -CH ₂ CH ₂ -) 1.90 (d, 3H x 2, vinyl CH ₃ ) Production example 7 O-chlorophenol (14 g), Production example 6 of phosphorus oxychloride (18g) and calcium chloride (2.5g)
The reaction was carried out in the same manner as above to obtain the following phosphoryl dichloride (26 g). This product (25 g) was reacted with 2-hydroxy methacrylate (28 g) and pyridine (16 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound. IR: ν _nax , cm ^-1 2950, 1720, 1680, 1600, 1370, 1160, 960 NMR (CDCl ₃ ): δ 7.20 (m, 4H×1, arom.protons) 6.10 (bs, 1H×2, vinyl protons) ) 5.55 (m, 1H x 2, vinyl proton) 4.85 (m, 1H x 2, -CH ₂ - C HCH ₃ ) 4.15 (m, 2H x 2, -CH ₂ - C HCH ₃ ) 1.90 (d, 3H x 2, vinyl CH ₃ ) 1.30 (m, 3H×2, -CH ₂ CHCH ₃ ) Production example 8 Production example of 4-tertiary butylphenol (15 g), phosphorus oxychloride (16 g) and calcium chloride (2.5 g) The reaction was carried out in the same manner as in 6 to obtain the following phosphoryl dichloride (26 g). This product (25.7 g) was reacted with allyl alcohol (11.6 g) and pyridine (16 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (26.5 g). IR: ν _nax , cm ^-1 2950, 1630, 1600, 1365, 1160, 960 NMR (CDCl ₃ ): δ 6.95 (ABq, 4H×1, arom.protons) 5.62 (m, 2H×2, vinyl protons) 4.10 (bs, 1H x 2, vinyl proton) 3.50 (t, 2H x 2, -CH ₂ -) 1.25 (s, 9H x 1, tert-butyl) Production example 9 β-naphthol (16g), phosphorus oxychloride (18g )
and calcium chloride (25 g) were reacted in the same manner as in Production Example 6 to form the following phosphoryl dichloride (27
g) was obtained. This product (26 g) was reacted with 2-hydroxyethyl acrylate (24 g) and pyridine (16 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (39.5 g). IR: ν _nax , cm ^-1 2900, 1720, 1680, 1600, 1365, 1160, 960 NMR (CDCl ₃ ): δ 7.80 to 7.05 (m, 7H×1, aroma.protons) 6.35 (m, 3H×2, vinyl protons) 4.25 (m, 4H x 2, -CH ₂ CH ₂ -) Production example 10 7-methoxy-α-naphthol (19g), phosphorus oxychloride (18g) and calcium chloride (2.5g)
were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (29 g). This product (29 g) was reacted with 2-hydroxyethyl methacrylate (24 g) and pyridine (16 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (45.4 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1365, 1160, 970 NMR (CDC ₃ : δ 7.70-6.70 (m, 6H×1, arom.protons) 6.10 (bs, 1H×2, vinyl proton) 5.55 (m, 1H x 2, vinyl proton) 4.25 (m, 4H x 2, -CH ₂ CH ₂ -) 3.90 (s, 3H x 1, -OCH ₃ ) 1.90 (d, 3H x 2, vinyl CH ₃ ) Production example 11 O-cresol (10.8g), phosphorus oxychloride (16g)
and calcium chloride (2.5 g) were reacted in the same manner as in Production Example 6 to form the following phosphoryl dichloride (22
g) was obtained. This product (22 g) was mixed with 2-chloro-3-hydroxypropyl methacrylate (35.6 g) in the same manner as in Production Example 6.
g) and pyridine (16 g) and treated in the same manner to synthesize the following phosphate compound (47 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1370, 1160, 1000,
760 NMR (CDCl ₃ ): δ 6.85 (m, 4H×1, arom.protons) 6.10 (bs, 1H×2, vinyl proton) 5.55 (m, 1H×2, vinyl proton) 3.65 (m, 1H×2, -CH ₂ CH (Cl) CH ₂ -) 4.20 (m, 4H x 2, -CH ₂ CH (Cl) CH ₂ -) 2.20 (s, 3H x 1, -CH ₃ ) 1.90 (d, 3H x 2, vinyl CH ₃ ) Production Example 12 4-bromoresorcinol (18.9 g), phosphorus oxychloride (32 g) and calcium chloride (5 g) were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (43 g). This product (42 g) was reacted with 2-hydroxypropyl methacrylate (57.5 g) and pyridine (32 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (81 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1370, 1160, 960 NMR (CDCl ₃ ): δ 7.40 (d, 1H×1, arom. protons) 6.40 (m, 2H×1, arom. protons) 6.10 (bs, 1H x 4, vinyl proton) 5.55 (m, 1H x 4, vinyl proton) 4.85 (m, 1H x 4, -CH ₂ CH CH ₃ ) 4.15 (m, 2H x 4, - CH ₂ CHCH ₃ ) 1.93 (d, 3H x 4, vinyl CH ₃ ) 1.30 (m.3H x 4, -CH ₂ CH CH ₃ ) Production example 13 1,3-dihydroxynaphthalene (16 g), phosphorus oxychloride (32 g) and Calcium chloride (5g)
were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (39 g). This product (39 g) was reacted with 2-hydroxyethyl methacrylate (48 g) and pyridine (32 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (73.0 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1365, 1160, 960 NMR (CDCl ₃ ): δ 8.00 to 6.80 (m, 6H×1, arom.protons) 6.10 (bs, 1H×4, vinyl proton) 5.55 (m, 1H x 4, vinyl proton) 4.25 (m, 4H x 4, -CH ₂ CH ₂ -) 1.90 (d, 3H x 4, vinyl CH ₃ ) Production example 14 Bisphenol A (34g) , phosphorus oxychloride (35
g) and calcium chloride (5 g) were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (57 g). This product (39 g) was reacted with 2-hydroxyethyl acrylate (48 g) and pyridine (32 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound (72 g). IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1365, 1295, 960 NMR (CDCl ₃ ): δ 7.10 (s, 4H×2, arom.protons) 6.10 (bs, 1H×4, vinyl proton ) 5.55 (m, 1H x 4, vinyl proton) 4.35 (m, 4H x 4, -CH ₂ CH ₂ -) 1.90 (d, 3H x 4, vinyl CH ₃ ) 1.70 (s, 3H x 4, -CH ₃ ) Production Example 15 Phosphoryl dichloride (39 g) obtained in the same manner as in Production Example 14 was reacted with 2-hydroxypropyl methacrylate (58 g) and pyridine (32 g) in the same manner as in Production Example 6, and treated in the same manner to produce the following phosphate. A compound (74g) was synthesized. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1370, 1290, 980 NMR (CDCl ₃ ): δ 7.10 (s, 4H×2, arom.protons) 6.10 (bs, 1H×4, vinyl proton ) 5.55 (m, 1H x 4, vinyl proton) 4.85 (m, 1H x 4, -CH ₂ CH CH ₃ ) 4.15 (m, 2H x 4, -CH ₂ CHCH ₃ ) 1.90 (d, 3H x 4, vinyl CH ₃ ) 1.70 (m, 3H x 4, -CH ₃ ) 1.30 (m.3H x 4, -CH ₂ CH CH ₃ ) Production example 16 3-chloro-4,4'-dihydroxybiphenyl (33 g), Phosphorus oxychloride (32 g) and calcium chloride (5 g) were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (55 g). This product (38 g) was reacted with 2-hydroxyethyl acrylate (48 g) and pyridine (32 g) in the same manner as in Production Example 6, and treated in the same manner to synthesize the following phosphate compound. IR: ν _nax , cm ^-1 2950, 1720, 1630, 1600, 1365, 1295, 960,
845 NMR (CDCl ₃ ): δ 7.80 (m, 3H×1, arom. protons) 7.10 (s, 4H×1, arom. protons) 6.35 (m, 3H×4, vinyl protons) 4.25 (m, 4H×4 , _-CH2CH2- ) Production Example 17 Bis(4-hydroxyphenyl) _{phenylmethane} (28g), phosphorus oxychloride (33g) and calcium chloride (5g) were reacted in the same manner as in Production Example 6 to produce the following phosphoryl dichloride. (37g) was obtained. This product (84 g) was reacted with allyl alcohol (22 g) and pyridine (32 g) in the same manner as in Production Example 6, treated in the same manner, and the following phosphate compound (45
g) was synthesized. IR: ν _nax , cm ^-1 3050, 2900, 1630, 1600, 1365, 1295, 960 NMR (CDCl ₃ ): δ 7.10 (m, 13H×1, arom.protons) 5.62 (m, 2H×4, vinyl protons) ) 5.60 (s, 1H x 1, - - C H) 4.10 (bs, 1H x 4, vinyl proton) 3.50 (t, 2H x 4, -CH ₂ -) Production example 18 Bis(4-hydroxyphenyl) ether (20
g), phosphorus oxychloride (32 g) and calcium chloride (5 g) were reacted in the same manner as in Production Example 6 to obtain the following phosphoryl dichloride (41 g). This product (41 g) was reacted with allyl alcohol (22 g) and pyridine (32 g) in the same manner as in Production Example 6, treated in the same manner, and the following phosphate compound (40
g) was synthesized. IR: ν _nax , cm ^-1 2900, 1630, 1600, 1365, 1295, 1100, 960 NMR (CDCl ₃ ): δ 7.10 (s, 4H×2, aroma.protons) 5.60 (m, 2H×4, vinyl protons) ) 4.10 (bs, 1H x 4, vinyl proton) 3.50 (t, 2H x 4, -CH ₂ -) The viscosity was measured for the compounds obtained in Production Examples 1 to 18 above and bisGMA as a reference. The results are shown in Table 1.

【table】

[Table] Next, examples of the present invention will be described. Example [1] Fused quartz sand was crushed using a porcelain ball mill to prepare 200 mesh passes. γ-Methacryloxypropyltrimethoxysilane in an amount equivalent to 0.5% by weight of quartz powder was added to an aqueous sodium hydroxide solution with a pH of 9.0 to 9.8, stirred and dissolved, and the above quartz powder was added to this. .
By thoroughly mixing and stirring this, a slurry was obtained. This slurry was dried at 130°C to obtain silane-treated quartz powder. The phosphate compound obtained in Production Example 14 (70 parts by weight) was mixed with the phosphate compound obtained in Production Example 1 (30 parts by weight) to obtain a resin binder. The above quartz powder (80 parts by weight) to this binder (20 parts by weight)
and colloidal silica (3 parts by weight) were added and thoroughly mixed to obtain a paste. This paste was divided into two parts, and to one part, 0.6 parts by weight of N,N'-dimethyl-P-toluidine and 2 parts by weight of P-tolylsulfonylhydrazine were added to the paste (100 parts by weight) and thoroughly mixed. A homogeneous dispersion was obtained. Paste (100 parts by weight) on the other side
Add 0.8 parts by weight of benzoyl peroxide to
A homogeneous dispersion was obtained in the same manner. Equal amounts of this uniform dispersion were mixed and kneaded, and the operability, physical properties, etc. were examined, and the results shown in Table 1 were obtained. Example [2] In the same manner as in Example [1], ethylene glycol dimethacrylate (20 parts by weight) was mixed with the phosphate obtained in Production Example 6 (80 parts by weight) to obtain a resin binder. Quartz powder (85 parts by weight) and the like were added to this binder (15 parts by weight), and a uniform dispersion was obtained in the same manner as in Example [1]. When its operability, physical properties, etc. were investigated, the results shown in Table 1 were obtained. Example [3] In the same manner as in Example [1], diethylene glycol dimethacrylate (25 parts by weight) was mixed with the phosphate obtained in Production Example 13 (75 parts by weight) to obtain a resin binder. Quartz powder (80 parts by weight) and the like were added to this binder (20 parts by weight), and a uniform dispersion was obtained in the same manner as in Example [1]. When its operability, physical properties, etc. were investigated, the results shown in Table 1 were obtained. Example [4] In the same manner as in Example [1], triethylene glycol dimethacrylate (30 parts by weight) was mixed with the phosphate obtained in Production Example 14 (70 parts by weight) to obtain a resin binder. Quartz powder (80 parts by weight) and the like were added to this binder (20 parts by weight), and a uniform dispersion was obtained in the same manner as in Example [1]. When its operability, physical properties, etc. were investigated, the results shown in Table 1 were obtained. Comparative Example In the same formulation as Example [4], conventionally known bisphenol A was used instead of phosphate.
Diglycidyl methacrylate was blended to obtain a uniform dispersion. When its operability and physical properties were examined, the results shown in Tables 2 and 3 were obtained.

[Table] Table 3 shows the viscosity during kneading in each Example and Comparative Example. For reference, Table 3 also includes data from another example (Reference Example 1) and the case where triethylene glycol dimethacrylate was used alone (Reference 2).

【table】

【table】

【table】

[Table] In the manner described above, a filler for human hard tissues with excellent mechanical properties, handling properties, etc. was completed.

Claims (1)

[Claims] 1. General formula (In the formula, R is alkenyl, acryloyloxy,
lower alkyl or aryl having one or more groups selected from the group consisting of methacryloyloxy, where lower alkyl denotes a group optionally further substituted with halogen, or one of R is of the formula -M [where M means alkyl or aryl, and these are aryl, halogen,
Alkyl, alkoxy, hydroxy and (wherein R has the same meaning as above), and the substituent is further substituted with one or more halogen and/or aryl. may be done,
The latter aryl is further (in the formula, R means a group substituted with a group represented by [optionally substituted with a group represented by the above)], and The main component is a polymerizable phosphoric acid ester derivative in which one or two groups of the formula (R in the formula have the same meaning as above) are present in one molecule, and if necessary, a molecule different from the main component. A filler for hard tissues of the human body, which contains a polymerizable monomer having at least two polymerizable double bonds, an inorganic filler, and/or a curing catalyst.