JPH0563483B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel carboxylic acid copolymer.
Specifically, it is a carboxylic acid copolymer that is water-soluble and has a high bonding property with metal ions, and is particularly useful as a curing agent component for glass ionomer cement and the like. (Prior art and problems to be solved by the invention) Conventionally, as water-soluble carboxylic acid copolymers,
Acrylic acid, methacrylic acid, α-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid,
Cutronic acid, citraconic acid, 3-butene-1,
Single or copolymers of 2,3-tricarboxylic acid and the like are known. The above-mentioned carboxylic acid-based (co)polymers are used in various fields, and are used, for example, as a hardening agent component of dental cements such as polycarboxylate cements or glass ionomer cements. Carboxylic acid-based (co)polymers, which are used as hardener components in dental cement, are mixed with metal oxide powder in the form of an aqueous solution, but they have a strong affinity with dental hard tissues and are not effective against living organisms. Because it has the advantage of having minimal harmful effects, it can be used to fill and restore teeth that have been damaged due to caries, as a lining to protect the pulp from thermal or chemical stimulation, and to fix metal or ceramic prostheses to teeth. Widely used for fittings etc. However, among the conventionally known carboxylic acid-based (co)polymers mentioned above, for example, polyacrylic acid and polymethacrylic acid have high viscosity in aqueous solutions even at low concentrations, so it is difficult to mix them with metal oxide particles. It has the disadvantage that it is difficult to perform uniformly and sufficient mechanical strength cannot be obtained. For this reason, in practice, copolymers of acrylic acid and polybasic acids such as maleic acid and itaconic acid are used, which can produce aqueous solutions with low viscosity even at relatively high concentrations, but this is still insufficient. First, it is desired to develop a carboxylic acid copolymer that can give cement even higher mechanical strength and adhesive strength. (Means for Solving the Problem) As a result of intensive research and exploration in order to solve the problem, the present inventors discovered that a specific functional group in which two carboxyl groups are bonded to the same carbon atom They discovered that if they discovered a new polymer electrolyte and used it as a curing agent component for cement, a cured product with excellent mechanical strength and adhesion to tooth tissue and metals could be obtained, leading to the completion of the present invention. Ivy. That is, the present invention provides a unit (A) represented by the following general formula. (However, R ₁ is a hydrogen atom or _an alkyl group,
X ₂ is the same or different hydrogen atom or alkali metal, Y is an alkylene group, and m is 0 or 1. ) and the unit (B) represented by the following general formula (However, R ₂ and R ₃ are hydrogen atoms, hydroxyl groups, or alkyl groups, Z is a hydrogen atom or an alkali metal, and n is 0 or 1.) The ratio is
It is a carboxylic acid copolymer with a molecular weight of 5,000 to 500,000. In the present invention, R ₁ of unit (A) represented by the above general formula represents hydrogen or an alkyl group,
In the case of an alkyl group, the number of carbon atoms is generally 1 to 3.
It is. Hardener components of dental cement include:
It has 1 to 2 carbon atoms, most preferably a methyl group.
Further, X ₁ and X ₂ represent hydrogen or an alkali metal, and as a cement hardening agent component, hydrogen or a portion thereof is preferably replaced with an alkali metal. Alkali metals include Li, Na, K,
Examples include Rb and Cs, among which Li, Na, and K are preferred. The alkylene group represented by Y is generally a branched or linear alkylene group having 1 to 9 carbon atoms,
To specifically illustrate them, −CH ₂ −, (—CH ₂
―) ₂ , (―CH ₂ ―) ₃ ,

[Formula] (-CH ₂ -) ₄ , (-CH ₂ -) ₅ , (-CH ₂ -) ₆ , (-CH ₂ -) ₇ , (-C
H ₂ -)
Examples include ₈ , (-CH ₂ -) ₉ , (-CH ₂ -) ₁₀ , etc. Among these, linear ones having 1 to 5 carbon atoms are preferred. Moreover, m is preferably 0. The alkyl group represented by R ₂ and R ₃ in unit (B) is preferably a methyl group or an ethyl group. In addition, Z represents hydrogen or an alkali metal,
The alkali metal is the same as the alkali metal represented by X ₁ and X ₂ above. Further, n is preferably 0. In the carboxylic acid copolymer of the present invention, R ₁ ,
R ₂ and R ₃ may be the same or different. The molar ratio of units (A) and (B) in the carboxylic acid copolymer of the present invention (hereinafter referred to as A/B) is
It is between 0.1 and 1.0. When A/B is lower than 0.1, the viscosity increases when made into an aqueous solution, making it difficult to mix with metal oxide powder when used as a cement hardener. Furthermore, if A/B is higher than 1.0, unreacted monomer tends to remain in the carboxylic acid copolymer, making production difficult. The molecular weight of the carboxylic acid copolymer of the present invention is 5000
~500000. When the molecular weight is less than 5000, the viscosity of the aqueous solution is low and it is easy to handle, but when it is used as a hardening agent for dental glass ionomer cement, for example, the mechanical strength of the cured product decreases. Furthermore, copolymers with a molecular weight higher than 500,000 have low water solubility, making it difficult to knead with metal oxide powder, making them impractical. In addition, the molecular weight as used in the present invention is a value determined as a relative molecular weight based on polyethylene glycol of known molecular weight using gel filtration chromatography (GPC), as described below. The carboxylic acid copolymer of the present invention is not subject to the above-mentioned restrictions on the bonding order of units (A) and units (B). The carboxylic acid copolymer of the present invention can be confirmed by known analytical means. For example, molecular weight is determined by GPC as described above.
Also, the molar ratio of unit (A) and unit (B) (A/
B) is determined by ¹³ C-NMR. That is, A/B can be determined from the area ratio of each peak based on the carbon of the carboxyl group of unit (A) and the carbon of the carboxyl group of unit (B), and in particular, when n of unit (B) is 0, In this case, A/B can also be determined from the ratio of the peak area based on the carbon of the alkylene group of unit (A) and the peak area based on all the carbons in the copolymer except for the carboxyl group carbon. . Also, the carbon of the methylene group in unit (A)

The existence of [Formula] can also be confirmed by ¹³ C-NMR. As mentioned above, the carboxyl group can also be confirmed by ¹³ C-NMR,
It can be confirmed from the peak (1550 to 1700 cm ^-1 ) due to carboxyl groups using an infrared spectrophotometer (IR). Further, the composition of the copolymer of the present invention is confirmed by comparing the elemental analysis values of carbon and hydrogen with the theoretical values calculated from the general formula. In addition, if X ₁ , X ₂ or Z in the copolymer is an alkali metal, the alkali metal can be determined by thermally decomposing the copolymer at 700°C and then performing atomic absorption spectrometry as an aqueous solution. . The method for producing the carboxylic acid copolymer of the present invention containing unit (A) and unit (B) represented by the above general formula as essential components is not particularly limited.
Any method may be used. Some specific examples of industrially suitable methods are as follows. In other words, the following formula () (However, R ₁ is a hydrogen atom or _an alkyl group,
X ₂ is the same or different hydrogen atom or alkali metal, Y is an alkylene group, and m is 0 or 1. ) and the following formula () (However, R ₂ and R ₃ are hydrogen atoms, hydroxyl groups, or alkyl groups, Z is hydrogen atoms or alkali metals,
and n represents 0 or 1. ) The carboxylic acid copolymer of the present invention can be obtained by reacting with the following. Typical examples of the compounds represented by the general formula () are allylmalonic acid, 1-pentene-5,5-dicarboxylic acid, 1-hexene-6,6
-dicarboxylic acid, 1-heptene-7,7-dicarboxylic acid, 1-octene-8,8-dicarboxylic acid,
1-nonene-9,9-dicarboxylic acid, 1-decene-10,10-dicarboxylic acid, 1-undeken-11,
11-dicarboxylic acid, 1-dodekene-12,12-dicarboxylic acid, 2-methyl-1-butene-4,4-dicarboxylic acid, 2-butene-pentene-5,5-dicarboxylic acid, 1-allyloxy-ethane- 2,2
-dicarboxylic acid, 1-allyloxy-propane-
3,3-dicarboxylic acid, 1-allyloxy-butane-4,4-dicarboxylic acid, 1-allyloxy-
Pentane-5,5-dicarboxylic acid, 1-allyloxy-hexane-6,6-dicarboxylic acid, 1-allyloxy-heptane-7,7-dicarboxylic acid,
Unsaturated dicarboxylic acids such as 1-allyloxy-octane-8,8-dicarboxylic acid and 1-allyloxy-nonane-9,9-dicarboxylic acid or their alkali metal salts are preferably used. The compound represented by the general formula () can be synthesized by a known method. For example, a compound in which m in the general formula () is 0 is a halogenated alkene compound and the following general formula () (However, R ₄ and R ₅ represent the same or different alkyl groups.) It can be obtained by reacting with a malonic acid ester represented by the following and hydrolyzing the resulting compound with an alkali. Further, the compound in which m in the general formula () is 1 can be obtained by, for example, reacting a dihalogenated alkane compound with a malonic acid ester represented by the general formula (), and then adding allyl alcohol to the obtained compound. It is obtained by further hydrolyzing the resulting ester compound with an alkali. As the compound represented by the general formula (), any known compound can be used without any restriction. For example, acrylic acid, α-hydroxyacrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, tiglic acid,
Vinyl acetic acid and the like are preferably used. By reacting the compound represented by the general formula () with the compound represented by the general formula (), a copolymer comprising the unit (A) and the unit (B) described above can be obtained. For the reaction, conventionally known methods can be employed without limitation. Examples include a polymerization reaction in water, an organic solvent, or a mixed solvent of a water-soluble organic solvent and water. As the above-mentioned organic solvent, any known solvent can be used without limitation as long as it dissolves the compound represented by the general formula () and the general formula (). For example, methanol, ethanol, isopropanol, acetone, etc. are suitable. These solvents may be used alone or as a mixture. In the above reaction, the concentration of the compounds represented by the general formulas () and () is preferably 5 to 95% by weight, more preferably 10 to 60% by weight.
The general formula () and the compound represented by the general formula () may be mixed in advance and reacted, and both the solution of the compound represented by the general formula () and the solution of the compound represented by the general formula () are prepared. Alternatively, the reaction may be carried out while adding one of them to the reaction system. In order to make the distribution of the unit (A) and unit (B) contained in the same molecule of the produced copolymer as uniform as possible and to reduce the amount of residual monomer, a general compound is added to the solution of the compound represented by formula (). formula()
A method of adding a solution of a compound represented by the formula () or a method of adding a solution of each of the compounds represented by the general formulas () and () dropwise to the reaction system to allow the polymerization reaction to proceed is preferably employed. A polymerization initiator is generally used in the reaction. As the polymerization initiator, any known polymerization initiator can be used without limitation. For example, persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; α,α-azo-bis-isobutyronitrile, 2,2'-azobis(2-amidinopropane)
Suitable radical initiators include azo compounds such as dihydrochloride and azobiscyclohexanenitrile; or peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, and hydrogen peroxide. It is. The polymerization initiator used in the reaction is generally dissolved in a known solvent. Suitable solvents include, for example, water, methanol, ethanol, isopropanol, and acetone.
In the reaction, the concentration of the polymerization initiator in the reaction system is not limited, but the concentration is 0.01 to 5.
The concentration is preferably 0.03 to 2% by weight, more preferably 0.03 to 2% by weight. In addition, the amount of polymerization initiator used in the above reaction is relative to the monomer used in the polymerization reaction.
The content is preferably 0.1 mol% or more, more preferably 1 to 2 mol%. The above reaction is performed in an inert gas atmosphere to prevent deactivation of radicals. Further, in order to proceed with the reaction uniformly, it is preferable to constantly stir the reaction solution during the reaction. In the above reaction, the polymerization initiator is preferably added little by little to the reaction system. For example, a method may be used in which a portion of the polymerization initiator used is dissolved in advance in the reaction system, and the remaining amount is added dropwise as a solution. Conditions other than those mentioned above in the reaction can be appropriately selected depending on the desired molecular weight and composition ratio of the copolymer. Examples of conditions suitably employed include a temperature of 40 to 120°C, more preferably 60 to 90°C.
℃, and the reaction time is 1 to 10 hours, more preferably 2 to 6 hours. The produced copolymer can be isolated and obtained by removing the solvent. For example, a suitable method is to concentrate the reaction solution using a rotary evaporator and then dry it using a constant temperature vacuum dryer. The temperature of the constant temperature vacuum dryer is preferably 30 to 90°C, more preferably 50 to 70°C. If the monomers used in the reaction remain as impurities, they can be removed by extracting the monomers remaining in the copolymer using a solvent such as ether or acetone as appropriate. In addition, the above general formula, unit (A) and unit (B)
When X ₁ , X ₂ and Z are alkali metals, it can be obtained by the following reaction. That is, it is obtained by reacting the carboxylic acid copolymer in which X ₁ , X ₂ and Z are hydrogen atoms obtained by the above reaction with an alkali metal or an alkali metal compound. Lithium, sodium, and potassium are suitable as alkali metals. Further, as the alkali metal compound, the above-mentioned alkali metal oxides, hydroxides, alkoxides, carbonates, etc. are preferable. The carboxylic acid copolymer of the present invention is suitably used as a curing agent component of dental cement, as is clear from the application examples described below. As mentioned above, dental cement is used in combination of a powder component mainly composed of metal oxide powder and a liquid component which is an aqueous solution of an electrolyte polymer. Further, a mixed powder in which an electrolyte polymer is mixed with a metal oxide powder may be prepared in advance, and water may be added to the mixed powder at the time of use. When the carboxylic acid copolymer of the present invention is used as an electrolyte polymer in the liquid component of dental cement, it is generally used as an aqueous solution, and its concentration is 30 to 30%.
80% by weight, more preferably 40-70% by weight.
This aqueous solution contains organic acids such as malonic acid, tartaric acid, malic acid, and citric acid; orthophosphoric acid, Phosphoric acids such as pyrophosphoric acid and polyphosphoric acid; or aluminum fluoride,
Fluorine compounds such as potassium fluoride, potassium hexafluorosilicate, sodium hexafluorotitanate, potassium hexafluorozirconate, etc. may be added. Further, the metal oxide powder is not particularly limited, and any known powder can be used without any restriction. for example,
Examples include powders of fluoroaluminosilicate glass, calcium phosphate, zinc oxide, and the like. The particle size of the metal oxide powder is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm. (Functions and Effects) The carboxylic acid copolymer of the present invention has a functional group in which two carboxyl groups are bonded to the same carbon (hereinafter referred to as
(called malonic acid group)

It is a polymer electrolyte with the following formula that is highly water-soluble and has a high bonding strength with metal ions. Dental cement using this as a hardener component exhibits superior adhesion to tooth tissue and metals compared to conventional dental cement. The carboxylic acid copolymer of the present invention has malonic acid groups that can chelate to metal ions and form a stable six-membered ring. For this reason, the carboxylic acid copolymers that have traditionally been used as cement hardeners in dental cements have been replaced by conventional carboxylic acid copolymers that only have carboxyl groups, which makes it difficult to form chelate rings. In comparison, the carboxylic acid copolymer of the present invention is thought to strongly bond to metal ions on the surface of teeth and metals and exhibit high adhesive strength. When the carboxylic acid copolymer of the present invention is used as a dental cement curing agent, it greatly contributes not only to adhesive strength but also to mechanical strength and operability, and its contribution is immeasurable. It is. Furthermore, the carboxylic acid copolymer of the present invention is not only suitable as a hardening agent for dental cement, but also
Due to its strong binding power to metal ions, it is also useful as a variety of industrial materials such as precipitating flocculants and dispersants. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, the definitions of various quantities related to the properties of materials shown in the text and examples and the methods for measuring them are as follows. (1) Molecular weight of carboxylic acid copolymer A 1.5 m Shodex gel filtration chromatograph (GPC) (manufactured by Nippon Waters Limited) was used.
An OHpak B-804 column was attached and a refractometer (RI) was used as a detector for measurement. The measurement conditions are:
The eluent was a 0.05M aqueous sodium chloride solution, the eluent flow rate was 0.1 ml/min, and the sample concentration was about 0.2% by weight.
Commercially available polyethylene glycol with a narrow molecular weight distribution and a known molecular weight (molecular weight, 3000,
^A calibration curve was created from the relationship ^between molecular weight and retention ^time . The molecular weight of the sample was determined as a relative molecular weight based on polyethylene glycol using the calibration curve described above based on the retention time determined by GPC measurement. (2) Viscosity of aqueous solution of carboxylic acid copolymer A 53% by weight aqueous solution of the polymer was prepared, and the viscosity of this solution at 23°C was measured using a rotational viscometer. (3) Composition ratio of copolymer An aqueous solution of the copolymer was measured by ¹³ C-NMR,
The composition ratio of unit (A) and unit (B) was determined from the area ratio of the peak due to carboxylic acid carbon. Note that the chemical shift of carbon was determined using benzene as an external standard substance. (4) Cement powder/liquid ratio Glass powder (Pg) cement hardener (Lg)
The weight ratio (P/L) to (5) Cement hardening time This was based on the hardening test for dental zinc phosphate cement described in JIS T-6602. That is, a Teflon mold with an inner diameter of 10 x 10 x 2 mm is filled with cement mixed with glass powder and cement hardener for 1 minute, the surface is flattened, and 2 minutes after the start of mixing, the mold is heated to a temperature
It was transferred to a constant temperature bath at 37°C and 100% relative humidity. After that, a beaker needle weighing 560 g (cross-sectional area of the needle 1
mm ² ) was gently dropped onto the surface of the test piece, and the time when no needle marks were left was defined as the curing time starting from the start of kneading. (6) Compressive strength of cement Based on JIS T-6602 crushing drag test for zinc phosphate cement. That is, cement prepared by kneading glass powder and a cement hardening agent for 1 minute was placed in a mold, kept in a constant temperature bath at 37° C. and 100% relative humidity for 1 hour, and then the hardened product was taken out from the mold. The size and shape of the test piece are cylindrical with dimensions of 12 mm x 6 mmφ. After that, this test piece was kept in distilled water at 37℃ for another 23 hours, and then pressurized using Tensilon (manufactured by Toyo Baldwin) until it fractured at a crosshead speed of 1 mm per minute. It was defined as compressive strength (Kg/cm ² ). The size and shape of the test piece were 6 mm x 12 mm cylindrical. (7) Cement disintegration rate Based on JIS T-6602 disintegration rate test. In other words, cement made by mixing glass powder and cement hardener for 1 minute is put into a mold and the diameter is
A 0.148mm nylon wire was inserted. This is 37℃,
After maintaining the relative humidity at 100% for 1 hour, the specimen was removed from the mold. The size and shape of the test piece was a disc with a diameter of 5 x 15 mm. Thereafter, the mixture was immediately put into a glass bottle with a known weight and internal volume of about 100 ml, stoppered, and weighed. Find the difference between this weight and the total weight of the bottle and nylon wire, and use this as the weight of the test piece. Pour 50ml of distilled water into this, suspend the test piece in water with a nylon wire, lightly stopper it, and let it cool to 37°C.
It was kept in a constant temperature bath at ℃ for 7 days. After taking out the nylon wire and test piece, the glass bottle was heated on a water bath to evaporate the water, and then dried in a thermostatic oven at a temperature of 150°C until the weight change of the bottle was less than 0.5 mg per 24 hours. . Next, the weight change of the evaporation residue was determined from the increased weight of the glass bottle, and the ratio to the original weight of the test piece was determined from this value, and this value was taken as the disintegration rate. (8) Cement adhesive strength A cement composition comprising a cement hardener prepared using the carboxylic acid copolymer of the present invention and fluoroaluminosilicate glass powder, bovine tooth enamel and dentin, and Ni-
The adhesive strength with Cr alloy was measured. The bond strength with enamel and dentin of bovine teeth was determined by the following method. Immediately before use, a cow's front tooth that has been stored in cold water is taken out immediately after extraction, and the enamel or dentin is scraped off using #800 emery paper while pouring water so that it is parallel to the labial surface. After washing the shaved surface with water, dry it by blowing compressed air for about 10 seconds, then apply double-sided tape with a thickness of 50 μm and a diameter of 4 mm on top of it, and then paste a paraffin wax board with a diameter of 4 mmφ and a thickness of 1 mm. Ta. A mixture of glass powder and cement hardener was applied to the hole, and an 8 mmφ x 20 mm stainless steel rod whose surface had been roughened by 50 μm sandblasting was pressed onto the mixture. This was kept in a constant temperature bath at 37°C and 100% relative humidity for 1 hour, and then immersed in water at 37°C for a further 23 hours, and then the tensile adhesive strength was measured using a tensile tester (crosshead speed 2 mm/
min). The adhesive strength between Ni-Cr alloy and cement was determined as follows. A Ni-Cr alloy measuring 10 mm long x 10 mm wide x 3 mm thick was polished with #320 abrasive paper, and the surface was roughened by sandblasting with 50 μm alumina. The following measurements were made in the same manner as the measurement of bond strength of bovine tooth enamel. Example 1 400 g of diethyl allylmalonate (manufactured by Tokyo Kasei) and
500 ml of a 24% by weight aqueous sodium hydroxide solution was placed in a round bottom flask, and reflux was continued for 30 hours while maintaining the temperature at 60°C. Subsequently, 417 g of 35% by weight hydrochloric acid was added to make an acidic solution, and then the reaction solution was concentrated using a rotary evaporator. Concentration was continued while precipitated sodium chloride was removed by filtration until there was no more precipitated sodium chloride. The concentrated liquid was stored in the refrigerator overnight to obtain needle-shaped crystals. The obtained needle crystals were recrystallized using ether as a solvent to obtain 175 g of allylmalonic acid. 14.4 g of allylmalonic acid thus obtained and 2,
2'-azobis-2-amidinopropane-dihydrochloride (manufactured by Wako Pure Chemical Industries, trade name V-50) 0.54
A solution prepared by dissolving g in 50 ml of ion-exchanged water is called Solution A. Solution B is a solution in which 21.6 g of alrylic acid is dissolved in 50 ml of ion-exchanged water. 50 0.54g of V-50
Two types of solutions were prepared in ml of ion-exchanged water. These will be referred to as liquid C and liquid D, respectively. A four-necked flask was prepared, with a reflux condenser attached to one neck, one glass tube for introducing nitrogen, and the other two glass tubes for introducing monomer. A silicone rubber tube connected to a microtube pump was connected to the glass tube for monomer introduction, so that liquids A and B could be delivered to the flask using the microtube pump. A Teflon stirring bar was placed in the flask so that the reaction system could be stirred using a magnetic stirrer. The flask was placed in a 90°C oil bath equipped with a magnetic stirrer. Pour C liquid into the flask and add nitrogen gas little by little to C.
into the liquid to remove oxygen. Introduction of nitrogen gas,
While continuing to stir the reaction system, liquid C, liquids A and B were simultaneously added dropwise to the reaction system using a microtube pump. The addition rate of liquid A is 1 per minute.
ml, and the addition rate of Solution B was 0.78 ml/min. When the addition of solution A is completed, add solution D at 1 ml per minute.
was added to the reaction system at a rate of After the addition of Solution D was completed, stirring was continued for another 2 hours at 90°C to prevent any monomer from remaining. Reduce the viscosity of the reaction solution using a rotary evaporator.
It was concentrated at around 5000 cps. This concentrated solution was taken into a separating funnel and washed twice with about 100 ml of diethyl ether. The washed liquid was placed in a polyethylene container and concentrated at 60°C for 48 hours to obtain a white solid. According to the following measurement, this white solid contains 25 to 75 units of units (A-1) and (B-1) shown in the following formula. It was a carboxylic acid copolymer with a molecular weight of 2.6×10 ⁴ . Also, 53% of the obtained copolymer
The viscosity of the aqueous solution was 1450 cps. According to IR measurement of the carboxylic acid copolymer, it was as shown in Figure 1 of the attached drawings. That is,
Absorption based on carbonyl group from 1750 to 1690 cm ^-1 ,
Absorption based on carbon-hydrogen bond of polymer chain at 1430-1480 cm ^-1 , C-O of carboxylic acid at 1400-1420 cm ^-1
Absorption based on -H was observed. ^{The 13} C-NMR spectrum is shown in Figure 2. 165
At ~180 ppm, one peak based on the carbon of the carboxylic acid of unit (B-1) and one peak based on the carbon of the carboxylic acid of unit (A-1) were observed. The composition ratio of unit (B-1) and unit (A-1) was determined from their respective peak area ratios. In addition, the elemental analysis values are C49.37% and H5.72%, and C50.00% calculated from the composition formula C ₃₃ H ₄₄ O ₂₂ ,
It matched well with H5.59%. Examples 2 to 6 Same as Example 1 except that the amounts of raw materials acrylic acid and allylmalonic acid, the amount of V-50, and the addition rates of solutions A, B, and D are as shown in Table 1. The following operations were performed to obtain the carboxylic acid copolymers listed in Table 2.

【table】

[Table] Examples 7 to 21 Example 1 except that the polymerization conditions were as shown in Table 3.
Copolymers shown in Table 3 were obtained in the same manner as above.

[Table] Example 22 A copolymer consisting of unit (A-1) and unit (B-1) was obtained in the same manner as in Example 1 except for the following conditions. Solution B described in Example 1 was a solution of 2.65 g of allyllic acid dissolved in 10 ml of water, Solution C was a solution of 4.33 g of allylmalonic acid and 0.14 g of V-50 dissolved in 10 ml of water, and Solution D was V-50. 0.14g water 10
ml solution was used, and Solution A was not used. The dropping rate of liquid B into the reaction system is 0.2 ml/min, D
After the addition of Solution B was completed, the solution was added dropwise to the reaction system at a rate of 0.4 ml/min. The temperature of the reaction system was maintained at 85°C. The obtained carboxylic acid copolymer has a molecular weight of 3.0
×10 ⁴ , a copolymer with a composition ratio of units (A-1) and (B-1) of 45:55, and the viscosity of a 53% by weight aqueous solution thereof was 1160 cps. Also, 1750 for IR measurement
Absorption based on carbonyl group at ~1690 cm ^-1 , 1430 ~
Absorption based on carbon-hydrogen bonds of the polymer chain was observed at 1480 cm ^-1 and absorption based on C-O-H of carboxylic acid was observed at 1400 to 1420 cm ^-1 . The elemental analysis values of the compound were C49.90% and H5.62%, which agreed well with the theoretical values of C50.00% and H5.59%. Example 23 30.0 g of diethyl malonate and 150 ethanol in a 300 ml three-necked flask equipped with a dropping funnel and a cooling tube.
ml, and while cooling on ice, 4.14 g of metallic sodium was added and stirred until a homogeneous solution was obtained. Subsequently, 22.51 g of 1-bromo-9-decene was added dropwise through the dropping funnel, and then heated at 80°C for 3 hours. The above solution was transferred to a 500 ml eggplant flask, and ethanol was distilled under reduced pressure. Next, 100 ml of 15% by weight aqueous sodium hydroxide solution was added, and after heating at 60°C for 24 hours, the ethanol produced by hydrolysis was distilled off by distillation. Subsequently, 100 ml of 23.36% by weight hydrochloric acid was added to acidify the solution. This solution was concentrated, and sodium chloride and sodium bromide precipitated during the solution were removed by filtration. The finally obtained precipitate was filtered out and thoroughly dried in a vacuum desiccator. The obtained compound was confirmed to be 1-undekene 11,11 dicarboxylic acid (or 9-dekenyl-propanedioic acid) by IR, ¹³ C-NMR, ¹ H-NMR, and elemental analysis. Next, a copolymer was synthesized in the same manner as in Example 1, using 24.2 g of 1-undekene-11,11 dicarboxylic acid obtained here in place of the allylmalonic acid described in Example 1. The obtained copolymer has a unit (A-2) represented by the following structural formula and the above-mentioned The unit (B-1) shown in the structural formula is 25:
75, a carboxylic acid copolymer with a molecular weight of 3.7×10 ⁴ . According to IR measurements of the copolymer,
Absorption based on carbonyl groups was observed between 1750 and 1690 cm ^-1 . Its elemental analysis values are C57.55%, H7.51
%, the value calculated from the composition formula, C57.63%,
It matched well with H7.47%. The viscosity of the copolymerization aqueous solution was 5580 cps. Examples 24 to 31 Various dicarboxylic acids represented by the following formulas were synthesized in the same manner as the synthesis procedure for 1-undekene-11,11-dicarboxylic acid described in Example 23, (However, Q represents an alkylene group of 1 to 10.) Using this and acrylic acid, the carboxylic acid copolymers shown in Table 4 were obtained in the same manner as in Example 1. The unit of the copolymer derived from the above dicarboxylic acid represented by the following formula is designated as (A-3). (However, Q represents an alkylene group of 1 to 10.)

[Table] Example 32 33.8g of diethyl malonate and 150g of ethanol in a 300ml three-necked flask equipped with a dropping funnel and a cooling tube.
ml, and while cooling on ice, 4.85 g of metallic sodium was added and stirred until a homogeneous solution was obtained. Subsequently, 50.0 g of 1,9-dibromo-nonane was added dropwise through the dropping funnel, and the mixture was heated at 80° C. for 3 hours. After drying the above solution using a rotary evaporator, the ether-soluble components were extracted. Thereafter, the ether was distilled off under reduced pressure to obtain a pale yellow compound. Next, 5.8 g of allyl alcohol, 150 ml of acetone, and 6.0 g of potassium carbonate were placed in a 300 ml three-necked flask equipped with a dropping funnel, and stirred until a homogeneous solution was obtained. Subsequently, 30.9 g of the pale yellow compound obtained in the above reaction was added little by little to the homogeneous solution,
Stirred at room temperature for 50 hours. Subsequently, the reaction solution was concentrated using a rotary evaporator, the precipitate was removed by filtration, and the acetone was distilled off to obtain a pale yellow compound. 34.2 g of the obtained pale yellow compound and 100 ml of a 10% by weight aqueous sodium hydroxide solution were placed in a 300 ml round bottom flask and kept at 50°C with stirring until a homogeneous solution was obtained. Then add 100ml of 2.5N hydrochloric acid to this solution.
The mixture was made acidic by adding and concentrated. During the process, precipitated sodium chloride was removed by filtration. Concentration and filtration were repeated until no more sodium chloride precipitated, and then a white powder precipitated. This was filtered, taken out, and dried in a vacuum desiccator. This compound was confirmed by ¹³ C-NMR and elemental analysis to be a dicarboxylic acid copolymer represented by the following formula. The obtained compound was reacted with acrylic acid in the same manner as in Example 1 to obtain a polymer. The obtained carboxylic acid copolymer has a molecular weight of 24:76 of the unit (A-4) shown by the following structural formula and the unit (B-1) shown by the above structural formula.
It was a copolymer with a molecular weight of 4.1×10 ⁴ . According to its IR measurements, Unit (A-4) Absorption based on carbonyl group was observed at 1750 to 1690 cm ^-1 . Also, according to elemental analysis, the measured values
C58.22% and H7.55%, which matched well with the values calculated from the composition formula, C57.19% and H7.57%. The viscosity of this carboxylic acid copolymer aqueous solution is 7450 cps.
It was hot. Examples 33 to 40 Carboxylic acid copolymers represented by the following formulas were obtained by the same operation as the synthesis of the dicarboxylic acid compound described in Example 32. (However, P represents an alkylene group having 1 to 9 carbon atoms.) Using the obtained compound, the copolymer listed in Table 5 was synthesized in the same manner as the synthesis method of the carboxylic acid copolymer in Example 1. A polymer was obtained. The unit in the carboxylic acid copolymer derived from the compound represented by the above general formula is referred to as the unit (A-5) represented by the following general formula. (However, P represents an alkylene group having 1 to 9 carbon atoms.)

[Table] Examples 41 to 80 The following general formulas synthesized in Examples 23 to 31 with methacrylic acid, α-hydroxyacrylic acid, crotonic acid, or vinyl acetic acid (including allylmalonic acid) (However, Q represents an alkylene group having 1 to 10 carbon atoms.) The carboxylic acid copolymers shown in Table 6 were produced in the same manner as in Example 1 using the compound shown below. Units derived from methacrylic acid in this carboxylic acid copolymer unit (B-2), similarly a unit from α-hydroxyacrylic acid (B-3), unit from crotonic acid (B-4), unit from vinyl acetic acid are shown in (B-5). Furthermore, the units derived from the carboxylic acid copolymers from the dicarboxylic acids synthesized in Examples 23 to 31 were as described above. It is indicated by unit (A-3).

【table】

【table】

[Table] Examples 81 to 115 The compounds represented by the general formula () above include methacrylic acid, α-hydroxyacrylic acid, crotonic acid, or vinyl acetic acid, and the compounds represented by the general formula () synthesized in Examples 32 to 39. l of the compound to be produced is O,
The following general formula where Y is a hydrogen atom (However, P represents an alkylene group having 1 to 9 carbon atoms.) Using a compound represented by I got it. Units derived from methacrylic acid, α-hydroxylallylic acid, crotonic acid and vinyl acetic acid in the copolymer are each (B-
2), (B-3), (B-4) and (B-5). In addition, the unit derived from the above dicarboxylic acid to the carboxylic acid copolymer used in this example is shown by (A-5) as described above.

【table】

[Table] Comparative Example 1 Using allylmaleic acid and acrylic acid, unit (A) and unit (B) were prepared by the method described in Example 1.
A carboxylic acid copolymer with a composition ratio of 5:95 and a molecular weight of 2.7×10 ⁴ was synthesized. The viscosity of the obtained 53% by weight aqueous solution of the carboxylic acid copolymer was 23,700. Application Examples 1 to 65 The powder/liquid ratio, curing time, compressive strength, disintegration rate, and adhesive strength of dental cement containing the carboxylic acid copolymer of the present invention as a curing agent component were measured. The components of the cement hardener were 50% by weight of carboxylic acid copolymer, 5% by weight of tartaric acid, and 45% by weight of water. As the glass powder for cement, commercially available fluoroaluminosilicate glass powder (trade name: Glass Ionomer F, manufactured by Shofu) was used.

【table】

【table】

[Table] Reference Examples 1 to 3 Instead of the copolymer of the present invention in the cement curing agent component of the application example, acrylic acid polymer, acrylic acid-
Using itaconic acid copolymer or acrylic acid-maleic acid copolymer, the physical properties were investigated in the same manner as in the application examples, and the results are shown in Table 9. The copolymer used contained 75 mol% of a unit derived from acrylic acid as unit (B). The molecular weight of the polymer is

[Formula] Itaconic acid

[Formula] Maleic acid Acrylic acid polymer (abbreviated as AA polymer) is 3.1×
10 ⁴ , acrylic acid-itaconic acid copolymer (AA-
(abbreviated as ITA copolymer) is 4.7×10 ⁴ , acrylic acid-
Maleic acid polymer (abbreviated as AA-MA copolymer)
was 2.9× ¹⁰⁴ .

【table】 [Brief explanation of the drawing]

Figures 1 to 10 are obtained in Examples 1 to 5.
These are IR and ¹³ C-NMR spectra.

【table】

Claims (1)

[Claims] 1. A unit (A) represented by the following general formula: (However, R ₁ is a hydrogen atom or _an alkyl group,
X ₂ is the same or different hydrogen atom or alkali metal, Y is an alkylene group, and m is 0 or 1. ) and the unit (B) represented by the following general formula (However, R ₂ and R ₃ are hydrogen atoms, hydroxyl groups, or alkyl groups, Z is a hydrogen atom or an alkali metal, and n is 0 or 1.) The ratio is
A carboxylic acid copolymer having a molecular weight of 0.1 to 1 and a molecular weight of 5,000 to 500,000.