CN1009707B - Surgical cement and method for preparation thereof - Google Patents
Surgical cement and method for preparation thereofInfo
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- CN1009707B CN1009707B CN85105933A CN85105933A CN1009707B CN 1009707 B CN1009707 B CN 1009707B CN 85105933 A CN85105933 A CN 85105933A CN 85105933 A CN85105933 A CN 85105933A CN 1009707 B CN1009707 B CN 1009707B
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Abstract
The present invention discloses a surgery cement used for filling the defective parts and the hollow parts of bones and teeth. The present invention contains (a) which is a component (A) at least having one ingredient, and (b) which comprises a component (B) of effective water-solubility poly (carboxylic acid) in surgery performance and water, wherein the component (A) is selected from an ingredient group composed of self-hardening alpha-tricalcium phosphate powder and self-hardening amorphism tricalcium phosphate powder. The present invention can be prepared by the mixed components (A), (B) and the water, or water solution of the mixed component (A) and component (B) is prepared; then, the mixture is kneaded.
Description
The present invention relates to surgical cement, more particularly be related to as the type alpha tricalcium phosphate of key component and (or) surgical cement of amorphism phosphoric acid DFP and the method for the above-mentioned cement of preparation.
So far, be used for biological body image plastic material and the such material of various types of metal, for example gold, silver, palldium alloy, nickel one evanohm, cobalt one evanohm, amalgam, rustless steel, titanium alloy all have been suggested and it has been used for many occasions of surgery and dentistry.These material majorities are applied to do crown and tooth root, and, tried hard to it is used for the artificial bone artificial joint or tissue like that.Its mechanical strength has high reliability and is easy to Precision Machining, yet, because the harsh environmental condition in the organism, they are subjected to the various bad variation as dissolving, burn into worsen, so produce fatigue and be accompanied by the generation foreign body reaction during life-time service.
Then, the ceramic material that has the good affinity of biological tissue has caused very big attention recently.
For example, proposed as by Al
2O
3Monocrystalline or its sintered body, artificial bones that those potteries that perhaps are made of apatite hydroxide are formed, artificial joint and tooth root.
But these embedded materials have too hard and too crisp such shortcoming, and these shortcomings are the general character of pottery just.For adopting its material, still leave over down many problems to be solved as artificial skelecton and tooth root.
On the other hand, orthophosphoric acid solution is common as solidifying solution in the field of surgical cement.Cement like that, known have, for example, by zinc oxide with knead made zinc phosphate cement and of about 70% aqueous orthophosphoric acid solution by the silicate cement of mediating the goods that constitute with silicate glass and water-bearing phosphate solution, and the like.Though owing to used phosphoric acid, making this cement is highly acidic, thereby it has the effect of injury dental pulp, moreover also is being inadequate aspect the bonding of tooth.
Just the opposite, United States Patent (USP) 3,655,605,3,741,926,3,751,391 and 3,804, No. 794 the zinc oxide polycarboxylate cement has been proposed, wherein, aqueous poly-(carboxylic acid) solution has weak injury effect.Be used for replacing aqueous orthophosphoric acid solution.
In addition, the ionomer cement develops, so that improve the comprcssive strength of cement, and in said ionomer, the silicon oxide aluminate is used to replace zinc oxide, and this silicon oxide aluminic acid is solidified (for example referring to United States Patent (USP) 3 with poly-(carboxylic acid) aqueous solution, 814,717,4,016,124,4,089, No. 1,316,129, No. 830 and British patent).But, be used for being different from its chemical properties of prescription of these cement those compositions of tooth and bone, therefore, still leave over many problems to be overcome, as these compositions and biological tissue seldom is compatible, the myeloid tissue inflammation that it makes, and can infiltrate through dental canaliculus or the like.
Then, in order to regulate the setting rate of the carboxylate of forming by zinc oxide and poly-(carboxylic acid), proposed by adding a kind of filler, be that a spot of calcium phosphate powder arrives by the prepared a kind of component of carboxylic acid cement, (referring to, United States Patent (USP) 3,655,605,3,751,391 and 4,288, No. 355) and by will be as the hydroxyapatite of main composition with as ZnO, CaO, Al
2O
3, Ca
3(PO
4)
2, SiO
2The inorganic powder of one class and poly-(carboxylic acid) mix the cement synthetic that obtains, (referring to, for example, Japan Patent, open application case 1983-83605 number).
In addition, Japanese Laid-Open Patent Application 1984-182263 number, it is delivered after this patent application, has disclosed the method for preparing surgical cement, it comprises the same nitric acid of type alpha tricalcium phosphate, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid and suchlike mineral acid or organic acid mix.
Thereby such surgical cement can not satisfy the requirement of biological tissue's compatibility, can not satisfy the requirement of comprcssive strength simultaneously.
The material that is applied to organism always is in the contact with biological tissue, and is in secular effect.Therefore, it must be safe, that is to say; They must not have illeffects to organism, for example, give birth to tumor.They can not make around the position inflammation of cement filling and application yet.In addition, they should have the good compatibility with biological cell, just, and to their good adhesion and have osteocomma of one's own, in other words, the assimilation between the newborn bone and the surface of material.
In these cases, development biologic artifact material has been had a kind of intensive requirement, this material contains the constituent of the Main Ingredients and Appearance that is similar to tooth and bone, and has fabulous comprcssive strength.
The main purpose of this invention provides the surgical cement that is suitable in medical science and dental field, this cement has ten minutes and is similar to the tooth of biologic artifact tissue and those compositions of bone, so that these cement can not cause the generation foreign body reaction, and these cement are being very good aspect the compatibility of biological organic organization.
Another purpose of this invention provides the pulp canal that can be packed into tooth, or the surgical cement of the damaged and cavity portion that causes because of disease or external factor.
A purpose again of this invention provides as repairing because the repair materials of the rotten alveolar bone that is disappeared, and as the applicable surgical cement of inserts in the crack of tooth that forms by tooth periosteopathy and the such external factor of vehicle accident and bone.
The other purpose of this invention provides the surgical cement of high compressive strength, and it also is applicable to just needs high-intensity occasion at once after filling.
Further object of the present invention provides surgical cement, and wherein, the 26S Proteasome Structure and Function at injured position and cavity (cavity) position is can repair with recoverable.
Above-mentioned purpose of the present invention can be realized by surgical cement what follows.
Surgery cement according to the present invention comprise self-hardening type alpha tricalcium phosphate and (or) the amorphous tricalcium phosphate of self-hardening, effectively water miscible poly-(carboxylic acid) and water on the surgery,
Be used for this invention surgical cement type alpha tricalcium phosphate and (or) the amorphism phosphoric acid DFP of self-hardening, term " self-hardening " means that these phosphoric acid are with effectively water miscible poly-(carboxylic acid) effect on the surgery of following more detailed announcement, so that solidify together.
In order to realize purpose of the present invention, must use the type alpha tricalcium phosphate (α-Ca of self-hardening
3(PO
4)
2] powder and (or) the amorphism phosphoric acid DFP [Ca of self-hardening
3(PO
4)
2XH
2O] powder.
Generally, said type alpha tricalcium phosphate can be by a kind of preparation the among the following method.For example, a kind of method comprises the calcium hydrogen phosphate dihydrate [CaHPO that heat drying is crossed
42H
2O]; So that under about 300～500 ℃ temperature, form γ-calcium pyrophosphate (γ-Ca
2P
2O
7), then molal quantity equal γ-calcium pyrophosphate and calcium carbonate uniform mixing, calcine this mixture, after sufficiently dry, under 1000～1300 ℃ temperature, preferably about 1,200 ℃ was heated about one hour down, finish grinding is by burnt goods, to obtain to have the powder that is equal to or less than 100 microns sizes.Preparation type alpha tricalcium phosphate [α-Ca
3(PO
4)
2] the another kind of method of powder comprise calcium hydrogen phosphate dihydrate and calcium phosphate equably mixed with mole ratio at 2: 1.Then, as the condition of above-mentioned announcement under this mixture of calcining and grinding by incinerating goods.
The type alpha tricalcium phosphate that is obtained can further be processed according to following process thus, it comprises compression type alpha tricalcium phosphate powder, in temperature from 1,200～1, calcine compressed powder down for 500 ℃, be preferably in 1,200～1,300 ℃ at least one hour, then, under above-mentioned said the sort of situation, grind by incinerating goods, so that form fine powder with 0.5～20 micron size granularity.
In addition, type alpha tricalcium phosphate can pass through at the amorphous tricalcium phosphate of pressure lower compression, and is prepared according to front same technical process calcining and grinding.
In one method of back, wherein calcining and milled processed are carried out secondary.Handle for the first time and make the generation type alpha tricalcium phosphate, handling for the second time is to improve the density of powder and improve comprcssive strength.But, by handling for the first time the goods that obtain really applicable to the surgical cement of mainly forming as it and satisfied effect is provided.
In addition, vacation before the first time or calcining for the second time and grinding steps, can add the aluminum phosphate by restatement 0.1%～10% if required, and best 0.1～2% aluminum phosphate is in binding agent, so that improve the comprcssive strength of surgical cement more or less.
On the other hand, general amorphous tricalcium phosphate can be by comprising aqueous solution and the phosphatic reactant aqueous solution that makes calcium salt, separates these goods with filter type and dry these goods are obtained under cryogenic conditions.
It is worth mentioning that for example, lime nitrate is as the best example of calcium salt, and ammonium phosphate is preferably as phosphoric acid.Said reaction is preferably in the wet synthetic method that pH carries out being similar to response class known calcium hydroxide apatite under the pH10-12, after reaction is finished, separates with filtering method, and dry and grinding is carried out at low temperatures.This is to maintain an essential condition that forms calcium phosphate under the amorphous state that does not produce any crystalline solid.
In said method, under temperature-10 ℃-+10 ℃, carry out isolated by filtration, drying and grinding operation.Especially, the upper limit of this temperature is the marginal value of technical process, and promptly this is to keep above-mentioned described amorphous state goods to react necessary.
When drying process, described have, for example, and lyophilization (lyophilizing).
In addition, except type alpha tricalcium phosphate and (or) the amorphism phosphoric acid DFP, another main component is effectively water miscible poly-(carboxylic acid) on the surgery.Be generally used for all of cement known poly-(carboxylic acids) of surgery, as contain as the cement of the zinc oxide of basic composition or at United States Patent (USP) 4,089, the cement of the ionomer that discloses for No. 830 can be used for the present invention without difficulty.
Best poly-(carboxylic acid) is homopolymerization and the copolymerization by aliphatic unsaturated carboxylic acid, and aliphatic unsaturated carboxylic acid copolymerization and these acid are with the copolymerization of other aliphatic unsaturated monomer those poly-(carboxylic acids).
According to the present invention, poly-(carboxylic acid) that be used for best surgical cement can be by arbitrary normally used polymerization technique technology preparation.For example, can be in there be the solution of Ammonium persulfate. in polymerization and containing in the various chain transfer agents of given solution of polymer about 30% and carry out, if necessary, this solution can be concentrated, to make more viscous solution, perhaps lyophilization is to make poly-(carboxylic acid) granule of solid, shaped.
Other various acrylic monomerss can be included in paradigmatic system so that polymers of carboxylic acid has the character of improvement, are water solubles fully because polymers of carboxylic acid is provided, and react with tricalcium phosphate powder on request.
Best poly-(carboxylic acid) is (ⅰ) acrylic acid homopolymer, or (ⅱ) (a) acrylic acid co-polymer, be preferably in quantitatively by weight 60～99.9%, according to this basic composition and (b) a small amount of, preferably have at least a kind of weight of unsaturated monomer to account for 0.1～40%, this monomer can be from by methylene-succinic acid, anti-(formula) butene dioic acid, methacrylic acid, aconitic acid, methyl is along (formula) butene dioic acid, glutaconate, anti-(formula) butene dioic acid of methyl, suitable (formula)-2-methyl-2-butene is sour and it is than lower alkyl ester (alkyl group has 1-5 carbon atom), acrylic acid lower alkyl esters (C
1-C
5Alkyl) chooses in the group of Zu Chenging.
Effective water-soluble poly (carboxylic acid) has from 2,000～200 on the surgical cement use surgery performance of the present invention, 000 viscosity-average molecular weight, and better from 5,000～150,000, at this moment, by, the method for Sakamoto is measured.(chemical abstracts 58 13160 C).
Poly-(carboxylic acid) can be used from the form of form of powder or aqueous solution, makes to have by weight scope from the concentration of 10-60% the best by weight 20%～55%.
Comprise (a) by weight 23%～75% according to best surgical cement of the present invention, best at least one group of 33%～75%(component A by weight), it can be chosen in the amorphism phosphoric acid DFP by the a-tricalcium phosphate of self-hardening and self-hardening.(b) 2-46% by weight, best poly-carboxyl is 7%～37%(B component by weight) and (C) by weight 10%～69%, best water by weight 12～50%.
Have concentration by weight during 10%～60% aqueous solution when (B component) is used to form, preferable by weight 25%～50%, (A) aqueous solution of component is 0.3: 1 to 3.0: 1 with (B) ratio of the aqueous solution of component, best 0.5: 1 to 2.5: 1.
Even this poly-(carboxylic acid) aqueous solution is employed, corresponding composition also must be adjusted, so that its quantity drops in the above-mentioned scope.
Surgical cement of the present invention is preferably adjusted, so that effectively water miscible poly-(carboxylic acid) drops in 0.4 to 0.6 scope with the weight ratio of the type alpha tricalcium phosphate of self-hardening on the surgery, and the weight ratio of the type alpha tricalcium phosphate of water and self-hardening drops in the scope of 0.4-0.7, especially, when this surgical cement was applied to the application's case, wherein high compressive strength was essential.
In addition, in the surgical cement of this invention, except that poly-(carboxylic acid), other many organic acid preferably contain and reach 10% of gross weight by weight, so that during repairing or repair canaliculi dentales etc. and using, can control setting rate.
Be used to form in the occasion of aqueous solution at organic acid, the amount that is present in the water in the aqueous solutions of organic acids is adjusted in advance, so that its total amount drops in the scope of narrating above.
As best used organic acid in the surgery cement of the present invention, noteworthy have, for example, hydroxyacetic acid, the amino the eleventh of the twelve Earthly Branches diacid of 2-, pantothenic acid, 2-hydroxy acid, 2, the 3-dyhydrobutanedioic acid, citric acid, hydroxyl succinic acid, it can use separately, or uses as the mixture that contains component more than two kinds.
Surgical cement of the present invention can be prepared according to following technical process, it comprises that (ⅰ) is (a) the powder of the component that is made of an ingredient at least (A), this ingredient be selected from the group formed by the amorphism phosphoric acid DFP of the a-tricalcium phosphate of self-hardening and self-hardening and (b) on the surgery performance effectively water miscible poly-(carboxylic acid) powder form (B) blended step, in the presence of an amount of water, mixture is mediated, to form the step of goods fluidization or plasticity, perhaps (ⅱ) adds an amount of water-soluble component (B) to component (A), the mixture that obtains is mediated, so that mixture is transformed into liquid condition or mecystasis.
Thereby, according to the present invention, the external cement can with the a-tricalcium phosphate and (or) amorphism phosphoric acid calcium made with poly-(carboxylic acid) chemical combination, this cement is to being used as the pulp canal packing material, the liner cement, the healant that is used for alveolar bone is suitable, and biology group tissue is had the good compatibility.
Now, will more specifically explain the present invention by following non-limiting instance.Technical term in these examples " part " and " % " are expressed as " part by weight " and " by weight percentage " respectively.
The preparation of reference example 1:a-tricalcium phosphate
Calcium phosphate dibasic dihydrate (CaHPO
42H
2O) calcined 2 hours down at 500C °, so that form γ-calcium pyrophosphate (γ-Ca
2P
2O
7).Resulting calcium pyrophosphate is equating mole CaCO together
3Further calcined 2 hours down behind the uniform mixing at 1,200 ℃, and cooling fast.Then, thus obtained goods are ground, and sieved, so that adjust the distribution of particles size through 300 mesh sieve.According to x-ray diffraction pattern, find that these goods are type alpha tricalcium phosphates.Below, these goods are called for short makes " α-TCP ".
Reference example 2; Synthesizing of amorphism phosphoric acid DFP
0.5 mol lime nitrate [Ca(NO
3)
2] 3 liters of same 0.5 mol phosphoric acid hydrogen ammonia [(NH of aqueous solution
4)
2HPO
4] 2 liters of aqueous solutions, by blended method, be equal to or less than in temperature under 5 ℃ the nitrogen current and react, but the opposing party, utilize to add ammonia and in this solution, adjust acid-base value (pH) to 11.
Resulting precipitate is filtering out and is using ammonia scrubbing below 0 ℃, lyophilizing is 24 hours then.Thus obtained goods grind to form particle size less than 300 purpose powder.Its X-ray diffraction figure only shows the ring of light, and does not observe by the caused crest of crystallization.Below, these goods abbreviate " A-TCP " as.
Example 1
According to the method for the T-6602 of Japanese Industrial Standards, mediate with moisture poly-(carboxylic acid) solution with reference to 2 synthetic α-TCP and A-TCP by reference example 1, after 24 hours, these goods stand intensity test.The result who is obtained is illustrated in table 1.The polymer of acrylic acid-methylene-succinic acid (during the content 15% of methylene-succinic acid, molecular weight 80,000 and 31,000) is as poly-(carboxylic acid) usefulness in this example.
Table 1
Powder moisture poly-(carboxylic acid) and solution weight are than * * comprcssive strength
Molecular weight * concentration (%) (kilograms per centimeter
2)
α-TCP 80，000 25 1.3 180
α-TCP 80，000 30 1.3 320
α-TCP 80，000 45 1.3 720
α-TCP 80，000 50 1.3 770
α-TCP 80，000 45 0.5 150
α-TCP 80，000 45 1.0 630
α-TCP 80，000 45 1.8 800
α-TCP 80，000 45 1.3 700
α-TCP 80，000 45 1.3 600
* viscosity-average molecular weight (following all molecular weight (MW) all are expressed as viscosity-average molecular weight).
* powder and solution weight ratio.
The result listed from table 1 can find out obviously that α-TCP and A-TCP have shown enough comprcssive strength to filler and the surgical cement as pulp canal.
Example 2
α-the TCP that is obtained by reference example 1 is pre-mixed with polypropylene acid and in the presence of an amount of water this mixture is mediated.Then, do the test of resulting goods comprcssive strength according to example 1 same process.The result who is obtained is by shown in the table 2, and in this example, acrylic acid-methylene-succinic acid polymer (when methylene-succinic acid content 15%, molecular weight 80,000) is as gathering (carboxylic acid) usefulness.
Table 2
The water gaging amount comprcssive strength of the amount of α-TCP poly-(carboxylic acid)
(gram) (gram) (gram) (kilograms per centimeter
2)
2 0.7 1.2 530
2 1.0 1.2 580
2 1.1 1.2 550
Example 3
Except using various types of poly-(carboxylic acids), just repeat the process of example 1.The test result of comprcssive strength is listed in table 3.
Table 3
Component molecules amount concentration (%) weight ratio comprcssive strength
(kilograms per centimeter
2)
Polyacrylic acid 5,000 40 1.0 120
Polyacrylic acid 30,000 40 1.0 350
Acrylic acid-5% methylene 66,000 40 1.3 680
Base succinic acid co-polymer
Acrylic acid-30% methylene 30,000 40 1.3 690
Base succinic acid co-polymer
Acrylic acid-5% is along (formula) 15,000 40 1.3 670
Butylene two co-polymers
Anti-(formula) 10,000 40 1.3 670 of acrylic acid-10%
The butene dioic acid co-polymer
Example 4
Mediate to synthetic α in solution and the reference example 1-TCP that solidifies that moisture poly-(carboxylic acid) solution obtains by adding 50% organic acid aqueous solution.According to the technical process of example 1, the product that obtains is carried out intensity test, what obtained the results are shown in table 4.Used moisture poly-(carboxylic acid) solution is the aqueous solution copolymerization compound (when containing 15% methylene-succinic acid, molecular weight 80,000) of 45% acrylic acid-methylene-succinic acid.
Table 4
The organic acid organic acid soln amount weight ratio comprcssive strength of using
(%) (kilograms per centimeter
2)
Hydroxyacetic acid 5 1.0 650
Hydroxyacetic acid 10 1.0 670
Hydroxyacetic acid 20 1.0 580
Citric acid 5 1.0 680
Organic acid adds makes cement can reduce setting time.
Example 5
The α that is obtained in reference example 1-TCP powder is in 500 kilograms per centimeter
2With 1,200 kilograms per centimeter
2Down compacting of pressure, in a mould, form tablet, then, this tablet 1,200 ℃ of calcining 2 hours down.At last, burnt tablet grind into powder and this powder are screened through 300 mesh sieves.When using consequent powder, repeat the technical process of example 1 and to the product compressive strength determination, and its result by under tabulate shown in 5.Wherein employed moisture poly-(carboxylic acid) solution be with in example 4, use those are identical.
Table 5
Applying pressure weight ratio comprcssive strength
(kilograms per centimeter) (kilograms per centimeter
2)
500 1.5 900
500 2.0 1，130
1，200 1.5 960
Comparative example 1
At first, bata-tricalcium phosphate (be designated hereinafter simply as (β-TCP) is with the mixture preparation by calcination of beta-calcium pyrophosphate and calcium carbonate of the method for routine, and carboxyl apatite also to be method according to routine prepared with the phosphate aqueous solution reaction by calcium hydroxide.These compositions are mediated (as those solution that use) with moisture poly-(carboxylic acid) solution in example 4, and the goods that obtain are measured comprcssive strength according to example 1, and thus obtained result is illustrated in table 6.
Table 6
Powder weight compares comprcssive strength
(kilograms per centimeter
2)
β-TCP 1.3 is non-sclerous
HAP 1.3 30
The result who lists from table 6 can find out that β-TCP does not have the self-hardening performance, and HAP has very low comprcssive strength.Though latter's solidifiable, it can not carry out actual use, because its intensity is low.
Comparative example 2
In reference example 1, the α-TCP of acquisition and the mixture of water have added small amounts of inorganic acid or organic acid, and have been mediated.Resulting goods stand intensity test according to the technical process of example 1.The result that table 7 expression is obtained.
Table 7
The amount comprcssive strength of the acid acid that α-TCP water uses
(gram) (gram) (milliliter) (kilograms per centimeter
2)
3 3.5 4NHNO
30.2 46
3 3.5 4NHCl 0.2 47
3 3.5 5%CH
3COOH 0.5 42
3 3.5 5%HCOOH 0.5 26
The result of table 7 shows, all thus obtained cement have and are lower than 50 kilograms per centimeter
2The actual performance of low anti-intensity, the result makes these cement can not enter actual use.
Claims (16)
1, a kind of surgery cement comprises
(a) be selected from the component (A) that is constituted by at least one ingredient (composition) in the amorphism phosphoric acid DFP powder constituent of the type alpha tricalcium phosphate powder of self-hardening and self-hardening basis set;
(b) effectively water miscible component (B) of gathering (carboxylic acid) on the surgery performance;
(c) water.
2, surgery cement according to claim 1, it comprises:
(a) by weight from the component (A) of 23%-75%;
(b) by weight from the component (B) of 2%-46%;
(c) by weight from the water of 10%-69%.
3, surgical cement according to claim 1, wherein, component (B) is the form with aqueous solution, it contains by weight the component (B) from 10%-60%.
4, surgical cement according to claim 1, it comprises
(a) component (A) and
(b) contain component (B) aqueous solution of 10%-60% by weight, and (a) and weight ratio (b) be 0.30: 1-3.0: in 1 the scope.
5, surgical cement according to claim 1, wherein, the type alpha tricalcium phosphate of self-hardening is the powder that is obtained by pressure lower compression type alpha tricalcium phosphate, with these powder temperatures from 1,200-1 calcined at least one hour down, then it is ground to form thin powder for 500 ℃.
6, surgical cement according to claim 1, wherein the type alpha tricalcium phosphate of self-hardening is by the resulting powder of the amorphous tricalcium phosphate of pressure lower compression, at temperature 1,200-1, calcine compressed tricalcium phosphate down for 500 ℃ and be at least 1 hour, grind at last then.
7, surgical cement according to claim 1, wherein poly-(carboxylic acid) is acrylic acid homopolymer or the co-polymer that closes monomeric (b) as (a) acrylic acid and at least one insatiable hunger of basic monomer, its (b) is selected from by dimethyl succinic acid, along (formula) butene dioic acid, anti-(formula) butene dioic acid, methacrylic acid, aconitic acid, methyl is along (formula) butene dioic acid, anti-(formula) butene dioic acid of methyl, along the acid of (formula)-2-methyl-2-butene, and their rudimentary Arrcostabs and lower acrylic acid lower alkyl esters form basis set in.
8, surgical cement according to claim 1, wherein poly-(carboxylic acid) be acrylic acid homopolymer or (a) acrylic acid weight meter from 60%-99.9% with the weight meter of (b) at least a unsaturated monomer from the 0.1-40% co-polymer, its (b) is selected from by methylene-succinic acid, along (formula) butene dioic acid, anti-(formula) butene dioic acid, methacrylic acid, aconitic acid, methyl is along (formula) butene dioic acid, anti-(formula) butene dioic acid of methyl, glutaconate, along (formula)-2-methyl-2 butenoic acid, with and the becoming in the grouping of the composition of lower Arrcostab and acrylic acid lower Arrcostab.
9, surgical cement according to claim 1, wherein the viscosity-average molecular weight of poly-(carboxylic acid) is 2,000-200 is within 000 the scope.
10, surgical cement according to claim 1, it further comprises at least a other organic acid, quantitatively reaches weight meter about 10%.
11, surgical cement according to claim 10, wherein said other organic acid is a component at least, it can be selected from by carboxyl acetic acid, lactic acid, 2 aminopentanedioic acid is washed acid, and 2,3-dihydroxy butanoic acid, citric acid is in the one-tenth grouping that hydroxyl succinic acid is formed.
12, the method for preparing surgical cement, it comprises by blending (a) at least one component component (A), it is selected from composition group neutralization (b) pulverous surgery performance that the type alpha tricalcium phosphate powder of self-hardening and amorphous tricalcium phosphate powder form effectively the component (B) of water-soluble poly (carboxylic acid) and adds an amount of water and is prepared into a mixture, and just the aqueous solution with component (B) is added to component (A); Mediate thus obtained mixture then, so that concentrate this mixture to liquid condition or mecystasis.
13, preparation method according to claim 12, wherein the amount of component (A) is in the scope of ordering 23-75% by weight, the amount of component (B) be the weight meter in the scope of 2-46% and the water consumption scope by weight within the 10-69%.
14, preparation method according to claim 12, wherein the ratio of the aqueous solution weight of component (A) and component (B) is in 0.3: 1 to 3.0: 1 scope.
15, preparation method according to claim 12, wherein the type alpha tricalcium phosphate of self-hardening is to obtain by pressure lower compression type alpha tricalcium phosphate, compressed type alpha tricalcium phosphate was calcined 1 hour down at temperature 1200-1500 ℃ at least, and ground this at last by burnt goods.
16, preparation method according to claim 12, wherein the type alpha tricalcium phosphate of self-hardening is the powder that is obtained by at the amorphous tricalcium phosphate powder of pressure lower compression, temperature 1200-1500 ℃ of following tricalcium phosphate that had been compressed calcining at least 1 hour, then, grind burnt goods at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105933A CN1009707B (en) | 1984-03-24 | 1985-07-13 | Surgical cement and method for preparation thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59056676A JPS60253454A (en) | 1984-03-24 | 1984-03-24 | Bone lack part and gap part filler composition |
| CN85105933A CN1009707B (en) | 1984-03-24 | 1985-07-13 | Surgical cement and method for preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105933A CN85105933A (en) | 1987-01-14 |
| CN1009707B true CN1009707B (en) | 1990-09-26 |
Family
ID=25741931
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|---|---|---|---|
| CN85105933A Expired CN1009707B (en) | 1984-03-24 | 1985-07-13 | Surgical cement and method for preparation thereof |
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| US9487443B2 (en) * | 2014-03-14 | 2016-11-08 | Ricoh Company, Ltd. | Layer stack formation powder material, powder layer stack formation hardening liquid, layer stack formation material set, and layer stack object formation method |
-
1985
- 1985-07-13 CN CN85105933A patent/CN1009707B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85105933A (en) | 1987-01-14 |
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