CN102532573B

CN102532573B - Rapid molding method of sericin/hydroxyapatite composite membrane

Info

Publication number: CN102532573B
Application number: CN 201210038174
Authority: CN
Inventors: 朱良均; 王雪云; 张海萍; 闵思佳; 杨明英
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2012-02-20
Filing date: 2012-02-20
Publication date: 2013-10-16
Anticipated expiration: 2032-02-20
Also published as: CN102532573A

Abstract

The invention relates to a rapid molding method of a sericin/hydroxyapatite composite membrane. Currently, a sericin/hydroxyapatite composite film molding method with mild preparation conditions and a green and environment-friendly production process is not disclosed yet. The method disclosed by the invention comprises the following steps: drying a sericin solution to obtain a sericin membrane; immersing the membrane into an ethanol solution with a volume concentration of 35-45%, and taking out the membrane after 7-15 minutes so as to obtain the sericin membrane treated by ethanol; and placing the sericin membrane treated by ethanol in a 100mmol/L CaCl2 solution to carry out dipping treatment for 5-20 seconds so as to obtain the sericin membrane treated by dipping, and then placing the sericin membrane treated by dipping in a 60mmol/L Na2HPO4 solution to carry out dipping treatment for 5-20 seconds to obtain the sericin/hydroxyapatite composite membrane treated by once interactive dipping; and repeatedly carrying out dipping treatment with the CaCl2 solution and the Na2HPO4 solution so as to obtain the sericin/hydroxyapatite composite membrane. The molding method disclosed by the invention is mild in preparation conditions and short in production period, and is green and environment-friendly.

Description

A kind of quick molding method of sericin/hydroxyapatite composite membrane

Technical field

The present invention relates to a kind of quick molding method of sericin/hydroxyapatite composite membrane, belong to a kind of working method of sericin.

Background technology

Bone tissue restoration is a great medical science health problem, and the bone recovery technique of for many years clinical application is mainly taked the mode from body or allogenic bone transplantation, yet autologous bone transplanting is subjected to the restriction of self donor finiteness, and there is the antigenicity problem in allogenic bone transplantation.Continuous progress along with science, the development and application of bone renovating material is transplanted the new bone source that provides for bone, wherein traditional bone renovating material has been applied to clinical, but majority is to use as permanent transplant, these bone renovating materials can not participate in the metabolism of human body, thereby the effect of life-time service is often unsatisfactory.Have the research of biocompatibility, osteoinductive isoreactivity bone renovating material and prepare the advanced subject that has become in world today's biomaterial scientific research, at present, studying one of more active bone tissue renovation material is organic polymer/hydroxyapatite composite material.As open day be on 04 14th, 2010, publication number is in the Chinese patent of CN101693126A, a kind of bone reparation preparation method of PLGA/hydroxyapatite nanofiber compound bracket is disclosed, this preparation method comprises the steps: hydroxyapatite nanoparticle is joined in the mixed solvent of tetrahydrofuran (THF) and dimethyl formamide, then add PLGA, obtain the mixed solution of hydroxyapatite and PLGA, mixed solution is carried out electrostatic spinning, obtain bone reparation PLGA/hydroxyapatite nanofiber composite membrane support, the method is mainly for the preparation of the composite membrane support, and preparation technology is also comparatively complicated, can not reach the purpose of the rapid shaping of composite membrane.

Sericin (silk sericin, SS) is comprised of 18 seed amino acids such as Serine, aspartic acid, glycine, contains a large amount of carboxyls, hydroxyl and amino isopolarity group.Sericin has the performances such as good biocompatibility, biological degradability and biomineralization activity, is expected to for the bone tissue restoration field.Sericin can be prepared into sericin/hydroxyapatite composite porous bracket by methods such as lyophilize, glutaraldehyde cross-linkings with hydroxyapatite crystal, this composite manufacture needs prior synthesizing hydroxylapatite crystal, the operation more complicated, also more time-consuming.

As open day be on 08 04th, 2010, publication number is in the Chinese patent of CN101791438A, a kind of bone reparation preparation method of biological activity PLGA/collagen/hydroxyapatite composite fiber membrane is disclosed, this preparation method's step comprises: with PLGA electro spinning nanometer fiber membrane coating collagen after Cement Composite Treated by Plasma, then it is immersed mineralising in the simulation Human Physiology body fluid, obtain PLGA/collagen/hydroxyapatite composite fiber membrane.The method is to dispose first the collagen ethanolic soln, then need the using plasma treatment process that collagen is guided in the PLGA electro spinning nano fiber, technique is comparatively complicated, and production cost is higher, can not reach the purpose of the rapid shaping of composite membrane.

In sum, also do not have at present a kind of technique simple, preparation condition is gentle, the forming method of production process environmental protection and sericin/hydroxyapatite composite membrane that can rapid shaping.

Summary of the invention

The object of the invention is to overcome above shortcomings in the prior art, and provide a kind of technique simple, preparation condition is gentle, the quick molding method of the sericin/hydroxyapatite composite membrane of with short production cycle and production process environmental protection.

The present invention addresses the above problem the technical scheme that adopts: the characteristics of the quick molding method of this sericin/hydroxyapatite composite membrane are: the method in turn includes the following steps:

(1), a certain amount of sericin solution is tiled on the polyethylene board, then this tiling there is the polyethylene board of sericin solution to place and carries out seasoning under the room temperature condition, thereby sericin solution is made the sericin film;

(2), to immerse concentration expressed in percentage by volume be in the ethanolic soln of 35%-45% for sericin film that step (1) is made, take out the sericin film behind the 7-15min and obtain Ethanol Treatment sericin film;

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 5-20s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film;

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 5-20s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film;

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), multiplicity is 5-50 time, thereby makes the sericin/hydroxyapatite composite membrane.The present invention places CaCl repeatedly successively with Ethanol Treatment sericin film ₂Solution and Na ₂HPO ₄Carry out mutual dip treating in the solution, form fast the sericin/hydroxyapatite composite membrane, have the preparation time weak point, production technique is simple, the characteristics such as mild condition and environmental protection.

As preferably, used sericin solution adopts following steps to be prepared from the step of the present invention (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 20-40min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopt at last rotatory evaporator that the sericin mother liquor is concentrated, thereby obtain the sericin solution that mass concentration is 6%-12%.So that the preparation of the sericin solution among the present invention is convenient, performance is more reliable thus.

As preferably, the thickness of the Ethanol Treatment sericin film that makes in the step of the present invention (2) is 45-55um.

As preferably, used CaCl in the step of the present invention (3) ₂The pH value of solution is 7.4.

As preferably, the Ethanol Treatment sericin film in the step of the present invention (3) is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃.Thus so that the present invention to the dip treating better effects if of Ethanol Treatment sericin film.

As preferably, the dip treating sericin film in the step of the present invention (4) is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃.Thus so that the present invention to the dip treating better effects if of dip treating sericin film.

As preferably, the number of times of repetitive operation step (3) and step (4) is 9-29 time in the step of the present invention (5).

As preferably, in the step of the present invention (3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution.

As preferably, in the step of the present invention (4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution.

As preferably, the time of degumming process of the present invention is 30min, and the mass concentration of the described sericin solution that is prepared from is 8%.

The present invention compared with prior art has the following advantages and effect: preparation time is short, and production technique is simple, reaction conditions gentleness and production process environmental protection.The present invention places CaCl repeatedly successively with Ethanol Treatment sericin film ₂Solution and Na ₂HPO ₄Carry out mutual dip treating in the solution, form fast the sericin/hydroxyapatite composite membrane, can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping.

The present invention makes hydroxyapatite self-assembly in this template form the sericin/hydroxyapatite matrix material take sericin as template, is conducive to simplify preparation technology, shortens preparation time, enhances productivity.Ethanol Treatment silk gum film has lower water-soluble and snappiness preferably, and Ethanol Treatment silk gum film be impregnated in CaCl successively ₂Solution and Na ₂HPO ₄In the solution, induce the hydroxyapatite self-assembly to form the sericin/hydroxyapatite composite film material, have potential application prospect in technical field of biological material.

Description of drawings

Fig. 1 is Ethanol Treatment silk gum Surface structure of membrane synoptic diagram among the embodiment of the invention 1, embodiment 2 and the embodiment 3.

Fig. 2 carries out the compound Surface structure of membrane synoptic diagram of sericin/hydroxyapatite that obtains after 10 mutual dip treating operations in the embodiment of the invention 1.

Fig. 3 carries out the compound Surface structure of membrane synoptic diagram of sericin/hydroxyapatite that obtains after 20 mutual dip treating operations in the embodiment of the invention 2.

Fig. 4 carries out the compound Surface structure of membrane synoptic diagram of sericin/hydroxyapatite that obtains after 30 mutual dip treating operations in the embodiment of the invention 3.

Embodiment

The present invention is described in further detail below in conjunction with accompanying drawing and by embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.

Embodiment 1.

Referring to Fig. 1 and Fig. 2, the quick molding method of sericin/hydroxyapatite composite membrane in turn includes the following steps in the present embodiment.

(1), measure a certain amount of sericin solution and be tiled on polyethylene (PE) plate, then this tiling is had the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): a, first Silkworm Cocoon Shell is cut into pieces, the area of Silkworm Cocoon Shell fragment is about lcm ², then the fragment of Silkworm Cocoon Shell being cleaned up to be placed on deionized water and carry out degumming process in the boiling water, bath raio is 1:30; B, Silkworm Cocoon Shell fragment behind degumming process 30min, are used the filtered through gauze removal of impurities in boiling water, obtain the sericin mother liquor; C, employing rotatory evaporator concentrate the sericin mother liquor, and adjustment acquisition concentration is 8% sericin solution.

(2), sericin film that step (1) is made immerses in 40% ethanolic soln, takes out behind the 10min, obtains Ethanol Treatment sericin film, the thickness of this film is 50 ± 5um, its Surface Microstructure as shown in Figure 1.

(3), it is that 100mmol/L and pH are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), being about to once alternately dip treating silk gum/hydroxyapatite composite membrane, to place successively concentration be that 100mmol/L and pH are 7.4 CaCl ₂Dip treating 10s and to place concentration be the Na of 60mmol/L in the solution ₂HPO ₄Dip treating 10s in the solution, the number of times of repetitive operation is 9 times, thereby make the sericin/hydroxyapatite composite membrane through 10 mutual dip treating, the polygon material appears in the surface of this sericin/hydroxyapatite composite membrane, be the hydroxyapatite crystal that mutual dip treating forms, the compound Surface structure of membrane of the sericin/hydroxyapatite that present embodiment is prepared from as shown in Figure 2.

The preparation time of the quick molding method of sericin/hydroxyapatite composite membrane is short in the present embodiment, production technique is simple, reaction conditions gentleness and production process environmental protection can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping, CaCl ₂10 required times of dip treating amount to 100s in the solution, at Na ₂HPO ₄10 required times of dip treating also are 100s altogether in the solution, thereby have greatly shortened production technique, have realized the function of rapid shaping.

Embodiment 2.

Referring to Fig. 1 and Fig. 3, the quick molding method of sericin/hydroxyapatite composite membrane in turn includes the following steps in the present embodiment.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), being about to once alternately dip treating silk gum/hydroxyapatite composite membrane, to place successively concentration be that 100mmol/L and pH are 7.4 CaCl ₂Dip treating 10s and to place concentration be the Na of 60mmol/L in the solution ₂HPO ₄Dip treating 10s in the solution, the number of times of repetitive operation is 19 times, thereby make the sericin/hydroxyapatite composite membrane through 20 mutual dip treating, the hydroxyapatite crystal of this sericin/hydroxyapatite composite membrane is annular protrusions, and the compound Surface structure of membrane of the sericin/hydroxyapatite that present embodiment is prepared from as shown in Figure 3.

The preparation time of the quick molding method of sericin/hydroxyapatite composite membrane is short in the present embodiment, production technique is simple, reaction conditions gentleness and production process environmental protection can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping, CaCl ₂20 required times of dip treating amount to 200s in the solution, at Na ₂HPO ₄20 required times of dip treating also are 200s altogether in the solution, have also greatly shortened production technique, have realized the function of rapid shaping.

Embodiment 3.

Referring to Fig. 1 and Fig. 4, the quick molding method of sericin/hydroxyapatite composite membrane in turn includes the following steps in the present embodiment.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), being about to once alternately dip treating silk gum/hydroxyapatite composite membrane, to place successively concentration be that 100mmol/L and pH are 7.4 CaCl ₂Dip treating 10s and to place concentration be the Na of 60mmol/L in the solution ₂HPO ₄Dip treating 10s in the solution, the number of times of repetitive operation is 29 times, thereby make the sericin/hydroxyapatite composite membrane through 30 mutual dip treating, the surface deposition of this sericin/hydroxyapatite composite membrane a large amount of hydroxyapatite crystals, be the lamella polygon of rule, the compound Surface structure of membrane of the sericin/hydroxyapatite that present embodiment is prepared from as shown in Figure 4.

The preparation time of the quick molding method of sericin/hydroxyapatite composite membrane is short in the present embodiment, production technique is simple, reaction conditions gentleness and production process environmental protection can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping, CaCl ₂30 required times of dip treating amount to 300s in the solution, at Na ₂HPO ₄30 required times of dip treating also are 300s altogether in the solution, have also shortened production technique, have realized the function of rapid shaping.

Embodiment 4.

The quick molding method of sericin/hydroxyapatite composite membrane in turn includes the following steps in the present embodiment.

(1), be that 8% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling there is the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 30min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 8% sericin solution thereby obtain mass concentration.The time of among the present invention the fragment of Silkworm Cocoon Shell being carried out degumming process is generally 20-40min, and the mass concentration of the sericin solution that is prepared from is generally 6%-12%, and the area of the fragment of Silkworm Cocoon Shell is generally 0.5-l.5cm ²

(2), to immerse concentration expressed in percentage by volume be in 40% the ethanolic soln, to take out the sericin film behind the 10min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 50um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.It is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that the present invention can make step (2) places concentration ₂Dip treating 5-20s in the solution.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.It is the Na of 60mmol/L that the dip treating sericin film that the present invention can make step (3) places concentration ₂HPO ₄Dip treating 5-20s in the solution.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 8 times successively, thereby makes the sericin/hydroxyapatite composite membrane.The number of times of repetitive operation step (3) and step (4) is generally 5-50 time in the step of the present invention (5), is preferably 9-29 time.

The preparation time of the quick molding method of sericin/hydroxyapatite composite membrane is short in the present embodiment, and production technique is simple, and reaction conditions gentleness and production process environmental protection can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping.

Embodiment 5.

(1), be that 10% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling there is the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

The present invention's said " a certain amount of " in step (1) is common practise for a person skilled in the art, is often referred to the thickness of the sericin solution on the polyethylene board that tiles between 40-100um, so locate no longer " a certain amount of " to be described in detail.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.It is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that the present invention can make step (2) places concentration ₂Dip treating 5-20s in the solution.

(5), it is that 100mmol/L and pH value are 7.4 CaCl that the once mutual dip treating silk gum/hydroxyapatite composite membrane that step (4) is made places concentration ₂Dip treating 10s in the solution, this once mutual dip treating silk gum/hydroxyapatite composite membrane at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out once mutual dip treating silk gum/hydroxyapatite composite membrane, first with washed with de-ionized water mutual dip treating silk gum/hydroxyapatite composite membrane once, clean once mutual dip treating silk gum/hydroxyapatite composite membrane with acetone again, then once mutual dip treating silk gum/hydroxyapatite composite membrane is air-dry.

(6), it is the Na of 60mmol/L that the once mutual dip treating silk gum/hydroxyapatite composite membrane that step (5) is made places concentration ₂HPO ₄Dip treating 10s in the solution, this once mutual dip treating silk gum/hydroxyapatite composite membrane at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out once mutual dip treating silk gum/hydroxyapatite composite membrane, first with washed with de-ionized water mutual dip treating silk gum/hydroxyapatite composite membrane once, clean once mutual dip treating silk gum/hydroxyapatite composite membrane with acetone again, then incite somebody to action once the mutual air-dry mutual dip treating silk gum/hydroxyapatite composite membrane of secondary that makes of dip treating silk gum/hydroxyapatite composite membrane.

(7), it is that 100mmol/L and pH value are 7.4 CaCl that the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary that step (6) is made places concentration ₂Dip treating 10s in the solution, the mutual dip treating silk gum/hydroxyapatite composite membrane of this secondary is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary, use first the mutual dip treating silk gum/hydroxyapatite composite membrane of washed with de-ionized water secondary, clean the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary with acetone again, then that the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary is air-dry.

(8), it is the Na of 60mmol/L that the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary that step (7) is made places concentration ₂HPO ₄Dip treating 10s in the solution, the mutual dip treating silk gum/hydroxyapatite composite membrane of this secondary is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary, use first the mutual dip treating silk gum/hydroxyapatite composite membrane of washed with de-ionized water secondary, clean the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary with acetone again, then make mutual dip treating silk gum/hydroxyapatite composite membrane three times with the mutual dip treating silk gum/hydroxyapatite composite membrane of secondary is air-dry.

(9), it is that 100mmol/L and pH value are 7.4 CaCl that three mutual dip treating silk gum/hydroxyapatite composite membranes that step (8) made place concentration ₂Dip treating 10s in the solution, these three times mutual dip treating silk gum/hydroxyapatite composite membranes are at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out mutual dip treating silk gum/hydroxyapatite composite membrane three times, use first three mutual dip treating silk gum/hydroxyapatite composite membranes of washed with de-ionized water, clean three mutual dip treating silk gum/hydroxyapatite composite membranes with acetone again, then that three mutual dip treating silk gum/hydroxyapatite composite membranes are air-dry.

(10), it is the Na of 60mmol/L that three mutual dip treating silk gum/hydroxyapatite composite membranes that step (9) made place concentration ₂HPO ₄Dip treating 10s in the solution, these three times mutual dip treating silk gum/hydroxyapatite composite membranes are at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out mutual dip treating silk gum/hydroxyapatite composite membrane three times, use first three mutual dip treating silk gum/hydroxyapatite composite membranes of washed with de-ionized water, clean three mutual dip treating silk gum/hydroxyapatite composite membranes with acetone again, then make mutual dip treating silk gum/hydroxyapatite composite membrane four times with three mutual dip treating silk gum/hydroxyapatite composite membranes are air-dry.

(11), it is that 100mmol/L and pH value are 7.4 CaCl that four mutual dip treating silk gum/hydroxyapatite composite membranes that step (10) made place concentration ₂Dip treating 10s in the solution, these four times mutual dip treating silk gum/hydroxyapatite composite membranes are at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out mutual dip treating silk gum/hydroxyapatite composite membrane four times, use first four mutual dip treating silk gum/hydroxyapatite composite membranes of washed with de-ionized water, clean four mutual dip treating silk gum/hydroxyapatite composite membranes with acetone again, then that four mutual dip treating silk gum/hydroxyapatite composite membranes are air-dry.

(12), it is the Na of 60mmol/L that four mutual dip treating silk gum/hydroxyapatite composite membranes that step (11) made place concentration ₂HPO ₄Dip treating 10s in the solution, these four times mutual dip treating silk gum/hydroxyapatite composite membranes are at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out mutual dip treating silk gum/hydroxyapatite composite membrane four times, use first four mutual dip treating silk gum/hydroxyapatite composite membranes of washed with de-ionized water, clean four mutual dip treating silk gum/hydroxyapatite composite membranes with acetone again, then with four air-dry sericin/hydroxyapatite composite membranes that make of mutual dip treating silk gum/hydroxyapatite composite membrane.

Step in the present embodiment (5) to step (12) is exactly the successively operation of repeating step (3) and step (4) of once mutual dip treating silk gum/hydroxyapatite composite membrane that step (4) is made in fact, namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 5 times successively, thereby makes the sericin/hydroxyapatite composite membrane.The preparation time of the quick molding method of sericin/hydroxyapatite composite membrane is short in the present embodiment, and production technique is simple, and reaction conditions gentleness and production process environmental protection can reach the purpose of sericin/hydroxyapatite composite membrane rapid shaping.

Embodiment 6.

(1), be that 6% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling is had the polyethylene board of sericin solution to place and carries out seasoning under the room temperature condition, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, the area of this fragment is 0.8 cm ²Then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 20min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 6% sericin solution thereby obtain mass concentration.The time of among the present invention the fragment of Silkworm Cocoon Shell being carried out degumming process is generally 20-40min, and the mass concentration of the sericin solution that is prepared from is generally 6%-12%, and the area of the fragment of Silkworm Cocoon Shell is generally 0.5-l.5cm ²

(2), to immerse concentration expressed in percentage by volume be in 35% the ethanolic soln, to take out the sericin film behind the 15min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 48um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 8s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.It is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that the present invention can make step (2) places concentration ₂Dip treating 5-20s in the solution.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 8s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.It is the Na of 60mmol/L that the dip treating sericin film that the present invention can make step (3) places concentration ₂HPO ₄Dip treating 5-20s in the solution.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 12 times successively, thereby makes the sericin/hydroxyapatite composite membrane.The number of times of repetitive operation step (3) and step (4) is generally 5-50 time in the step of the present invention (5), is preferably 9-29 time.

Embodiment 7.

(1), be that 12% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling there is the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

(2), to immerse concentration expressed in percentage by volume be in 45% the ethanolic soln, to take out the sericin film behind the 7min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 55um.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 15s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 15s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 50 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 8.

(1), be that 11% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling there is the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 40min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 11% sericin solution thereby obtain mass concentration.

(2), to immerse concentration expressed in percentage by volume be in 42% the ethanolic soln, to take out the sericin film behind the 9min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 51um.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 12s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 12s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 18 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 9.

(1), be that 7% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling is had the polyethylene board of sericin solution to place and carries out seasoning under the room temperature condition, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, the area of the fragment of this Silkworm Cocoon Shell is 0.9cm ²Then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 35min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 7% sericin solution thereby obtain mass concentration.

(2), to immerse concentration expressed in percentage by volume be in 38% the ethanolic soln, to take out the sericin film behind the 13min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 53um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 11s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 11s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 27 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 10.

(2), to immerse concentration expressed in percentage by volume be in 40% the ethanolic soln, to take out the sericin film behind the 10min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 51um.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 9s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 9s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 15 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 11.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 40min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 8% sericin solution thereby obtain mass concentration.The time of among the present invention the fragment of Silkworm Cocoon Shell being carried out degumming process is generally 20-40min, and the mass concentration of the sericin solution that is prepared from is generally 6%-12%, and the area of the fragment of Silkworm Cocoon Shell is generally 0.5-l.5cm ²

(2), to immerse concentration expressed in percentage by volume be in 39% the ethanolic soln, to take out the sericin film behind the 11min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 50um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 9s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 36 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 12.

(1), be that 10% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling is had the polyethylene board of sericin solution to place and carries out seasoning under the room temperature condition, thereby sericin solution is made the sericin film.

(2), to immerse concentration expressed in percentage by volume be in 38% the ethanolic soln, to take out the sericin film behind the 15min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 49um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 16 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 13.

(1), be that 9% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling there is the polyethylene board of sericin solution to place under 25 ℃ the room temperature condition and carries out seasoning, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, the area of the fragment of this Silkworm Cocoon Shell is for l.5cm ²Then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 30min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 9% sericin solution thereby obtain mass concentration.

(2), to immerse concentration expressed in percentage by volume be in 41% the ethanolic soln, to take out the sericin film behind the 10min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 52um.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 12s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.It is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that the present invention can make step (2) places concentration ₂Dip treating 5-20s in the solution.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 12s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.It is the Na of 60mmol/L that the dip treating sericin film that the present invention can make step (3) places concentration ₂HPO ₄Dip treating 5-20s in the solution.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 22 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 14.

(1), be that 8% sericin solution tiles on the polyethylene board with a certain amount of mass concentration, then this tiling is had the polyethylene board of sericin solution to place and carries out seasoning under the room temperature condition, thereby sericin solution is made the sericin film.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, the area of the fragment of this Silkworm Cocoon Shell is 0.5cm ²Then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 25min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 8% sericin solution thereby obtain mass concentration.The time of among the present invention the fragment of Silkworm Cocoon Shell being carried out degumming process is generally 20-40min, and the mass concentration of the sericin solution that is prepared from is generally 6%-12%, and the area of the fragment of Silkworm Cocoon Shell is generally 0.5-l.5cm ²

(2), to immerse concentration expressed in percentage by volume be in 43% the ethanolic soln, to take out the sericin film behind the 8min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 51um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 11s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 33 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 15.

(2), to immerse concentration expressed in percentage by volume be in 40% the ethanolic soln, to take out the sericin film behind the 12min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 49um.

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 9s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 25 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Embodiment 16.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, the area of the fragment of this Silkworm Cocoon Shell is for l.2cm ²Then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 40min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 8% sericin solution thereby obtain mass concentration.The time of among the present invention the fragment of Silkworm Cocoon Shell being carried out degumming process is generally 20-40min, and the mass concentration of the sericin solution that is prepared from is generally 6%-12%, and the area of the fragment of Silkworm Cocoon Shell is generally 0.5-l.5cm ²

(2), to immerse concentration expressed in percentage by volume be in 42% the ethanolic soln, to take out the sericin film behind the 9min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 51um.Generally, it is in the ethanolic soln of 35%-45% that the sericin film that present embodiment makes step (1) immerses concentration expressed in percentage by volume, takes out the sericin film behind the 7-15min and obtains Ethanol Treatment sericin film.The thickness of Ethanol Treatment sericin film is generally 45-55um among the present invention.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 27 times successively, thereby makes the sericin/hydroxyapatite composite membrane.The number of times of repetitive operation step (3) and step (4) is generally 5-50 time in the step of the present invention (5), is preferably 9-29 time.

Embodiment 17.

Used sericin solution adopts following steps to be prepared from the present embodiment step (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 28min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopting at last rotatory evaporator that the sericin mother liquor is concentrated, is 7% sericin solution thereby obtain mass concentration.

(2), to immerse concentration expressed in percentage by volume be in 41% the ethanolic soln, to take out the sericin film behind the 9min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 52um.

(3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, this Ethanol Treatment sericin film is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution, this dip treating sericin film is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.

Embodiment 18.

(2), to immerse concentration expressed in percentage by volume be in 40% the ethanolic soln, to take out the sericin film behind the 10min and obtain Ethanol Treatment sericin film for sericin film that step (1) is made, the thickness of this Ethanol Treatment sericin film is 50um.

(3), it is that 100mmol/L and pH value are 7.4 CaCl that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution, then take out Ethanol Treatment sericin film, use first washed with de-ionized water Ethanol Treatment sericin film, clean Ethanol Treatment sericin film with acetone again, then with the air-dry dip treating sericin film that makes of Ethanol Treatment sericin film.It is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that the present invention can make step (2) places concentration ₂Dip treating 5-20s in the solution.

(4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution, then take out dip treating sericin film, use first washed with de-ionized water dip treating sericin film, clean dip treating sericin film with acetone again, then with the air-dry alternately dip treating silk gum/hydroxyapatite composite membrane that makes once of dip treating sericin film.It is the Na of 60mmol/L that the dip treating sericin film that the present invention can make step (3) places concentration ₂HPO ₄Dip treating 5-20s in the solution.

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), namely first will be once alternately dip treating silk gum/hydroxyapatite composite membrane place CaCl ₂Carry out dip treating in the solution, again with this once mutual dip treating silk gum/hydroxyapatite composite membrane place Na ₂HPO ₄Carry out dip treating in the solution, the multiplicity of operation steps (3) and step (4) is 24 times successively, thereby makes the sericin/hydroxyapatite composite membrane.

Although the present invention with embodiment openly as above; but it is not to limit protection scope of the present invention; any technician who is familiar with this technology not breaking away from change and the retouching of doing in the spirit and scope of the present invention, all should belong to protection scope of the present invention.

Claims

1. the quick molding method of a sericin/hydroxyapatite composite membrane, it is characterized in that: the method in turn includes the following steps:

(5), once mutual dip treating silk gum/hydroxyapatite composite membrane repeating step (3) that step (4) is made and the operation of step (4), multiplicity is 8-50 time, thereby makes the sericin/hydroxyapatite composite membrane.

2. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1, it is characterized in that: used sericin solution adopts following steps to be prepared from the described step (1): first Silkworm Cocoon Shell is cut into pieces, then the fragment of Silkworm Cocoon Shell is cleaned up to be placed on deionized water and carry out degumming process in the boiling water, behind the degumming process 20-40min, use the filtered through gauze removal of impurities, obtain the sericin mother liquor, adopt at last rotatory evaporator that the sericin mother liquor is concentrated, thereby obtain the sericin solution that mass concentration is 6%-12%.

3. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2, it is characterized in that: the thickness of the Ethanol Treatment sericin film that makes in the described step (2) is 45-55 μ m.

4. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2 is characterized in that: used CaCl in the described step (3) ₂The pH value of solution is 7.4.

5. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2, it is characterized in that: the Ethanol Treatment sericin film in the described step (3) is at CaCl ₂The temperature of carrying out dip treating in the solution is 37 ℃.

6. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2, it is characterized in that: the dip treating sericin film in the described step (4) is at Na ₂HPO ₄The temperature of carrying out dip treating in the solution is 37 ℃.

7. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2 is characterized in that: the number of times of repetitive operation step (3) and step (4) is 9-29 time in the described step (5).

8. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2 is characterized in that: in the described step (3), it is the CaCl of 100mmol/L that the Ethanol Treatment sericin film that step (2) is made places concentration ₂Dip treating 10s in the solution.

9. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 1 and 2 is characterized in that: in the described step (4), it is the Na of 60mmol/L that the dip treating sericin film that step (3) is made places concentration ₂HPO ₄Dip treating 10s in the solution.

10. the quick molding method of sericin/hydroxyapatite composite membrane according to claim 2, it is characterized in that: the time of described degumming process is 30min, the mass concentration of the described sericin solution that is prepared from is 8%.