JP4762785B2 - Gelatin sponge - Google Patents

Gelatin sponge Download PDF

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Publication number
JP4762785B2
JP4762785B2 JP2006138972A JP2006138972A JP4762785B2 JP 4762785 B2 JP4762785 B2 JP 4762785B2 JP 2006138972 A JP2006138972 A JP 2006138972A JP 2006138972 A JP2006138972 A JP 2006138972A JP 4762785 B2 JP4762785 B2 JP 4762785B2
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gelatin
sponge body
sodium
gelatin sponge
body according
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JP2007009185A (en
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健夫 因
雅文 椙山
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西川ゴム工業株式会社
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Description

  The present invention relates to a gelatin sponge body, and in particular, relates to a gelatin sponge body having a dense cell structure that is reinforced in strength when wet with water and has a good feel when dried.

Conventionally, sponge-like molded bodies made of gelatin or the like have been used as wound dressings, wound grafts, and cultured skin base materials that are applied to the side of skin defects caused by burns and bruises to promote treatment. (For example, Patent Document 1)
In such a sponge-like molded product, in wound dressings and wound grafts, blood vessels and fibroblasts are infiltrated into the sponge to reconstruct the defective skin cells, and in the cultured skin substrate, fibroblasts are reconstructed. Since a suspension of cells, keratinized cells, etc. is dropped onto the base material and intimately cultured for a certain period of time, the pore size and continuity of the sponge surface / internal continuity and the shape of the internal pores affect skin cell formation. .

Cultured skin is generally composed of a base material, skin-derived fibroblasts, keratinized cells, and the like. When the cultured skin is applied to a skin defect site, migration / proliferation of fibroblasts, keratinocytes, and vascular endothelial cells from the wound edge is caused by humoral factors produced by the fibroblasts and keratinocytes. It is said to promote and rebuild the skin. The cultured skin can be prepared by dropping a suspension of the fibroblasts, keratinized cells, and the like onto a base material, allowing them to adhere, and culturing for a certain period. If the cultured skin base material is a sponge-like molded body, it is considered that if the pore diameter on the sponge surface is constant and the shape of the internal pores is also constant, the dropped cells can adhere to the base material uniformly. The prepared cultured skin is expected to have a certain wound healing ability.
However, the conventional cultured skin base material composed of a sponge-like molded body cannot have uniform adhesion of the dropped cells because the size of the internal pores is non-uniform and it does not have orientation. Also, a certain wound healing ability cannot be expected.

International Publication No. 01/051211 Pamphlet

In addition, the conventional gelatin sponge body was manufactured by cooling the gelatin aqueous solution to gel and freezing, followed by vacuum lyophilization. However, since gelatin gelatinizes during gelation, it has a mottled cell structure. However, only a rough sponge body was obtained.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a gelatin sponge body having a dense cell structure and a smooth feel.

As a result of repeated arbitrary studies, the present inventor has achieved the above object by adopting the following configuration, and has achieved the present invention.
That is, the present invention is as follows.
(1) A gelatin sponge body obtained by mixing an aqueous gelatin solution and a polyanion under conditions of pH 5 to 11, cooling to gel, freezing, and then vacuum lyophilization.
(2) The gelatin sponge body according to (1) using a polyanion in a salt state.
(3) The gelatin sponge body according to (1), wherein the amount of polyanion added is 1 to 50 parts per 100 parts of gelatin.
(4) The gelatin sponge body according to (1), which is heated at 120 to 140 ° C. for 10 to 48 hours under reduced pressure after vacuum freeze-drying or a crosslinking agent is added during the mixing.
(5) The gelatin sponge body according to (1) to (4), wherein the acid-treated gelatin aqueous solution is adjusted to pH 5 to 7, and then mixed with a salt-state polyanion.
(6) The gelatin sponge body according to any one of (1) to (5), wherein the isoionic point of the acid-treated gelatin is pH 8-9.
(7) The gelatin sponge body according to any one of (1) to (6), wherein the acid-treated gelatin is derived from fish.

(8) The gelatin sponge body according to any one of (1) to (7), wherein a fibrous material is dispersed during the mixing.
(9) The gelatin sponge body according to (8), wherein the fibrous material is cellulose.
(10) The gelatin sponge body according to (8), wherein the fibrous material has a fiber diameter of 10 to 500 μm and a fiber length of 0.1 to 5 mm.
(11) The gelatin sponge body according to any one of (1) to (8), wherein silk powder is dispersed during the mixing.
(12) The gelatin sponge body according to (11), wherein the particle size of the silk powder is 100 μm or less.
(13) The gelatin sponge body according to (11) or (12), wherein the particle size of the silk powder is 10 μm or less.
(14) The gelatin sponge body according to any one of (11) to (13), wherein the addition amount of silk powder is 1% or more by dry weight ratio.
(15) The gelatin sponge body according to any one of (11) to (14), wherein the addition amount of the silk powder is 10% or more and less than 50% by dry weight ratio.
(16) The gelatin sponge body according to (1), wherein a plasticizer is added during the mixing.

(17) A method for producing a gelatin sponge body in which an aqueous gelatin solution and a polyanion are mixed under conditions of pH 5 to 11, cooled, gelled and frozen, and then vacuum freeze-dried.
(18) The method for producing a gelatin sponge body according to (17), wherein a polyanion in a salt state is used.
(19) The method for producing a gelatin sponge according to (17), wherein the polyanion is added in an amount of 1 to 50 parts per 100 parts of gelatin.
(20) The method for producing a gelatin sponge according to (17), wherein after the freeze-drying under vacuum, heating is performed at a temperature of 120 to 140 ° C. for 10 to 48 hours, or a crosslinking agent is added during the mixing.
(21) The method for producing a gelatin sponge body according to (17) to (20), wherein the acid-treated gelatin aqueous solution is adjusted to pH 5 to 7, and then a salt polyanion is mixed.
(22) The method for producing a gelatin sponge body according to any one of (17) to (21), wherein the isoionic point of the acid-treated gelatin is pH 8-9.
(23) The method for producing a gelatin sponge body according to any one of (17) to (22), wherein the acid-treated gelatin is derived from fish.

(24) The method for producing a gelatin sponge according to any one of (17) to (23), wherein the fibrous material is dispersed during the mixing.
(25) The method for producing a gelatin sponge body according to (24), wherein the fibrous material is cellulose.
(26) The method for producing a gelatin sponge body according to (24), wherein the fibrous material has a fiber diameter of 10 to 500 μm and a fiber length of 0.1 to 5 mm.
(27) The method for producing a gelatin sponge body according to any one of (17) to (24), wherein silk powder is dispersed during the mixing.
(28) The method for producing a gelatin sponge body according to (27), wherein the particle size of the silk powder is 100 μm or less.
(29) The method for producing a gelatin sponge body according to (27) or (28), wherein the particle size of the silk powder is 10 μm or less.
(30) The method for producing a gelatin sponge body according to any one of (27) to (29), wherein the addition amount of the silk powder is 1% or more by dry weight ratio.
(31) The method for producing a gelatin sponge body according to any one of (27) to (30), wherein the addition amount of the silk powder is 10% or more and less than 50% by dry weight ratio.
(32) The method for producing a gelatin sponge according to (17), wherein a plasticizer is added during the mixing.

The gelatin sponge body of the present invention has a dense cell structure by mixing an aqueous gelatin solution and a salt polyanion under the conditions of pH 5 to 11, cooling to gel, freezing, and then vacuum lyophilization. Can do.
Further, after vacuum freeze-drying, heating at 120 to 140 ° C. under reduced pressure for 10 to 48 hours, adding a crosslinking agent when mixing the gelatin aqueous solution and the polyanion, or mixing the gelatin aqueous solution and the polyanion with the fiber and silk powder By dispersing, the strength of the sponge body when wet with water can be made excellent, and the feel when dry and wet can be made smooth.

Hereinafter, the gelatin sponge body and the method for producing the gelatin sponge body of the present invention will be described in detail.
The gelatin sponge body of the present invention can be obtained by mixing an aqueous gelatin solution and a polyanion under the conditions of pH 5 to 11, cooling to gel, freezing, and vacuum lyophilization.
When an aqueous gelatin solution and a polyanion are mixed, a polyion complex is formed, and a precipitate is formed depending on the pH condition of the aqueous gelatin solution. For this reason, pH of gelatin aqueous solution is pH 5-11 in which a precipitate does not generate | occur | produce, even if a polyion complex is formed, and pH 5-7 are preferable.
Further, when a polyanion that is not converted to a salt is added to the gelatin aqueous solution, the pH of the gelatin aqueous solution is lowered according to the amount added. As described above, when the pH is 5 or less, polyion complex precipitates abruptly. Therefore, although not particularly limited, it is preferably added in a salt state such as sodium salt, potassium salt or ammonium salt.

The mixing ratio when mixing the gelatin aqueous solution and the polyanion is not particularly limited, but is preferably 1 to 50 parts of the polyanion with respect to 100 parts of the gelatin.
If the amount of polyanion mixed is small, the effect of densifying the cell structure is lacking, and if it is large, the characteristics and feel inherent to gelatin may be reduced.
The gelatin of the gelatin aqueous solution used in the present invention is not particularly limited, but is preferably acid-treated gelatin called A-type gelatin, and is not particularly limited, but the isoionic point is preferably pH 8-9. The acid-treated gelatin is not particularly limited, but is preferably derived from fish.

  The polyanion included in the present invention is not particularly limited, but is soluble in water and has a functional group such as xanthan gum, sodium alginate, sodium hyaluronate, sodium chondroitin sulfate, sodium polyglutamate, sodium polyacrylate, sodium carboxymethylcellulose, etc. As long as it is a polymer having a carboxyl group and does not show strong toxicity to the living body, either a natural polymer derived from a living body or a synthetic polymer may be used. As described above, the polyanion is preferably in a salt state.

  In addition, the gelatin sponge according to the present invention is heated at 120 to 140 ° C. under reduced pressure for 10 to 48 hours after vacuum freeze-drying, or a cross-linking agent is added at the time of mixing an aqueous gelatin solution with a salt polyanion, or an aqueous gelatin solution When the fiber is dispersed with a polyanion in a salt state or a plasticizer is added, the strength when wet with water is improved.

The crosslinking agent added at the time of mixing the gelatin aqueous solution and the polyanion is not particularly limited, but a polyvalent isocyanate compound such as hexamethylene diisocyanate, a polyvalent epoxy compound such as ethylene glycol diglycidyl ether, and the like are preferable. The fibrous material added at the time of mixing the aqueous gelatin solution and the polyanion is not particularly limited, but hydrophilic fibers represented by cellulose are preferable. It is sufficient that a hydrophobic fiber is subjected to a hydrophilic treatment and can be uniformly dispersed in a gelatin / polyanion mixed aqueous solution.
The fiber diameter of the fibrous material is preferably 10 to 500 μm, and the fiber length is preferably 0.1 to 5 mm. If the fiber diameter is too thin, the reinforcing effect is weakened, and if it is too thick, the feel to the skin may be deteriorated. If the fiber length is too short, the reinforcing effect will be weak, and if it is too long, the feel may not be excellent.
The addition amount of the fibrous material in the gelatin sponge body of the present invention is not particularly limited, but 10 to 200 parts is appropriate with respect to 100 parts of gelatin. If there is too much, it may become weak.

  In the gelatin sponge body according to the present invention, the silk powder is dispersed at the time of mixing the gelatin aqueous solution and the salt-state polyanion, so that the feeling upon drying becomes smooth.

The silk powder added at the time of mixing the gelatin aqueous solution and the polyanion is not particularly limited as long as it can be uniformly dispersed in the gelatin and polyanion mixed aqueous solution.
The silk powder preferably has a particle size of 100 μm or less, and more preferably 10 μm or less. If the particle size is 100 μm or more, a smooth feel may not be obtained.
The amount of the silk powder added to the gelatin sponge body of the present invention is not particularly limited, but is preferably 1% or more, more preferably 10% or more and less than 50%, based on the dry weight of gelatin. When the addition amount is 1% or less, the smoothness peculiar to silk powder cannot be obtained, and when it exceeds 50%, the difference in feel may be lost.

  Note that the viscosity of the mixed solution of gelatin and polyanion mixed without forming a precipitate of the polyion complex increases in viscosity, and the fibrous material and silk powder settle and separate while the mixture is cooled and gelled. There is no.

  Moreover, when flexibility is required for the sponge body at the time of drying, a plasticizer may be added to impart flexibility. The plasticizer is not particularly limited, and any of glycerin, polyethylene glycol, liquid paraffin, and the like may be used. When adding a water-insoluble plasticizer, combined use with an emulsifier is preferable.

Hereinafter, the method for producing the gelatin sponge body of the present invention will be described more specifically.
A mixture of an aqueous gelatin solution and a polyanion is filled in a stainless steel container so that bubbles do not mix, precooled in a refrigerator at 5 ° C. to stabilize the bubble structure, and then frozen in a -60 ° C. blow-type freezer.
The obtained frozen gelatin solution block is vacuum lyophilized at a degree of vacuum of 50 Pa or less to obtain a block-like sponge body. The end point of vacuum freeze-drying can be confirmed by the pressure rise method.

  Further, the block-like sponge body is subjected to heat dehydration crosslinking in a vacuum dryer at 100 Pa or less and 120 ° C. By performing heat dehydration crosslinking, a sponge body imparted with strength when wet with water can be obtained. Moreover, when adding a crosslinking agent to the said liquid mixture, it is not necessary to perform heat dehydration crosslinking.

  The shape of the sponge body is determined by the shape at the time of gelation, and the sheet-like sponge body, the block-like sponge body, and the gelatin of the shape according to the use such as the sheet-like sponge body by slicing the block-like sponge body A sponge body can be obtained.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
Degreased salmon skin, washed with water, and using gelatin extracted with hot water, 250 g of 0.5% xanthan gum aqueous solution (10 parts with respect to gelatin solid content of 100) was added to 250 g of 5% gelatin aqueous solution at pH 5.8, and 50 ° C. Mix well with a stirrer in a warm water bath. At this time, the viscosity of the aqueous solution increased, but no precipitation was observed.
Further, 250 g of slurry pulp (80 parts with respect to gelatin solid content of 100) in which 4% of the pulp pulverized to 3 mm was dispersed in water was added and mixed with a stirrer in a hot water bath at 50 ° C. to obtain a pulp-dispersed gelatin solution. Obtained.
The pulp-dispersed gelatin solution was carefully filled into a 120 mm × 170 mm × 50 mm (depth) stainless steel container to a thickness of 30 mm so that air bubbles would not mix, and the stainless steel container was left in a refrigerator at 5 ° C. for 12 hours or longer. The gelatin solution was frozen for 1 hour in a -60 ° C blast freezer to obtain a frozen block.
The freeze block was vacuum freeze-dried at a vacuum degree of 50 Pa or less to obtain a block-like sponge body. Further, the block-like sponge body was left in a vacuum dryer at 100 Pa or less and 120 ° C. for 48 hours to carry out heat dehydration crosslinking.
The block-like sponge body was sliced to a thickness of 1.5 mm to obtain a sponge body sheet. The appearance image photograph of the obtained sponge body sheet is shown in FIG. 1, and the electron micrograph is shown in FIG. The obtained sponge sheet had a uniform cell structure and a good feel.
Moreover, the brightness index was measured with a color difference meter (CR-300 manufactured by Minolta Co., Ltd.) as an index of the fineness of the surface of the sponge sheet. The brightness index measured at five random locations was 88.9 ± 2.52 (mean ± SD).
Next, the sponge body sheet was cut into a size of 50 mm × 50 mm and immersed in water to absorb water instantly. The water-absorbed sheet was not torn even if it was picked up and lifted, and had sufficient strength as a pack sheet to adhere to the skin without using a crosslinking agent.

Example 2
A sponge sheet was prepared in the same manner as in Example 1 except that xanthan gum was replaced with sodium γ-polyglutamate. The appearance image photograph of the sponge body sheet obtained is shown in FIG. 3, and the electron micrograph is shown in FIG.
The obtained sponge sheet had a uniform cell structure and a good feel.
In addition, the brightness index of the sponge body sheet measured at five random locations was 86.2 ± 3.54 (average ± SD).
Further, both the water absorption and strength of the sponge sheet were the same as those in Example 1.

Example 3
Degreased, acid-treated, washed with water, washed with hot water, extracted with hot water and adjusted to pH 6.0 with citric acid, 0.5% sodium carboxymethylcellulose (CMC1280: Daicel Chemical Industries, Ltd.) )) 250 g of aqueous solution (10 parts with respect to gelatin solid content of 100) was added and mixed well in a warm water bath at 50 ° C. with a stirrer. Furthermore, 125 g of slurry pulp in which 4% of pulp pulverized to 3 mm is dispersed in water (40 parts with respect to gelatin solid content of 100) and 4% of silk powder having an average particle diameter of 5 μm dispersed in water Add 62.5 g of powder (20 parts to 100% gelatin solids, 11.6% in total solids), 0.25 g of ethylene glycol diglycidyl ether (2 parts to gelatin solids 100) as a crosslinking agent, The mixture was mixed with a stirrer in a warm water bath at 50 ° C. for 1 hour.
The above aqueous solution was carefully filled in a 120 mm × 170 mm × 50 mm deep stainless steel container so that no air bubbles would be mixed into a thickness of 20 mm, and the stainless steel container was left in a refrigerator at 5 ° C. for 12 hours or longer. The gelatin solution was frozen for 1 hour in a blow-type freezer to obtain a frozen block.
The freeze block was vacuum freeze dried at a vacuum degree of 50 Pa or less to obtain a block-like sponge foam. The block-like sponge foam was sliced to a thickness of 1.5 mm to prepare a sponge foam sheet.
The obtained sponge body sheet had a uniform and dense cell structure, was soft and had a good touch, and was unique and smooth with silk powder.
In addition, the brightness index of the sponge body sheet measured at five random locations was 89.0 ± 1.67 (average ± SD).
Further, the water absorption and strength of the sponge body sheet were the same as those in Example 1, and the adhesion to fine parts of the skin was also good.

Example 4
A sponge sheet was prepared in the same manner as in Example 3 except that the amount of slurry pulp was increased in place of the slurry silk powder.
The obtained sponge body sheet had a uniform cell structure and was soft and good in touch, but lacked smoothness.
In addition, the brightness index of the sponge body sheet measured at five random locations was 86.5 ± 1.77 (average ± SD).
Further, both the water absorption and strength of the sponge sheet were the same as those in Example 3.

Comparative Example 1
A sponge sheet was prepared in the same manner as in Example 1 except that 250 g of 0.5% xanthan gum aqueous solution was replaced with 250 g of water. The appearance image photograph of the sponge body sheet obtained is shown in FIG. 5, and the electron micrograph is shown in FIG.
The obtained sponge sheet had a mottled appearance and a rough feel.
In addition, the brightness index of the sponge body sheet measured at five random locations was 69.5 ± 1.29 (average ± SD).

Comparative Example 2
A sponge body sheet was prepared in the same manner as in Example 1 except that xanthan gum was replaced with guar gum having no anionic functional group. An appearance image photograph of the obtained sponge sheet is shown in FIG. 7, and an electron micrograph is shown in FIG.
The obtained sponge sheet had a mottled appearance and a rough feel.
In addition, the brightness index of the sponge body sheet measured at five random locations was 72.5 ± 1.77 (average ± SD).

Comparative Example 3
250 g of 0.5% xanthan gum aqueous solution was added to the gelatin aqueous solution prepared by adding citric acid to the gelatin aqueous solution of Example 1 to adjust the pH to 4.5, and the mixture was mixed with a stirrer in a 50 ° C. warm water bath. Even when the solution was left in a refrigerator at 5 ° C. for 12 hours, gelation was not possible.

Comparative Example 4
When 10% citric acid aqueous solution was added to the pulp-dispersed gelatin solution of Example 1 to adjust the pH to 4.5, a precipitate was generated, and gelation occurred even when the solution was left in a refrigerator at 5 ° C. for 12 hours. could not.

Comparative Example 5
The same operation as in Example 3 was conducted except that sodium carboxymethylcellulose was changed to guar gum which is a thickener having no anionic functional group.
The resulting sponge sheet had a mottled and rough feel, and no improvement in feel due to the silk powder was observed.
Further, the brightness index obtained by randomly measuring five sponge body sheets was a low value of 70.5 ± 1.57 (average ± SD).

  As is clear from the above, the gelatin sponge bodies of Examples 1 to 4 according to the present invention have a dense cell structure and excellent strength when wet with water. Moreover, the gelatin sponge body of Example 3 has a smooth feel when dried.

The molded product obtained from the gelatin sponge body of the present invention can be used as a skin care sheet impregnated with a substrate for culturing cells, lotion or the like.

2 is a photograph of the appearance of the gelatin sponge body obtained in Example 1. 2 is an electron micrograph image of the gelatin sponge body obtained in Example 1. 3 is a photograph of an appearance image of a gelatin sponge body obtained in Example 2. 2 is an electron micrograph of the gelatin sponge body obtained in Example 2. 2 is a photograph of an appearance image of a gelatin sponge body obtained in Comparative Example 1. 2 is an electron micrograph image of a gelatin sponge body obtained in Comparative Example 1. 3 is a photograph of an appearance image of a gelatin sponge body obtained in Comparative Example 2. 2 is an electron micrograph of a gelatin sponge body obtained in Comparative Example 2.

Claims (8)

  1. Gelatin aqueous solution and polyanion as xanthane gum, sodium alginate, sodium hyaluronate, sodium chondroitin sulfate, sodium polyglutamate, sodium polyacrylate, sodium carboxymethylcellulose are mixed under the conditions of pH 5-11,
    Disperse cellulose insoluble in water as a fibrous material during the mixing,
    Gelatin sponge body obtained by cooling, gelling, freezing, and vacuum lyophilization.
  2. The gelatin sponge body according to claim 1, wherein the fibrous material has a fiber diameter of 10 to 500 µm and a fiber length of 0.1 to 5 mm.
  3. The gelatin sponge body according to claim 1 or 2, wherein the amount of the fibrous material added is 10 to 200 parts with respect to 100 parts of gelatin.
  4. The gelatin sponge body according to any one of claims 1 to 3, wherein silk powder is dispersed during the mixing.
  5. The gelatin sponge body according to claim 4, wherein the silk powder has a particle size of 100 μm or less.
  6. The gelatin sponge body according to claim 4 or 5, wherein the addition amount of the silk powder is 1% or more by dry weight ratio with respect to gelatin.
  7. With gelatin aqueous solution
    Mix at least one of xanthan gum, sodium alginate, sodium hyaluronate, sodium chondroitin sulfate, sodium polyglutamate, sodium polyacrylate, sodium carboxymethylcellulose as a polyanion under the conditions of pH 5-11 ,
    A method for producing a gelatin sponge body comprising cooling, gelling, freezing, and then vacuum lyophilization.
  8. The method for producing a gelatin sponge body according to claim 7, wherein the pH is 5-7.
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US7361368B2 (en) 2002-06-28 2008-04-22 Advanced Cardiovascular Systems, Inc. Device and method for combining a treatment agent and a gel
US7641643B2 (en) 2003-04-15 2010-01-05 Abbott Cardiovascular Systems Inc. Methods and compositions to treat myocardial conditions
US8821473B2 (en) 2003-04-15 2014-09-02 Abbott Cardiovascular Systems Inc. Methods and compositions to treat myocardial conditions
US8187621B2 (en) 2005-04-19 2012-05-29 Advanced Cardiovascular Systems, Inc. Methods and compositions for treating post-myocardial infarction damage
US8828433B2 (en) 2005-04-19 2014-09-09 Advanced Cardiovascular Systems, Inc. Hydrogel bioscaffoldings and biomedical device coatings
US20080125745A1 (en) 2005-04-19 2008-05-29 Shubhayu Basu Methods and compositions for treating post-cardial infarction damage
US9539410B2 (en) 2005-04-19 2017-01-10 Abbott Cardiovascular Systems Inc. Methods and compositions for treating post-cardial infarction damage
US7732190B2 (en) 2006-07-31 2010-06-08 Advanced Cardiovascular Systems, Inc. Modified two-component gelation systems, methods of use and methods of manufacture
US9242005B1 (en) 2006-08-21 2016-01-26 Abbott Cardiovascular Systems Inc. Pro-healing agent formulation compositions, methods and treatments
US9005672B2 (en) 2006-11-17 2015-04-14 Abbott Cardiovascular Systems Inc. Methods of modifying myocardial infarction expansion
US8741326B2 (en) 2006-11-17 2014-06-03 Abbott Cardiovascular Systems Inc. Modified two-component gelation systems, methods of use and methods of manufacture
US8192760B2 (en) * 2006-12-04 2012-06-05 Abbott Cardiovascular Systems Inc. Methods and compositions for treating tissue using silk proteins
JP5724108B2 (en) * 2009-04-22 2015-05-27 メドスキン ソリューションズ ドクター ズベラック アーゲーMedSkin Solutions Dr.Suwelack AG Lyophilized composition

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JPH01293143A (en) * 1988-05-21 1989-11-27 Ain Kk Method for crushing gelatin and manufacture of silk, resin film, resin coating film, and paint using such
JPH0749490B2 (en) * 1989-04-06 1995-05-31 新田ゼラチン株式会社 Method for producing a collagen sponge
JP2995353B2 (en) * 1991-05-02 1999-12-27 宮城化学工業株式会社 Silver halide photographic light-sensitive material for gelatine composition
JPH0910294A (en) * 1995-06-30 1997-01-14 Kyowa Hakko Kogyo Co Ltd Heat insulating film or sheet
JPH11279296A (en) * 1998-03-25 1999-10-12 Bmg:Kk Bioabsorbable heat-treated gelatin and collagen sheet
JP2003149777A (en) * 2001-11-16 2003-05-21 Konica Corp Silver halide color photographic sensitive material
JP2004002521A (en) * 2002-05-31 2004-01-08 Nishikawa Rubber Co Ltd Process for producing foamed body of hydrophilic natural polymer compound
JP2005095331A (en) * 2003-09-24 2005-04-14 Ihara Suisan Kk Foamed body sheet containing fishskin dermal collagen and its use

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