CN1174777C - 压敏粘合剂组合物 - Google Patents
压敏粘合剂组合物 Download PDFInfo
- Publication number
- CN1174777C CN1174777C CNB988086174A CN98808617A CN1174777C CN 1174777 C CN1174777 C CN 1174777C CN B988086174 A CNB988086174 A CN B988086174A CN 98808617 A CN98808617 A CN 98808617A CN 1174777 C CN1174777 C CN 1174777C
- Authority
- CN
- China
- Prior art keywords
- adhesive composition
- hydrocolloid
- skin
- weight
- polybutene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title abstract 2
- 230000001070 adhesive effect Effects 0.000 claims abstract description 65
- 239000000853 adhesive Substances 0.000 claims abstract description 64
- 239000000416 hydrocolloid Substances 0.000 claims abstract description 41
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229920001083 polybutene Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008240 homogeneous mixture Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000001814 pectin Substances 0.000 claims description 13
- 235000010987 pectin Nutrition 0.000 claims description 13
- 229920001277 pectin Polymers 0.000 claims description 13
- 108010010803 Gelatin Proteins 0.000 claims description 11
- 229920000159 gelatin Polymers 0.000 claims description 11
- 239000008273 gelatin Substances 0.000 claims description 11
- 235000019322 gelatine Nutrition 0.000 claims description 11
- 235000011852 gelatine desserts Nutrition 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004821 Contact adhesive Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229920000161 Locust bean gum Polymers 0.000 claims description 3
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 235000010980 cellulose Nutrition 0.000 claims description 3
- 235000010420 locust bean gum Nutrition 0.000 claims description 3
- 239000000711 locust bean gum Substances 0.000 claims description 3
- 229910052652 orthoclase Inorganic materials 0.000 claims description 3
- 210000002700 urine Anatomy 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000015125 Sterculia urens Nutrition 0.000 claims description 2
- 240000001058 Sterculia urens Species 0.000 claims description 2
- 230000003187 abdominal effect Effects 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229940014259 gelatin Drugs 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000292 pectin Drugs 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940080313 sodium starch Drugs 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 210000001835 viscera Anatomy 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002367 Polyisobutene Polymers 0.000 description 14
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- 208000027418 Wounds and injury Diseases 0.000 description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000008591 skin barrier function Effects 0.000 description 7
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 3
- 229920002633 Kraton (polymer) Polymers 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001135 Friedman test Methods 0.000 description 2
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- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- -1 hydroxypropyl Chemical group 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 229920001206 natural gum Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 230000008961 swelling Effects 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BHELIUBJHYAEDK-OAIUPTLZSA-N Aspoxicillin Chemical compound C1([C@H](C(=O)N[C@@H]2C(N3[C@H](C(C)(C)S[C@@H]32)C(O)=O)=O)NC(=O)[C@H](N)CC(=O)NC)=CC=C(O)C=C1 BHELIUBJHYAEDK-OAIUPTLZSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002785 Croscarmellose sodium Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040943 Skin Ulcer Diseases 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007455 ileostomy Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 230000005808 skin problem Effects 0.000 description 1
- 231100000019 skin ulcer Toxicity 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 108010001894 stomadhesive Proteins 0.000 description 1
- 239000009318 stomadhesive Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
- A61F5/44—Devices worn by the patient for reception of urine, faeces, catamenial or other discharge; Portable urination aids; Colostomy devices
- A61F5/443—Devices worn by the patient for reception of urine, faeces, catamenial or other discharge; Portable urination aids; Colostomy devices having adhesive seals for securing to the body, e.g. of hydrocolloid type, e.g. gels, starches, karaya gums
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
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- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
- A61L15/585—Mixtures of macromolecular compounds
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0031—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/043—Mixtures of macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/14—Adhesives for ostomy devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/06—Pectin; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Surgery (AREA)
- Hematology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Biomedical Technology (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nursing (AREA)
- Materials For Medical Uses (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
一种适用于医疗目的的压敏粘合剂组合物，它包含了橡胶状弹性基质和一种或多种水溶性或水溶胀性水解胶体，所述的粘合剂组合物包含了35-50%的一种或多种聚丁烯，5-20%的一种或多种苯乙烯的共聚物和20-60%的一种或多种水解胶体的基本上均匀的混合物，它作为粘合剂用于造口术应用时显示了很好的性能。
Description
本发明的领域
本发明涉及到压敏粘合剂组合物，它们适合不同的医疗应用，并且特别适合用于粘接到皮肤，特别在造口术保护的领域。更具体地，本发明涉及到粘合剂组合物，它包含了一种橡胶状的弹性基质和分散在其中的一种或多种水溶性或水溶胀性水解胶体，将这种粘合剂组合物用于制备伤口包扎带，或用作造口术装置的粘合剂片，以及包含这种粘合剂组合物的伤口包扎带或造口术装置。
本发明的背景
现在多种皮肤粘合剂被用于上述目的。
一种皮肤粘合剂的很广范围具体实施方案包含了一种自粘接性弹性材料，在其中分散了吸水性溶胀的颗粒，即所谓的水解胶体。
包含水解胶体的粘合剂组合物已被知道许多年了。美国专利编号3,339,549公开了一种由橡胶状弹性体，例如聚异丁烯和一种或多种水溶解或水溶胀性水解胶体，例如果胶、明胶和羧甲基纤维素的一种粉末状混合物组成的一种共混物。该粘合剂材料带有作用于一个表面的一种水不溶性膜。从E.R.Squibb & Sons Inc.的商标“Stomadhesive”下可在商业上得到了这类组合物，并且被用作开口周围的皮肤阻隔剂，以防止由于开口排泄的腐蚀性流体对皮肤的破坏。
在这类粘合剂组合物中，聚异丁烯负责提供粘接性能，而分散的水解胶体粉末吸收流体并使粘合剂也能够粘接到湿的皮肤上(湿粘)。在作为皮溃疡、烧伤和其它渗出性伤口的伤口包扎带上，这些组合物也获得了日益增加的接受。
包含水解胶体的常规粘合剂组合物已经遇到的一个主要问题是当暴露于身体流体时，它们易于破坏。当这些组合物被用作皮肤阻隔剂时，如在开口周围，流体的吸收性是需要的，但是过量的溶胀会造成组合物失去它的整体性，对渗漏开口，并且从皮肤保护的观点看，阻隔剂要比需要的更多次地被再放置，并且残余物很经常地保留在皮肤上，这在许多场合下是难以除去的。
为了解决上述的缺点，在已经进行了一些尝试，以提高粘合剂组合物的性能。
美国专利编号4,192,785和4,551,490介绍了将内聚增强剂结合到粘合剂组合物中，例如天然或合成的纤维状材料、细碎的纤维素、交联的葡聚糖、交联的羧甲基纤维素或淀粉-丙烯腈接枝共聚物。据称内聚增强剂控制了组合物的水合速率，因此，提高了对于身体流体破坏的抵抗力。美国专利编号4,477,325介绍了将乙烯和醋酸乙烯酯(EVA)的共聚物的混合物结合到粘合剂组合物中。在混合和模塑后，将该组合物进行离子辐射以形成EVA或包含EVA和其它交联树脂的交联聚合物网络。交联的材料据称提供了可控制的溶胀性。
美国专利编号4,496,357介绍了将煅制二氧化硅结合到粘合剂组合物中来控制溶胀。
欧洲专利编号0 122 344 B1介绍了将水合时可以形成弹性体性能的一种或多种天然或合成聚合物，例如谷蛋白和甲基乙烯基醚/马来酸的长链聚合物结合到粘合剂组合物中。据说该粘合剂组合物可以抵抗湿气和身体流体的腐蚀。
欧洲专利编号0 340 945 B1介绍了将聚阳离子水解胶体颗粒结合到水解胶体组合物中。据说聚阳离子、聚阴离子和中性水解胶体提供了改善了的完整性而没有伴随吸收性能的降低。
苯乙烯共聚物被结合在其它的具体实施方案中，这在许多专利说明书中公开了。
在美国专利编号4,231,369中，Sorensen等公开了一种造口术皮肤阻隔剂，它由在其中分散了一种水溶性水解胶体树胶和一种增粘剂的苯乙烯共聚物组成。
在美国专利编号4,367,732中，Poulsen等公开了一种造口术皮肤阻隔剂，它是由分散在由苯乙烯共聚物、烃类增粘剂、增塑剂、抗氧剂和油性增量剂组成的连续相中的一种水溶性水解胶体组成。
在美国专利编号4,551,490(Doyle等)中公开了医疗级压敏粘合剂组合物，它包括了由5-30％的一种或多种聚异丁烯、3-20％的一种或多种苯乙烯的辐射状或嵌段类共聚物、矿物油、一种或多种水溶性水解胶体树胶和一种增粘剂组成的一种均相混合物。也可以将一种或多种水溶胀性内聚增强剂、抗氧剂和其它多种非必须的组分包含在粘合剂组合物中。
欧洲专利公开编号81907公开了一种造口术装置，它包含了一种在开口周围的皮肤阻隔剂(A)和一种包含了与皮肤阻隔剂(A)永久粘着的一种向外扩展的凸缘的结合元件(B)和一种具有上部孔状层的微孔状粘合剂层(C)。该皮肤阻隔剂粘合剂(A)包含了均相的30-70％的共混物，该共混物由低分子量聚异丁烯和一种或多种非必须的选自中等分子量的聚异丁烯、丁基橡胶和苯乙烯异戊二烯共聚物的热塑性弹性体组成和其中分散了35-65％的一种或多种水溶性水解胶体和一种或多种水溶胀性或惰性的内聚增强剂。
一般来说，这些以前的方法在提高粘合剂组合物的整体性上是优异的。然而，对于具有对生物流体抵抗力以及具有对皮肤的改善的粘接和拉伸性性能的更好粘合剂组合物的需求仍存在。
现在已经发现可以得到具有抵抗生物流体以及具有对皮肤的改善的粘接性和延伸性性能的改善的粘合剂组合物。
本发明的简单介绍
本发明涉及到适合用于不同医疗应用，并且特别适合用于粘合到皮肤上的应用，特别在造口术保护领域中的压敏粘合剂组合物。更具体地，本发明涉及到粘合剂组合物，它包含了橡胶状弹性体基质和被分散的一种或多种水溶性或水溶胀性水解胶体，涉及到包含这种粘合剂组合物的造口术装置和将这种粘合剂组合物用于制备伤口包扎带或造口术装置的应用。
本发明的详细介绍
本发明涉及到一种适用于医疗目的的压敏粘合剂组合物，它包含了橡胶状弹性体基质和一种或多种水溶性或水溶胀性水解胶体，所述的粘合剂组合物由25-60％重量的一种或多种聚丁烯，3-35％重量的一种或多种苯乙烯的共聚物和20-60％重量的一种或多种水解胶体的均匀混合物组成，其中一种或多种聚丁烯和一种或多种苯乙烯共聚物构成了所述橡胶状弹性基质。
不将本发明限定到任何假定，可以确信的是苯乙烯辐射状或嵌段共聚物组分与一种或多种聚丁烯以上面说明的比例的结合为组合物提供了伸展性和模量应变上的同时快速和完全的恢复。聚丁烯的粘合性能和水解胶体的吸收性能的结合使本发明的粘合剂组合物特别适合用于造口术装置。
优选的是苯乙烯共聚物为苯乙烯-丁二烯-苯乙烯的嵌段共聚物或苯乙烯-异戊二烯-苯乙烯的嵌段共聚物。优选地，采用一种或多种苯乙烯-异戊二烯-苯乙烯(SIS)嵌段类共聚物。
苯乙烯嵌段共聚物的用量优选地为总的粘合剂组合物的5到20％。
丁烯组分适合地为选自聚丁二烯和聚异戊二烯的共轭丁二烯聚合物。
根据本发明被采用的聚丁烯的Flory分子量优选地为50,000到60,000。
聚丁烯优选地以总的粘合剂组合物的35到50％的用量存在。
结合到本发明的粘合剂组合物的适当的水解胶体选自天然存在的水解胶体、半合成类水解胶体和合成类水解胶体。
更具体地，水解胶体优选地选自瓜耳树胶、刺槐豆胶(LBG)、果胶、藻酸盐、明胶、黄原胶、刺梧桐树胶、纤维素衍生物(如羧甲基纤维素的盐例如羧甲基纤维素的钠盐、甲基纤维素和羟丙基甲基纤维素)、淀粉甘醇酸钠、聚乙烯醇和聚乙二醇。
优选的是采用两种或多种水解胶体的组合。特别优选的是采用果胶、明胶、和羧甲基纤维素的组合作为水解胶体组分。
水解胶体的总量优选地为总的组合物的30-50％。
根据本发明的一个特别优选的组合物包含了50％的聚异丁烯和SIS的混合物和50％的包含明胶、果胶和CMC的水解胶体的混合物。
在被用于造口术装置的本发明的一个优选的具体实施方案中，粘合剂组合物包括在WO 89/05619中公开类型的“Swiss roll”粘合剂中的粘合剂组分，更有吸收性的其它的组分，如包含了PIB和水解胶体的混合物或任何其它适当的粘合剂。
在其它方面，本发明涉及到将粘合剂组合物用于将造口术装置固定到皮肤上和用于造口术周围的密封，用于将伤口包扎带或伤口排泄绷带固定到皮肤上，用于将收集尿的装置固定到皮肤上，或用于将正长石(orthoses)或修补物固定到皮肤上，该组合物包含了橡胶状弹性体基质和一种或多种水溶性或水溶胀性水解胶体，所述的粘合剂组合物由25-60％的一种或多种聚丁烯，3-35％的一种或多种苯乙烯的共聚物和20-60％的一种或多种水解胶体的均匀的混合物组成。
在另一方面，本发明涉及到放置到病人的腹部用于收集内脏内容物的排泄物的造口术装置，它包含了含有橡胶状弹性基质和一种或多种水溶性或水溶胀性水解胶体的粘合剂组合物，该粘合剂组合物由25-60％的一种或多种聚丁烯，3-35％的一种或多种苯乙烯的共聚物和20-60％的一种或多种水解胶体的均匀的混合物组成。
根据本发明的造口术装置可以是一种开口或封闭的装置，它适合用于与结肠造口术、回肠造口术或尿道造口术(urostomy)有关的应用。它可以是单件装置或身体侧构件或包括身体侧部造口构件和分离的收集袋的两件装置的面板形成部分。可以以任何本质上已知的常规方式，即通过结合环或通过覆盖了粘合剂的法兰将分离的收集袋结合到身体侧构件上。
可以以本质上在本领域中已知的方式，由常规用于制备造口术装置的材料来制备根据本发明的造口术装置。
在下面公开了本发明的具体实施方案的实施例中，本发明被更详细地说明了。
材料和方法
PIB：以级别LM-MH从Exxon化学公司的Vistanex商标下得到的聚异丁烯。Kraton D1107：具有分子量212,000-260,000(GPC)和二嵌段含量15-25％的苯乙烯-异戊二烯-苯乙烯共聚物。
明胶：从ED.Geistlich Sohne AG得到的明胶P.S.98.240.233。
果胶：从哥本哈根果胶A/S得到的果胶LM 12CG Z或果胶USP/100。
CMC：从Akzo的商标Akucell AF2881下得到，或从Hercules公司的商标Blanose 9H4XF下得到的羧甲基纤维素钠。
采用从Herman-Linden来的型号LKB 025的Z混合器。
实验部分
实施例1
根据本发明制备粘合剂材料
制备了具有在下面表1中陈述的成分的粘合剂组合物。
表1
| 成分 | 重量百分数 |
| PIBKraton D1107(SIS)明胶果胶CMC | 41,58,517,51022,5 |
在150℃下将100克PIB加入到Z混合器中并软化5分钟。然后将100克Kraton D1107加入并在150℃和50mbar下继续混合直到混合物均匀化。将物质冷却到80℃，从混合器中移出166克物质。向残余的物质中加入66克PIB、35克明胶、20克果胶和45克CMC。在80℃和50mbar下继续混合直到得到一种均匀的面团状混合物。
当还是热和软的时候，将得到的面团状物质从混合器中移出，并在大约90℃和100mbar下在两片聚硅氧烷脱离纸之间，通过压模粘合剂物质成型成具有大约1毫米厚的片材。然后将得到的平板切成具有所需形状的片。
该粘合剂组合物可用来将造口术装置固定到皮肤上和用于造口术周围的密封，用于将伤口包扎带或伤口排泄绷带固定到皮肤上，用于将收集尿的装置固定到皮肤上，或用于将正长石或修补物固定到皮肤。造口术装置或伤口包扎带可以是任何这种本质上已知的产品，并且可以以与采用常规的粘合剂组合物制备类似产品的相似的方法来制备。
实施例2-9
按照实施例1的过程，制备在下面表2和3中陈述的成分的粘合剂组合物。
表2
| 成分 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
| PIB | 40 | 45 | 35 | 50 |
| KratonD1107 | 10 | 5 | 15 | 10 |
| 明胶 | 17,5 | 17,5 | 17,5 | 10 |
| 果胶pomosin | 10 | 10 | 10 | 20 |
| CMC | 22,5 | 22,5 | 22,5 | 10 |
表3
| 成分 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
| PIB | 50 | 42,5 | 37,5 | 45 |
| KratonD1107 | 20 | 12,5 | 17,5 | 15 |
| 明胶 | 10 | 15 | 15 | 10 |
| 果胶pomosin | 10 | 15 | 15 | 10 |
| CMC | 10 | 15 | 15 | 20 |
实施例10
比较具有包含了根据本发明的粘合剂的粘合剂片的结肠造口术袋与商业上得到的袋。
在一个公开、多中心、交叉的临床实验中，将Naturess造口术袋(ConvaTec)和单件Dansac Light造口术袋(Dansac A/S)与带有粘合剂片的结肠造口术袋进行比较，该粘合剂片包含了具有在实施例2中说明的根据本发明的组合物的粘合剂，其目的是为了比较粘合剂的性能。
包括的标准
下面的测试人员可适合包括到本研究中：
已经出院至少一个月的结肠造口者，并且是：
年龄大于18岁，
能够给出书面同意的，
能够完成登记表，
良好的常规健康。
排除的标准：
下面人员没有资格包括到本研究中：
有严重的皮肤问题并且正在进行治疗的结肠造口者，
怀孕或喂奶的结肠造口者。
对下面的参数进行评价：
磨损时间，脱移的原因，和瞬粘性，柔韧性，脱移时疼痛，根据等级1-5的残余物-外面区域和残余物-内部区域，其中5为最好：
与粘合剂的应用关联，对皮肤的瞬粘性被评价为：
对皮肤的瞬粘性和柔韧性被评价为：
5＝优异
4＝中等
3＝可接受
2＝差
1＝很差
脱移时疼痛，从粘合剂的外部区域在皮肤上的残余物和从粘合剂的内部区域在开口周围皮肤上的残余物被评价为：
5＝完全没有
4＝一点点
3＝可接受
2＝有一些
1＝很多
结果总结在下面表4和5中。
表4
根据本发明的粘合剂与Naturess造口术袋的粘合剂的比较(总共67个造口者)
| 功效参数 | 用根据本发明的粘合剂的袋 | Naturess造口术袋 | P-值 |
| 磨损时间 | 12.79小时 | 12.82小时 | 0.941 |
| 脱移的原因常规途径卫生性粘合下渗漏粘合剂部分不粘粘合剂完全不粘刺激皮肤 | 29.4％58.4％8.1％6.3％0.4％4.3％ | 22.9％52.9％8.4％6.7％0.2％12.7％ | 0.039*0.4970.7660.8880.5640.027 |
| 瞬粘性 | 4.16 | 3.52 | 0.00007* |
| 柔韧性 | 4.25 | 3.82 | 0.0003* |
| 脱移时疼痛 | 4.74 | 4.29 | 0.001* |
| 残余物-外面区域 | 4.79 | 4.55 | 0.021* |
| 残余物-开口周围 | 4.82 | 4.51 | 0.003* |
*在Friedman测试或在Wilcoxon标记等级测试中有相当大的区别(α＝0.05)
％为所有采用的袋的％
表5
根据本发明的粘合剂与单件Dansac Light造口术袋的粘合剂的比较(总共80个造口者)
| 功效参数 | 用根据本发明的粘合剂的袋 | 单件DansacLight造口术袋 | P-值 |
| 磨损时间 | 10.88小时 | 10.11小时 | 0.101 |
| 脱移原因常规途径卫生性粘合下渗漏粘合剂部分不粘粘合剂完全不粘刺激皮肤 | 62.0％43.1％4.0％4％0.5％1.1％ | 54.3％46.4％5.3％7.4％0.2％4.3％ | 0.035*0.4340.5740.2030.6550.127 |
| 瞬粘性 | 4.38 | 4.14 | 0.041* |
| 柔韧性 | 4.20 | 4.16 | 0.741 |
| 脱移时疼痛 | 4.71 | 4.00 | 0.00003* |
| 残余物-外面区域 | 4.70 | 4.23 | 0.001* |
| 残余物-开口周围 | 4.77 | 4.48 | 0.011* |
*在Friedman测试或在Wilcoxon标记等级测试中有相当大的区别(α＝0.05)
％为所有采用的袋的％
结论
从根据本发明的粘合剂可以注意到该粘合剂具有更好的瞬粘性，它在开口的内部和外部都能抵抗洗脱，并且还比已知的产品具有更小的脱除痛苦。这些区别在统计上是明显的。
在磨损时间上没有大的区别。
对于变化的原因，在“常规途径”上发现了相当大的区别，它有利于带有根据本发明的粘合剂的袋，因此根据本发明的袋可以保持在皮肤上只要造口者愿意。
在本发明的袋和Dansac袋的粘合剂之间，在柔韧性上没有发现太大的区别，而本发明的袋的粘合剂比Naturess袋上的粘合剂有更好的柔韧性。
Claims (11)
1.适合于医疗目的的压敏粘合剂组合物，它包含橡胶状弹性基质和一种或多种水溶性或水溶胀性水解胶体，所述的粘合剂组合物由25-60％重量的一种或多种聚丁烯，3-35％重量的一种或多种苯乙烯共聚物和20-60％重量的一种或多种所述水解胶体的均匀混合物组成，其中所述一种或多种聚丁烯和一种或多种苯乙烯共聚物构成所述橡胶状弹性基质，和其中所述一种或多种聚丁烯和一种或多种苯乙烯共聚物和一种或多种水解胶体的重量百分数合计达所述粘合剂组合物的100％。
2.权利要求1的粘合剂组合物，其中苯乙烯共聚物为苯乙烯-丁二烯-苯乙烯的嵌段共聚物或苯乙烯-异戊二烯-苯乙烯嵌段共聚物。
3.权利要求2的粘合剂组合物，其中苯乙烯的共聚物为苯乙烯-异戊二烯-苯乙烯嵌段共聚物。
4.权利要求2或3的粘合剂组合物，其中一种或多种苯乙烯嵌段共聚物的存在量为粘合剂组合物总量的5-20％重量。
5.权利要求1-3任何一项的粘合剂组合物，其中的聚丁烯是选自聚丁二烯和聚异戊二烯的共轭丁二烯聚合物。
6.权利要求1-3任何一项的粘合剂组合物，其中一种或多种聚丁烯的存在量为粘合剂组合物总量的35-50％重量。
7.权利要求1-3任何一项的粘合剂组合物，其中的水解胶体选自天然存在的水解胶体、半合成水解胶体和合成水解胶体。
8.权利要求7的粘合剂组合物，其中水解胶体选自瓜耳树胶、刺槐豆胶、果胶、藻酸盐、明胶、黄原胶、刺梧桐树胶、纤维素衍生物、淀粉甘醇酸钠、聚乙烯醇和聚乙二醇。
9.权利要求1-3任何一项的粘合剂组合物，其中一种或多种水解胶体的存在量为粘合剂组合物总量的30-50％重量。
10.一种用来放置在病人的腹部用来收集内脏内容物的排泄物的造口术装置，它包括权利要求1的粘合剂组合物。
11.权利要求1的粘合剂组合物的用途，用于将造口术装置固定到皮肤上和用于造口术周围的密封，用于将伤口包扎带或伤口排泄绷带固定到皮肤上，用于将收集尿的装置固定到皮肤上，或用于将正长石或修补物固定到皮肤上。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK0993/1997 | 1997-08-29 | ||
| DK0993/97 | 1997-08-29 | ||
| DK199700993A DK99397A (da) | 1997-08-29 | 1997-08-29 | Klæbemiddel samt anvendelse af dette middel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268892A CN1268892A (zh) | 2000-10-04 |
| CN1174777C true CN1174777C (zh) | 2004-11-10 |
Family
ID=8099818
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988086174A Expired - Lifetime CN1174777C (zh) | 1997-08-29 | 1998-08-27 | 压敏粘合剂组合物 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6451883B1 (zh) |
| EP (3) | EP1007108B2 (zh) |
| JP (2) | JP2001514051A (zh) |
| CN (1) | CN1174777C (zh) |
| AT (2) | ATE288287T1 (zh) |
| AU (1) | AU750502B2 (zh) |
| CA (1) | CA2299242C (zh) |
| DE (2) | DE69828887T3 (zh) |
| DK (3) | DK99397A (zh) |
| ES (2) | ES2348729T3 (zh) |
| WO (1) | WO1999011302A1 (zh) |
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-
1997
- 1997-08-29 DK DK199700993A patent/DK99397A/da not_active Application Discontinuation
-
1998
- 1998-08-27 ES ES05001976T patent/ES2348729T3/es not_active Expired - Lifetime
- 1998-08-27 CN CNB988086174A patent/CN1174777C/zh not_active Expired - Lifetime
- 1998-08-27 AT AT98939490T patent/ATE288287T1/de not_active IP Right Cessation
- 1998-08-27 AU AU87985/98A patent/AU750502B2/en not_active Ceased
- 1998-08-27 DK DK98939490T patent/DK1007108T4/da active
- 1998-08-27 JP JP2000508403A patent/JP2001514051A/ja active Pending
- 1998-08-27 ES ES98939490T patent/ES2235351T5/es not_active Expired - Lifetime
- 1998-08-27 EP EP98939490A patent/EP1007108B2/en not_active Expired - Lifetime
- 1998-08-27 CA CA002299242A patent/CA2299242C/en not_active Expired - Fee Related
- 1998-08-27 US US09/485,697 patent/US6451883B1/en not_active Expired - Lifetime
- 1998-08-27 EP EP05001976A patent/EP1541180B1/en not_active Expired - Lifetime
- 1998-08-27 AT AT05001976T patent/ATE473766T1/de not_active IP Right Cessation
- 1998-08-27 WO PCT/DK1998/000368 patent/WO1999011302A1/en active IP Right Grant
- 1998-08-27 DE DE69828887T patent/DE69828887T3/de not_active Expired - Lifetime
- 1998-08-27 EP EP10159480A patent/EP2221067A1/en not_active Withdrawn
- 1998-08-27 DE DE69841765T patent/DE69841765D1/de not_active Expired - Lifetime
- 1998-08-27 DK DK05001976.9T patent/DK1541180T3/da active
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2010
- 2010-03-23 JP JP2010066465A patent/JP2010158551A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1007108A1 (en) | 2000-06-14 |
| AU750502B2 (en) | 2002-07-18 |
| WO1999011302A1 (en) | 1999-03-11 |
| EP2221067A1 (en) | 2010-08-25 |
| EP1541180A3 (en) | 2007-01-31 |
| CA2299242C (en) | 2008-12-02 |
| DK1007108T4 (da) | 2009-05-18 |
| ATE288287T1 (de) | 2005-02-15 |
| DE69828887T2 (de) | 2006-04-06 |
| AU8798598A (en) | 1999-03-22 |
| DK1541180T3 (da) | 2010-11-08 |
| US6451883B1 (en) | 2002-09-17 |
| ATE473766T1 (de) | 2010-07-15 |
| ES2235351T3 (es) | 2005-07-01 |
| DK1007108T3 (da) | 2005-06-06 |
| EP1541180B1 (en) | 2010-07-14 |
| DE69828887D1 (de) | 2005-03-10 |
| EP1007108B2 (en) | 2009-01-21 |
| EP1541180A2 (en) | 2005-06-15 |
| DE69841765D1 (de) | 2010-08-26 |
| EP1007108B1 (en) | 2005-02-02 |
| DK99397A (da) | 1999-05-05 |
| ES2348729T3 (es) | 2010-12-13 |
| JP2001514051A (ja) | 2001-09-11 |
| CA2299242A1 (en) | 1999-03-11 |
| ES2235351T5 (es) | 2009-05-22 |
| JP2010158551A (ja) | 2010-07-22 |
| CN1268892A (zh) | 2000-10-04 |
| DE69828887T3 (de) | 2009-07-30 |
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