AU5232698A - Adhesives - Google Patents
AdhesivesInfo
- Publication number
- AU5232698A AU5232698A AU52326/98A AU5232698A AU5232698A AU 5232698 A AU5232698 A AU 5232698A AU 52326/98 A AU52326/98 A AU 52326/98A AU 5232698 A AU5232698 A AU 5232698A AU 5232698 A AU5232698 A AU 5232698A
- Authority
- AU
- Australia
- Prior art keywords
- cross
- linked polyurethane
- diamine
- linked
- isocyanate
- 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.)
- Abandoned
Links
- 239000000853 adhesive Substances 0.000 title description 19
- 230000001070 adhesive effect Effects 0.000 title description 18
- 239000004814 polyurethane Substances 0.000 claims description 44
- 229920002635 polyurethane Polymers 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012948 isocyanate Substances 0.000 claims description 21
- 150000002513 isocyanates Chemical class 0.000 claims description 21
- 150000004985 diamines Chemical class 0.000 claims description 15
- 229920000768 polyamine Polymers 0.000 claims description 10
- 229920001021 polysulfide Polymers 0.000 claims description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 230000000887 hydrating effect Effects 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- -1 alkyl diamine Chemical class 0.000 claims 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 239000000499 gel Substances 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical class C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000001464 adherent effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960003260 chlorhexidine Drugs 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OKKDHVXHNDLRQV-UHFFFAOYSA-N 6-[3-(6-isocyanatohexyl)-2,4-dioxo-1,3-diazetidin-1-yl]hexyl n-(6-isocyanatohexyl)carbamate Chemical compound O=C=NCCCCCCNC(=O)OCCCCCCN1C(=O)N(CCCCCCN=C=O)C1=O OKKDHVXHNDLRQV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010046543 Urinary incontinence Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940124326 anaesthetic agent Drugs 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 150000004283 biguanides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- UEJSSZHHYBHCEL-UHFFFAOYSA-N silver(1+) sulfadiazinate Chemical compound [Ag+].C1=CC(N)=CC=C1S(=O)(=O)[N-]C1=NC=CC=N1 UEJSSZHHYBHCEL-UHFFFAOYSA-N 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GKCBAIGFKIBETG-UHFFFAOYSA-N tetracaine Chemical compound CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 GKCBAIGFKIBETG-UHFFFAOYSA-N 0.000 description 1
- 229960002372 tetracaine Drugs 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 238000013271 transdermal drug delivery Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940072358 xylocaine Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/834—Chemically modified polymers by compounds containing a thiol group
- C08G18/835—Unsaturated polymers modified by compounds containing a thiol group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2210/00—Compositions for preparing hydrogels
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
ADHESIVES
The present invention relates to adhesives, their preparation and their use.
Adhesives which are suitable for use on the skin and which comprise polyurethane polymers are known from European Patent No.0271292B1. Adhesives described therein are prepared by reacting an isocyanate precursor with an acrylate comprising hydroxyl-containing esters of acrylic or methacrylic acid to produce a prepolymer. The prepolymer so formed may be cross-linked to form a polyurethane polymer by irradiation. In addition, prior art cross- linked polyurethane systems tend to be sensitive to water and when in contact with water produce carbon dioxide which results in bubbles appearing in gels.
We have now found that such isocyanate precursors may be reacted with hydroxylated alkyl acrylates to produce a non-cross linked polyurethane hereinafter referred to as the prepolymer. Such prepolymers may then be reacted with a polyamine (i.e. polymer with amine groups) or a disulphide to produce a cross-linked polyurethane.
Thus according to the invention we provide a cross-linked polyurethane wherein the polyurethane comprises an acrylated isocyanate cross-linked with polyamine or polysulphide groups.
The cross-linked polyurethanes according to the invention are advantageous in that they provide a skin friendly non-self adherent pressure sensitive adhesive which is inherently tacky.
The cross-linked polyurethane of the invention absorbs water, eg. from 5 to 95% of the weight of the cross-linked polyurethane, to form a polyurethane gel. The cross-linked polyurethane will absorb water and become hydrated and when hydrated may contain up to 95%, typically from 35 to 95% by weight of water, aptly 50% to 92%, preferably 70 to 90% by weight of water and most preferably 75 to 85% by weight of water.
The water absorption of the cross-linked polyurethane can be obtained by taking a known weight of the cross-linked polyurethane and immersing it in water for 24 hours. The resulting polyurethane gel is removed from the water, surface water is removed by lightly blotting with absorbent paper and then the weight of the polyurethane gel is taken. The water absorption of the cross-linked polyurethane (% by weight) can then be calculated.
The polyurethane gels are also suited to providing skin friendly non-self adherent pressure sensitive adhesives and such adhesives are a further feature of the present invention.
Thus according to a further feature of the invention we provide a skin friendly non-self adherent pressure sensitive adhesive which comprises a cross-linked polyurethane wherein the polyurethane comprises an acrylated isocyanate which is cross-linked with polyamine or disulphide groups.
The adhesives of the invention are skin friendly, ie. that they can be removed from the skin without causing discomfort and because of their inherent tackiness can be replaced and adhere again. The adhesives also have the advantage that they are non- self-adherent so that if for example the adhesive surface becomes creased during the application of a dressing the contracting surfaces of the adhesive may be easily peeled apart and the dressing is not wasted.
Any isocyanate precursors known βeι §e_ may be used, but the preferred isocyanate precursors are those described in European Patent No.0271292B.
The non-cross-linked polyurethane may be prepared using one or more hydroxy alkyl acrylates. In the acrylate moiety, the alkyl group may be C1 to 10, preferably C1 to 6, eg. ethyl.
The polyamines or disulphides act as cross-linking agents when reacted with the prepolymer. Thus, preferred polyamines are
diamines. Any diamines known Q§L se may be used such as alkyl C1 to 10 diamines such as ethylene diamine. Preferred diamines are the class of compounds known as Jeffamines (Trade Mark) available from Huntsman Corporation in the UK.
Jeffamines are high molecular weight diamines with a polymeric backbone. Jeffamines may have a molecular weight ranging from 200 to 6000.
The Jeffamine ED-Series products are polyether diamines which are based on a predominately polyethylene oxide backbone. This imparts complete water solubility to each of the members of this series. The Jeffamine ED-Series products have the following structure:
H 2 NC . HCH 2 -[ lOCHCH 21α a -[ lOCH 2 CH 2 ]J b -[ lOCH CH 21J c -NH 2
CH. CH CH.
The Jeffamine DU Series are urea condensates of Jeffamine D-Series products. The DU-Series products are made by coupling a Jeffamine D-Series product with urea, in order to form a diamine product of increased molecular weight. This is exemplified by the following structure:
O
H 2 NC. HCH 2 -[lOCH 2 C, H] n -NH-C-NH-[C . HCH 2 O]J n -CH 2 .HNH 2
CH, 3 CH, 3 CH, 3 CH, 3
Preferred disulphides are polysulphides of the following general structure:
HS(C2H4OCH2θC2H4Sx)nC2H4θCH2θC2H4SH
wherein x is an integer, and n is an integer from 1 to 30.
Polysulphides may vary in molecular weight, eg. when n is 6 the polysulphide may have a molecular weight of about 1000, and when n=23 the polysulphide may have a molecular weight of about 4000. Such polysulphides are known per §e_ and are available from Morton International, Speciality Chemicals Group in the UK.
Optionally, the cross-linking reaction may be promoted by the presence of an effective amount of catalyst.
The present invention also provides a method of preparation of cross-linked polyurethane as hereinbefore described, which comprises; (i) reacting an isocyanate with an hydroxylated acrylate to produce a prepolymer; and
(ii) reacting the prepolymer with a polyamine or a disulphide to produce a cross-linked polyurethane.
In another aspect the present invention also provides a process for the preparation of a pressure sensitive adhesive in the form of an inherently tacky polyurethane gel which comprises hydrating a cross-linked polyurethane as hereinbefore described with from 5 to 95% w/w of water.
In a further aspect, the present invention provides adhesive products comprising an adhesive gel in accordance with the invention.
The adhesives of the present invention are suitable for use in a number of applications such applications include use as an adhesive when coated on a substrate for bandages, absorbent wound dressings, burns dressings, incise drapes, first aid dressings, intravenous catheter dressing, ostomy devices, condom attachment in urinary incontinence devices, transdermal drug delivery devices, adhesive tapes (surgical tapes, wound closure tapes and the like), protection devices such as napkins, diapers, incontinence pads and protection pads, electroconductive gels. However the main use is
envisaged to be in dressings and drapes of the types above when the adhesive is in contact with the skin.
The adhesives of the invention may be employed in the manufacture of bacteria proof wound dressings such as those which comprise a backing layer which has upon substantially the whole of the wound facing surface thereof a layer of pressure sensitive adhesive in accordance with the invention.
The cross-linked polyurethanes of the invention are advantageous in that they may be prepared without the need of a radical initiator or a UV irradiation source.
Many medicinal agents may be incorporated into the adhesives of the present invention. By the term agents it is meant pharmacologically active agents and agents including topical anaesthetics such as amethocaine, xylocaine, bactβriostatic agents such as silver nitrate; antibacterial agents of which preferred agents include silver sulphadiazine, chlorhexidine salts, PVP-I, and biguanides antibiotics; topical steroids, enzyme stimulants, coagulants and anticoagulants and antifungal agents.
Advantageously water soluble medicaments such as chlorhexidine and its salts may be dissolved in water which is used to hydrate the cross-linked polyurethane. It is found that chlorhexidine is unaffected during the hydrating process and the resulting adhesive provides effective release of chlorhexidine when placed onto a surface.
The invention will now be illustrated but in no way limited with reference to the following examples.
Raw Materials
Example 1
673g Emkarox VG680W (0.280 moles OH from H2O and OH values), 175g Desmodur N3200 (NCO/OH ratio = 3.5) and 0.2% w/w Metatin 812ES catalyst were mixed in a 1 litre flange flask on a water bath at 80° for 2 hours.
The percentage isocyanate in the resulting prepolymer was determined in the standard way and was found to be 2.97% w/w NCO in this case.
Other prepolymers were synthesised which were formulated to give different residual isocyanate concentrations. This would be expected to affect the degree of cross-linking in the gel adhesive.
The residual isocyanate functionalities in the prepolymer were reactecj, for example, with hydroxyethylacrylate in order the synthesise the acrylated prepolymer.
The isocyanate/hydroxyethylacrylate reaction was performed at a 1 :1 NCO/OH mole ratio. The two components were stirred at room temperature for approx 6 hours and the disappearance of isocyanate was monitored by infra-red spectroscopy. Infra-red spectra of isocyanate terminated prepolymers contain a strong isocyanate peak at 2270cm-'' .
The Michael addition was performed by mixing equimolar ratios of acrylate groups to amine (or thiol) functionalities. This reaction generally proceeds more quickly at room temperature than at elevated temperatures. Catalysts were added, where applicable, dropwise to the two component mixture.
Example 2
Preparation of Prepolymer
Emkarox VG680W, polyisocyanate and Metatin 812ES catalyst were weighed into a flange flask fitted with a stirrer, nitrogen inlet and bubbler. This was stirred at 80°C for 2 hours under nitrogen and then allowed to cool to room temperature. The oligomer was then mixed, at room temperature, stoichiometrically with hydroxyacrylate to cap-off the remaining isocyanate groups. The reaction mix was then analysed periodically by infra-red spectroscopy to monitor the disappearance of the isocyanate peak at 2250cm"1. The prepolymer stored at room temperature after synthesis in a sealed container.
The polyol: isocyanate ratio was such to give a suitable number of acrylate groups which could be effectively crosslinked to give a tacky gel. The isocyanate content of the prepolymer varied
between 0.64% and 2.5% and was dependant on the isocyanate and end-capping acrylate (see Table 1).
Table 1
Example 3
Crosslinking of Prepolymer
A sample of acrylate terminated prepolymer was mixed in a 1 : 1 vinyl:NH (or NH2, depending on the sample) ratio with the crosslinker and poured into a tray and left to gel via the Michael Addition reaction.
3a) Crosslinking of Prepolymer PC0896039
Hydroxyethylacrylate capped Desmodur N3200 - derived prepolymer (PC0896039) was crosslinked with a range of amines of different molecular weight and functionality. These took between V2 hour and 5 days to give a tacky clear (some bubbles present from mixing), gel. The lower molecular weight amines crosslinked first (1 ,3-diaminopropane) and higher molecular weight last (Jeffamine D2000). All of these gels when placed in water dissolved in 13 - 48 hours. Only Versalink P650 did not gel the prepolymer successfully. When polysulphide was used as a crosslinker this gave a gel in 3 days and did not dissolve in water, but gave a 71% water uptake.
3b) Crosslinking of Prepolymer PC0896173
Hydroxyethylacrylate capped Suprasec 5005 - derived prepolymer (PC0896173) was crosslinked with Jeffamine D2000
and N.N-dimethylethylenediamine and gave a tacky clear gel in less than three days. Both of these gels when placed in water dissolved in five days.
3c Crosslinking of Prepolymer PC1196045
Hydroxypropylacrylate capped Desmodur prepolymer (PC1196045) was crosslinked with Jeffamine D2000 to give a tacky gel which dissolved in water in several days.
Once the sample had gelled it was subjectively assessed for its appearance and then a sample was placed in distilled water to assess its hydrophilicity.
Claims
1. A.cross-linked polyurethane wherein the polyurethane comprises an acrylated isocyanate cross-linked with polyamine or disulphide group.
2. A cross-linked polyurethane according to claim 1 wherein the acrylate moiety is a hydroxylated alkyl acrylate.
3. A cross-linked polyurethane according to claim 2 wherein the alkyl moiety is a C to C10 group.
4. A cross-linked polyurethane according to claim 3 wherein the alkyl moiety is a C^ to C6 group.
5. A cross-linked polyurethane according to claim 4 wherein the alkyl moiety is an ethyl group.
6. A cross-linked polyurethane according to any preceding claim wherein the polyamine is a diamine.
7. A cross-linked polyurethane according to claim 6 wherein the diamine is an alkyl diamine.
8. A cross-linked polyurethane according to claim 7 wherein the alkyl diamine is a C1 to C10 diamine.
9. A cross-linked polyurethane according to claim 8 wherein the C1 to C10 diamine is ethylene diamine.
10. A cross-linked polyurethane according to claim 6 wherein the diamine is a polyoxyalkene diamine.
11. A cross-linked polyurethane according to claim 6 wherein the diamine is a polyoxylkene diamine with a urea coupling.
12. A cross-linked polyurethane according to any of claims 1 to 5 wherein the disulphide groups is a polysulphide with the general formula
HS(C2H4OCH2OC2H4Sx)nC2H4OCH2OC2H4SH
wherein x is an integer and
n is an integer from 1 to 30.
13. A'pressure sensitive adhesive comprising a cross-linked polyurethane wherein the polyurethane comprises an acrylated isocyanate which isocyanate is cross-linked with polyamine or disulphide group.
14. A process for the preparation of a pressure sensitive adhesive which comprises reacting an isocyanate with hydroxylated acrylate to produce a prepolymer and reacting the prepolymer with a polyamine or disulphide group to produce a cross-linked polyurethane and,
hydrating the cross-linked polyurethane with from 5 to 95% w/w of water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9625422.2A GB9625422D0 (en) | 1996-12-06 | 1996-12-06 | Adhesives |
| GB9625422 | 1996-12-06 | ||
| PCT/GB1997/003340 WO1998024826A1 (en) | 1996-12-06 | 1997-12-04 | Adhesives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU5232698A true AU5232698A (en) | 1998-06-29 |
Family
ID=10804079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU52326/98A Abandoned AU5232698A (en) | 1996-12-06 | 1997-12-04 | Adhesives |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0942941A1 (en) |
| JP (1) | JP2001505245A (en) |
| AU (1) | AU5232698A (en) |
| CA (1) | CA2273962A1 (en) |
| GB (1) | GB9625422D0 (en) |
| WO (1) | WO1998024826A1 (en) |
| ZA (1) | ZA9710860B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU779402B2 (en) | 1999-04-12 | 2005-01-20 | Genentech Inc. | Tumor necrosis factor homologs and nucleic acids encoding the same |
| JP4716603B2 (en) | 2001-05-30 | 2011-07-06 | 日東電工株式会社 | Removable pressure-sensitive adhesive composition and re-peelable pressure-sensitive adhesive sheet |
| WO2003011173A2 (en) * | 2001-07-31 | 2003-02-13 | Tyco Healthcare Group Lp | Bioabsorbable adhesive compunds and compositions |
| JP2017145276A (en) * | 2016-02-15 | 2017-08-24 | 日東電工株式会社 | Polysulfide-based adhesive tape |
| FR3078339B1 (en) * | 2018-02-23 | 2020-01-24 | Bostik Sa | POLYURETHANE COMPOSITION COMPRISING AT LEAST TWO ACRYLIC FUNCTIONS |
| KR102135577B1 (en) * | 2018-12-19 | 2020-07-20 | 전자부품연구원 | UV curing oligomers, manufacturing method thereof, UV curing adhesives and adhesive tape comprising the same |
| EP3738990A1 (en) * | 2019-05-15 | 2020-11-18 | Covestro Deutschland AG | Polyurethane foams having reduced cold-flow effect and method for producing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1462730A (en) * | 1974-11-11 | 1977-01-26 | Prod Res & Chem Corp | Mercaptan-terminated polymers and cured polymers derived there from |
| JPS5736115A (en) * | 1980-08-12 | 1982-02-26 | Mitsui Tekisako Chem Kk | Curing agent composition for polyurethane |
| CA1213396A (en) * | 1982-09-16 | 1986-10-28 | Fernando E. Blanco | .alpha.-.beta. UNSATURATED UREIDE POLYMERS, METHOD FOR MAKING SAME AND CURED ELASTOMERS PRODUCED THEREFROM |
| US4822841A (en) * | 1987-10-06 | 1989-04-18 | Desoto, Inc. | Strong and elastic polyurethane, polyurea, polyarylates and electron beam-cured coatings containing the same |
| US5306764A (en) * | 1992-09-03 | 1994-04-26 | China Technical Consultants Inc. | Water dispersible polyurethane and process for preparation thereof |
| US5426157A (en) * | 1994-03-16 | 1995-06-20 | Air Products And Chemicals, Inc. | Flexibilized polyepoxide resins incorporating poly-N-methylated secondary amines |
-
1996
- 1996-12-06 GB GBGB9625422.2A patent/GB9625422D0/en active Pending
-
1997
- 1997-12-03 ZA ZA9710860A patent/ZA9710860B/en unknown
- 1997-12-04 WO PCT/GB1997/003340 patent/WO1998024826A1/en not_active Application Discontinuation
- 1997-12-04 CA CA002273962A patent/CA2273962A1/en not_active Abandoned
- 1997-12-04 JP JP52535498A patent/JP2001505245A/en active Pending
- 1997-12-04 AU AU52326/98A patent/AU5232698A/en not_active Abandoned
- 1997-12-04 EP EP97947177A patent/EP0942941A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB9625422D0 (en) | 1997-01-22 |
| EP0942941A1 (en) | 1999-09-22 |
| WO1998024826A1 (en) | 1998-06-11 |
| ZA9710860B (en) | 1998-06-08 |
| CA2273962A1 (en) | 1998-06-11 |
| JP2001505245A (en) | 2001-04-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK5 | Application lapsed section 142(2)(e) - patent request and compl. specification not accepted |