CN101541416A - Microcapsules, their use and processes for their manufacture - Google Patents
Microcapsules, their use and processes for their manufacture Download PDFInfo
- Publication number
- CN101541416A CN101541416A CNA2007800425175A CN200780042517A CN101541416A CN 101541416 A CN101541416 A CN 101541416A CN A2007800425175 A CNA2007800425175 A CN A2007800425175A CN 200780042517 A CN200780042517 A CN 200780042517A CN 101541416 A CN101541416 A CN 101541416A
- Authority
- CN
- China
- Prior art keywords
- microcapsules
- weight
- polymer
- wax
- hydrophobic
- 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.)
- Granted
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 202
- 239000000203 mixture Substances 0.000 claims abstract description 112
- 229920000642 polymer Polymers 0.000 claims abstract description 93
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 60
- 239000008199 coating composition Substances 0.000 claims abstract description 21
- 239000004744 fabric Substances 0.000 claims abstract description 21
- 239000004753 textile Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- 239000012782 phase change material Substances 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 22
- 239000002775 capsule Substances 0.000 claims description 19
- -1 diacrylate alkane diol ester Chemical class 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
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- 238000004040 coloring Methods 0.000 claims description 6
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- 239000000700 radioactive tracer Substances 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
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- 230000000994 depressogenic effect Effects 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
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- 230000001376 precipitating effect Effects 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 claims 1
- 239000011162 core material Substances 0.000 description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 238000009987 spinning Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
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- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
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- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 2
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 2
- 239000013529 heat transfer fluid Substances 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- YKNWIILGEFFOPE-UHFFFAOYSA-N pentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCC YKNWIILGEFFOPE-UHFFFAOYSA-N 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
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- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 2
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- 230000003204 osmotic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- FEBNTWHYQKGEIQ-SUKRRCERSA-N valerenic acid Chemical compound C[C@@H]1CC[C@@H](\C=C(/C)C(O)=O)C2=C(C)CC[C@H]12 FEBNTWHYQKGEIQ-SUKRRCERSA-N 0.000 description 1
- FUHPCDQQVWLRRY-UHFFFAOYSA-N valerenic acid Natural products CC1CCC(C=C(/C)C(=O)O)C2C1CC=C2C FUHPCDQQVWLRRY-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
A microcapsule comprising A) a core containing a hydrophobic liquid or wax, B) a polymeric shell comprising a) a polymer formed from a monomer mixture containing: i) 1 to 95% by weight of a hydrophobic mono functional ethylenically unsaturated monomer, ii) 5 to 99% by weight of a polyfunctional ethylenically unsaturated monomer, and iii) 0 to 60% by weight of other mono functional monomer, and b) a further hydrophobic polymer which is insoluble in the hydrophobic liquid or wax. The invention includes a process for the manufacture of particles and the use of particles in articles, such as fabrics, and coating compositions, especially for textiles.
Description
The present invention relates to such microcapsules (microcapsule), these microcapsules have the core that is surrounded by polymer shell, and wherein said core comprises hydrophobic liquid or hydrophobic wax.Described shell is formed by hydrophobicity simple function ethylenically unsaturated monomers, multifunctional ethylenically unsaturated monomers, optional other monomers and other hydrophobic polymer.In the present invention, described core can comprise active component, for example ultraviolet ray (UV) absorbent, fire retardant or phase change material.Desirable is can easily granular composition be incorporated in the multiple product (for example coating, sun-screening agent or multiple textile product).
In many cases, desirable provide such capsule, this capsule comprises the shell that surrounds core material.For example, described core can comprise the active component of slowly-releasing, for example aromatic, pesticide, various medicaments etc.In other cases, for the core material in being encapsulated in described shell, desirable is permanently or at least induces described core to be kept perfectly substantially before being released in suitable triggering agent.In many cases, importantly described core material is not released from described capsule.This comprises that (for example) is used for the ultra-violet absorber of sealing of sun-screening agent and clothes goods.
Another kind of important use comprises can be as the phase-change material through sealing of thermal energy storage product.This series products comprises fabric, and clothes particularly.What have special value is that (for example) comprises the microcapsules phase transformation hydrocarbon material, that combine with fiber spinning dope, and it is extruded subsequently, thereby forms filament, and this filament is collected after solidifying again.Because the spinning technique stoste that need be extruded usually often is higher than under the environment of about 150 ℃ or 200 ℃ through excess temperature, and may in addition up to 350 ℃ or higher, so desirable be that whole basically core material is maintained in the described shell.Fiber such as nylon and polyester fiber can be made by melt-spinning technology, and it is usually directed to high temperature, for example above 300 ℃ or 350 ℃.But, be difficult to find suitable chemical measure (right chemistry) that sealing and durable shell wall are provided, this shell wall be directed in the fiber, but can not be subjected to injurious effects in the spinning technique process.
The multiple method that is used to prepare capsule has been proposed in the document.For example, knownly seal hydrophobic liquid: hydrophobic liquid is distributed in the aqueous medium that comprises melamino-formaldehyde precooling condensate by following process; Reduce pH then, surround described hydrophobic liquid, impervious amino resin shell wall thereby formed.Many such technologies are described among AU-A-27028/88 and the GB-A-1507739 to some extent at GB-A-2073132, and wherein said capsule is preferred for being provided at the ink through sealing that uses in the pressure-sensitive carbonless copy paper.
Yet though be impervious and durable based on the capsule of melamine resin, they often have the lower shortcoming of impermeability at high temperature.In addition, also has the risk that formaldehyde is derived and evolved.
WO-A-9924525 has described such microcapsules, and it contains the lipophilicity latent heat storage material (it undergoes phase transition under 120 ℃ at-20 ℃) as core.Described capsule by 30 to 100wt% (methyl) acrylic acid C1-24 Arrcostab, at the most 80 weight % two or polyfunctional monomer and at the most other monomer polymerizations of 40 weight % form.It is said that described microcapsules are used for the mineral molded products.But described specific polymer composition is unsuitable for being exposed in the high temperature, and this is because described lipophilicity phase-change material can very fast forfeiture.In addition, enough strong without any a kind of specific polymeric material, thus can tolerate high pressure.
US2003118822 has described such microcapsules, and it comprises one or more lipophilic substances as core material, and the polymer latex softgel shell.Described lipophilic substance comprises that average diameter is the solid-state inorganic particle of 45nm to 1000nm.Oil-in-water emulsion polymer reaction takes place by monomer and obtains in described microcapsules, wherein said monomer comprises C1-C24 Arrcostab and the difunctionality or the polyfunctional monomer of 80 weight % at the most of the acrylic or methacrylic acid of 30 to 100 weight %, and these monomers are dissolved in the water slightly, and described in addition monomer also comprises other monomers of 40% at the most.Reportedly, in course of reaction, described inorganic particle has played the effect of protective colloid aspect stable.
WO 2005002719 has described the method that adopts thin (mini) emulsion polymerization to come preparation size and the uniform microcapsules of shape.Described method has adopted by mix monomer, emulsifying agent, super-hydrophobicity reagent, low viscosity hydrophobic material and deionized water and has formed miniemulsion.Reportedly, the existence of super-hydrophobicity reagent can be stablized monomer stoste by osmotic pressure.A large amount of feasible super-hydrophobicity reagent suggestions comprise: C12 to C20 aliphatic hydrocarbon, C12 to C20 aliphatic alcohol, C12 to C20 alkyl acrylate, C12 to C20 alkyl hydrosulfide, organic dyestuff, fluor alkaline, silicon oil compound, natural oil, artificial oil, molecular weight are 1000 to 500,000 oligomer and molecular weight are 1000 to 500,000 polymer.Use a large amount of listed examples to come typical super-hydrophobicity reagent is described, wherein said all super-hydrophobicity reagent are monomeric substance.All super-hydrophobicity reagent of being given an example all are dissolvable in water in the described core material.
Need such microcapsules, it comprises impervious substantially (impervious) shell wall, and this shell wall is at high pressure (surpassing 200psi usually), particularly at high temperature kept hydrophobic material.Desirable provide such microcapsules, these microcapsules are in the harsh conditions that fabric is applied and to can not discharge the hydrophobicity core material after the fabric that applies is handled.In addition, also need provide alternative microcapsules especially, when these microcapsules even be exposed to harsh conditions (for example high temperature in the fibre spinning process) following times and also can not discharge described core material.In addition, also need such microcapsules, these microcapsules just can discharge described core material afterwards up to suitable release triggering agent (for example pH) occurring.And described core material is can not be d/d triggering under the non-existent condition of agent.In addition, also need realize all these targets under the condition of formaldehyde enriched product avoiding using.
WO-A-01/54809 provides such capsule, and it can easily be incorporated in the fiber and can the active core material be incurred loss.Described capsule comprises polymer shell, and this polymer shell is made of grams of monomer blend, and described grams of monomer blend comprises: the A) methacrylic acid of 30 to 90 weight %; B) (methyl) acrylic acid Arrcostab of 10 to 70 weight %, it can form the homopolymers that glass transition temperature surpasses 60 ℃; And C) other ethylenically unsaturated monomers of 0 to 40 weight %.
Though obtaining significant improvement aspect the maintenance of core, still need the microcapsules that provide alternative, when these microcapsules being exposed to extreme exacting terms (comprising high temperature) following time in the fibre spinning process, it can not discharge described core material.Desirable especially is also can achieve the above object when described microcapsules experience high pressure.
In addition, also need such microcapsules, up to existing suitable release to trigger agent (for example pH), it just can discharge described core material.Yet, triggering under the non-existent condition of agent, described core material can not be released.
In addition, also need realize all these targets under the condition of formaldehyde enriched product avoiding using.
WO 2,005 105291 has described and has comprised grains of composition, and wherein said particle comprises the core material that is in the polymer shell, and wherein said core material comprises lyophobic dust.Above-mentioned purpose is by the incompatible realization of particular group that utilizes feature, wherein: described polymer shell must account at least 8% of particle gross weight, and polymer shell is formed by grams of monomer blend, described grams of monomer blend comprises the unsaturated water-soluble monomer of ethylenic of 5 to 90 weight %, the polyfunctional monomer of 5 to 90 weight % and other monomers of 0 to 55 weight %, and wherein the ratio of these monomers is selected, made half-peak (half height) temperature of described particle be at least 350 ℃.
Yet, desirable providing such microcapsules, it particularly can show the maintenance effect to the improvement of core material equally under the high temperature and high pressure condition.One object of the present invention is to have utilized thereby monomer is selected to be achieved widely equally.
Therefore, according to the present invention, we provide microcapsules, and it comprises:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) at least a hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) at least a multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %,
Wherein composition (i), (ii) and (iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
We find to exist other hydrophobic polymer can improve the intensity of microcapsules, and can further trend towards improving the impenetrability of shell, thereby keep described core material better.This hydrophobic polymer can be embedded in the described polymer shell, and/or can be positioned on the inner surface of described shell.Therefore, the described shell internal layer that can comprise polymeric material (forming) outer (can also randomly comprise other hydrophobic polymers) and form by other hydrophobic polymers by monomer mixture.In addition, the sub-fraction hydrophobic polymer can be arranged in whole core material.Usually, described other hydrophobic polymers are less than 5%.Usually, be present in the whole core material without any described hydrophobic polymer basically.Preferably, at least a portion hydrophobic polymer is present on the inner surface of described shell wall.In addition, preferably, hydrophobic polymer to small part applies the inner surface of shell component (being obtained by described monomer mixture).In addition, also find, this hydrophobic polymer can on the inner surface of described shell, form basic adhere to layer, and preferably this is the unbroken layer that covers on the inner surface of described shell.
Hydrophobic liquid is included in 25 ℃ and is liquid lyophobic dust down.
We have found that, compare that microcapsules of the present invention have makes us unexpected stronger capsule shells with the microcapsules that lack hydrophobic polymer.The elasticity of this shell is compressed aspect (for example in the processing of microcapsules is handled or in the application of formation goods) and all is being favourable aspect the processing of any harshness that formed goods are carried out in opposing.
In addition, the present invention includes the method for making microcapsules
This method may further comprise the steps:
1) provide grams of monomer blend, it comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %;
2) described hydrophobic polymer is dissolved in the described grams of monomer blend, thereby forms monomer mixture;
3) described monomer mixture is combined with described hydrophobic liquid or fusion hydrophobic wax, thereby form monomer solution;
4) with described monomer solution in the aqueous phase homogenizing, thereby form emulsion;
5) make described emulsion experience polymeric reaction condition; And
6) make described monomer polymerization be formed at the dispersion of microcapsules of aqueous phase;
Wherein said microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by grams of monomer blend (mixture), and
B) be insoluble to hydrophobic polymer in hydrophobic liquid or the wax.
Though described hydrophobic polymer will be dissolved in the described grams of monomer blend, thereby wherein said blend can combine with hydrophobic liquid or wax phase subsequently and form monomer solution, but along with the carrying out of polymerisation and the polymerization of grams of monomer blend, described hydrophobic liquid or the wax grams of monomer blend that can become exhausts, and described hydrophobic polymer can become insoluble and precipitates.Described hydrophobic polymer can be deposited on the inner surface of described shell, and it can form or be embedded in the polymer shell like this.With regard in being insoluble to hydrophobic liquid or wax, we are meant that described hydrophobic polymer is insoluble in described hydrophobic liquid or the wax substantially under the non-existent substantially condition of monomer that forms shell.Usually, under 25 ℃, described hydrophobic polymer should be insoluble in the pure hydrophobic liquid or wax basically.Under the normal condition, solubility is lower than 2g/100cm
3Hydrophobic liquid or wax.Preferably, solubility is lower than 1g/100cm
3, more preferably be lower than 0.1g/100cm
3
Described method can be used emulsifying systems, for example emulsifying agent, other surfactants and/or polymerization stabilizer.Therefore, in a preferred form of the invention, before the described monomer solution of emulsification, the emulsifiers dissolve that can have high HLB is in water.Alternatively, can make described monomer solution be dissolved with emulsification in the water of polymerization stabilizer therein.Stable polymers can be for example both sexes polymerization stabilizer.Described polymerisation stabilizing agent can be hydrophilic polymer, is preferably water-soluble hydroxyl polymer-containing, for example polyvinyl alcohol or hydroxy ethyl cellulose.Usually, preferably use the polyvinyl alcohol of deriving and obtaining, wherein 85 to 95%, be preferably 88 to 90% ethyl acetate group and be hydrolyzed into vinyl alcohol units by polyvinyl acetate.
Except stable polymers, the stable material of other that can preferably use in the method for the invention comprises ion monomer.Typical cationic monomer comprises dialkyl aminoalkyl acrylate or dialkyl aminoalkyl methacrylate (comprising quaternary ammonium or acid-addition salts) and dialkyl aminoalkyl acrylamide or dialkyl aminoalkyl Methacrylamide (comprising quaternary ammonium or acid-addition salts).Typical anionic monomer comprises ethylenic unsaturated carboxylic acid or sulfonic acid monomer, for example acrylic acid, methacrylic acid, itaconic acid, allyl sulphonic acid, vinyl sulfonic acid, particularly their alkali metal or ammonium salt.Particularly preferred anionic monomer is ethylenic unsaturated sulfonic acid and salt thereof, particularly 2-acrylamido-2-methyl propane sulfonic acid and salt thereof.
Can influence polymerization procedure by making described aqueous monomers solution experience any traditional polymeric reaction condition.Usually, by using suitable initiator compounds to influence polymerisation.Desirable is that this can realize by using redox initiator and/or thermal initiator.Usually, redox initiator comprises reducing agent (for example sodium sulfite, sulfur dioxide) and oxidized compound (for example ammonium persulfate) or suitable per-compound (for example t-butyl hydroperoxide etc.).Can use at the most 1000ppm, be generally 1 to 100ppm, be generally 4 to 50ppm redox system.
Preferably, by using independent thermal initiator or using the thermal initiator that combines with other initiator systems (for example redox initiator) to influence polymerization procedure.Thermal initiator comprises any suitable initiator compounds that can at high temperature discharge free radical; for example azo-compound is (as azodiisobutyronitrile (AZDN), 4; 4 '-azo is two-(4-cyano group valerenic acid (valereic acid)) (ACVA)) or the neopentanoic acid tert-butyl ester (t-butyl pervivalate) or peroxide (as Luperox LP (two bay acyl peroxides) (deriving from Elf Atochem, France)).Usually, the consumption of thermal initiator accounts at the most 50 of monomer weight, 000ppm.But in most of the cases, the consumption of thermal initiator is 5,000 to 15,000ppm, preferably approximately 10,000ppm.Preferably, influence emulsification and polymerisation suitable thermal initiator and monomer before by emulsion being heated to suitable temperature (for example 50 or 60 ℃ or higher).
Desirable is that microcapsules of the present invention can have the weight average particle diameter less than 10 microns.Usually, average grain diameter is often littler, and often less than 4 microns, and in some cases, average grain diameter is 200nm to 4 micron.Preferably, average grain diameter is greater than 1 micron, often is greater than 1 micron to 3 microns at the most, usually greater than about 1 micron to 2 microns at the most.Use the SympatecHELOS particle size analyzer, measure average grain diameter according to the good standard method of discussing in the document.
Usually, account at least 5% of microcapsules gross weight by monomer mixture or the blend polymer shell composition that obtains of deriving.In addition, the amount that hydrophobic polymer exists is generally at least 0.05% of microcapsules weight, and often be at least 0.1%, wherein said hydrophobic polymer preferably be distributed in whole microcapsules polymer shell composition (derive obtain by monomer mixture or blend) in all substances contact.Under the normal condition, the amount that hydrophobic liquid or wax exist is at least 40% of a microcapsules gross weight, is generally at least 45%.Preferably, described microcapsules comprise hydrophobicity oil or the wax form of 45 to 94 weight %, 0.05 hydrophobic polymer (it is insoluble in hydrophobic liquid or the wax) to 10 weight %, and the shell of 5 to 50 weight %, wherein the total amount of each composition is 100%, and all percentage all are based on, and the gross weight of microcapsules obtains.
More preferably, the amount that hydrophobic liquid or wax exist is 60 to 92% of a microcapsules weight, particularly preferably is 70 to 92%, especially 80 to 90%.The amount of described hydrophobic polymer is more preferably 0.1 to 5% of microcapsules weight before being comprised in the microcapsules, and especially 0.1 to 1%.
Other hydrophobic polymers amount in microcapsules can be 0.05 to 20 weight % of the gross weight of hydrophobic liquid or wax and hydrophobic polymer usually.Preferably, this amount is 0.1 to 10% of the weight of hydrophobic liquid or wax, more preferably 0.2 to 2%.
Alternatively, the amount of the polymer shell composition that can obtain according to being derived by monomer mixture or blend is determined the amount of other hydrophobic polymers.Other hydrophobic polymers can exist with effective amount of improving the intensity of shell.Preferably, the amount of other hydrophobic polymers is at least 0.2% of shell component (it is derived by monomer mixture or blend and an obtains) weight in the microcapsules, and is preferably 1 to 40% of shell component weight.Particularly, this amount desirably is 1 to 10% of shell component (it is derived by monomer mixture or blend and obtains) weight, and is in particular 1.5 to 5 weight %.
Preferably, described shell accounts for 8 or 10 to 20% of microcapsules weight, is in particular 10 to 15%.
Consider existing at least a multifunctional ethylenically unsaturated monomers, described microcapsule shell should be crosslinked.Usually, this crosslinked polymer shell that makes is insoluble, but this polymer shell may can adsorb some solvent liquid, and precondition is that described polymer shell does not dissolve.
Preferably, the amount that described hydrophobicity simple function ethylenically unsaturated monomers exists in monomer mixture is 30 to 70% of a monomer mixture weight, particularly 40 to 65%.Preferably, the amount that described multifunctional ethylenically unsaturated monomers exists is 30 to 70% of a monomer mixture weight, particularly 35 to 60%.And other any monofunctional monomers of nonessential existence, but under the condition that other monofunctional monomers exist, its amount is at most 40% of monomer mixture weight, and 5 to 20 weight % more preferably.In some cases, for various compositions, desirable is the monomer that comprises more than a kind of.For example, desirable is to comprise two or more hydrophobicity simple function ethylenically unsaturated monomers and/or two or more multifunctional ethylenically unsaturated monomers and/or two or more other monofunctional monomers.
Described hydrophobicity simple function ethylenically unsaturated monomers can be so any suitable monomers, and this monomer has an ethylene linkage group, and its under 25 ℃ the solubility in water for being lower than 5g/100ml, but be usually less than 2 or 1g/100cm
3Desirable is, described hydrophobic monomer comprises the ester of one or more styrene or cinnamic derivative, single ethylenic unsaturated carboxylic acid.Preferably, described hydrophobic monomer comprises methacrylic acid or acrylic acid Arrcostab.More preferably, the described hydrophobic monomer C 1-12 Arrcostab that is acrylic or methacrylic acid.This type of hydrophobic monomer can comprise that (for example) can form the acrylate or the methacrylate of homopolymers, and the glass transition temperature of wherein said homopolymers (Tg) is at least 60 ℃, is preferably at least 80 ℃.The instantiation of these monomers comprises: styrene, methyl methacrylate, metering system tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.
The glass transition temperature of polymer is at the Encycopedia of ChemicalTechnology, Volume 19, the 4th edition, have been described in detail in the 891st page, when temperature was lower than described glass transition temperature, 40 to 50 carbon atom sections curled and unties all frozen in the transformation campaign of (1) whole molecule and (2) chain.Therefore, be lower than the Tg of polymer, this polymer just can not show flowability or caoutchouc elasticity.Can adopt poor formula scanning calorimeter (DSC) to measure the Tg of polymer.
Described multifunctional ethylenically unsaturated monomers can be any monomer, and induces crosslinked in polymerization process.Preferably two ethylenically unsaturated monomers or multi-ethylenical unsaturated monomer promptly, have two or more ethylenic unsaturated groups.Alternatively, described multifunctional ethylenically unsaturated monomers at least one reactive group that can comprise at least one ethylenic unsaturated group and can react with other functional groups in any monomer component.Preferably, described polyfunctional monomer is water insoluble, and perhaps the solubility in water is low at least, for example is lower than 5g/100cm under 25 ℃
3, but be usually less than 2 or 1g/100cm
3In addition, described polyfunctional monomer should be soluble, perhaps at least with core material in hydrocarbon materials be mixable.Suitable polyfunctional monomer comprises: divinylbenzene, the bisphenol a diacrylate of ethoxylation, propenoxylated neopentylglycol diacrylate, three (2-ethoxy) chlorinated isocyanurates triacrylate, trimethylolpropane triacrylate and alkane omega-diol diacrylate (for example 1,3-butanediol diacrylate, 1,6-hexanediyl ester, but preferred 1, the 4-butanediol diacrylate).
Other monofunctional monomers can be for having any monomer of single polymerizable groups.Be preferably any ethylenically unsaturated monomers.Usually, these other monomer comprises the ester that is selected from following: the formed ester of the material of ethylenic unsaturated carboxylic acid and salt thereof, ethylenic unsaturated carboxylic acid or the formed aminoalkyl ester of its salt, the N-of acrylamide or Methacrylamide (aminoalkyl) derivative or its salt, other water-soluble acrylic monomer (comprising acrylamide), the ester of ethylenic unsaturated carboxylic acid, the water-soluble phenylethene derivative, methacrylic acid or its salt, acrylic acid or its salt, vinyl sulfonic acid or its salt, allyl sulphonic acid or its salt, itaconic acid or its salt, 2-acrylamido-2-methyl propane sulfonic acid or its salt, acrylamide, and vinyl acetate.
With contacted other hydrophobic polymers of polymer shell composition (derive obtain by monomer mixture) should not be crosslinked, but it can be a branching, or other are structurized, and precondition is that this polymer is dissolvable in water in the suitable solvent (for example forming the monomer of this polymer).Preferably, described hydrophobic polymer is linear.
Usually, other hydrophobic polymers are formed by monomer mixture, and described monomer mixture comprises at least a hydrophobicity ethylenically unsaturated monomers.Usually, described monomer mixture comprises so any suitable monomers, and this monomer has an ethylenic unsaturated group, and its solubility in water is lower than 5g/100cm under 25 ℃
3, but be usually less than 2 or 1g/100cm
3Desirable is, described hydrophobic monomer comprises the ester of one or more styrene or styrene derivative, single ethylenic unsaturated carboxylic acid.Preferably, described hydrophobic monomer comprises methacrylic acid or acrylic acid Arrcostab.More preferably, the described hydrophobic monomer C1-12 Arrcostab that is acrylic or methacrylic acid.The representative instance of these monomers comprises: styrene, methyl methacrylate, metering system tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.In addition, for monomer mixture same desirable be to comprise two or more these hydrophobic monomers (for example styrene and methyl methacrylate or other acrylate).
With regard to the formation of polymer shell, if other hydrophobic polymers are structurized, but dissolve in the solvent, then it can prepare by comprising a spot of multifunctional ethylenically unsaturated monomers as hereinbefore defined.Usually, this type of monomer is usually less than 500ppm, and is usually less than 100ppm in being comprised in 1% the amount that is lower than monomer mixture weight, and for example 0.5 to 10ppm.So that the polymer of gained is dissolvable in water definite amount and polymeric reaction condition that mode in the suitable solvent is selected polyfunctional monomer.Preferably, there is not polyfunctional monomer to be comprised in the described monomer mixture basically.Preferably, described hydrophobic polymer is by (iii) forming with identical hydrophobicity simple function ethylenically unsaturated monomers (i) and optional other monofunctional monomers of using in forming the grams of monomer blend of polymer shell.More preferably, described hydrophobic polymer is by composition (i) and (iii) form, but does not have any multifunctional ethylenically unsaturated monomers.Also will be more preferably, under other simple functions or the non-existent condition of polyfunctional monomer, described hydrophobic polymer is to be formed by one or more hydrophobicity simple function ethylenically unsaturated monomers (i) fully.Particularly preferably be, (ii) and under the (iii) non-existent condition, described one or more hydrophobicity simple function ethylenically unsaturated monomers are identical with those simple function ethylenically unsaturated monomers (i) that use in the grams of monomer blend that forms described shell at composition.Particularly preferably be, described hydrophobic polymer is cinnamic polymer, is preferably cinnamic homopolymers.
Described hydrophobic polymer can prepare by conventional technology (for example those of summarizing in the preparationof poly (styrene) in Vogel (third edition, Longmans (1962) publishes)).Its weight average molecular weight is generally at least 200.Its weight average molecular weight can be up to 100 ten thousand, but is no more than 500,000 usually.Usually, weight average molecular weight is 500 to 100,000, is 500 to 50,000 often, is in particular 600 to 5,000.
If necessary, described microcapsules can comprise other compositions.Particularly, desirable usually is to comprise stable polymers.This stable polymers is usually located on the outer surface of microcapsule shell.It is such that stable polymers can define as mentioned.Can be contained in interior and can be positioned at water soluble anion that other stable polymers on the microcapsules outer surface comprise that one or more are mentioned above and the polymer of water-soluble cationic monomer.
Microcapsules of the present invention are included in the core in the polymer shell, and wherein said core comprises hydrophobic liquid or wax, and part or all of (art or all of a core material) of core material.Can comprise other materials in the described core, for example change the additive of the character of hydrophobic liquid or wax.The other materials that exists in the described core material can be for hydrophilic, and be suspended in hydrophobic liquid or the wax, for example is inorganic salt hydrate.Alternatively, but described other additives can for mixing in or be dissolved in polymeric additive in described hydrophobic liquid or the wax.Usually, under described these other materials were comprised in situation in the described core, what these materials accounted for whole core material weight was no more than 10%.Usually, described other materials account for described core less than 5%, often be lower than 2%, for example 0.5 to 1.5%.Therefore, described core comprises at least 90% hydrophobic liquid or wax usually.Preferably, the hydrophobic liquid that is comprised in the described core or the amount of wax are higher than 95 weight %, more preferably are higher than 98%, and particularly 98.5 to 99.5%.
Described core material can comprise active component, and it is selected from UV absorbent, UV reflective agent, fire retardant, reactive dye tracer material, pigment, dyestuff, colouring agent, enzyme, washing assisant and spices.Usually, with regard to active component to be discharged, it is also nonessential in content of the present invention.For example, under the not d/d situation of pigment importantly, the pigment through sealing can be used for articles colored, for example pottery.Colouring agent be can also use, that is, dyestuff and pigment in many other application (for example at the preparation textile product) are used for through sealing.Therefore, the microcapsules that comprise pigment or dyestuff can be incorporated into or adhere on fiber or the textile fabrics.Color can be maintained by microcapsules, and does not have color by the risk of elimination (leach).Alternatively, the colouring agent through sealing can be used for packaging material, for example packaging for foodstuff.Therefore, pigment that can be by will be through sealing or dyestuff are included in and prepare masking paper or the plate that uses in the paper technology in packagings for foodstuff.Described in WO-A-00/61689, colouring agent can be C.I. pigment violet 19, C.I. pigment blue 15, C.I. pigment blue 60, C.I. paratonere 177 usually.
Alternatively, as US-A-5,382,433, US-A-5,320,835 or WO-A-98/50002 described in, the application of the pigment through sealing comprises cosmetics.Usually, described colouring agent can be mica, talcum, D﹠amp; The red 7 calcium color lakes of C, D﹠amp; The red 6 barium color lakes of C, iron oxide red, iron oxide yellow, D﹠amp; The red 6 barium color lakes of C, Timiron MP-1001, Mineral (carnation is white), Helindon Pink, Red 218, Japan Blue No.1Al color lake, the odenite of handling through polysiloxanes.
In other aspects of the present invention, we provide such microcapsules, and up to suitable trigger mechanism takes place, described microcapsules just can discharge core material and/or active component.In this case, described triggering agent is that pH is increased to greater than pH10.
Thus, this alkalescence can discharge microcapsules and can be used for wherein adopting high pH to be used as in the various application of releasing mechanism.Described active component can also be for waiting to be discharged into the material in the aqueous environments.Described aqueous environments can be the recirculated water of operating usually, for example cooling water system under alkali condition.The suitable active component that is discharged in the submarine system comprises scale preventative (antiscalent), corrosion inhibitor, antimicrobial, dispersant and antioxidant.
Usually, hydrophobic liquid that is comprised in the described core or wax can be organic material.For example, described hydrophobic liquid can be oil or molten wax.Preferably, described hydrophobic liquid or wax are non-polymer material.More preferably, described hydrophobic liquid or wax are hydrocarbon.Described oil or wax can comprise active material, for example are dispersed or dissolved in wherein UV absorbent, UV reflective agent or fire retardant.Therefore, described core material can perhaps alternatively, can comprise the dispersion that is scattered in the solid-state active material in the continuous core medium that spreads all over hydrophobic liquid or wax for uniformly.When described core material comprised phase-change material, then this phase-change material was oil or the wax that is in a liquid state under-30 ℃ to 150 ℃ usually.
The representative instance that is applicable to fire retardant of the present invention comprises: as bromo benzoic ether or the salt described at US-A-5728760, and the Firemaster 836 that in US-A-3912792, provides or salt, thiophosphate or salt or D2EHDTPA chlorine.
Suitable UV absorbers of the present invention comprises naphthalene-dimethyl malenate that (for example) mentioned in US-A-5508025, perhaps as composition required for protection among the US-A-5498345 (mixture that comprises BTA and 2-Viosorb 110).
When described core material is phase change material, its can for (for example) at-30 ℃ of any known hydrocarbons to 150 ℃ of following fusions.Common described material is wax or oil, and preferably its fusing point is 20 to 80 ℃, normal about 40 ℃.Desirable is that described phase change material can be C
8-40Alkane perhaps can be cycloalkane.Suitable phase-change material comprises all isomers of alkane or cycloalkane.In addition, desirable is the mixture that can also use these alkane or cycloalkane.Described phase-change material can be selected from any compound in n-octadecane, n-tetradecane, n-pentadecane, n-heptadecane, n-octadecane, NSC 77136, n-docosane, n-tricosane, pentacosane, n-hexacosane, cyclohexane, cyclooctane, cyclodecane and their isomers and/or their mixture for (for example).
In a preferred form of the present invention, described core (for example at least 90%) basically is made of hydrophobic liquid or wax, and this hydrophobic liquid or wax are non-polymer material, and for example oil or wax are in particular phase-change material.Though preferred hydrophobic liquid or wax comprise than the small amount of polymer additive also within the scope of the invention in phase transformation non-polymer material scope for being the phase-change material of non-polymer basically.Usually, its amount be lower than described core gross weight 10%, often be lower than 5 weight %, for example 0.5 to 1.5 or 2 weight %.Desirable especially polymeric additive is the material that can change the character of phase-change material.For example, known, phase-change material may obviously be different from it by the temperature that absorbs heat fusion takes place and lose the temperature that heat solidifies.Therefore, desirable especially polymeric additive is for can make melt temperature and the more approaching material of solidification temperature.This change in the minimum aspect the fusing point/freezing point of phase-change material is in multiple domestic. applications or may all be important for clothing.
Alternatively, in the described core comprise phase-change material and can be other materials except hydrocarbon.
Described phase-change material can be for absorbing and discharge the inorganic substances of potential heat in liquefaction and the transition process mutually of solidifying.These inorganic substances can be for discharging or absorb the compound of heat in dissolving/crystalline transition process.Suitable inorganic compound comprises (for example) sodium sulphate decahydrate or calcium chloride hexahydrate.Therefore, any inorganic substances of heat energy can be for taking place to absorb or discharge in the transforming process in described inorganic phase-changing material under specified temp.Described inorganic phase-changing material can be for being dispersed in the crystal that spreads all over the fine dispersion in the core matrix, and wherein said core matrix comprises hydrophobic liquid or wax.In one form, described inorganic phase-changing material is scattered in and spreads all in the solid-state lyophobic dust (for example wax).
Alternatively, the hydrophobic liquid or the cerul that are comprised in the described core originally remain liquid state, and comprise and be scattered in the crystal that spreads all over the inorganic phase-changing material in the liquid.Preferably, described hydrophobic liquid is a hydrocarbon.During phase transformation, described crystal becomes and is dispersed in the drop that spreads all in the liquid.Maybe advantageously in hydrophobic liquid, comprise suitable surfactant (for example water-in-oil emulsifier), thereby the drop that prevents the dispersion of liquid merges.Preferably, described inorganic phase-changing material is scattered in the matrix that spreads all over hydrocarbon phase-change material (it is wax or oil).In this embodiment preferred, described hydrocarbon and inorganic material can absorb heat or release heat.Alternatively, described hydrocarbon mutually can be for being not must be the carrier oil of phase-change material.In this case, described carrier oil can be processing aid.
When described hydrophobic liquid or wax are when being used for the phase-change material of thermmal storage, it can unite use with suitable nucleator, thereby prevented cold, for example described in the U.S.5456852, perhaps for example described in International Patent Application PCT/EP 2006/066934 (international file number No 22375) (till the submission date of the present invention, this patent documentation was not open).
Microcapsules of the present invention can be used in the multiple application, comprise textile (for example in corpus fibrosum, perhaps alternatively being coated on fiber or the textile), automobile application (comprising the circulating cooling fluid or the cooling agent that are used for indoor design), building industry (for example passive type or active ventilating system) or heat transfer fluid (capsule in the modification heat transfer fluid).Microcapsules of the present invention can also be incorporated in any suitable goods, for example fiber, textile product, pottery, coating etc.Therefore, in other aspects of the present invention, we provide the goods that comprise microcapsules.Thus, according to the present invention, can provide such goods, it comprises fire retardant, UV absorbent, reactive dye tracer material or phase-change material through sealing.Under the situation of the fire retardant through sealing, desirable is that fire retardant is kept in any procedure of processing (for example fiber formation).
Therefore, in other aspects of the present invention, we provide the goods that comprise microcapsules, and wherein each microcapsules all comprises:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
Described goods can be the mineral goods of textile product or paper or plate packaging material or moulding.In addition, can provide such goods, it comprises fire retardant, UV absorbent, reactive dye tracer material or phase-change material through sealing.Under the situation of the fire retardant through sealing, desirable is such fire retardant, and in relating to (for example) 150 ℃ any procedure of processing (for example fiber formation) to about 350 ℃ temperature, described fire retardant is kept; And be exposed to when surpassing about 400 or 500 ℃ too high temperature, described fire retardant is released subsequently.In embodiment preferred of the present invention, described microcapsules comprise such core material, and it had not only comprised phase-change material (it is wax or oil), but also has comprised the fire retardant matter that is dispersed or dissolved in wherein.Therefore, in a kind of preferred form of the present invention, exist fire retardant (if it is released under too high temperature) can suppress or reduce the risk that burning takes place phase-change material in the capsule.
In other aspects of the present invention, we provide the coating composition that comprises microcapsules, and wherein each microcapsules all comprises:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
Described coating composition can be used in any suitable substrate, for example paper, wood, metal, plastics, pottery etc.Preferably, described composition is used to apply textile, and can be (for example) polyurethane or polyacrylic acid textile coating composition.Usually, coating composition of the present invention is by combining prepares with traditional coating composition (for example acrylic compounds or polyurethane textile product coating composition) (it comprises the traditional components of using with conventional amounts) with granular composition of the present invention.Described coating composition is the desirable formulation for preparing by the following method, and described method is that the dry state graininess microcapsules of the present invention with 30 to 90 weight % mix with traditional polyurethane or the polyacrylic acid textile coating composition of 10 to 70 weight %.Preferably, described coating formulation comprises the dry state microcapsules of 60 to 80 weight % and traditional polyurethane or the polyacrylic textile coating composition of 20 to 40 weight %.Can prepare particularly preferred coating formulation, it comprises 70% dry state capsule and 30% polyurethane or polyacrylic textile coating.
We also provide the method for coated fabric, and this method may further comprise the steps:
1) provide the textile coating composition,
2) described coating composition is applied on the surface of fabric, and
3) make described coating drying, thereby obtain fabric through applying,
Wherein said coating composition comprises granular composition, and said composition comprises microcapsules, and described microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
Usually, preparation is including (for example) the composition of dry state capsule of the present invention as indicated above and traditional textile coating, and wherein need described composition is stirred the sufficiently long time (for example 10 minutes), spread all in the coating composition thereby make described microcapsules be distributed in, at once said composition is coated on the fabric basically then.Described textile can be Woven fabric, perhaps alternatively, can be supatex fabric.Usually, the coating that is applied on the fabric is 50g/m at least
2, and can be for reaching 180g/m
2Usually, 80 to 120g/m
2(particularly about 100g/m
2) coating weight often be desirable.Usually, in laboratory, can adopt the many different technique known of using in the industry to apply described coating.Can use k rod (k-bar) to apply coating.Then, can be at the middle dry fabric of suitable drying device (for example under 100 ℃ to 200 ℃ temperature, be retained to many 10 minutes, thereby make the dry and curing of coating) through applying.Usually, the pressure that adopt to surpass 200psi (for example 250psi) rolls the fabric through applying.
In order to prove in fabric through applying, described active material has been maintained in the capsule, microcapsules can be incorporated in the textile coating formulation, be coated on the fabric, re-using the pressure that surpasses 200psi (for example 250psi) rolls, then experience again on the melt temperature of described wax and under heating and cooling (thermal cycle), for example, with regard to octadecane above-mentioned circulation can 10 ℃ to 60 ℃ the circulation 50 times.Then, use hydrocarbon cosolvent (for example hexane) washs the fabric through applying, and use difference formula scanning calorimeter is measured the enthalpy through the microcapsules of coating.With before the enthalpy that records and experience calendering and the continuous heating and cooling, initially the enthalpy of the capsule through applying compares.
Other goods according to the present invention comprise fiber and by described fibroplastic fabric, wherein said fiber comprises microcapsules, and these microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
In this one side of the present invention, described fiber comprises the microcapsules in the matrix that is distributed in fiber.Usually, the diameter of microcapsules should be less than half of fiber cross section diameter.Usually, if described microcapsules are a lot of greatly, then have such risk, that is, the existence of this large-scale capsule may cause fiber easily in the fracture of the position of microcapsules in the fiber.Usually, the particle diameter of described microcapsules is less than 30% of fibre diameter, preferably less than 10% of fibre diameter.
The fiber that comprises microcapsules of the present invention can prepare by described microcapsules are incorporated in the spinning solution.Can carry out spinning to spinning solution according to the spining technology (for example described in the EP-A-269393) of standard then.Usually, spinning solution is entered in the atmosphere of heating by nozzle, under such condition, the stoste through extruding is solidified, thereby forms fiber, collects this fiber then.
The microcapsules that comprised in the present composition are applicable to and are incorporated in any fiber, for example acrylic resin, polyester, nylon, polypropylene.
According to this aspect of the invention, we provide the method that forms the fiber that comprises microcapsules, and this method may further comprise the steps:
1) described microcapsules is combined with the liquid spinning solution;
2) extrude described spinning solution;
3) make the stoste of extruding be at least 150 ℃ atmosphere by temperature; And
4) collect formed fiber;
Wherein said microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %; And
B) be insoluble to other hydrophobic polymers in hydrophobic liquid or the wax.
Desirable is, described polymer microcapsule is impermeable fully for hydrophobic liquid or the wax that described core comprised, and in the forming process of fiber, hot conditions can not cause hydrophobic liquid or wax that any tangible loss is arranged like this.We against expectation find, even be exposed to when surpassing 150 ℃ spinning temperature at polymer microcapsule, described core material still can keep most of or all core material.Find that also when spinning temperature was higher, when for example surpassing 200 ℃, situation also was like this.Therefore, we find that when making microcapsules through spinning technique, it can keep at least 98 weight %, is preferably hydrophobic liquid or the wax of 99 weight %.
The application of particular importance of the present invention relates to capsule is incorporated in the fiber, and wherein said microcapsules comprise phase change material as core material.Described polymer shell can make described microcapsules be introduced in the fiber to the durability and the impenetrability of phase-change material, and does not have any tangible loss of described phase-change material.Then, will contain phase-change material through the dipping fiber inweave in the textile product.Textile product can comprise multiple clothes and other fabrics.
Below be embodiment.
Embodiment
The preparation method
Poly-(styrene) solution is as hydrophobic polymer.
By preparing poly-(styrene) solution in the styrene monomer that 10g poly-(styrene) (derive from Dajac: molecular weight is～1000) is dissolved in 90g.This mixture is stirred, dissolve fully up to polymer.
Embodiment 1:
Hydrophobicity oil (polymer that comprises adding) microcapsules
Prepare oil phase by mixing 4.94g styrene, 2.3g methacrylic acid, poly-(styrene) solution of 4.76g (as above preparation) and 7.89g diacrylate butanediol ester.The Alperox LP (deriving from ELF Atochem) that adds 1.4g adds the hydrophobic liquid of 152g then.
(50% activity derives from Lubrizol, France) prepares water by mixing poly-(vinyl alcohol) (deriving from the GohsenolGH20R of Nippon Gohseii) of 5.4g, the water of 169g and the Sodium AMPS of 0.64g.
Water and oil phase are warmed to 40 ℃, and use Silverson L4R laboratory homogenizer they emulsification together.After 10 minutes, obtain stable emulsion.
Pour the emulsion of gained into equipment and be used for the reaction vessel of polymerisation, and be placed in 75 ℃ the water-bath.This temperature was kept 3 hours, and add water-based ammonium persulfate solution (0.6g is in 10g water).Polymeric material is heated to 80 ℃, and under this temperature, stirred 2 hours, be cooled to room temperature then, thereby obtain end-product.This end-product is the dispersion by the microcapsules with wax core and polymer shell in the water, and the average grain diameter of wherein said microcapsules is 3 microns.
Embodiment 2 (Comparative Examples): hydrophobicity oil (polymer that does not comprise adding) microcapsules
Prepare oil phase by mixing 4.94g styrene, 2.3g methacrylic acid and 7.89g diacrylate butanediol ester.The Alperox LP (deriving from ELF Atochem) that adds 1.4g adds the hydrophobic liquid of 152g then.
(50% activity derives from Lubrizol, France) prepares water by mixing poly-(vinyl alcohol) (deriving from the GohsenolGH20R of Nippon Gohseii) of 5.4g, the water of 169g and the Sodium AMPS of 0.64g.
Water and oil phase are warmed to 40 ℃, and use Silverson L4R laboratory homogenizer they emulsification together.After 10 minutes, obtain stable emulsion.
Pour the emulsion of gained into equipment and be used for the reaction vessel of polymerisation, and be placed in 75 ℃ the water-bath.This temperature was kept 3 hours, and add water-based ammonium persulfate solution (0.6g is in 10g water).Polymeric material is heated to 80 ℃, and under this temperature, stirred 2 hours, be cooled to room temperature then, thereby obtain end-product.This end-product is the dispersion of the microcapsules with wax core and polymer shell in the water, and the average grain diameter of wherein said microcapsules is 2.5 microns.
Analyze
Particle diameter
The Sympatec Analyser (deriving from Sympatec GmbH) that use is provided with Quixcel decentralized system and R4 lens carries out granularmetric analysis.
Thermogravimetric analysis (TGA)
The serviceability temperature scope is that 110 ℃ to 500 ℃ Perkin Elmer TGA carries out thermogravimetric analysis.
The result
1: the effect that adds insoluble polymer
Table 1
1Half-peak: it is the half-peak height place of attenuation curve.
2In the mass loss under 300 ℃: it is in the amount (representing with percentile form) that derives from the material unaccounted-for (MUF) of sample between the initial conditions, 110 ℃ and 300 ℃.
3Gross weight (monomer adds hydrophobic polymer) based on polymer shell.
By the half-peak value in the contrast table---the half-peak value is high more, then microcapsules are high more to the resistance of break (this is because the formation of interior pressure), that is, shell wall is firm more, introduces the effect of hydrocarbon insoluble polymer as can be seen.
2: the effect that adds soluble polymer
Table 2
aPolymer is poly-(the methacrylic acid stearyl-copolymerization-Bisomer mpeg 3 50A) of the 90wt that forms 40% solution in hydrocarbon: 10wt.
By The above results as can be known, compare, comprise character (measuring) deterioration that the hydrocarbon soluble polymer can cause microcapsules by effective mass loss with the useful effect of introducing the hydrocarbon insoluble polymer.
Claims (27)
1. microcapsules, it comprises:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %,
Wherein composition (i) (ii) and (iii) adds up to 100%; And
B) be insoluble to other hydrophobic polymers in described hydrophobic liquid or the wax.
2. according to the microcapsules of claim 1, it comprises:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) 0.05 to 10 weight % be insoluble to hydrophobic polymer in described hydrophobicity oil or the wax, and
Bb) polymer that forms by described monomer mixture of 5 to 50 weight %,
Wherein said composition adds up to 100%.
3. according to the microcapsules of claim 1 or claim 2, wherein said simple function ethylenically unsaturated monomers is selected from: acrylic acid C
1To C
12Arrcostab, and the C of methacrylic acid
1To C
12Arrcostab.
4. according to the microcapsules of above-mentioned any claim, wherein said multifunctional ethylenically unsaturated monomers is a diacrylate alkane diol ester, is preferably diacrylate 1, the 4-butanediol ester.
5. according to the microcapsules of above-mentioned any claim, the insoluble hydrophobic polymer of wherein said oil is cinnamic polymer, is preferably cinnamic homopolymers.
6. according to the microcapsules of above-mentioned any claim, wherein stable polymers is positioned on the outer surface of described capsule shells, and wherein said stable polymers is water-soluble hydroxyl polymer-containing.
7. according to the microcapsules of claim 6, wherein said stable polymers is a polyvinyl alcohol.
8. according to the microcapsules of above-mentioned any claim, wherein said hydrophobic liquid or wax are preferably hydrocarbon.
9. according to the microcapsules of above-mentioned any claim, wherein said hydrophobic liquid or wax are that melting temperature is-30 ℃ to 150 ℃ oil or a wax.
10. according to the microcapsules of above-mentioned any claim, wherein said core comprises active component, and this active component is selected from: UV absorbent, UV reflective agent, fire retardant, reactive dye tracer material, pigment, dyestuff, colouring agent, scale preventative, corrosion inhibitor, antioxidant, pour-point depressant, wax precipitating inhibitor, dispersant, antimicrobial, enzyme, washing assisant, spices, phase-change material and silicone oil.
11., wherein be insoluble to 0.05 weight % to the 20 weight % that amount that the described hydrophobic polymer in described hydrophobic liquid or the wax exists accounts for the gross weight of described hydrophobic liquid or wax and hydrophobic polymer in described microcapsules according to the microcapsules of above-mentioned any claim.
12., wherein be insoluble to the inner surface that described hydrophobic polymer in described hydrophobic liquid or the wax applies the described polymer shell composition that is formed by described monomer mixture at least in part according to the microcapsules of above-mentioned any claim.
13. according to the microcapsules of above-mentioned any claim, the described hydrophobic polymer that wherein is insoluble in described hydrophobic liquid or the wax forms adhesion layer on the inner surface of the described polymer shell composition that is formed by described monomer mixture.
14. according to the microcapsules of claim 13, wherein said hydrophobic polymer forms complete layer on the inner surface of the described polymer shell composition that is formed by described monomer mixture.
15. according to the microcapsules of above-mentioned any claim, wherein said shell accounts for 10 weight % to 20 weight % of described microcapsules gross weight.
16. according to the microcapsules of above-mentioned any claim, wherein weight average particle diameter is greater than 1 micron and 4 microns at the most.
17. make the method for microcapsules, these microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, and
B) be insoluble to hydrophobic polymer in described hydrophobic liquid or the wax;
This method may further comprise the steps:
1) provide grams of monomer blend, this grams of monomer blend comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %,
Wherein composition (i), (ii) and (iii) add up to 100%;
2) described hydrophobic polymer is dissolved in the described grams of monomer blend, thereby forms monomer mixture;
3) hydrophobic wax of described monomer mixture with described hydrophobic liquid or fusion combined, thereby form monomer solution;
4) with described monomer in the aqueous phase homogenizing, thereby form emulsion;
5) make described emulsion experience polymeric reaction condition; And
6) make described monomer polymerization be dispersion at the microcapsules of aqueous phase.
18. according to the method for claim 17, it is included in defined any feature among any of claim 2 to 16.
19., wherein make described monomer experience Raolical polymerizable according to the method for claim 17 or claim 18.
20. the method according among any of claim 17 to 19 wherein combines thermal initiator with described monomer, and described emulsion is heated at least 50 ℃ temperature keeps time enough to implement polymerisation.
21. according to the method among any of claim 17 to 20, wherein stable polymers is comprised in described aqueous phase.
22. according to the method among any of claim 17 to 21, wherein said stable polymers is water-soluble hydroxyl polymer-containing, is preferably polyvinyl alcohol.
23. according to the method for claim 22, wherein described emulsion was kept under 50 ℃ to 80 ℃ temperature 90 minutes to 150 minutes, under at least 80 ℃ temperature, kept at least 30 minutes then.
24. goods that comprise microcapsules, wherein each microcapsules all comprises:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %,
Wherein composition (i) (ii) and (iii) adds up to 100%; And
B) be insoluble to other hydrophobic polymers in described hydrophobic liquid or the wax.
25. a coating composition that comprises microcapsules, wherein each microcapsules all comprises:
A) contain the core of hydrophobic liquid or wax;
B) comprise the polymer shell of monomer mixture, this polymer shell comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %,
Wherein composition (i) (ii) and (iii) adds up to 100%; And
B) be insoluble to other hydrophobic polymers in described hydrophobic liquid or the wax.
26. the method for a coated fabric, this method may further comprise the steps:
1) provide the textile coating composition,
2) described coating composition is applied on the surface of described fabric, and
3) make described coating drying, thereby obtain fabric through applying,
Wherein said coating composition comprises microcapsules, and these microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %;
Wherein composition (i) (ii) and (iii) adds up to 100%; And
B) be insoluble to other hydrophobic polymers in described hydrophobic liquid or the wax.
27. comprise the fiber of microcapsules, these microcapsules comprise:
A) contain the core of hydrophobic liquid or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, described monomer mixture comprises:
I) the hydrophobicity simple function ethylenically unsaturated monomers of 1 to 95 weight %,
The ii) multifunctional ethylenically unsaturated monomers of 5 to 99 weight %, and
Iii) other monofunctional monomers of 0 to 60 weight %;
Wherein composition (i) (ii) and (iii) adds up to 100%; And
B) be insoluble to other hydrophobic polymers in described hydrophobic liquid or the wax.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0622894.4 | 2006-11-17 | ||
| GB0622894A GB0622894D0 (en) | 2006-11-17 | 2006-11-17 | Microcapsules, their use and processes for their manufacture |
| GB0709421.2 | 2007-05-17 | ||
| GB0709421A GB0709421D0 (en) | 2007-05-17 | 2007-05-17 | Microcapsules, their use and processes for their manufacture |
| PCT/EP2007/061933 WO2008058868A1 (en) | 2006-11-17 | 2007-11-06 | Microcapsules, their use and processes for their manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101541416A true CN101541416A (en) | 2009-09-23 |
| CN101541416B CN101541416B (en) | 2012-11-14 |
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|---|---|---|---|
| CN2007800425175A Expired - Fee Related CN101541416B (en) | 2006-11-17 | 2007-11-06 | Microcapsules, their use and processes for their manufacture |
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| GB (1) | GB0622894D0 (en) |
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| CN105078787A (en) * | 2015-05-04 | 2015-11-25 | 上海应用技术学院 | Styrene crosslinking polymer particle loaded with liposoluble pigment and preparation method of styrene crosslinking polymer particle |
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| CN107385933A (en) * | 2017-06-29 | 2017-11-24 | 北京宇田相变储能科技有限公司 | A kind of washable one-way wet-guide composite functional fabric of free-floride |
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|---|---|---|---|---|
| US6753083B2 (en) * | 2000-11-06 | 2004-06-22 | Ciba Specialty Chemicals Water Treatments Ltd. | Particles |
| EP1443058A1 (en) * | 2003-01-29 | 2004-08-04 | Firmenich Sa | Polymeric particles and fragrance delivery systems |
| TWI299101B (en) * | 2003-01-30 | 2008-07-21 | Sipix Imaging Inc | High performance capsules for electrophoretic displays |
| JP4189960B2 (en) * | 2003-05-28 | 2008-12-03 | 日東電工株式会社 | Hydrophilized porous membrane and method for producing the same |
| GB0409570D0 (en) * | 2004-04-29 | 2004-06-02 | Ciba Spec Chem Water Treat Ltd | Particulate compositions and their manufacture |
-
2006
- 2006-11-17 GB GB0622894A patent/GB0622894D0/en not_active Ceased
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2007
- 2007-11-06 CN CN2007800425175A patent/CN101541416B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101541416B (en) | 2012-11-14 |
| GB0622894D0 (en) | 2006-12-27 |
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