CN101541416B - Microcapsules, their use and processes for their manufacture - Google Patents
Microcapsules, their use and processes for their manufacture Download PDFInfo
- Publication number
- CN101541416B CN101541416B CN2007800425175A CN200780042517A CN101541416B CN 101541416 B CN101541416 B CN 101541416B CN 2007800425175 A CN2007800425175 A CN 2007800425175A CN 200780042517 A CN200780042517 A CN 200780042517A CN 101541416 B CN101541416 B CN 101541416B
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- Prior art keywords
- microcapsules
- weight
- wax
- polymer
- hydrophobicity
- Prior art date
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 138
- 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
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- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 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
- 229920002223 polystyrene 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 easily granular composition to 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 said shell, desirable is permanently or at least induces described core to be kept perfectly basically before being released out in the suitable trigger agent.In many cases, importantly described core material is not released out 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 maybe 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 through melt-spinning technology, and it is usually directed to high temperature, for example above 300 ℃ or 350 ℃.But, be difficult to find suitable chemical (right chemistry) that sealing and durable shell wall are provided, this shell wall be directed in the fiber, but in the spinning technique process, can not receive injurious effects.
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 through following process; Reduce pH then, surround said hydrophobic liquid, impervious amino resin shell wall thereby formed.Many such technologies are described among AU-A-27028/88 and the GB-A-1507739 at GB-A-2073132 to some extent, 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 inappropriate for and is exposed in the high temperature, and this is because described lipophilicity phase-change material can be lost very soon.In addition, have no a kind of specific polymeric material enough strong, thereby 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.It is said that in course of reaction, described inorganic particle has played the effect of protective colloid aspect stable.
WO 2,005 002719 has described the method that adopts thin (mini) emulsion polymerization to come preparation size and the uniform microcapsules of shape.Described method has adopted through mix monomer, emulsifying agent, super-hydrophobicity reagent, low viscosity hydrophobic property material and deionized water and has formed miniemulsion.It is said that the existence of super-hydrophobicity reagent can be stablized monomer stoste through 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 basically (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 after handling through the fabric that applies, can not discharge the hydrophobicity core material.In addition, also especially alternative microcapsules need be provided, when these microcapsules even be exposed to harsh conditions (the 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 under the condition that avoids the use of the formaldehyde enriched product, realize all these targets.
WO-A-01/54809 provides such capsule, and it can easily be incorporated in the fiber and can the active core material incurred loss.Described capsule comprises polymer shell, and this polymer shell is made up 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 having obtained significant improvement aspect the maintenance of core, still alternative microcapsules need be provided, when in the fibre spinning process, these microcapsules being exposed to extreme exacting terms (comprising high temperature) following time, it can not discharge described core material.Desirable especially is when described microcapsules experience high pressure, also can achieve the above object.
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 under the condition that avoids the use of the formaldehyde enriched product, realize all these targets.
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 through the incompatible realization of particular group that utilizes characteristic; 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 said 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 said 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, have no described hydrophobic polymer to be present in the whole core material basically.Preferably, at least a portion hydrophobic polymer is present on the inner surface of said shell wall.In addition, preferably, hydrophobic polymer at least partly 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 said shell, form basic adhere to layer, and preferably this is the unbroken layer that covers on the inner surface of said 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 to the processed of microcapsules or in the formation Product Application) 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) grams of monomer blend is provided, 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 to form monomer solution subsequently with hydrophobic liquid or wax phase; 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 said 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 basically under the non-existent basically 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, other stable materials that can preferably use in the method for the invention comprise ion monomer.Typical cationic monomer comprises dialkyl aminoalkyl acrylic acid ester 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.Special preferred anionic surfactants monomer is ethylenic unsaturated sulfonic acid and salt thereof, particularly 2-acrylamido-2-methyl propane sulfonic acid and salt thereof.
Can influence polymerization procedure through making described aqueous monomers solution experience any traditional polymeric reaction condition.Usually, through using suitable initiator compounds to influence polymerisation.Desirable is that this can realize through 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, through using independent thermal initiator, perhaps 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 (like azodiisobutyronitrile (AZDN), 4; 4 '-azo is two-(4-cyanic acid valerenic acid (valereic acid)) (ACVA)) or the neopentanoic acid tert-butyl ester (t-butyl pervivalate) or peroxide (like 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 through 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 materials 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%.
The amount of the polymer shell composition that alternatively, can obtain according to being derived by monomer mixture or blend is confirmed 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 possibly 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 kinds or more kinds of hydrophobicity simple function ethylenically unsaturated monomers and/or two kinds or more kinds of multifunctional ethylenically unsaturated monomers and/or two kinds or more kinds of 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, described hydrophobic monomer is the C1-12 Arrcostab of acrylic or methacrylic acid.This type of hydrophobic monomer can comprise that (for example) can form the acrylic acid ester 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; Specify in the 891st page, when temperature was lower than described glass transition temperature, 40 to 50 carbon atom sections curled and unties all and freezed 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 in polymerization process, induces crosslinked.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 under 25 ℃, is lower than 5g/100cm
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, described hydrophobic monomer is the C1-12 Arrcostab of 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 kinds or more kinds of these hydrophobic monomers (for example styrene and methyl methacrylate or other acrylic acid ester).
With regard to the formation of polymer shell, if other hydrophobic polymers are structurized, but dissolve in the solvent, then it can a spot ofly prepare like the defined multifunctional ethylenically unsaturated monomers of preceding text through comprising.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 in forming the grams of monomer blend of polymer shell, using.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 in the grams of monomer blend that forms said shell, use at composition.Particularly preferably be, described hydrophobic polymer is cinnamic polymer, is preferably cinnamic homopolymers.
Described hydrophobic polymer can prepare through conventional technology (those of for example in the preparationof poly (styrene) in Vogel (third edition, Longmans (1962) publishes), summarizing).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.Stable polymers can be as the preceding text definition.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 said 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 the polymeric additive in described hydrophobic liquid or the wax.Usually, be comprised under the situation in the described core at described these other materials, what these materials accounted for whole core material weight is no more than 10%.Usually, described other materials account for said 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, can be used for through the pigment of sealing articles colored, pottery for example.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, can the microcapsules that comprise pigment or dyestuff be incorporated into or adhere on fiber or the textile fabrics.Color can be maintained through microcapsules, and does not have color by the risk of elimination (leach).Alternatively, can be with being used for packaging material through the colouring agent of sealing, for example packaging for foodstuff.Therefore, can be prepared in masking paper or the plate that uses in the packaging for foodstuff in the paper technology through being included in through the pigment sealed or dyestuff.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, like US-A-5,382,433, US-A-5,320,835 or WO-A-98/50002 described in, comprise cosmetics through the application of the pigment sealed.Usually, the odenite that can handle for mica, talcum, the red 7 calcium color lakes of D&C, the red 6 barium color lakes of D&C, iron oxide red, iron oxide yellow, the red 6 barium color lakes of D&C, Timiron MP-1001, Mineral (carnation is white), Helindon Pink, Red 218, Japan Blue No.1 Al color lake, through polysiloxanes of described colouring agent.
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 under alkali condition, operating usually, for example cooling water system.The suitable activity component that is discharged in the submarine system comprises scale preventative (antiscalent), corrosion inhibitor, antimicrobial, dispersant and anti-oxidant.
Usually, the hydrophobic liquid or the wax that are comprised in the described core 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 under-30 ℃ to 150 ℃, is in a liquid state usually.
The representative instance that is applicable to fire retardant of the present invention comprises: like bromo benzoic ether described in US-A-5728760 or salt, 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 like 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 up 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 said 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 possibly obviously be different from it through 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 possibly all be important for clothing perhaps in multiple domestic. applications.
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.Possibly 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), automotive applications (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).Can also microcapsules of the present invention 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, such goods can be provided, it comprises through the fire retardant of sealing, UV absorbent, reactive dye tracer material or phase-change material.Under the situation of the fire retardant sealed, desirable is that fire retardant is able to keep 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, such goods can be provided, it comprises through the fire retardant of sealing, UV absorbent, reactive dye tracer material or phase-change material.Under the situation of the fire retardant sealed, desirable is such fire retardant, and in any procedure of processing (for example fiber formation) under relating to (for example) 150 ℃ to about 350 ℃ temperature, described fire retardant is able to keep; 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 out 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 through combining prepares with traditional coating composition (for example acrylic compounds or polyurethane textile article coating composition) (it comprises the traditional components of using with conventional amounts) with granular composition of the present invention.Described coating composition is for through the desirable formulation for preparing of 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 especially 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) the textile coating composition is provided,
2) described coating composition is applied on the surface of fabric, and
3) make described coating dry, 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 comprises the composition of (for example) dry state capsule of the present invention as indicated above and traditional textile coating; And wherein need described composition be 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, adopt the pressure that surpasses 200psi (for example 250psi) to roll fabric through applying.
In order to prove in the fabric that applies; Described active material has been maintained in the capsule, can microcapsules be incorporated in the textile coating formulation, is coated on the fabric; Re-using the pressure that surpasses 200psi (for example 250psi) rolls; Then experience again on the melt temperature of said wax with 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) to wash fabric, and use difference formula scanning calorimeter to measure enthalpy through the microcapsules that apply through applying.With before the enthalpy that records and experience calendering and the continuous heating and cooling, initial enthalpy through the capsule that applies 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.What usually, the diameter of microcapsules should be less than the fiber cross section diameter is half the.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 said 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 through 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, make spinning solution pass through nozzle subsequently and get in the atmosphere that heats, under such condition, solidify through the stoste of extruding, thereby form fiber, collect 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 through 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 said 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 find against expectation that even when polymer microcapsule is exposed to the spinning temperature above 150 ℃, 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 said 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
Gather (styrene) solution as hydrophobic polymer.
Gather (styrene) solution through 10g being gathered prepare in the styrene monomer that (styrene) (derive from Dajac: molecular weight is～1000) be dissolved in 90g.This mixture is stirred, dissolve fully up to polymer.
Embodiment 1:
Hydrophobicity oil (polymer that comprises adding) microcapsules
Through mix 4.94g styrene, 2.3g methacrylic acid, 4.76g gathers (styrene) solution (as above preparation) and 7.89g diacrylate butanediol ester prepares oil phase.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 for water that gathers (vinyl alcohol) (deriving from the GohsenolGH20R of Nippon Gohseii), 169g through mixing 5.4g 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 through 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 for water that gathers (vinyl alcohol) (deriving from the GohsenolGH20R of Nippon Gohseii), 169g through mixing 5.4g 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.
2Mass loss under 300 ℃: it is for deriving from the amount (representing with percentile form) of the material unaccounted-for (MUF) of sample in initial conditions, between 110 ℃ and 300 ℃.
3Gross weight (monomer adds hydrophobic polymer) based on polymer shell.
Through 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, can find out the effect of introducing the hydrocarbon insoluble polymer.
2: the effect that adds soluble polymer
Table 2
aPolymer is for forming gather (the methacrylic acid stearyl-copolymerization-Bisomer mpeg 3 50A) of the 90wt of 40% solution: 10wt in hydrocarbon.
Can know by The above results, compare, comprise character (measuring) deterioration that the hydrocarbon soluble polymer can cause microcapsules through effective mass loss with the useful effect of introducing the hydrocarbon insoluble polymer.
Claims (34)
1. microcapsules, it comprises:
A) contain the core of hydrophobicity oil 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 %,
Component i wherein), ii) and iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%.
2. according to the microcapsules of claim 1, 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.
3. according to the microcapsules of claim 1, wherein said multifunctional ethylenically unsaturated monomers is a diacrylate alkane diol ester.
4. according to the microcapsules of claim 1, wherein said multifunctional ethylenically unsaturated monomers is a diacrylate 1, the 4-butanediol ester.
5. according to the microcapsules of claim 1, the hydrophobic polymer that wherein is insoluble in said hydrophobicity oil or the wax is cinnamic polymer.
6. according to the microcapsules of claim 1, the hydrophobic polymer that wherein is insoluble in said hydrophobicity oil or the wax is cinnamic homopolymers.
7. according to the microcapsules of claim 1, wherein stable polymers is positioned on the outer surface of said microcapsule shell, and wherein said stable polymers is water-soluble hydroxyl polymer-containing.
8. according to the microcapsules of claim 7, wherein said stable polymers is a polyvinyl alcohol.
9. according to the microcapsules of claim 1, wherein said hydrophobicity oil or wax are hydrocarbon.
10. according to the microcapsules of claim 1, wherein said hydrophobicity oil or wax are that melting temperature is-30 ℃ to 150 ℃ oil or a wax.
11. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from: UV absorbent and UV reflective agent.
12. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from fire retardant, reactive dye tracer material, pigment and dyestuff.
13. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from colouring agent.
14. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from scale preventative, corrosion inhibitor, dispersant and antimicrobial.
15. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from anti-oxidant, pour-point depressant, wax precipitating inhibitor and washing assisant.
16. according to the microcapsules of claim 1, wherein said core comprises active component, this active component is selected from enzyme, spices, phase-change material and silicone oil.
17., wherein be insoluble to 0.05 weight % to the 20 weight % that amount that the said hydrophobic polymer in said hydrophobicity oil or the wax exists accounts for the gross weight of said hydrophobicity oil or wax and hydrophobic polymer in said microcapsules according to the microcapsules of claim 1.
18., wherein be insoluble to the inner surface that said hydrophobic polymer in said hydrophobicity oil or the wax applies the said polymer shell composition that is formed by said monomer mixture at least in part according to the microcapsules of claim 1.
19. according to the microcapsules of claim 1, the said hydrophobic polymer that wherein is insoluble in said hydrophobicity oil or the wax forms adhesion layer on the inner surface of the said polymer shell composition that is formed by said monomer mixture.
20. according to the microcapsules of claim 19, wherein said hydrophobic polymer forms complete layer on the inner surface of the said polymer shell composition that is formed by said monomer mixture.
21. according to the microcapsules of claim 1, wherein said polymer shell accounts for 10 weight % to 20 weight % of said microcapsules gross weight.
22. according to the microcapsules of claim 1, wherein weight average particle diameter is greater than 1 micron and 4 microns at the most.
23. make the method for microcapsules, these microcapsules comprise:
A) contain the core of hydrophobicity oil or wax;
B) polymer shell, it comprises:
A) polymer that forms by monomer mixture, and
B) be insoluble to hydrophobic polymer in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%;
This method may further comprise the steps:
1) grams of monomer blend is provided, 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 %,
Component i wherein), 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 hydrophobicity oil 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) making described monomer polymerization is the dispersion at the microcapsules of aqueous phase.
24. according to the method for claim 23, it is included in defined any characteristic among any of claim 1 to 22.
25., wherein make described monomer experience Raolical polymerizable according to the method for claim 23 or claim 24.
26., wherein thermal initiator is combined with described monomer, and described emulsion is heated at least 50 ℃ temperature keeps time enough to implement polymerisation according to the method for claim 23 or 24.
27. according to the method for claim 23 or 24, wherein stable polymers is comprised in described aqueous phase.
28. according to the method for claim 23 or 24, wherein said stable polymers is water-soluble hydroxyl polymer-containing.
29. according to the method for claim 23 or 24, wherein said stable polymers is for being polyvinyl alcohol.
30. according to the method for claim 28, 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.
31. goods that comprise microcapsules, wherein each microcapsules all comprises:
A) contain the core of hydrophobicity oil 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 %,
Component i wherein), ii) and iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%.
32. a coating composition that comprises microcapsules, wherein each microcapsules all comprises:
A) contain the core of hydrophobicity oil 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 %,
Component i wherein), ii) and iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%.
33. the method for a coated fabric, this method may further comprise the steps:
1) the textile coating composition is provided,
2) described coating composition is applied on the surface of said fabric, and
3) make described coating dry, thereby obtain fabric through applying,
Wherein said coating composition comprises microcapsules, and these microcapsules comprise:
A) contain the core of hydrophobicity oil 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 %;
Component i wherein), ii) and iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%.
34. comprise the fiber of microcapsules, these microcapsules comprise:
A) contain the core of hydrophobicity oil 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 %;
Component i wherein), ii) and iii) add up to 100%; And
B) be insoluble to other hydrophobic polymers in said hydrophobicity oil or the wax;
Wherein, these microcapsules comprise:
A) hydrophobicity oil or the wax of 45 to 94 weight %;
And shell component
Ba) polymer that forms by described monomer mixture of 5 to 50 weight %, and
Bb) 0.05 to 10 weight % be insoluble to the hydrophobic polymer in said hydrophobicity oil or the wax,
Wherein said composition adds up to 100%.
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 |
| GB0709421A GB0709421D0 (en) | 2007-05-17 | 2007-05-17 | Microcapsules, their use and processes for their manufacture |
| GB0709421.2 | 2007-05-17 | ||
| 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 CN101541416A (en) | 2009-09-23 |
| CN101541416B true CN101541416B (en) | 2012-11-14 |
Family
ID=37605424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800425175A Expired - Fee Related CN101541416B (en) | 2006-11-17 | 2007-11-06 | Microcapsules, their use and processes for their manufacture |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101541416B (en) |
| GB (1) | GB0622894D0 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102726383B (en) * | 2012-07-05 | 2015-03-18 | 常州美胜生物材料有限公司 | Slow release type insect pest attractant microcapsule and preparation method thereof |
| 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 |
| CN104790234A (en) * | 2015-05-06 | 2015-07-22 | 苏州市吴中区甪直明达漂染厂 | Manual batik cotton yarns |
| KR102675505B1 (en) | 2015-09-03 | 2024-06-14 | 타그라 바이오테크놀로지스 리미티드 | Microcapsules encapsulating reflectors |
| AU2017207981B2 (en) * | 2016-01-14 | 2020-10-29 | Isp Investments Llc | Friable shell microcapsules, process for preparing the same and method of use thereof |
| US20200108367A1 (en) * | 2016-04-12 | 2020-04-09 | Croda International Plc | Microcapsules |
| CN106190042B (en) * | 2016-08-14 | 2019-11-19 | 张天奇 | A kind of hot energy storage material |
| CN106149095A (en) * | 2016-08-14 | 2016-11-23 | 张天奇 | A kind of fabric lining containing hot energy storage material |
| CN107385933B (en) * | 2017-06-29 | 2019-12-03 | 北京宇田相变储能科技有限公司 | A kind of one-way wet-guide composite functional fabric that free-floride is washable |
| JP2019209020A (en) * | 2018-06-08 | 2019-12-12 | パナソニックＩｐマネジメント株式会社 | Steam generation device and steam iron |
| JPWO2021065400A1 (en) * | 2019-09-30 | 2021-04-08 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020058732A1 (en) * | 2000-11-06 | 2002-05-16 | Mistry Kishor Kumar | Particles |
| WO2004068234A1 (en) * | 2003-01-30 | 2004-08-12 | Sipix Imaging, Inc. | High performance capsules for electrophoretic displays |
| CN1572821A (en) * | 2003-05-28 | 2005-02-02 | 日东电工株式会社 | Hydrophilized porous film and process for producing the same |
| WO2005105291A1 (en) * | 2004-04-29 | 2005-11-10 | Ciba Specialty Chemicals Water Treatment Limited | Particulate compositions and their manufacture |
| CN1742024A (en) * | 2003-01-29 | 2006-03-01 | 弗门尼舍有限公司 | Polymeric particles and fragrance delivery systems |
-
2006
- 2006-11-17 GB GB0622894A patent/GB0622894D0/en not_active Ceased
-
2007
- 2007-11-06 CN CN2007800425175A patent/CN101541416B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020058732A1 (en) * | 2000-11-06 | 2002-05-16 | Mistry Kishor Kumar | Particles |
| CN1742024A (en) * | 2003-01-29 | 2006-03-01 | 弗门尼舍有限公司 | Polymeric particles and fragrance delivery systems |
| WO2004068234A1 (en) * | 2003-01-30 | 2004-08-12 | Sipix Imaging, Inc. | High performance capsules for electrophoretic displays |
| CN1572821A (en) * | 2003-05-28 | 2005-02-02 | 日东电工株式会社 | Hydrophilized porous film and process for producing the same |
| WO2005105291A1 (en) * | 2004-04-29 | 2005-11-10 | Ciba Specialty Chemicals Water Treatment Limited | Particulate compositions and their manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101541416A (en) | 2009-09-23 |
| GB0622894D0 (en) | 2006-12-27 |
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