CN103372409B - Non-expansion type Hollow polymer particle and manufacture method thereof - Google Patents

Non-expansion type Hollow polymer particle and manufacture method thereof Download PDF

Info

Publication number
CN103372409B
CN103372409B CN201310129892.0A CN201310129892A CN103372409B CN 103372409 B CN103372409 B CN 103372409B CN 201310129892 A CN201310129892 A CN 201310129892A CN 103372409 B CN103372409 B CN 103372409B
Authority
CN
China
Prior art keywords
organic solvent
hollow
polymer particles
polymer particle
particulate
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.)
Active
Application number
CN201310129892.0A
Other languages
Chinese (zh)
Other versions
CN103372409A (en
Inventor
村田晃二
小宫直城
木原崇雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SANKO CO Ltd
Original Assignee
SANKO CO Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SANKO CO Ltd filed Critical SANKO CO Ltd
Publication of CN103372409A publication Critical patent/CN103372409A/en
Application granted granted Critical
Publication of CN103372409B publication Critical patent/CN103372409B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Abstract

A kind of Hollow polymer particle and manufacture method thereof.The invention provides the generation of the concavity particulate reducing the low depression of hollow rate, increase the manufacture method of the Hollow polymer particle of the high particulate of hollow rate.A kind of manufacture method of Hollow polymer particle, it is characterized in that, in aqueous medium, make to comprise and disperse for the formation of the polymerizable monomer of polymer particles shell and the emulsifying mixture of organic solvent, and aforementioned polymeric monomer suspension polymerizing is made under the existence of polymerization initiator, thus form the inner polymer particles comprising organic solvent, the organic solvent being included in this polymer particles inside is made to gasify and remove through the shell of this particulate, thus manufacture Hollow polymer particle, in the method, the state be dispersed in aqueous medium with polymer particles is carried out the organic solvent being included in aforementioned polymer interparticle is gasified and is removed thus particulate is made hollow operation.

Description

Non-expansion type Hollow polymer particle and manufacture method thereof
Technical field
The present invention relates to the manufacture method of Hollow polymer particle, it can manufacture non-expansion type and the high Hollow polymer particle of hollow rate; And the non-expansion type to be obtained by this manufacture method and the high Hollow polymer particle of hollow rate.Hollow polymer particle of the present invention can be used as such as light material, improve light scattering material and heat-barrier material etc. contained in the intermediate layer that formed between supporter and heat-sensitive color layer in order to the recording sensitivity improving thermosensitive recording body.The feature of the manufacture method of Hollow polymer particle of the present invention is, is increasing non-expansion type and while the generation of the high particulate of hollow rate, water dispersible is good and coating preparation is simple, is not dispersing during process, environmentally friendly.
Background technology
Up to now, the manufacture method as Hollow polymer particle there will be a known patent document 1 and patent document 2.Hollow polymer particle described in these documents is for object with intumescent hollow particle.That is: formed by suspension polymerization and there is the shell of thermoplastic polymer, after inside includes the microsphere of volatile foaming agent, heat the blowing agent volatilization that this microsphere makes inside comprise, the internal pressure improving microsphere, thus make shell expand (expansion).
The intumescent Hollow polymer particle of patent document 1 and the method manufacture described in patent document 2 is utilized to have the particle diameter after expansion different and do not concentrate such shortcoming.When particle diameter is not concentrated, there is the shortcoming of the using adaptability lacked in following field: require that the coating composition employing Hollow polymer particle has the field of stability; Or seek the field (such as, seeking the thermosensitive recording body of the stability of recording sensitivity) of controlled particle diameter.
As the method manufacturing the Hollow polymer particle that particle diameter is concentrated, there will be a known patent document 3.The manufacture method of the hollow particle described in the document is called as so-called seeded polymerization.The basic fundamental of seeded polymerization is from after first making polymerizable monomer (such as: styrene) carry out emulsification in water under the existence of emulsifying agent thus to form particulate, polymerization forms seed (core).Then, make other polymerizable monomer (such as: acrylate) be adsorbed in this seed, around this seed, then utilize other polymerizable monomer to form outer shell.Then, add in system and make inner seed swelling, the material (such as: ammonia spirit) of dissolving through this outer shell, make seed dissolve thus, and make this dissolved matter and the displacement of outside water, and then heat drying removes inner water, thus make hollow method.
For the Hollow polymer particle utilizing this seeded polymerization, generally speaking, owing to forming particulate the existing emulsified of emulsifying agent, only can obtain particle diameter little to less than 1 μm or 1 μm, hollow rate mostly be most about 50% particulate.When this hollow particle is used as such as thermosensitive recording body heat-barrier material, have the shortcoming that effect of heat insulation becomes insufficient.Therefore, how seeded polymerization existence makes particle diameter become several μm and improves the problem of hollow rate.
Patent document 4 describes in a kind of voided layer formed between supporter and heat-sensitive color layer and contains the thermosensitive recording body that average grain diameter is 0.1 ~ 20 μm (preferably 2 ~ 10 μm), hollow rate is the non-foamed type polymeric hollow particulate of 60 (preferably 90) more than %.But what do not provide about the non-foamed type Hollow polymer particle how manufacturing satisfied such condition in the document is technical open.
Patent document 5 discloses a kind of manufacture method of Hollow polymer particle, wherein, prepare volatile hydrocarbon, the suspension that hydrophilic monomer and cross-linkable monomer coexist, in this suspension, make aforementioned monomer composition be polymerized, thus obtain the dispersion liquid that inside comprises the polymer particles of this volatile hydrocarbon, then from this dispersion liquid isolating polymer particulate and carry out drying process, or do not carry out being separated and in dispersion, being blown into air, nitrogen, steam etc., or combinationally use these means, the volatile hydrocarbon of rising isolating polymer interparticle thus, thus manufacture the method for hollow bead.
But, utilize the Hollow polymer particle of the method manufacture described in patent document 5 to have the part of polymer wall (shell) or seriously cave in, formed the shortcoming of the concavity particulate of depression in a few place.This is along with the gasification transpiration of comprised volatile hydrocarbon is separated, granule interior pressure reduces, namely the polymeric membrane (shell) forming spherical particle cannot be resisted inner pressure relief and inhale produced phenomenon inwards, can think that its reason is hardness, the intensity deficiency of this polymeric membrane.The hollow rate of the concave polymeric particulate of depression reduces, even if also cannot give full play to desirable effect of heat insulation as the insulation agent in the intermediate layer being used for thermosensitive recording body.
prior art document
patent document
Patent document 1: Japanese Patent Publication 42-26524 publication
Patent document 2: Japanese Patent Publication 5-86746 publication
Patent document 3: Japanese Laid-Open Patent Publication 56-32513 publication
Patent document 4: Japanese Unexamined Patent Publication 5-169818 publication
Patent document 5: Japanese Laid-Open Patent Publication 61-87734 publication
Summary of the invention
the problem that invention will solve
As mentioned above, the particle diameter of the Hollow polymer particle of existing known, intumescent is uneven, is difficult to form uniform particulate.The particle diameter of the Hollow polymer particle utilizing seeded polymerization to be formed is for several μm and be not suitable for the situation expecting high hollow rate particulate.The part of particulate or a few place depression can be there is and become the concavity particulate of depression, form the problems such as the low particulate of hollow rate in non-expansion type Hollow polymer particle.It should be noted that, hollow rate described herein refers to the volume of hollow bead hollow core part and the ratio of the volume of hollow bead, represents with following formula (1).
Hollow rate (%)=[(radius of hollow parts) 3/ (radius of hollow bead) 3] × 100 (1)
Major subjects of the present invention is, thering is provided a kind of comprises the non-expansion type polymer particles of organic solvent when being gasified by organic solvent and remove thus make hollow by particulate from inside, reduce the generation of the concavity particulate of the low depression of hollow rate, increase the manufacture method of the Hollow polymer particle of the high particulate of hollow rate.Problem of the present invention is also, on the basis of described problem, there is provided a kind of when forming water-based paint compositions, to the compatibility of water and favorable dispersibility and coating preparation is simple, process time do not disperse, the manufacture method of environment amenable non-expansion type Hollow polymer particle.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research repeatedly for the solution solving foregoing problems, result is conceived, have studied a kind of new method, it does not adopt existing method (from using thermoplastic resin as isolated by filtration polymer particles the polymer fine particles dispersion of shell, such as use the drying device of conical dryer and so on to carry out heat drying thus powdered time, gasification is rising removes organic solvent thus makes hollow method), but in the aqueous dispersions being dispersed with this polymer particles, carry out the gasification of the organic solvent being included in non-expansion type polymer particles inside and remove, make hollow (in solution desolventizing), thus complete the present invention.
The invention is characterized in, in the manufacture of non-expansion type polymer particles, increasing the high Hollow polymer particle of hollow rate by introducing described new method, temporarily taking out from aqueous dispersions from the existing methodical polymer particles that inside is comprised organic solvent, be dried and make hollow existing method while making powder, in scheme, effect, there are the different of essence.
The invention provides a kind of manufacture method of non-expansion type Hollow polymer particle, it is characterized in that, in aqueous medium, make to comprise and disperse as the polymerizable monomer of the material for the formation of polymer particles shell and the emulsifying mixture of crosslinking agent and organic solvent, and under the existence of polymerization initiator, make aforementioned polymeric monomer and crosslinking agent suspension polymerisation, thus form the inner polymer particles comprising organic solvent, the organic solvent being included in this polymer particles inside is made to gasify and remove through the shell of this particulate, thus manufacture non-expansion type Hollow polymer particle, in the method, be dispersed in the state of the aqueous dispersions in aqueous medium according to the mode that volumetric concentration is in the scope of 20 ~ 65% with polymer particles, carry out the organic solvent being included in aforementioned polymer interparticle is gasified under the condition fluid temperature of this aqueous dispersions being set as the temperature higher than the azeotropic point of aqueous medium and organic solvent and remove thus particulate is made hollow operation.
For the manufacture method of Hollow polymer particle of the present invention, preferably, when making aforementioned polymeric monomer and crosslinking agent suspension polymerisation, in aqueous medium, add one or more additives in the group being selected from and being made up of dispersant, dispersing aid.
For the manufacture method of Hollow polymer particle of the present invention, preferably, gasify making the organic solvent being included in aforementioned polymer interparticle and remove thus particulate is made hollow and obtain Hollow polymer particle aqueous dispersions in water be separated, be in the scope of 12 ~ 70 quality % to make solid component concentration.
For the manufacture method of Hollow polymer particle of the present invention, preferably, in aqueous medium, make to comprise as when disperseing for the formation of the polymerizable monomer of polymer particles shell and the emulsifying mixture of crosslinking agent and organic solvent, make the mixture comprising aforementioned polymeric monomer and crosslinking agent and organic solvent carry out emulsion dispersion with the volumetric concentration of the scope of 20 ~ 65%.
For the manufacture method of Hollow polymer particle of the present invention, preferably, after formation inside comprises the polymer particles of organic solvent, add dilution and dilute, be in the scope of 20 ~ 65% with the volumetric concentration of the aqueous dispersions making this polymer particles.
For the manufacture method of Hollow polymer particle of the present invention, preferably, this normal-temperature water is added to after diluting aforementioned aqueous dispersions as aforementioned dilution in use normal-temperature water, fluid temperature is warming up to the temperature higher than the azeotropic point of aqueous medium and organic solvent, thus makes the organic solvent being included in polymer particles inside gasify and remove.
In addition, also the warm water that can be serviceability temperature higher than the azeotropic point of aqueous medium and organic solvent is as aforementioned dilution, aforementioned aqueous dispersions is warming up to the temperature higher than aforesaid azeotropic, thus the organic solvent being included in polymer particles inside is gasified and the technical scheme removed.
In addition, the invention provides a kind of manufacture method by aforesaid non-expansion type Hollow polymer particle and the non-expansion type Hollow polymer particle obtained.
the effect of invention
The manufacture method of Hollow polymer particle of the present invention is disperseed for the formation of the polymerizable monomer of polymer particles shell and the emulsifying mixture of organic solvent by making to comprise in aqueous medium, and aforementioned polymeric monomer suspension polymerizing is made under the existence of polymerization initiator, thus form the inner polymer particles comprising organic solvent, the organic solvent being included in this polymer particles inside is made to gasify and remove through the shell of this particulate, thus manufacture Hollow polymer particle, in the method, the state be dispersed in aqueous medium with polymer particles carries out making the organic solvent being included in aforementioned polymer interparticle gasify and remove, thus particulate is made hollow operation, thus there is the generation of the concavity particulate reducing depression, increase non-foamed and the effect of the generation of the high Hollow polymer particle of hollow rate.
In addition, according to the manufacture method of Hollow polymer particle of the present invention, except can reduce the concavity particulate of depression generation, increase the high moistening Hollow polymer particle of hollow rate generation except, also have the moistening Hollow polymer particle of gained to the compatibility of water and excellent dispersion therefore coating preparation simple, process time can not disperse therefore do not worry being caused damage to the health of operation task personnel by breathing, environment amenable effect.
The high polymer particles of a large amount of hollow rate is comprised according to the Hollow polymer particle of gained of the present invention, make it as the heat-barrier material in the intermediate layer of such as thermosensitive recording body by containing sometimes, have can intercept Joule heat that hot head gives when recording and improve effect of heat insulation, make recording sensitivity tremendous the effect that improves.
Accompanying drawing explanation
Fig. 1 is the electron microscope enlarged image of the polymer particles group manufactured in comparative example 1, comparative example 1 based on comprise from inside organic solvent polymer particles aqueous dispersions in be separated this polymer particles, be made into hollow existing method while making its drying.
Fig. 2 is the electron microscope enlarged image of the Hollow polymer particle group manufactured in embodiment 1 based on the present invention's (use normal-temperature water as dilution).
Fig. 3 is the electron microscope enlarged image of the non-expansion type Hollow polymer particle group manufactured in example 2 based on the present invention's (use and can be warming up to the temperature warm water higher than the azeotropic point of aqueous medium and this organic solvent as dilution).
Detailed description of the invention
As the polymerizable monomer for the formation of polymer particles shell used in the present invention, from vinylpyridine, glycidyl acrylate, GMA, (methyl) acrylate, (methyl) acrylic acid, acrylonitrile, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, itaconic acid, fumaric acid, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, select in styrene, wherein, (methyl) acrylic acid, the dissolubility that (methyl) acrylate or (methyl) acrylonitrile compare water with the inner organic solvent comprised is high, and the periphery of the solvent comprised in inside excellently forms polymeric membrane, therefore more applicable.
These polymerizable monomers can be used alone, and also such as (methyl) acrylic acid and (methyl) acrylate, (methyl) acrylic acid and acrylonitrile can be combinationally used.
Comprise for the polymer particles of organic solvent for forming inside by being used alone or in combination by aforementioned polymeric monomer, preferably with other crosslinking agent, polymerization initiator, dispersant, dispersing aid using.
The feature of the organic solvent used in the present invention is, being selected from any one in Anaesthetie Ether, neohexane, pentane, hexane, heptane, isooctane, octane, cyclohexane, hexahydrotoluene, can not gasifying under the state being included in interparticle after the polymerization neutralization polymerization that can be preferably used in polymerizable monomer terminates and can by the dispersion liquid of this particulate being heated to 60 ~ 130 DEG C and carry out gasifying thus successfully from hexane, heptane, octane etc. that the polymeric membrane (shell) of particulate is removed.
The consumption of organic solvent uses 400 mass parts ~ 2000 mass parts relative to 100 mass parts polymerizable monomers, preferably uses 800 mass parts ~ 1700 mass parts, preferably uses 1200 mass parts ~ 1400 mass parts further.Along band, during use quantity not sufficient 400 mass parts of organic solvent, the thickness of the shell of the particulate formed increases and hollow rate decline relatively, cannot form the polymer particles that hollow rate is high.On the other hand, even if use more than 2000 mass parts, being difficult to expect the technique effect corresponding with the amount exceeded, is not very wise move economically yet.
Aforementioned for the formation of the polymerizable monomer of polymer particles shell and the mixture of aforementioned organic solvents emulsion dispersion in aqueous medium.
In aforementioned aqueous medium, except aforementioned polymeric monomer and organic solvent, various additive can also be added.As this additive, preferably add one or more additives in the group being selected from and being made up of crosslinking agent, dispersant, dispersing aid.In addition, when suspension polymerisation is carried out to aforementioned polymeric monomer, add the polymerization initiator of aforementioned polymeric monomer.
Aforementioned crosslinking agent also can affect hardness, the intensity of polymeric membrane, is thus associated with polymerizable monomer and selects.Specifically, divinylbenzene, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid triglycol ester, trimethacrylate acid trimethylolpropane, two (methyl) acrylic acid 1 can be listed, 3-butanediol ester and (methyl) allyl acrylate etc., when selecting (methyl) acrylic acid, (methyl) acrylate, acrylonitrile or their combination as polymerizable monomer, two (methyl) acrylic acid glycol ester or three (methyl) acrylic acid trimethylolpropane are applicable as crosslinking agent.
For the consumption of crosslinking agent, studied with associating of used polymerizable monomer by it, use 10 mass parts ~ 200 mass parts relative to 100 mass parts polymerizable monomers, preferably use 40 mass parts ~ 150 mass parts, preferably use 60 mass parts ~ 100 mass parts further.Along band, during use quantity not sufficient 10 mass parts of crosslinking agent, be difficult to be formed the hard and non-expansion type of excellent strength hollow property polymer particles, even and if use more than 200 mass parts, being difficult to expect the technique effect corresponding with the amount exceeded, is not very wise move economically yet.
Dispersant be in order to formed inner comprise the dispersion of the particulate of organic solvent after maintain the stable dispersiveness of particulate and necessity.As long as the material with such function just can use as dispersant, the present inventor etc. investigate for the effect of phosphorus system dispersant, water soluble polymer system dispersant, cataloid etc., results verification arrives: wherein, cataloid himself has positive charge, be attached to the polymeric membrane periphery of particulate and each particulate is repelled mutually, thus that stop gathering, excellent dispersion effect can be played.
In the present invention, the reason that cataloid plays excellent dispersion effect is: by making polymerizable monomer polymerization reaction take place in acid condition, cataloid himself with positive charge.Positively charged silica embeds the polymeric membrane of particulate and makes each particulate become the particle with positive charge.Can think positively charged each particles repel one another thus prevent assemble.
When dispersant is cataloid, the consumption of dispersant, for use 30 mass parts ~ 100 mass parts relative to 100 mass parts polymerizable monomers, preferably uses 40 mass parts ~ 80 mass parts, preferably uses 50 mass parts ~ 70 mass parts further.Along band, during use quantity not sufficient 30 mass parts of dispersant, dispersion effect cannot be obtained.In addition, even if use more than 100 mass parts, being difficult to expect the technique effect corresponding with the amount exceeded, is not very wise move economically yet.
Dispersing aid is by using with dispersant, cooperative effect is played to forming/maintaining more stable dispersion liquid, therefore the condensation product etc. of the condensation product of the condensation product of such as adipic acid and diethanol amine, adipic acid and AMPD, adipic acid and MEA is suitable.
When dispersing aid is the condensation product of adipic acid and diethanol amine, the consumption of dispersing aid, for use 1 mass parts ~ 10 mass parts relative to 100 mass parts polymerizable monomers, preferably uses 2 mass parts ~ 7 mass parts, more preferably uses 3 mass parts ~ 5 mass parts.Along band, during use quantity not sufficient 1 mass parts of dispersing aid, the effect of dispersing aid cannot be obtained.In addition, even if use more than 10 mass parts, being difficult to expect the technique effect corresponding with the amount exceeded, is not very wise move economically yet.
As long as polymerization initiator oil-soluble and the material that can produce free radical just can use, under the temperature range of the organic solvent comprised in inside not generating gasification, it is excellent for making polymerizable monomer in Best Times, terminate polymerisation, such as can use 2,2 '-azobis isobutyronitrile, hydrogen phosphide cumene, TBHP, cumyl peroxide, di-tert-butyl hydrogen peroxide, benzoyl peroxide, lauroyl peroxide etc.Use normal heptane as organic solvent time, the half-life at 60 DEG C be 10 hours 2,2 '-azobis isobutyronitrile is excellent.
For obtaining for Hollow polymer particle according to the present invention, make to comprise the emulsifying mixture dispersion of aforementioned each material, suspension polymerisation thus form the inner polymer particles comprising organic solvent, the compounding ratio of each material decides with the associating of Hollow polymer particle obtaining having which kind of feature according to it, is not particularly limited.
First aforesaid emulsion dispersion method uses the emulsification mixer of homogeneous mixer and so on.Suspension polymerisation proceeds to carry out in the process stirred by other mixer under the state making emulsified dispersed liquid be warming up to set point of temperature.
Suspension polymerisation is advanced and the polymer particles of formation, then make the organic solvent being included in interparticle gasify and remove thus make hollow, the invention is characterized in, the gasification of organic solvent to remove thus make hollow be carry out (in solution desolventizing) under the condition being set as the temperature higher than the azeotropic point of aqueous medium and this organic solvent in the aqueous dispersions being dispersed with this polymer particles and by the fluid temperature of this dispersion liquid.
The volumetric concentration being dispersed with the aqueous dispersions of this polymer particles is now in 20 ~ 65%, is preferably in 30 ~ 50%, is preferably in the scope of 40 ~ 45% further.Along band, this is because, when volumetric concentration is less than 20%, extremely decline along with low concentration, manufacture efficiency; On the other hand, when being more than 65%, the viscosity of dispersion liquid uprises, and easily causes and foam when the organic solvent gasified to be removed in dispersion liquid and to distillate outside system, thus removal efficiency is deteriorated, manufactures efficiency and extremely decline.
In order to make volumetric concentration be 20 ~ 65% polymer microparticle aqueous to fall apart liquid, have following methods: make to comprise aqueous medium, the mixture of polymerizable monomer, crosslinking agent, organic solvent, dispersant and dispersing aid for the formation of polymer particles carries out emulsion dispersion method become the compounding conditions of 20 ~ 65% in its volumetric concentration under; And add dilution and regulate, with the method making the volumetric concentration of the aqueous dispersions being dispersed with this polymer particles become 20 ~ 65% after formation polymer particles.Any method can also be adopted, if but the emulsion dispersion efficiency of consideration mixture, the method for the latter is favourable.
When adding the method for dilution after forming polymer particles as previously mentioned, this dilution for object, in order to reduce the generation of the low concavity particulate of hollow rate, increase the generation of the high particulate of hollow rate, uses warm water to have more effect with normal-temperature water and warm water.
Along band, the organic solvent that temperature when making inside comprise the particle suspension polymerization of organic solvent comprises with inside sets for benchmark.Such as, when using normal heptane as this organic solvent, be set as less than 79 DEG C.
If use normal-temperature water as dilution herein, the periostracum not arriving the state terminating crosslinked region due to hardness and intensity insufficient, shrink under quick-frozen.And the organic solvent comprised by making inside gasifies and removes thus make hollow, and the internal pressure of particulate reduces further.The overlap of these factors causes shell to be internally attracted, and particulate presents the state being easy to the concavity particulate forming depression.
But, about this problem of the present invention of generation increasing the high particulate of hollow rate, by carrying out the gasification of the organic solvent being included in polymer particles inside and remove thus make hollow in the aqueous dispersions being dispersed with polymer particles, its effect is compared with the Hollow polymer particle (Fig. 1) manufactured based on existing method, and it is apparent for seeing improvement from (Fig. 2).
On the other hand, when the fluid temperature of this suspension polymerisation liquid can be set as the warm water of the temperature higher with the azeotropic point of this organic solvent than aqueous medium as dilution by use, form the crosslinked of the polymeric membrane (shell) of particulate to carry out continuously, its hardness, intensity improve further, the internal pressure that formation can tolerate particulate declines and shell is internally attracted the particulate of such power, the concavity particulate of depression reduces, and the particulate that hollow rate is high increases further.By (Fig. 3) with based on existing method, the Hollow polymer particle (Fig. 1) manufactured and the Hollow polymer particle using normal-temperature water to manufacture (Fig. 2) are compared, this is also apparent.
So, the polymer particles group manufactured based on existing method almost all presents the concavity micronize of depression, substantially cannot observe the high spheroidal particle of hollow rate.On the other hand, if compared with (Fig. 1), it is apparent that the Hollow polymer particle group (Fig. 2) manufactured based on the present invention, (Fig. 3) generate the high particulate of a large amount of hollow rate.
Along band, about the reason that can obtain foregoing advantages, the present inventor etc. consider as follows.This reason and following operation closely related: for Hollow polymer particle of the present invention, in the aqueous dispersions being dispersed with this particulate, volumetric concentration is 20 ~ 65% and the fluid temperature of this dispersion liquid carries out the gasification of the organic solvent being included in polymer particles inside under being set as the condition of the temperature higher than the azeotropic point of aqueous medium and this organic solvent and removes thus make hollow.
When carrying out the gasification of organic solvent subject to the foregoing and remove thus make hollow, be included in the organic solvent generating gasification of interparticle and depart from through the shell of particulate to outside, this disengaging mode to be suppressed thus slowly owing to covering the hydraulic pressure of outside aqueous dispersions.Therefore, particulate makes internal pressure rise due to the delay of organic solvent of having gasified, and its pressure puts on the inwall of particulate.Now, compared with the internal pressure reduced with the disengaging of the organic solvent because having gasified, the rising of the internal pressure caused by the delay of the organic solvent gasified is more obvious.And, due to the organic solvent time dependent that gasified depart from, cause internal pressure to reduce gradually.But during this period, the shell of particulate is still being cross-linked, can think that tolerating internal pressure reduces, can maintain spherical hardness, the particulate increase of intensity.
On the other hand, existing method is that the polymer particles that inside is comprised organic solvent temporarily takes out from aqueous dispersions, makes hollow while being heated drying.Now, there is not the organic solvent gasified and depart from factor to being suppressed during outside through the shell of particulate.Therefore, can think: the organic solvent limit in particulate is carried out gasification limit and departed from successively thus make internal pressure decline, internally be attracted by shell, its result, causes particulate substantially to become the concavity particulate of depression.
Then, the fluid temperature of dispersion liquid when making the organic solvent being included in polymer particles inside gasify and remove thus make hollow is set as the temperature higher with the azeotropic point of this organic solvent than aqueous medium is important.Specifically, decide according to the kind of the organic solvent used.
The fluid temperature of dispersion is set as follows: be more than 89.6 DEG C when such as using octane as organic solvent, to use when heptane be more than 79.2 DEG C, use cyclohexane when be more than 69.5 DEG C, use hexane when be more than 61.6 DEG C.
The inner fluid temperature comprising the polymer particles dispersion liquid of organic solvent of setting, is included in the organic solvent generating gasification of polymer particles inside as described above, is departed to outside, thus form Hollow polymer particle by the shell of polymer particles.
The Hollow polymer particle dispersion liquid that the spherical particle that gained hollow rate is high increases can be adjusted to the form being suitable for purposes.Such as, can the laggard row drying of moisture be separated thus make powder Hollow polymer particle, or also can make moistening Hollow polymer particle.Such as, if make the form of moistening Hollow polymer particle, then can not externally disperse during operation thus environmentally friendly, to the compatibility of water and excellent dispersion, therefore coating preparation becomes simple.Along band, in order to make moistening Hollow polymer particle, with solid component concentration for 12 ~ 70%, be preferably 20 ~ 50%, more preferably the mode of 30 ~ 40% is separated and removes water.Along band, if less than 12%, then it is aqueous dispersion state and do not become moisture state.On the other hand, if more than 70%, then there is Hollow polymer particle and become and easily disperse and the health of operation task personnel caused damage by breathing thus becomes unworkable worry.
Embodiment
Below, further illustrate the present invention by embodiment and comparative example, but the present invention is not by any restriction of these embodiments.
[embodiment 1]
The condensation product 0.6g dissolving adipic acid and diethanol amine in the four-hole boiling flask of 1000ml adding 201.2g deionized water, as dispersing aid, adds 8.5g colloidal silica as dispersant.With 3% dilute sulfuric acid aqueous solution 4.5g, the pH of this aqueous solution is adjusted to 3.0 and is used as aqueous phase.
Using 11.2g methyl methacrylate, 1.3g acrylonitrile as polymerizable monomer, 12.5g trimethacrylate acid trimethylolpropane is as crosslinking agent, and 150.0g normal heptane carries out mixing as organic solvent and is used as oil phase.
Mixing aqueous phase and oil phase, 6 minutes are stirred with rotating speed 12000rpm by T.K automatic homogeneous mixer M type (Tokushu Kika Kogyo K.K's manufacture), after particle diameter being adjusted to 1 ~ 10 μm, add 2,2 '-azobis isobutyronitrile 0.1g is as polymerization initiator, carry out nitrogen displacement, within 4 hours, be polymerized while stir limit under reaction temperature 78 DEG C, rotating speed 180rpm.
385.0g normal-temperature water is added in water system polymer dispersion after terminating to polymerization, while stirring dispersion is heated to 79 ~ 100 DEG C in atmospheric conditions, carried out the gasification of the normal heptane being included in polymer particles inside through 8 hours and remove, thus polymer particles being made hollow (in solution desolventizing).Now, by adding normal-temperature water, temperature when making dispersion carry out polymerisation is temporarily cooled to 40 DEG C by 78 DEG C.
The amount of the normal heptane eliminated from polymer particles is 141g, can confirm the normal heptane roughly equal with input amount and carry out gasifying and being removed by shell at micro polymer intragranular.
Normal heptane is gasified and after removing, suction filtration is carried out to this water-based system polymer dispersion, obtains the polymer particles that 155.3g solid constituent is the moisture state of 18.7%.The particle diameter of resulting polymers particulate is 4.0 μm.(particle diameter refers to and uses laser diffraction formula particle size distribution device " SALD-2000 (Shimadzu Seisakusho Ltd.'s manufacture) " to measure, and volumetric particle size distribution is accumulated as the particle diameter of 50%.)
To photograph by the Hollow polymer particle of electron microscope to gained non-expansion type and the enlarged image obtained is shown in Fig. 2.Can be confirmed by this image, resulting polymers particulate is compared with the Hollow polymer particle (Fig. 1) manufactured based on existing method, and the particulate that concavity particulate reduces, hollow rate is high of depression increases.
Because gained non-expansion type Hollow polymer particle is moisture state, therefore for the compatibility of water and favorable dispersibility and coating preparation is simple, process time can not disperse, environment amenable particulate.
In embodiment 1, the visual shape of the particulate of gained is recorded in table 1, uses this particulate to be recorded in table 2 as the recording sensitivity of thermosensitive recording body during heat-barrier material.
[embodiment 2]
Comprise normal heptane as inside, terminate the dilution of the microparticle dispersion be polymerized, the azeotropic point adding normal heptane and water i.e. warm water (85 DEG C) 385.0g of more than 79 DEG C, in addition, operate similarly to Example 1, thus the polymer particles that the hollow rate manufacturing moisture state is high.
Maintain from polymerisation to the gasification of organic solvent and remove dispersion temperature from without cooling state, operate similarly to Example 1, carry out the gasification of the normal heptane being included in interparticle and remove, thus obtaining the particulate making hollow moisture state.
With electron microscope, resulting polymers particulate to be photographed and the enlarged image obtained is shown in Fig. 3.Can be confirmed by this Fig. 3, resulting polymers particulate is compared with the Hollow polymer particle (Fig. 1) manufactured based on existing method, or compared with the Hollow polymer particle (Fig. 2) of the embodiment 1 using normal-temperature water to manufacture as dilution, the Hollow polymer particle that concavity particulate reduces, hollow rate is high of depression increases further.
In addition, during by gained particle epoxy resin embedding and with electron microscope observation sectional view, the shape of particle is compared with the concavity particulate of the depression adopting existing method to obtain, spheroidal particle generates in a large number, average grain diameter is 4.0 μm and the thickness of periostracum is about 0.05 μm, has the high hollow rate of hollow rate more than 90%.The bulk density of gained Hollow polymer particle is 0.1g/ml.
Can think, the reason of this effect is as follows: by using warm water, can to maintain from polymerisation to the gasification of organic solvent and remove thus make hollow the temperature of dispersion from the state without cooling, thus the polymeric membrane of formation particulate is not shunk be cross-linked continuously, the hardness of this polymer particles, intensity are improved.
In embodiment 2, the visual shape of the particulate of gained is recorded in table 1, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[embodiment 3]
The deionized water used when preparing aqueous phase is set to 586.2g, after emulsion dispersion, suspension polymerisation, do not use dilution, in addition, operate similarly to Example 2, thus carry out the gasification of the normal heptane being included in interparticle and remove, thus obtain the particulate making hollow moisture state.
Can confirm, the Hollow polymer particle that concavity particulate reduces, hollow rate is high of the depression in polymer particles increases further, and this degree and embodiment 2 are roughly same degree.
In embodiment 3, the visual shape of the particulate of gained is recorded in table 1, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[comparative example 1]
The mixing aqueous phase identical with embodiment 1 and oil phase, 6 minutes are stirred with rotating speed 12000rpm by T.K automatic homogeneous mixer M type (Tokushu Kika Kogyo K.K's manufacture), after particle diameter being adjusted to 1 ~ 10 μm, add 2,2 '-azobis isobutyronitrile 0.1g is as polymerization initiator, carry out nitrogen displacement, within 4 hours, be polymerized while stir limit under reaction temperature 78 DEG C, rotating speed 180rpm.
What finish from polymerization comprises a polymer microparticle aqueous prose style free from parallelism for normal heptane, utilizes suction filtration to carry out Separation of Solid and Liquid to this polymer particles, thus obtains the polymer particles comprising normal heptane.
By this polymer particles in atmospheric conditions, at 40 DEG C through 24 hours the normal heptane being included in interparticle gasified and remove, thus obtain the polymer particles of drying regime.
With electron microscope, resulting polymers particulate to be photographed and the enlarged image obtained is shown in Fig. 1.As can be clear and definite by this image, the particle of this polymer particles group be all almost the concavity particulate of depression.
In comparative example 1, the visual shape of the particulate of gained is recorded in table 1, uses this particulate to be recorded in table 2 as the recording sensitivity of the thermosensitive recording body of heat-barrier material.
[comparative example 2]
Except being set to except 72.6g by the deionized water used when preparing aqueous phase, carry out emulsion dispersion, suspension polymerisation similarly to Example 2, thus obtain volumetric concentration and be 70% and the dispersion comprising the polymer particles of normal heptane.
Trial limit is stirred this dispersion limit and is heated to 79 ~ 100 DEG C in atmospheric conditions thus gasifies and remove the normal heptane being included in polymer particles inside, but the concentration of dispersing aid uprises, ability as surfactant rises, the normal heptane comprised in inside is removed in dispersion liquid by the shell of polymer particles, it is serious to foam in flask when distillating outer to system, is difficult to gasify and removes normal heptane.
[comparative example 3]
Operate similarly to Example 1, thus obtain the polymer particles comprising normal heptane.The azeotropic point adding normal heptane and water i.e. warm water (85 DEG C) 385.0g of more than 79 DEG C, attempt this dispersion under the reduced pressure of 300mmHg, make the normal heptane being included in polymer particles inside gasify and remove, but the temperature in flask does not rise to more than 79 DEG C, only there is the water in dispersion be vaporized and remove, be therefore difficult to gasify and remove normal heptane.
Its reason is: due to dispersion is placed in 300mmHg reduced pressure under, the vapour pressure of water declines, and the temperature in flask is lower than 79 DEG C.In the particulate that this composition is formed, in order to the shell of normal heptane by polymer particles is removed, need normal heptane is gasified.Now, because normal heptane is included in the inside of polymer particles, become and be difficult to reduce vapour pressure by decompression.Can think, if even if will just cannot not carry out near the boiling point be heated in flask close to normal heptane gasifying and removing at reduced pressure conditions, thus the vapour pressure of water reduces at reduced pressure conditions, temperature in flask significantly declines than the boiling point of the inner normal heptane comprised, and is therefore difficult to gasify and removes normal heptane.
[table 1]
[hollow rate and effect of heat insulation]
Respectively using the dry particles obtained in the moistening particulate obtained in embodiment 1 ~ 3, comparative example 1 and utilize seeded polymerization to obtain hollow particle as heat-barrier material blending in the intermediate layer of thermosensitive recording body, investigation thermosensitive recording body developing sensitivity.
For the structure of thermosensitive recording body, prepare priming coat coating and heat sensitive recording layer coating according to following formula.
(preparation of priming coat coating)
For the Hollow polymer particle obtained in the Hollow polymer particle obtained in embodiment 1 ~ 3, comparative example 1 and the commercially available hollow particle (Rohm and Haas company manufactures " trade name: Ropaque SN-1055: particle diameter 1 μm, hollow rate about 50%) utilizing seeded polymerization to synthesize, prepare priming coat coating according to following formula composition respectively.
(preparation of recording layer coating)
Coating is prepared according to following formula composition as recording layer coating.
(making of thermosensitive recording body)
At basic weight 64g/m 2high-quality neutralized paper one side on be 4g/m by each priming coat coating with dry weight 2mode carry out coating and dry, and be 3g/m by recording layer coating with dry weight on this priming coat 2mode carry out coating and dry, thus obtain thermosensitive recording body.In addition, after forming each layer, supercalender process is carried out.
(colour rendering test)
For each thermosensitive recording body of gained, carry out colour rendering test as follows.
Use Ohkura Electric Co., Ltd. the trade name " TH-PMD (thermal head 1653 Ω) " manufactured, at 24V, under 0.6 millisecond, 0.8 millisecond and 1.6 milliseconds, thermosensitive recording body is developed the color, use Macbeth (Macbeth) densimeter " RD-914 " to measure record concentration.Its result is recorded in table 2.
[table 2]
(evaluation)
All can clearly be gone out with data by table 2: compared with the hollow particle utilizing the seeded polymerization of " Ropaque " and so on to be made, the raising that the effect of heat insulation of the Hollow polymer particle of the non-foamed obtained according to the present invention is high, effectively contribute to the developing sensitivity of thermosensitive recording body, in addition, for the Hollow polymer particle of non-foamed, along with the minimizing of the concavity particulate of depression, the increase of Hollow polymer particle that hollow rate is high, effect of heat insulation uprises, and more effectively contributes to the raising of the developing sensitivity of thermosensitive recording body.
utilizability in industry
The manufacture method of the Hollow polymer particle that non-expansion type of the present invention and the high particle of hollow rate increase is as manufacturing the generation doing one's utmost the concavity particulate reducing the low depression of hollow rate, the method increasing the non-expansion type Hollow polymer particle of the generation of the high Hollow polymer particle of hollow rate is useful, the non-expansion type Hollow polymer particle obtained according to the present invention is as light material, improve light scattering material or liquid component contains retention agent, and then the heat-barrier material etc. contained in the intermediate layer to be formed between supporter and heat-sensitive color layer as the recording sensitivity for improving thermosensitive recording body is useful, and then, the moistening non-expansion type Hollow polymer particle obtained according to the present invention is good and coating preparation is simple to the compatibility of water and water dispersible, also can not to disperse during process and also friendly to environment, thus can effectively utilize.

Claims (8)

1. the manufacture method of a non-expansion type Hollow polymer particle, it is characterized in that, in aqueous medium, make to comprise and disperse as the polymerizable monomer of the material for the formation of polymer particles shell and the emulsifying mixture of crosslinking agent and organic solvent, and under the existence of polymerization initiator, make described polymerizable monomer and crosslinking agent suspension polymerisation, thus form the inner polymer particles comprising organic solvent, the organic solvent being included in this polymer particles inside is made to gasify and remove through the shell of this particulate, thus manufacture non-expansion type Hollow polymer particle
In the method, with polymer particles according to the mode that volumetric concentration is in the scope of 20 ~ 65% be dispersed in the aqueous dispersions in aqueous medium state, carry out the organic solvent being included in described polymer particles inside being gasified and removing thus particulate is made hollow operation under the condition fluid temperature of this aqueous dispersions being set as the temperature higher than the azeotropic point of aqueous medium and organic solvent.
2. the manufacture method of non-expansion type Hollow polymer particle according to claim 1, it is characterized in that, when making described polymerizable monomer and crosslinking agent suspension polymerisation, in aqueous medium, add one or more additives in the group being selected from and being made up of dispersant, dispersing aid.
3. the manufacture method of non-expansion type Hollow polymer particle according to claim 1 and 2, it is characterized in that, gasify making the organic solvent being included in described polymer particles inside and remove thus particulate is made hollow and obtain Hollow polymer particle aqueous dispersions in water be separated, be in the scope of 12 ~ 70 quality % to make solid component concentration.
4. the manufacture method of non-expansion type Hollow polymer particle according to claim 1 and 2, it is characterized in that, in aqueous medium, when making to comprise the emulsifying mixture dispersion as the material of the polymerizable monomer of the material for the formation of polymer particles shell and organic solvent, the mixture comprising aforementioned polymeric monomer and crosslinking agent and organic solvent is made to carry out emulsion dispersion with the volumetric concentration of the scope of 20 ~ 65%.
5. the manufacture method of non-expansion type Hollow polymer particle according to claim 1 and 2, it is characterized in that, after formation inside comprises the polymer particles of organic solvent, add dilution to dilute, be in the scope of 20 ~ 65% with the volumetric concentration of the aqueous dispersions making this polymer particles.
6. the manufacture method of non-expansion type Hollow polymer particle according to claim 5, it is characterized in that, this normal-temperature water is added to after diluting described aqueous dispersions as described dilution in use normal-temperature water, fluid temperature is warming up to the temperature higher than the azeotropic point of aqueous medium and organic solvent, thus makes the organic solvent being included in polymer particles inside gasify and remove.
7. the manufacture method of non-expansion type Hollow polymer particle according to claim 5, it is characterized in that, the serviceability temperature warm water higher than the azeotropic point of aqueous medium and organic solvent is as described dilution, described aqueous dispersions is warming up to the temperature higher than described azeotropic point, thus makes the organic solvent being included in polymer particles inside gasify and remove.
8. a non-expansion type Hollow polymer particle, it is obtained by the manufacture method of the non-expansion type Hollow polymer particle described in any one in claim 1 ~ 7.
CN201310129892.0A 2012-04-16 2013-04-15 Non-expansion type Hollow polymer particle and manufacture method thereof Active CN103372409B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-093174 2012-04-16
JP2012093174A JP5727962B2 (en) 2012-04-16 2012-04-16 Method for producing non-expandable hollow polymer fine particles

Publications (2)

Publication Number Publication Date
CN103372409A CN103372409A (en) 2013-10-30
CN103372409B true CN103372409B (en) 2015-09-02

Family

ID=49458621

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310129892.0A Active CN103372409B (en) 2012-04-16 2013-04-15 Non-expansion type Hollow polymer particle and manufacture method thereof

Country Status (3)

Country Link
JP (1) JP5727962B2 (en)
KR (1) KR101774079B1 (en)
CN (1) CN103372409B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019026899A1 (en) 2017-08-01 2019-02-07 日本ゼオン株式会社 Method for manufacturing latex and method for manufacturing hollow resin particle
US20210009816A1 (en) * 2018-02-22 2021-01-14 Arkema Inc. Water resistant voided polymer particles
JP7310797B2 (en) 2018-03-30 2023-07-19 日本ゼオン株式会社 Hollow resin particles and sheets
JP6513273B1 (en) * 2018-08-31 2019-05-15 三井化学株式会社 Resin particles
EP3858473A4 (en) * 2018-09-28 2022-03-30 Zeon Corporation Hollow particles, production method therefor, and aqueous dispersion containing hollow particles
US20220153881A1 (en) * 2019-02-06 2022-05-19 Zeon Corporation Method for producing hollow resin particles
CN113993918B (en) * 2019-06-27 2024-01-16 日本瑞翁株式会社 Method for producing hollow resin particles
CN111978441B (en) * 2020-08-07 2021-09-10 华东师范大学 Hollow polystyrene nano-particles and preparation method and application thereof
WO2022092076A1 (en) * 2020-10-30 2022-05-05 日本ゼオン株式会社 Method for prducing hollow particles, and hollow particles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5653922A (en) * 1994-06-06 1997-08-05 Biopore Corporation Polymeric microbeads and method of preparation
CN1525982A (en) * 2001-03-14 2004-09-01 ��Ԩ��ѧ��ҵ��ʽ���� Hollow polymer particles, method for preparing hollow polymer particles, porous ceramic filter, and method for preparing porous ceramic filter
CN101920180A (en) * 2009-06-09 2010-12-22 中国科学院理化技术研究所 Preparation method of millimeter-sized hollow polymer microsphere

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62201231A (en) * 1986-02-28 1987-09-04 Matsumoto Yushi Seiyaku Kk Preparation of minute foamed body
JP2003181274A (en) * 2001-12-18 2003-07-02 Sekisui Chem Co Ltd Method for manufacturing hollow polymer particles
JP4217200B2 (en) * 2004-09-24 2009-01-28 積水化学工業株式会社 Method for producing hollow resin fine particles, hollow resin fine particles, coating agent for antireflection film, and antireflection film
JP2006326501A (en) * 2005-05-26 2006-12-07 Casio Electronics Co Ltd Hollow microcapsule and its production method
CN101541415B (en) * 2006-11-14 2012-08-22 巴斯夫欧洲公司 Method for production of a mini suspoemulsion or suspension of sub-micron core/shell particles
JP2008231241A (en) * 2007-03-20 2008-10-02 Sanyo Chem Ind Ltd Hollow resin particle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5653922A (en) * 1994-06-06 1997-08-05 Biopore Corporation Polymeric microbeads and method of preparation
CN1525982A (en) * 2001-03-14 2004-09-01 ��Ԩ��ѧ��ҵ��ʽ���� Hollow polymer particles, method for preparing hollow polymer particles, porous ceramic filter, and method for preparing porous ceramic filter
CN101920180A (en) * 2009-06-09 2010-12-22 中国科学院理化技术研究所 Preparation method of millimeter-sized hollow polymer microsphere

Also Published As

Publication number Publication date
CN103372409A (en) 2013-10-30
KR20130116817A (en) 2013-10-24
JP2013221070A (en) 2013-10-28
KR101774079B1 (en) 2017-09-01
JP5727962B2 (en) 2015-06-03

Similar Documents

Publication Publication Date Title
CN103372409B (en) Non-expansion type Hollow polymer particle and manufacture method thereof
JP5484673B2 (en) Thermally foamable microspheres and their production methods and applications
JP5478824B2 (en) Polymer particles
CN104762066B (en) Compound microcapsules of storing energy through phase change and preparation method thereof
KR20150138012A (en) Cosmetic composition comprising amphiphilic anisotropic particles and method for manufacturing the same
SE2051007A1 (en) Heat-expandable microspheres and application thereof
JPWO2014109413A1 (en) Microcapsule heat storage material, manufacturing method thereof and use thereof
KR100648051B1 (en) Process for producing heat-expandable microcapsules
CN104804711B (en) Embedded enhanced thermal conduction microcapsules of storing energy through phase change and preparation method thereof
TW201735899A (en) Bi-continuous emulsion type composition comprising amphiphilic anisotropic particles
CN105732905A (en) Raspberry-shaped organic/organic compound emulsion particles and preparation method thereof
KR101889327B1 (en) Hybrid emulsion composition comprising different emulsion particle size and method for manufacturing the same
Tan et al. Preparation, characterization, and drug‐release properties of PEG‐DA‐based copolymer hydrogel microspheres
CN103933913B (en) The preparation method of notch cuttype temperature adjustment phase-change microcapsule emulsion
Nguyen et al. Janus particles by simplified RAFT-based emulsion polymerization process for polymer coating
KR20150138011A (en) Amphiphilic anisotropic particles and method for manufacturing the same
TW201726105A (en) Emulsion type cosmetic composition comprising pigment powder and method for preparing same
CN107022220A (en) The manufacture method of composite aggregation resin particle group and the particle swarm and the composition containing the particle swarm
JP2004217788A (en) Dispersion of colored fine particle and aqueous ink containing it
WO2016108659A1 (en) Surface-modified amphiphilic anisotropic powder, emulsion composition containing same, and method for preparing same
KR20170062057A (en) Hybrid emulsion composition comprising different emulsion particle size and method for manufacturing the same
KR20160081823A (en) Surface-modified amphiphilic anisotropic particles and emulsion composition comprising the same and method for manufacturing the same
KR20100103952A (en) Expandable microsphere for light weight material and manufacturing method thereof
KR20170061945A (en) Emulsion type cosmetic composition comprising wax microparticles
KR20170062058A (en) Chemically anisotropic particles and cosmetic composition comprising the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant