• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Provided is a process for efficiently producing heat-expandable microspheres having high solvent resistance. The process produces the heat.-expandable microspheres composed of a shell of a thermoplastic resin and a blowing agent encapsulated therein and vaporissable by heating, and includes the steps of preparing an aqueous suspension by dispersing an oily mixture containing a polymemable component, the blowing agent, and a polymerisation initiator containing, as an essential component, a peroxide A having a theoretical active oxygen content of at least 7.8 %, and polymerising the polymerisahle component hi the oily mixture.
    公开号:SE1650395A1
    申请号:SE1650395
    申请日:2014-08-25
    公开日:2016-03-24
    发明作者:Koichi Sakabe；Katsushi Miki；Yasuyuki Nomura
    申请人:Matsumoto Yushi-Seiyaku Co Ltd；
    IPC主号:
    专利说明:

    [1] Certain implementations refer to a .. process for producing hea.t-expandable microsphoros Background 100021 Heat-expandable microspheres composed of a shell of thermoplastic resin and a blowing agent encapsulated therein are generally called heat-expandable microcapsales. The monomers constituting the thermoplastic resin usually include vinylidene chloride, (meth.) Acrylonitrile mon.omers, and (meth) acrylate ester monomers. The blowing agent mainly used includes -hydrocarbons such as isobutane and. isopentane (refer to 'PT' ', 1).
    [3] Pill .: UST '3015972 PTL .2: d1997- 196 Summary 30 Technical Problem
    [4] The object of the present invention is to provide a process for efficiently producing beat-expandable in iCTOSp hOrCs having high solvent resistance.
    [5] [0005] The inventors diligently studied to solve the problem mentioned above, and found that the 5 problem could be solved by using a specific polymei'l4atien taitiaton to achieve the present invention.
    [15] The weight ratio of the nitrite monomers is not specifically restricted, and should preferably so no -Prom 20 to 100 wt% of the monomer COmponent, niqm preferably from 30 to 100 wt%, further more preferably from 40 to 100 wt. %, yet further more preferably from 50 to 100 wt%, and most preferably from CIO to 100 wt%. A monomer component containing less than 20 wt% of the nitrite monomers can cause poor solvent resista.nee of resultant microspheres. The weight ratio of the nitrile monomers in the monomer component for the beat-exparidable microspheres which is contained in the fihn-forming composition mentioned below should preferably at least 50 wt%, more preferably at least 60 wt%, further more preferably at least 70 wt%, yet further more preferably at least 80 wt%, and most preferably at least 90 wt%. The upper limit of the preferable weight ratio of the nitrile monomers is 100 wt%, The weight ratio of the nitrite monomers within the range mentioned above will contribute to good storage stability of the Elni-lbrining composition containing the microspheres.
    [22] [0022] Peroxyesters and / or peroxyketals used for the peroxide A are preferable for improved. solvent resistance of resultant ancrospheres. .A peroxide A having a ring structure to. the molecule is preferable kw improved heat resistance of resultant microspheres. The ring structure includes those composed of .aliphatic hydrocarbons or aromatic hydrocarbcm.s, and a ring structure composed of an aliphatic hydrocarbons is preferable f.or improved heat resistance of reSU ta nt microspheres.
    [26] [0026] The amount of the polymerization initiator (active ingredient) is not specifically restricted, and should preferably range from 0.3 to 8A.) Parts by weight to 100 parts by weight of the monomer component.
    [29] [0029] The aqueous dispersion medium can contain a dispersion stabilizer or dispersion stabilizing auxiliary in addition to the electrolytes and water-soluble compounds, The dispersion stabilizer is not specifically restricted, and includes, for example, calcium triphosphate, magnesium pyrophosphate and calcium pyrophosphate produced by double reaction: colloidal silica, alumina sal, and magnesium hydroxide. One of or a combination of at least two of those dispersion stabilizers can be used.
    [30] [0030] The amount of the dispersion stabilizer should prefe.rably range from 0.1 to 2.0 parts by weight to 1.00 parts by weight of the polymerizahle component, and more preferably from 0.5 to 10 parts by weight.
    [31] The aqueous dispersion medium is prepared by blending a water-soluble compound and optionally a dispersion stabilizer and / or dispersion stabilizing auxiliary with water (delonized water). The pH of the aqueous dispersion medium during polymerization is adjusted depending on the variants of the water-soluble, compound, dispersion stabilizer, and dispersion stabilizing auxiliary.
    [37] [0037] (where s is a standard deviation of the particle size of the microspheres, is a mean. Particle size of the micrespheres, "xi 'is the particle size of the i-th particle, and a represents the number of particles) The thermal expansion p: 1: .............. of the heat-expandable microspheres usually decreases after the microspheres are laitInersed in a solvent. The solvent resistance of 10 heat-expandable ralcrospheres is evaluated by comparing the thermal expansion perlbrmance of the heat-expandable microspheres after immersion in a solvent (thermal expansion performance after solvent immersion) to the thermal expansion performance of the heat expandablemierespheres before immersion in a solvent (initial thermal expansion performance), and by calculating the percentage of the thermal expansion performance retained after the solvent immersion. The solvent resistance of the heat-expandable mieroisphere „s is measured and evaluated by the methods described in the following examples. [ 00381 The solvent resistance of heat-expandable microspheres (represented by the thermal expansion performance retained after solvent immersion) is preferably at least 60 of the 20 initial thermal expansion performance, more preferably at least 70 further more preferably at least 80%, „yet further more preferably at least 85%, yet further more preferably- at least 90%, particularly more preferably at least 95%. „and most preferably 100 IX. The upper limit of the solvent resistance of heat-expandablelicrowheres is 100%. fleat-expandable microspheres retaining less than 60% of thermal expansion performance after solvent immersion have poor solvent resistance, and a film-forming composition containing such heat-expandable microsphere -, ‘, .. can have poor storage stability.
    [55] [0055] The amount of the plasticizer contained in the film-forming composition is not specifically restricted, and should preferably range from 5 to 2000 parts by weight to 100 parts by weight of a film-forming base component., More preferably from 10 to 1500 parts by. weight, further more preferably from 15 to 1000 parts by weight, and most preferably from. 20 to 500 parts by weight. The amount of the plasticizer beyond the range mentioned above can result in extremely high or low viscosity of the film -fh ing eompositiOn to impair the workability in painting.
    [68] [0068] True specific gravity of the fine.-partieleceated hollow particles The true specific gravity of the fine-particle-coated hollow particles V : .. W determined by the liquid substitution method (Archimedeen method) with isopropyl alcohol in an atmosphere at 25 '' 'C and 50' I.2.11 (relative humidity) as described below.
    [82] [0082] Expansion ratio (times) DI / D2 Then the vinyl chloride resin paint composition was stored at 40 "C for 7 days, and farmed into an expanded vinyl chloride resin coating Min in the same ma user as mentioned above, 20 The expansion ratio of the vinyl chloride resin coating film was 2 times, which was the same as that mentioned above and proved that the expansion ratio did not change during storage.
    [84] [0084] Comparative example ill A vinyl chloride resin paint, eofftposition was prepared in the sarne manner as that in 10 Example B1 except that the heat-expandable microspheres A were replaced by the heat-expandable microspheres G obtained in Comparative example 2. The properties of the composition were measured in the same manner as that in Example 131 ..
    [90] Example D2 2.0An adhesive composition was prepared in the same manner as that in Example Di except that the fine-particle-coated hollow particles A was replaced by the fine-particle-conted particles E obtained in Example C2, The composition was made into two samples of coating film .. One of the samples was cured under the curing condition 1 to be made into the cured sample I. which had the density of 0,91 glem ''. 9Another sample was cured under the curing condition 2 to be made into the cured sample 2, which also had the density of 0,91 gfcras, The same density of the cured samples 1 and 2 shows that the adhesive composition had good storage stability. (0091.
    [93] The low-density polyethylene composition was: injection molded at 160 ue. by a 85If rij e C f, ion molder (J85A11), manufactured by The Japan Steel Works, Ltd., equipped with a shut-off nozzle which controls the expansion of the lied-expandable microspheres in the cylinder to stabilize the lightweight effect) to be made into a forrned product. The expansion ratio of the resultant formed product was 2,3 times, The: expansion ratio of the formed product was calculated from the densities of the composition and formed product. The densities of the formed product eD2) made of the low-density polyethylene composition and the density (1) 1) of the low-density polyethylene 25 composition before molding were determined in the liquid substitution method with a precision AX200 (manufactured by Shimadzu Corporation ). The expansion ratio was calculated from D1 and D2 by the following expression.
    Expansion ratio (times) .1.) 1 / E) 2 Industrial Appity l009,11 The process efficiently produces heat-expandable microspheres -having -high solvent resistance. The heat-expandable mierospheres retain stable expansion ratio in an organic P CT / JP20 11/072084 (WO2015 / 029916 Al) solvent, and are useful for -film-fortaing compositions, such as paint co compositions and. synthetic-leather compositions.
    'Reference Signs List [0095I 11 Shell of thermoplastic resin 12 Blowing agent 1 Hollow particles (fine-particle-coated hollow particles) 2 Shell' 3 Hollow 4 Fine particle (in a state of adhesion) 5 Fine particle (in a state of fixation) in a dent) 34
    权利要求:
    Claims (12)
    [1] 1. [Claim 41 The process for producing heat-expandable microspheres according to any one of Claims 1 to 3, wherein the peroxide A is a compound containing a ring structure in a molecule. [Claim 51 The process for producing heat-expandable microsphores according to any one of Claims 1 to 4, wherein the number of the active oxygen bonds of the peroxide A is in the range of 2 to 5 per molecule. [Claim 61 The process for producing heat-expandable microspheres according to any one of Claims 1 to 5, wherein the molecular weight of the peroxide A is at least 275, [Claim 7] The heat-expandable microspheres produced in the process according to any one of Claims I to :6. [Claim 8] Hollow particles produced by heating and expanding the heat-expandable micrt-)spheres according to Claim 7, [Claim 91 The hollow particles according to Claim 8, wherein enters surface of the hollow particles are coated with fine particles. [Claim 101 A composition containing a base component and at least one particulate material selected from the group consisting of the heat-expandable microspheres according to Claim 7 30 and the hollow particles according to Claims 8 and 9. [Claim 111 The composition according to Claim 10, the composition 'being a film-forming composition, [Claim 121 A product manufactured using the composition according to Claim 10 or 11. CO Patentansokan nr / Patent application No: 1650395- 1 fOljande bilaga finns en oversattning av patentkraven till svenska. Observera att det är patentkravens lydelse pa engelska som galler. A Swedish translation of the patent claims is enclosed. Please note that only the English claims have legal effect.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3615972A|1967-04-28|1971-10-26|Dow Chemical Co|Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same|
    JP2894990B2|1996-06-14|1999-05-24|松本油脂製薬株式会社|Thermally expandable microcapsules with excellent heat resistance and solvent resistance|
    JP4620812B2|1998-01-26|2011-01-26|株式会社クレハ|Method for producing foamable microspheres|
    JP2003251170A|2002-02-27|2003-09-09|Sekisui Chem Co Ltd|Method for producing thermally expandable microcapsule|
    JP2004155999A|2002-11-08|2004-06-03|Sekisui Chem Co Ltd|Thermally expandable microcapsule|
    WO2004074396A1|2003-02-24|2004-09-02|Matsumoto Yushi-Seiyaku Co., Ltd.|Thermoexpansible microsphere, process for producing the same and method of use thereof|
    JP5107718B2|2005-10-20|2012-12-26|松本油脂製薬株式会社|Thermally expandable microsphere and method for producing the same|
    JP4297974B2|2007-10-16|2009-07-15|松本油脂製薬株式会社|Thermally expansible microspheres, production method and use thereof|
    JP2011094068A|2009-10-30|2011-05-12|Kaneka Corp|Polypropylene-based resin composition for injection foam molding and injection foam molded article comprising the resin composition|
    JP5650960B2|2010-09-06|2015-01-07|積水化学工業株式会社|Method for producing foamable thermoplastic resin masterbatch|US10774192B2|2016-08-02|2020-09-15|Matsumoto Yushi-Seiyaku Co., Ltd.|Hollow resin particles and application thereof|
    CN108219182B|2016-12-15|2020-11-24|上海略发化工科技有限公司|Preparation method of thermal expansion microspheres|
    EP3680306A4|2017-09-06|2021-01-27|NOF Corporation|Heat-expandable microcapsules, production method therefor, and foamed molded article|
    CN108929459A|2018-08-01|2018-12-04|张陈钇衡|A kind of preparation method of the polymer foaming expandable microspheres for decorative wall paper|
    CN109293250A|2018-09-25|2019-02-01|丹阳博亚新材料技术服务有限公司|It is a kind of to be conducive to demould convenient and breakage-proof film plating process|
    CN109851995B|2018-12-20|2021-04-27|武汉理工大学|Preparation method of wave-absorbing composite material|
    EP3819333A1|2019-11-07|2021-05-12|Rouven Seitner|Foamed spheres, moulded part formed from a plurality of foamed spheres and method for producing foamed spheres|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013176293|2013-08-28|
    PCT/JP2014/072084|WO2015029916A1|2013-08-28|2014-08-25|Method for producing thermally expandable microspheres|
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