• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    A process for producing heat-expandable microspheres including a thermoplastic resin shell and a blowing agent encapsulated therein. The process includes the steps of dispersing a polymerizable component and the blowing agent in an aqueous dispersion medium having a pH of 7 or less and containing a fine-particle metal compound having a mean particle size ranging from 1.0 to 10 nm, and polymerizing the polymerizable component. The amount of the fine-particle metal compound ranges from 0.15 to 20 parts by weight to 100 parts by weight of the total amount of the polymerizable component and the blowing agent. Also disclosed are heat-expandable microspheres produced by dispersing a polymerizable component and a blowing agent in an aqueous dispersion medium containing colloidal silica and polymerizing the polymerizable component. Also disclosed is a composition containing the heat-expandable microspheres and a base component, a formed product, a slurry composition for use in forming a negative electrode of a lithium-ion secondary battery and a negative electrode.
    公开号:SE1651073A1
    申请号:SE1651073
    申请日:2014-12-15
    公开日:2016-07-18
    发明作者:Nakatomi Daisuke；Ueda Kazunari；Miki Katsushi
    申请人:Matsumoto Yushi-Seiyaku Co Ltd；
    IPC主号:
    专利说明:

    [28] [28]FIG. 2 is a schematic diagram of an example of the hollow particles Reference Numerals List
    [29] [29]Reference numerals used to identify various features in the drawings include the following: 11Shell of thermoplastic resin 12Blowing agent 1Hollow particles (fine-particle-coated hollow particles) 2Shell 3Hollow 4Fine particle (in a state of adhesion) Fine particle (in a state of fixation in a dent) DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
    [30] [30]The invention will now be described in greater detail with reference to the drawings. However, the present invention should not be construed as being limited thereto. Process for producing heat-expandable microspheres
    [31] [31]The process of the present invention produces heat-expandable microspheres essentially comprising a thermoplastic resin shell and a blowing agent encapsulated therein. The process comprises the steps of dispersing a polymerizable component and the blowing agent in an aqueous dispersion medium of pH 7 or less containing a fine-particle metal compound having a mean particle size ranging from 1.0 to 10 nm, and polymerizing the polymerizable component, wherein the amount of the fine-particle metal compound ranges from 0.15 to 20 parts by weight to 100 parts by weight of the total amount of the polymerizable component and the blowing agent.
    [32] [32]The blowing agent is not specifically restricted except that it should be a thermally vaporizable substance, and includes, for example, C3-C13 hydrocarbons such as propane, (iso)butane, (iso)pentane, (iso)hexane, (iso)heptane, (iso)octane, (iso)nonane, (iso)decane, (iso)undecane, (iso)dodecane and (iso)tridecane; hydrocarbons having a carbon number greater than 13 and not greater than 20, such as (iso)hexadecane and (iso)eicosane; hydrocarbons from petroleum fractions such as pseudocumene, petroleum ether, and normal paraffins and isoparaffins having an initial boiling point ranging from 150 to 260 °C and/or being distilled at a temperature ranging from 70 to 360 °C; halides of C1-C12 hydrocarbons, such as methyl chloride, methylene chloride, chloroform and carbon tetrachloride ; fluorine-containing compounds, such as hydrofluoroether; silanes having C1-05 alkyl groups, such as tetramethyl silane, trimethylethyl silane, trimethylisopropyl silane and trimethyl-n-propyl silane; and compounds which thermally decompose to generate gases, such as azodicarbonamide, N,N'-dinitrosopentamethylenetetramine and 4,4'-oxybis(benzenesulfonyl hydrazide). One of or a combination of at least two of those blowing agents can be employed. The aforementioned blowing agents can be any of linear, branched or alicyclic compounds, and should preferably be aliphatic compounds.
    [202] [202]Table 2 Examples Comparative examples 11 1 2 3 4 6 7 Aqueous dispersion medium Deionized water (g) 690 6400 400 600 680 500 798 7 NaCl(g) 180 Colloidal silica dispersion A(g) --- --- - 400 --------- 2 60 Colloidal silica dispersion B(g) Colloidal silica dispersion C(g) Colloidal silica dispersion D(g) 200 E(g) Colloidal silica dispersion Colloidal silica dispersion F(g) 80 --- --- --- --- --- --- --- --- Colloidal silica dispersion G(g) ADA-DEA(g) --- 6 6.0 6.0 6.0 6.0 --- --- --- PVP(g) 1.0 1.6 0.3 0.
    [203] [203]Table 3 Abbreviation Detail NaCl Sodium chloride Colloidal silica dispersion A Containing -wt% of colloidal silica with the mean particle size of 5 nm and specific surface are of 550 m2/g Colloidal silica dispersion B Containing -wt% of colloidal silica with the mean particle size of 11 nm and specific surface are of 260m2/g Colloidal silica dispersion C Containing -wt% of colloidal silica with the mean particle size of 12 nm and specific surface are of 238 m2/g Colloidal silica dispersion D Containing -wt% of colloidal silica with the mean particle size of 0.8 nm and specific surface are of 3400 m2/g Colloidal silica dispersion E Containing -wt% of colloidal silica with the mean particle size of 1.3 nm and specific surface are of 2090 m2/g Colloidal silica dispersion F Containing 18-wt% of colloidal silica with the mean particle size of 2.9 nm and specific surface are of 938 m2/g Colloidal silica dispersion G Containing 20-wt% of colloidal silica with the mean particle size of 8.5 nm and specific surface are of 320 m2/g PVP Polyvinyl pyrrolidone ADA-D EA Adipic acid-diethanolamine condensate (effective concentration 50 wt%) CMPEI Polyethyleneimines (having -CH2COONa as the substituent with 80 % substitution ratio, having a weight-average molecular weight of 50,000), also referred to as carboxymethylated polyethyleneimine sodium salt EDTA Ethylenediaminetetraacetic acid tetrasodium salt A1C13.6HAluminum chloride hexahydrate AN Acrylonitrile MAN Methacrylonitrile MA Methyl acrylate MMA Methyl methacrylate IBX Isobornyl methacrylate 49 VC12 Vynilidene chloride PMI N-Phenylmaleimide MAA Methacrylic acid Cross-linking agent A Trimethylolpropane trimethacrylate Cross-linking agent B Ethyleneglycol dimethacrylate Isobutane 2-Methyl propane Neopentane 2,2-Dimethylpropane Isopentane 2-Methylbutane Isooctane 2,2,4-Trimethylpentane Initiator A 2,2'-Azobis(2,4-dimethyDvaleronitrile Initiator B Di-2-ethylhexylperoxydicarbonate (70 %) The colloidal silica used in the processes of Examples 1 to 11, which have mean particle size from 1.3 to 8.5 nm, are estimated to have contributed to the low viscosity of the polymerization liquids during polymerization step. The low viscosity enabled efficient removal of the heat generated in the polymerization and control of the viscosity increase of the polymerization liquid due to agglomeration of the components and reaction products. Thus the advantage and stability of the processes were clearly demonstrated. The amount of particulate silica coating the surface of the heat-expandable microspheres of small particle size is estimated to be the minimum required to produce the microspheres, and it contributes to good dispersibility of the microspheres and controlling the viscosity increase of paints or similar materials blended with the microspheres.
    The aqueous dispersion medium in Comparative example 1 contained a high amount of colloidal silica in order to produce heat-expandable microspheres of small particle size. Thus the polymerization liquid had high viscosity and the heat generated in the polymerization could not be removed efficiently.The resultant heat-expandable microspheres contained a high amount of ash and did not fuse when thermally expanded owing to the high amount of silica coating their surface. Such microspheres, however, cannot be dispersed well in paints to adversely affect the smoothness of the paint film surface.
    In Comparative example 2, the amount of colloidal silica, which had a mean particle size of 5 nm, in the aqueous dispersion medium was excessive for the total amount of the polymerizable monomers and blowing agent. The excessive colloidal silica made unstable globules of the oily mixture in the aqueous dispersion medium to cause the agglomeration and solidification of the components during polymerization and failure in production of the heat-expandable microspheres.
    In Comparative example 3, the colloidal silica, which had a mean particle size of 0.8 nm, in the aqueous dispersion medium could not stabilize the globules of the oily mixture dispersed in the aqueous dispersion medium. The unstable globules resulted in the agglomeration and solidification of the components during polymerization and failure in production of the heat-expandable microspheres.
    In Comparative example 4, the components agglomerated during polymerization and impaired the stability of the production. The surface of the resultant heat-expandable microspheres was coated with silica of comparatively large particle size which could not sufficiently control fusing of the heat-expandable microspheres during thermal expansion.
    In Comparative example 5, the aqueous dispersion medium contained a large amount of colloidal silica having large mean particle size. Thus the resultant heat-expandable microspheres contained a considerable amount of ash which can inhibit dispersion of the microspheres in paints to adversely affect the smoothness of the paint film surface.
    In Comparative example 6, the aqueous dispersion medium contained only a small amount of colloidal silica, and caused agglomeration and solidification of the components during polymerization and failure in the production of heat-expandable microspheres.
    In Comparative example 7, the aqueous dispersion medium had a pH higher than 7 which made unstable globules of the oily mixture in the aqueous dispersion medium to cause agglomeration and solidification of the components during polymerization and failure in the production of heat-expandable microspheres. 51 The heat-expandable microspheres could be processed into hollow particles as in Example Al and Comparative example Al mentioned below, according to the wet thermal expansion method described in Japanese Patent Application Publication 1987-201231. Example Al Preparation of hollow particles by wet thermal expansion An aqueous dispersion (slurry) containing 5 wt% of the heat-expandable microspheres produced in Example 2 was prepared. The microspheres in the slurry were expanded in the wet thermal expansion method described in Japanese Patent Application Publication 1987-201231, where the slurry was fed through a slurry introducing pipe to an expansion tube (specified as SUS304TP in JIS, 16 mm in diameter, 120-ml capacity) at a flow rate of 5 L/min. Steam (at 147 °C, of a pressure of 0.3 MPa) was fed to the tube through a steam introducing pipe to be mixed with the slurry so as to thermally expand the microspheres under wet condition. The temperature of the mixture of the slurry and steam was controlled at 115 °C.
    The slurry containing the hollow particles was flowed out through the tip of the expansion tube and mixed with cooling water (at 15 °C) to be cooled down to 50 to 60 °C. The cooled slurry was dehydrated with a centrifugal dehydrator to obtain a composition containing 10 wt% of hollow particles (and 90 wt% of water).
    The resultant hollow particles were isolated. The hollow particles had a mean particle size of 2.7 ium and a true specific gravity of 0.20, and contained 5.5 wt% of ash.
    Fifty grams of the resultant hollow particles was added to 950 g of a water- based acrylic coating (Water-based coating for versatile use, manufactured by Asahipen Corporation), mixed in a mixer with a dispersion blade, and defoamed with a planetary mixer (ARE-500, manufactured by Thinky) to be prepared into a paint composition. The paint composition was screened through a 200-mesh polyester mesh fabric, and no residue was left 52 on the mesh fabric to prove good dispersibility of the hollow particles.
    The paint composition was applied to a steel plate to make 0.6-mm thick dry film. The film was smooth enough and imparted thermal insulation property to the plate. Comparative example Al Wet hollow particles and a paint composition were prepared in the same manner as that in Example Al except that the heat-expandable microspheres of Example 2 were replaced by the heat-expandable microspheres of Comparative example 1.
    The resultant hollow particles had a mean particle size of 3.1 tm and a true specific gravity of 0.20, and contained 13.6 wt% of ash. The resultant paint composition was screened through a 200-mesh polyester mesh fabric in the same manner as that in Example Al, and agglomerated materials about 1 mm particle size were left on the mesh fabric to prove poor dispersibility of the hollow particles due to high ash content.
    Twenty parts by weight of the heat-expandable microspheres of Example 4 (with a thermoplastic resin shell having a softening point of 109 °C) and 80 parts by weight of titanium oxide (TIPAQUE CR-50, with a mean particle size about 0.25 ium, manufactured by Ishihara Sangyo Kaisha, Ltd.) were mixed in a separable flask. Then the mixture was heated to 140 °C with agitation to obtain fine-particle-coated hollow particles.
    The resultant fine-particle-coated hollow particles had a mean particle size of 4.1 lam and a true specific gravity of 0.53. The content in the measuring flask after measuring the true specific gravity of the fine-particle-coated hollow particles was stood still for 30 minutes, and the separated liquid phase was clear to show that the titanium oxide firmly coated the hollow particles and none of them left the surface of the hollow particles. Comparative example A2 Fine-particle-coated hollow particles were produced in the same manner as that in Example A2 except that the heat-expandable microspheres were replaced by the heat- 53 expandable microspheres of Comparative example 1.
    The resultant fine-particle-coated hollow particles had a mean particle size of 3.1 lam and a true specific gravity of 0.83. The content in the measuring flask after measuring the true specific gravity of the fine-particle-coated hollow particles was stood still for 30 minutes. The separated liquid phase was turbid to imply that the titanium oxide did not firmly coat the hollow particles. The turbid liquid phase was caused by high amount of ash and silicon contained in the heat-expandable microspheres used to produce the hollow particles, in other words, the surface of the heat-expandable microspheres was covered with silica which prohibited the adhesion of titanium oxide to the surface of the hollow particles or released the titanium oxide. Such fine-particle-coated hollow particles causing high amount of released titanium oxide increased the viscosity of paints and sealants.
    A slurry composition for the negative electrode of a lithium-ion secondary battery was prepared with the hollow particles produced in the aforementioned processes to test the lifespan of the resultant lithium-ion secondary battery.
    Example of production B1 A slurry composition for the negative electrode was prepared by mixing 100 parts by weight of graphite (MCMB2528, produced by Osaka Gas Co., Ltd.) as the negative electrode active material, 1.0 parts by weight of carboxymethyl cellulose (CELLOGEN 7A, produced by DKS Co., Ltd.) as a viscosity improver, 2.5 parts by weight of a SBR binder (BM-400B, 40 wt% concentration, produced by Zeon Corporation) and 50 parts by weight of deionized water. The slurry composition was applied to the surface of a 20-ium thick copper foil with a Comma coater to make a 150-ium thick film. The slurry was then vacuum-dried at 120 °C for 1 hour, pressed with a pressure ranging from 1 x 2 to 3 x 2 Nimm2, and dried in a vacuum oven at 120 'V for 12 hours to be processed into a 80-ium thick negative electrode sheet. 54 A slurry composition for the positive electrode was prepared by mixing 100 parts by weight of LiCo02 having a volumetric mean particle size of 12 gm as the positive electrode active material, 2 parts by weight of acetylene black (HS-100, produced by Denka Company Limited) as a conductive auxiliary, 25 parts by weight of a polyvinylidene difluoride binder (#7208, 8-wt% N-methylpyrrolidone solution, produced by Kureha Corporation) and N-methylpyrrolidone to make a solid concentration of 70 wt%. The slurry composition for the positive electrode was applied to the surface of a 20-um thick aluminum foil to make a 150-tam thick dry film. The slurry was then dried at 60 °C for 2 min and heated at 120 °C for 2 min to be processed into a positive electrode sheet.
    An aluminum casing was prepared for the battery casing. The positive electrode mentioned above was cut into a 4-cm square and placed on the casing to make the surface without the slurry film contact to the casing.
    Then a separator (Celgard 2500, manufactured by Celgard LLC.) was cut into a 5-cm square and placed on the surface of the positive electrode active material layer of the positive electrode. Then the negative electrode sheet mentioned above was cut into a 4.2-cm square and placed on the separator to make the negative electrode active material contact to the separator. A liquid electrolyte (consisting of 68.5: 30: 1.5 mixture of ethylene carbonate, diethyl carbonate and vinylene carbonate in volumetric ratio and 1 M of LiPF6) was poured in the aluminum casing without introducing air bubbles. Then the aluminum casing was closed by heat-sealing at 150 °C to make a laminated lithium-ion secondary battery (laminated cell). Capacity retention of the battery The laminated lithium-ion secondary battery was stood still at 25 °C for 24 hours, then charged to 4.2 V at 1C and discharged to 3.0 V at 1C at 25 °C to measure the initial capacity, Co. Then the battery was charged to 4.2 V at 1C and discharged to 3.0 V at 1C at 60 °C repeatedly, and the capacity after 1,000 cycles of charge/discharge, C2, was measured. The capacity retention of the battery, AC, was calculated by the following expression.
    AC (%) = C2 Co X 100 Example Cl A composition containing 10 wt% of hollow particles (and 90 wt% of water) was prepared in the same manner as the wet thermal expansion method of Example Al except that the heat-expandable microspheres of Example 2 were replaced by the heat-expandable microspheres of Example 6.
    The resultant hollow particles were isolated. The hollow particles had a mean particle size of 7.0 ium and a true specific gravity of 0.09, and contained 4.8 wt% of ash and 1.4 wt% of silicon.
    Then a hollow particles-containing slurry composition for the negative electrode was prepared by adding 10 parts by weight of the composition containing 10 wt% of hollow particles mentioned above to the slurry composition for the negative electrode of Example of production Bl.
    A lithium-ion secondary battery was made in the same manner as that in Example of production B1 except that the slurry composition for the negative electrode of Example of production B1 was replaced by the hollow particles-containing slurry composition for the negative electrode.
    The capacity retention of the resultant lithium-ion secondary battery calculated was in the ratio of 118 to 100 of the capacity retention of the lithium-ion secondary battery of Example of Production B1 which was made without the hollow particles. The result proves the improvement in the capacity retention.
    Comparative example Cl A composition containing 10 wt% of hollow particles (and 90 wt% of water) 56 was prepared in the same manner as the wet thermal expansion method of Example Cl except that the heat-expandable microspheres of Example 6 were replaced by the heat-expandable microspheres of Comparative example 1.
    The resultant hollow particles were isolated. The hollow particles had a mean particle size of 4.5 lam and a true specific gravity of 0.2, and contained 14 wt% of ash and 5.5 wt% of silicon.
    Then a lithium-ion secondary battery was made in the same manner as that in Example Cl, and the negative electrode of the battery swelled. Comparative example C2 A composition containing 10 wt% of hollow particles (and 90 wt% of water) was prepared in the same manner as the wet thermal expansion method of Example Cl except that the heat-expandable microspheres of Example 6 were replaced by the heat-expandable microspheres of Comparative example 4 and the slurry temperature for the wet thermal expansion (expansion temperature) was set at 110 °C.
    The resultant hollow particles were isolated. The hollow particles had a mean particle size of 49 um and a true specific gravity of 0.02, and contained 4.0 wt% of ash and 1.2 wt% of silicon. In addition, the hollow particles contained agglomerated materials.
    Then a lithium-ion secondary battery was made in the same manner as that in Example Cl. The capacity retention of the resultant lithium-ion secondary battery calculated was in the ratio of 78 to 100 of the capacity retention of the lithium-ion secondary battery of Example of Production B1 which was made without the hollow particles. The result proves the decrease in the capacity retention.
    The improved capacity retention of the battery of Example Cl can be attributed to the hollow particles having small particle size and containing small amount of silicon, which contributed to the decrease of the binder between the particles of the active 57 material.
    The negative electrode of the battery of Comparative example Cl can have been swelled by the liquid electrolyte in the battery due to the hollow particles containing high amount of silicon.
    The decreased capacity retention of the battery of Comparative example C2 can have been caused by the agglomerated materials in the hollow particles though the hollow particles contained only a small amount of silicon.
    Industrial Applicability The process of the present invention produces heat-expandable microspheres having a small particle size, containing minimum ash and which are thermally expanded into hollow particles having good dispersibility.
    The heat-expandable microspheres of the present invention can be used as a lightweight additive for putties, paints, inks, sealants, mortar, paper clay, ceramic, etc., and also as an additive to matrix resins processed in injection molding, extrusion molding and pressure molding to be made into foamed products having excellent sound insulation, thermal insulation, heat-shielding, and sound absorbency.
    The invention has been described in detail with reference to the above embodiments. However, the invention should not be construed as being limited thereto. It should further be apparent to those skilled in the art that various changes in form and detail of the invention as shown and described above may be made. It is intended that such changes be included within the spirit and scope of the claims appended hereto. 58
    权利要求:
    Claims (14)
    [1] 1. Process for producing heat-expandable microspheres essentially comprising a shell of thermoplastic resin and a blowing agent encapsulated therein, the process comprising the steps of; dispersing a polymerizable component and the blowing agent in an aqueous dispersion medium having a pH of 7 or less and containing a fine-particle metal compound having a mean particle size ranging from 1.0 to 10 nm; and polymerizing the polymerizable component; wherein the amount of the fine-particle metal compound ranges from 0.15 to 20 parts by weight to 100 parts by weight of the total amount of the polymerizable component and the blowing agent.
    [2] 2. Claim 2 The process for producing heat-expandable microspheres according to Claim 1, wherein the fine-particle metal compound is colloidal silica.
    [3] 3. Claim 3 The process for producing heat-expandable microspheres according to Claim 2, wherein the heat-expandable microspheres contain 5 wt% or less of silicon.
    [4] 4. Claim 4
    [5] 5. The process for producing heat-expandable microspheres according to any one of Claims 1 to 3, wherein the pH of the aqueous dispersion medium ranges from 1.5 to 5. Claim 5 The process for producing heat-expandable microspheres according to any one of Claims 1 to 4, wherein the specific surface area of the fine-particle metal compound ranges from 270 to 2720 m2/g.
    [6] 6. Claim 6 The process for producing heat-expandable microspheres according to any one of Claims 1 to 5, wherein the mean particle size of the heat-expandable microspheres ranges from 0.01 to 10 gm.
    [7] 7. Claim 7
    [8] 8. The process for producing heat-expandable microspheres according to any one of Claims 1 to 6, wherein the heat-expandable microspheres contain 10 wt% or less of ash. Claim 8 Heat-expandable microspheres essentially comprising a shell of thermoplastic resin and a blowing agent encapsulated therein, the microspheres being produced by 59 dispersing a polymerizable component and the blowing agent in an aqueous dispersion medium containing colloidal silica and polymerizing the polymerizable component; wherein the heat-expandable microspheres have a mean particle size ranging from 0.01 to 10 gm and contain 5 wt% or less of silicon.
    [9] 9. Claim 9 Hollow particles produced by thermally expanding the heat-expandable microspheres produced in the process according to any one of Claims 1 to 7 and/or the heat-expandable microspheres according to Claim 8. Claim
    [10] 10. The hollow particles according to Claim 9, wherein the hollow particles contain fine particles coating their outer surface.
    [11] 11. Claim 11 A composition containing at least one particulate material selected from the group consisting of the heat-expandable microspheres produced in the process according to any one of Claims 1 to 7, the heat-expandable microspheres according to Claim 8 and the hollow particles according to Claim 9 or 10; and a base component.
    [12] 12. Claim 12 A formed product produced by forming the composition according to Claim 11.
    [13] 13. Claim 13 A slurry composition for the negative electrode of a lithium-ion secondary battery, the slurry composition containing at least one particulate material selected from the group consisting of the heat-expandable microspheres produced in the process according to any one of Claims 1 to 7, the heat-expandable microspheres according to Claim 8 and the hollow particles according to Claim 9 or 10; a negative electrode binder; and a negative electrode active material.
    [14] 14. Claim 14 A negative electrode of a lithium-ion secondary battery manufactured by applying the slurry composition for the negative electrode of a lithium-ion secondary battery according to Claim 13 to a current collector. 60 Patentansokan nr / Patent application No: 1651073-7 foljande bilaga finns en oversattning av patentkraven till svenska. Observera att det är patentkravens lydelse pa engelska som A Swedish translation of the patent claims is enclosed. Please note that only the English claims have legal effect.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013268170|2013-12-26|
    PCT/JP2014/083075|WO2015098586A1|2013-12-26|2014-12-15|Method for producing thermally expandable microspheres and use of same|
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