JP2006096963A - Luminous composite hollow particle and its resin composition - Google Patents
Luminous composite hollow particle and its resin composition Download PDFInfo
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本発明は、蓄光性複合中空粒子およびこれを含有する樹脂組成物に関する。The present invention relates to a luminous composite hollow particle and a resin composition containing the same.
米国特許第４，７２２，９４３号明細書には、中空球状重合体の表面に無機微粒子が付着してなるハイブリッド中空粒子を開示している。しかしながらこの米国特許は発泡性のマイクロスフェアを発泡させる際に粒子同士が凝集するのを防止するため、無機微粒子の存在下にマイクロスフェアを発泡させる技術を提供するものであり、上記ハイブリッド中空粒子を得ること自体を目的とするものではなく、また、そのハイブリッド中空粒子自体に固有の有用性を開示するものでもない。
一方、蓄光顔料は、夜光顔料とも呼ばれ、時計をはじめ、電子機器、インテリア、標識、防災機器、家電、照明、ファッション、自動車、釣り具、玩具、アウトドア用品など様々な分野で実用されている。また、従来の蓄光顔料は、その比重が２〜５もあり、例えば塗料として用いるとき、顔料が沈降してビヒクルと混合分散しにくく分散状態を長時間維持することが困難であるという問題がある。
その解決策として、特開昭６０−５５０５１号公報および特開平８−３２５４７７号公報には、シロップに予めメタクリル酸メチル系重合体をメタクリル酸メチル系単量体に溶解する方法、メタクリル酸メチル系単量体の一部を予備重合させる方法が開示されており、増粘剤等の分散安定剤を添加する方法があるが、粘度による塗工効率性等、問題点がある。
On the other hand, phosphorescent pigments, also known as luminescent pigments, are put to practical use in various fields such as watches, electronic equipment, interiors, signs, disaster prevention equipment, home appliances, lighting, fashion, automobiles, fishing gear, toys, outdoor products, etc. . Further, the conventional phosphorescent pigment has a specific gravity of 2 to 5, for example, when used as a paint, there is a problem that when the pigment is settled, it is difficult to mix and disperse with the vehicle and to maintain the dispersed state for a long time. .
As a solution, Japanese Patent Application Laid-Open No. 60-55051 and Japanese Patent Application Laid-Open No. 8-325477 disclose a method in which a methyl methacrylate polymer is previously dissolved in a syrup in a methyl methacrylate monomer. A method of prepolymerizing a part of the monomer is disclosed, and there is a method of adding a dispersion stabilizer such as a thickener, but there are problems such as coating efficiency due to viscosity.
本発明の蓄光性複合中空粒子は、増粘剤を用いることなく蓄光顔料を塗工表面に浮上させ、より高い輝度を満たすものである。
また同時に塗料の軽量化、蓄光顔料の実質添加量の削減を可能にする。The phosphorescent composite hollow particles of the present invention float a phosphorescent pigment on the coated surface without using a thickener and satisfy a higher luminance.
At the same time, it is possible to reduce the weight of the paint and reduce the amount of phosphorescent pigment added.
本発明の蓄光性複合中空粒子は、中空球状重合体の表面に蓄光顔料粉末が付着してなる複合中空粒子である。
また本発明の樹脂組成物は、上記の複合中空粒子を樹脂中に含有することを特徴とする。The phosphorescent composite hollow particles of the present invention are composite hollow particles obtained by attaching phosphorescent pigment powder to the surface of a hollow spherical polymer.
The resin composition of the present invention is characterized in that the above-described composite hollow particles are contained in the resin.
本発明に用いられる中空球状重合体は、例えば特公昭４２−２６５２４号公報、特公昭６０−２１７７０号公報等に開示されている方法で得られる熱膨張性マイクロカプセルを熱膨張させることにより得ることができる。即ち、重合性不飽和結合を有するモノマーを揮発性膨張剤および重合開始剤と混合し、これを適当な乳化分散剤等を含む水性媒体中で重合させて熱膨張性マイクロカプセルを得、これを加熱することにより熱膨張させて得ることができる。
熱膨張性マイクロカプセルを前述の米国特許第４，７２２，９４３号明細書に記載のごとく無機微粉末と共に加熱するとマイクロカプセルが微粉末がその表面に付着した状態で膨張するため一工程で複合中空粒子を得ることができる。The hollow sphere polymer used in the present invention is obtained by thermally expanding a thermally expandable microcapsule obtained by a method disclosed in, for example, Japanese Patent Publication No. 42-26524, Japanese Patent Publication No. 60-21770. Can do. That is, a monomer having a polymerizable unsaturated bond is mixed with a volatile swelling agent and a polymerization initiator, and this is polymerized in an aqueous medium containing a suitable emulsifying dispersant and the like to obtain thermally expandable microcapsules. It can be obtained by thermal expansion by heating.
When the heat-expandable microcapsule is heated together with the inorganic fine powder as described in the aforementioned US Pat. No. 4,722,943, the microcapsule expands with the fine powder adhering to the surface, so that the composite hollow is formed in one step. Particles can be obtained.
揮発性膨張剤としてはエタン、エチレン、プロパン、ブタン、イソブタン、ブテン、イソブテン、ネオペンタン、アセチレン、ヘキサン、ヘプタン等の脂肪族炭化水素、トリクロロフロロメタン、ジクロロジフロロメタン等のハロゲン化炭化水素、テトラアルキルシラン等の低沸点化合物が例示される。Volatile expanding agents include aliphatic hydrocarbons such as ethane, ethylene, propane, butane, isobutane, butene, isobutene, neopentane, acetylene, hexane, heptane, halogenated hydrocarbons such as trichlorofluoromethane and dichlorodifluoromethane, tetra Examples include low boiling point compounds such as alkylsilanes.
マイクロカプセルを構成する熱可塑性重合体としてはアクリル酸、メタクリル酸、イタコン酸、シトラコン酸、マレイン酸、フマル酸、ビニル安息香酸あるいはそれらのエステル、アクリロニトリル、メタクリロニトリル、スチレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、酪酸ビニル等のモノマーの単独または共重合体が例示される。特に好ましい重合体はアクリル酸、メタクリル酸あるいはそれらのエステル類、アクリロニトリル、塩化ビニリデン、メタクリロニトリル等から選ばれるモノマーの二種以上からなる共重合体である。これらの重合体はジビニルベンゼン、エチレングリコールジメタクリレート、トリアクリルフォルマール等で架橋されていてもよい。The thermoplastic polymer constituting the microcapsule includes acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, vinyl benzoic acid or esters thereof, acrylonitrile, methacrylonitrile, styrene, vinyl chloride, vinylidene chloride. Monomers or copolymers of monomers such as vinyl acetate and vinyl butyrate are exemplified. A particularly preferred polymer is a copolymer comprising two or more monomers selected from acrylic acid, methacrylic acid or esters thereof, acrylonitrile, vinylidene chloride, methacrylonitrile and the like. These polymers may be crosslinked with divinylbenzene, ethylene glycol dimethacrylate, triacryl formal, or the like.
熱膨張性マイクロカプセルは上述の発泡剤の存在下、上記モノマー類を必要ならば架橋性モノマー類と共に水性媒体中で乳化重合させる等の方法により製造することができる。この方法については特公昭４２−２６５２４号公報等に詳述されている。Thermally expandable microcapsules can be produced by a method such as emulsion polymerization of the above monomers together with crosslinkable monomers in an aqueous medium in the presence of the above foaming agent. This method is described in detail in Japanese Patent Publication No. 42-26524.
熱膨張性マイクロカプセルは平均粒径１〜１００μｍ、好ましくは１〜５０μｍのものが好ましく、これを加熱膨張することにより、平均粒径２〜５００μｍ、より好ましくは２〜３００μｍの中空球状重合体とすればよい。ここに平均粒径とはレーザ回折式粒度分布測定装置（例、日本電子株式会社ＨＥＲＯＳ ＆ ＲＯＤＯＳ）で測定した粒度分布のうち、累積分布の５０％点の粒径を云う。The heat-expandable microcapsules preferably have an average particle diameter of 1 to 100 μm, preferably 1 to 50 μm. By heating and expanding this, a hollow spherical polymer having an average particle diameter of 2 to 500 μm, more preferably 2 to 300 μm, and do it. Here, the average particle size refers to the particle size at the 50% point of the cumulative distribution among the particle size distributions measured by a laser diffraction type particle size distribution measuring apparatus (eg, JEOL HEROS & RODOS).
本発明において複合中空粒子を得るには、熱膨張性マイクロカプセルを加熱膨張させるに際し、これを蓄光顔料粉末の存在下に行なう等の方法により製造することができる。この様な方法は例えば米国特許第４，７２２，９４３号明細書に記載されている。具体的には例えば熱膨張性マイクロカプセルの含水ケーキまたは乾燥品と蓄光顔料粉末を任意の割合に混合し、これを適当な方法により加熱することにより得ることができる。加熱は一般的な接触伝熱型または直接加熱型の混合式乾燥装置を用いればよい。その機能として温度調節可能で原料を分散混合する能力、場合により乾燥を早めるため減圧装置や冷却装置を備えたものが好ましい。
加熱温度は熱膨張カプセルの最適膨張温度とするのが好ましく約６０〜２００℃、より好ましくは、熱膨張カプセルの種類にもよるが、９０〜１５０℃程度である。In order to obtain the composite hollow particles in the present invention, the thermally expandable microcapsules can be produced by a method of heating and expanding them in the presence of a phosphorescent pigment powder. Such a method is described, for example, in US Pat. No. 4,722,943. Specifically, it can be obtained, for example, by mixing the water-containing cake or dried product of heat-expandable microcapsules and phosphorescent pigment powder in an arbitrary ratio and heating them by an appropriate method. Heating may be performed using a general contact heat transfer type or direct heating type mixed drying apparatus. As its function, it is preferable to adjust the temperature and disperse and mix the raw materials, and in some cases, equipped with a decompression device or a cooling device in order to speed up drying.
The heating temperature is preferably about 60 to 200 ° C., more preferably about 90 to 150 ° C., although it depends on the type of the thermally expanded capsule.
蓄光顔料粉末としては例えば、ＣａＳ：Ｂｉ、ＺｎＳ：Ｃｕ、ＺｎＣｄＳ：Ｃｕなどの硫化物蛍光体、ＳｒＡｌ２Ｏ４、ＣａＡｌ２Ｏ４、ＢａＡｌ２Ｏ４などのアルミン酸化物などがあげられ、これらの１種または２種以上を混合して使用する。
蓄光顔料の好ましい粒径は平均粒径で０．０１〜５００μｍ、より好ましくは１〜５０μｍであり、特に中空球状重合体の平均粒径を１００としたとき０．１〜１００、より好ましくは１〜７０の粒径を有するものである。０．０１μｍ以上としたのは、それ以下のものは作製や取り扱いが困難であるとともに、発光効率が低下するおそれがあるからであり、５００μｍ以下としたのは、蓄光部材の被貼着性を向上させるためである。
蓄光顔料粉末の形状は特に限定的でなく、所望の物性、特に塗料などの樹脂に複合中空粒子を配合したときの分散性、輝度、被覆性等を考慮して選択すればよい。中空球状重合体と無機微粒子の配合比は重量比で５対９５〜５０対５０が好ましく、特に１０対９０〜４０対６０が好ましい。
本発明の蓄光性複合中空粒子は、これを従来の蓄光顔料粉末に代えて塗料に配合すれば好適である。Examples of the phosphorescent pigment powder include sulfide phosphors such as CaS: Bi, ZnS: Cu, ZnCdS: Cu, and aluminium oxides such as SrAl2O4, CaAl2O4, BaAl2O4, and the like, and one or more of these are mixed. And use it.
A preferable particle diameter of the phosphorescent pigment is 0.01 to 500 μm, more preferably 1 to 50 μm in terms of an average particle diameter, and particularly 0.1 to 100, more preferably 1 when the average particle diameter of the hollow sphere polymer is 100. It has a particle size of ˜70. The reason why the thickness is 0.01 μm or more is that production and handling is difficult for those smaller than that, and the luminous efficiency may be reduced. It is for improving.
The shape of the phosphorescent pigment powder is not particularly limited, and may be selected in consideration of desired physical properties, particularly dispersibility, luminance, covering property, etc. when composite hollow particles are blended with a resin such as a paint. The blending ratio of the hollow sphere polymer and the inorganic fine particles is preferably 5 to 95 to 50 to 50, and more preferably 10 to 90 to 40 to 60, by weight.
The phosphorescent composite hollow particle of the present invention is suitable if it is blended in a paint instead of the conventional phosphorescent pigment powder.
以下、実施例を挙げて本発明を詳細に説明する。
複合中空粒子（１）の製造
松坂貿易（株）レーディゲミキサーに熱膨張マイクロカプセル（松本油脂製薬製マツモトマイクロスフェアーＦ−８１ＧＳＤ、平均粒径５．７μｍ）と蓄光顔料（根本特殊化学株式会社製ＧＬＬ−３００ＦＦＳ、ＳｒＡｌ２Ｏ４、平均粒径 ３．４μｍ）を重量比１５／８５の比率で投入し、３分間混合後、ジャケット温度１４０℃で１０分間加熱した後９０℃に冷却して複合中空粒子（１）を得た。
得られた複合中空粒子（１）は真比重０．４、平均粒径は２４μｍであった。
複合中空粒子（２）の製造Hereinafter, the present invention will be described in detail with reference to examples.
Manufacture of composite hollow particles (1) Matsusaka Trading Co., Ltd.'s Ladige Mixer with thermal expansion microcapsules (Matsumoto Microsphere F-81GSD, average particle size 5.7 μm) and phosphorescent pigment (Nemoto Special Chemical Co., Ltd.) Company-made GLL-300FFS, SrAl 2 O 4 , average particle size 3.4 μm) is added at a ratio of 15/85 by weight, mixed for 3 minutes, heated at jacket temperature 140 ° C. for 10 minutes, and then cooled to 90 ° C. Thus, composite hollow particles (1) were obtained.
The obtained composite hollow particles (1) had a true specific gravity of 0.4 and an average particle size of 24 μm.
Production of composite hollow particles (2)
松坂貿易（株）レーディゲミキサーに熱膨張マイクロカプセル（松本油脂製薬製マツモトマイクロスフェアーＦ−６０Ｄ、平均粒径１７μｍ）と蓄光顔料（根本特殊化学株式会社製ＧＳＳ−Ｆ、ＺｎＳ：Ｃｕ、平均粒径１７μｍ）を重量比２０／８０の比率で投入し、３分間混合後、ジャケット温度１６０℃で１０分間加熱した後９０℃に冷却して複合中空粒子（２）を得た。
得られた複合中空粒子（２）は真比重０２、平均粒径は４５μｍであった。Matsusaka Trading Co., Ltd.'s Ladige Mixer with thermal expansion microcapsules (Matsumoto Yushi Seiyaku Matsumoto Microsphere F-60D, average particle size 17 μm) and phosphorescent pigment (Nemoto Special Chemical Co., Ltd. GSS-F, ZnS: Cu, An average particle diameter of 17 μm) was added at a weight ratio of 20/80, mixed for 3 minutes, heated at a jacket temperature of 160 ° C. for 10 minutes, and then cooled to 90 ° C. to obtain composite hollow particles (2).
The obtained composite hollow particles (2) had a true specific gravity of 02 and an average particle size of 45 μm.
塗料組成物（１〜３）の製造
攪拌機を取り付けた容器に水３００重量部を投入、攪拌状態にして、ポリアクリル酸系分散剤２０重量部、シリコン系消泡剤１重量部を投入した。続いて、上記複合中空粒子（１）２０重量部を投入した。１５分攪拌分散後、アクリル酸エステル樹脂系エマルジョン１０００重量部を投入、さらに１５分攪拌後、水系蓄光塗料組成物（１）を得た。
上記複合中空粒子（１）２０重量部の代わりに、蓄光顔料（根本特殊化学株式会社製ＧＬＬ−３００ＦＦＳ、平均粒径３．４μｍ）１７重量部を用い、同様の条件にて水系蓄光塗料組成物（２）を得た。
上記複合中空粒子（１）２０重量部の代わりに、蓄光顔料（根本特殊化学株式会社製ＧＬＬ−３００ＦＦＳ、平均粒径３．４μｍ）５０重量部を用い、同様の条件にて水系蓄光塗料組成物（３）を得た。
次いで、得られた水系蓄光塗料組成物（１）、（２）、（３）をコーターにて塗工後、常温乾燥し、各塗工表面の平滑性を観察した。また、これらの塗工面に蛍光灯にて３０分照射、直後の輝度を比較した。塗装表面の評価結果を表１に示す。Production of coating composition (1-3) 300 parts by weight of water was put into a container equipped with a stirrer and stirred, and 20 parts by weight of a polyacrylic acid dispersant and 1 part by weight of a silicon-based antifoaming agent were added. Subsequently, 20 parts by weight of the composite hollow particles (1) were charged. After stirring and dispersing for 15 minutes, 1000 parts by weight of an acrylate resin emulsion was added, and after further stirring for 15 minutes, a water-based phosphorescent coating composition (1) was obtained.
In place of 20 parts by weight of the composite hollow particles (1), 17 parts by weight of a phosphorescent pigment (GLL-300FFS, manufactured by Nemoto Special Chemical Co., Ltd., average particle size: 3.4 μm) is used, and a water-based phosphorescent paint composition under the same conditions. (2) was obtained.
In place of 20 parts by weight of the composite hollow particles (1), 50 parts by weight of a phosphorescent pigment (GLL-300FFS manufactured by Nemoto Special Chemical Co., Ltd., average particle size 3.4 μm) is used, and a water-based phosphorescent coating composition under the same conditions. (3) was obtained.
Subsequently, the obtained water-based phosphorescent paint compositions (1), (2), and (3) were coated with a coater and then dried at room temperature, and the smoothness of each coated surface was observed. Further, the coated surfaces were irradiated with a fluorescent lamp for 30 minutes, and the luminance immediately after the comparison was compared. The evaluation results of the painted surface are shown in Table 1.
塗料組成物（４〜６）の製造
攪拌機を取り付けた容器に水３００重量部を投入、攪拌状態にして、ポリアクリル酸系分散剤２０部、シリコン系消泡剤１重量部を投入した。続いて、上記複合中空粒子（２）２０重量部を投入した。１５分攪拌分散後、アクリル酸エステル樹脂系エマルジョン１０００重量部を投入、さらに１５分攪拌後、水系蓄光塗料組成物（４）を得た。
上記複合中空粒子（２）２０重量部の代わりに、蓄光顔料（根本特殊化学株式会社製ＧＳＳ−Ｆ、ＺｎＳ：Ｃｕ、平均粒径１７μｍ）１６重量部を用い、同様の条件にて水系蓄光塗料組成物（５）を得た。
上記複合中空粒子（２）２０重量部の代わりに、蓄光顔料（根本特殊化学株式会社製ＧＳＳ−Ｆ、ＺｎＳ：Ｃｕ、平均粒径１７μｍ）５０重量部を用い、同様の条件にて水系蓄光塗料組成物（６）を得た。得られた水系蓄光塗料組成物（６）では、蓄光顔料が沈降して混合分散しにくくまた分散状態を長時間維持することが特に困難であった。
次いで、得られた水系蓄光塗料組成物（４）、（５）、（６）をコーターにて塗工後、常温乾燥し、各塗工表面の平滑性を観察した。また、これらの塗工面に蛍光灯にて３０分照射、直後の輝度を比較した。塗装表面の評価結果を表１に示す。Production of Coating Composition (4-6) 300 parts by weight of water was put into a container equipped with a stirrer and stirred, and 20 parts of a polyacrylic acid-based dispersant and 1 part by weight of a silicon-based antifoaming agent were added. Subsequently, 20 parts by weight of the composite hollow particles (2) were charged. After stirring and dispersing for 15 minutes, 1000 parts by weight of an acrylate resin emulsion was added. After stirring for 15 minutes, a water-based phosphorescent coating composition (4) was obtained.
Instead of 20 parts by weight of the composite hollow particles (2), 16 parts by weight of a phosphorescent pigment (GSS-F manufactured by Nemoto Special Chemical Co., Ltd., ZnS: Cu, average particle size 17 μm) is used, and a water-based phosphorescent paint under the same conditions. A composition (5) was obtained.
Instead of 20 parts by weight of the composite hollow particles (2), 50 parts by weight of a phosphorescent pigment (GSS-F manufactured by Nemoto Special Chemical Co., Ltd., ZnS: Cu, average particle size 17 μm) is used, and a water-based phosphorescent paint under the same conditions. A composition (6) was obtained. In the obtained water-based phosphorescent coating composition (6), the phosphorescent pigment settled and it was difficult to mix and disperse, and it was particularly difficult to maintain the dispersed state for a long time.
Subsequently, the obtained water-based phosphorescent paint compositions (4), (5), and (6) were coated with a coater and then dried at room temperature, and the smoothness of each coated surface was observed. Further, the coated surfaces were irradiated with a fluorescent lamp for 30 minutes, and the luminance immediately after the comparison was compared. The evaluation results of the painted surface are shown in Table 1.
本発明の蓄光性複合中空粒子を含有する塗料は、塗工面の平滑性を損なうことなく、塗工面上部に蓄光顔料を浮上、分散させることができ、少量添加での高輝度性能を可能にした。これにより、広範囲の用途分野に好適に用いることができる。The paint containing the phosphorescent composite hollow particles of the present invention can float and disperse the phosphorescent pigment on the top of the coating surface without impairing the smoothness of the coating surface, enabling high luminance performance with a small amount of addition. . Thereby, it can be used suitably for a wide range of application fields.
Claims (4)
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| JP2004313106A JP2006096963A (en) | 2004-09-28 | 2004-09-28 | Luminous composite hollow particle and its resin composition |
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| JP2004313106A JP2006096963A (en) | 2004-09-28 | 2004-09-28 | Luminous composite hollow particle and its resin composition |
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| WO2007058379A1 (en) | 2005-11-21 | 2007-05-24 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microsphere, process for producing the same, and use |
| JP2008280144A (en) * | 2007-05-10 | 2008-11-20 | Sumitomo Rubber Ind Ltd | Paper feeding driven roller |
| WO2008142849A1 (en) | 2007-05-21 | 2008-11-27 | Matsumoto Yushi-Seiyaku Co., Ltd. | Process for production of thermally expandable beads and application thereof |
| WO2009050863A1 (en) | 2007-10-16 | 2009-04-23 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres, process for production of the same and uses thereof |
| WO2010143512A1 (en) | 2009-06-09 | 2010-12-16 | 松本油脂製薬株式会社 | Heat-expandable microsphere, method for producing same and use of same |
| WO2018025575A1 (en) | 2016-08-02 | 2018-02-08 | 松本油脂製薬株式会社 | Hollow resin particles and use of same |
| US11746205B2 (en) | 2018-01-31 | 2023-09-05 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres and applications thereof |
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2004
- 2004-09-28 JP JP2004313106A patent/JP2006096963A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058379A1 (en) | 2005-11-21 | 2007-05-24 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microsphere, process for producing the same, and use |
| JP2008280144A (en) * | 2007-05-10 | 2008-11-20 | Sumitomo Rubber Ind Ltd | Paper feeding driven roller |
| JP4593591B2 (en) * | 2007-05-10 | 2010-12-08 | 住友ゴム工業株式会社 | Paper-driven driven roller |
| WO2008142849A1 (en) | 2007-05-21 | 2008-11-27 | Matsumoto Yushi-Seiyaku Co., Ltd. | Process for production of thermally expandable beads and application thereof |
| WO2009050863A1 (en) | 2007-10-16 | 2009-04-23 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres, process for production of the same and uses thereof |
| US8247465B2 (en) | 2007-10-16 | 2012-08-21 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres, process for producing the same, and application thereof |
| WO2010143512A1 (en) | 2009-06-09 | 2010-12-16 | 松本油脂製薬株式会社 | Heat-expandable microsphere, method for producing same and use of same |
| EP2529830A2 (en) | 2009-06-09 | 2012-12-05 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres and a method of making heat-expandable microspheres and application thereof |
| WO2018025575A1 (en) | 2016-08-02 | 2018-02-08 | 松本油脂製薬株式会社 | Hollow resin particles and use of same |
| US10774192B2 (en) | 2016-08-02 | 2020-09-15 | Matsumoto Yushi-Seiyaku Co., Ltd. | Hollow resin particles and application thereof |
| US11746205B2 (en) | 2018-01-31 | 2023-09-05 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres and applications thereof |
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