JP3523075B2 - Fine particle aggregate and its manufacturing method - Google Patents
Fine particle aggregate and its manufacturing methodInfo
- Publication number
- JP3523075B2 JP3523075B2 JP22041898A JP22041898A JP3523075B2 JP 3523075 B2 JP3523075 B2 JP 3523075B2 JP 22041898 A JP22041898 A JP 22041898A JP 22041898 A JP22041898 A JP 22041898A JP 3523075 B2 JP3523075 B2 JP 3523075B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particle
- vinyl
- emulsion
- weight ratio
- particle aggregate
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗料や各種の表面処理
剤に使用される微粒子集合体およびその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine particle aggregate used for paints and various surface treatment agents and a method for producing the same.
【０００２】[0002]
【従来の技術】微粒子集合体は、塗料や各種の表面処理
剤に広く使用されているが、より耐熱性や強度の高い架
橋重合体微粒子の集合体が要求されている。2. Description of the Related Art Fine particle aggregates are widely used in paints and various surface treatment agents, but aggregates of crosslinked polymer fine particles having higher heat resistance and strength are required.
【０００３】微粒子集合体を製造する一般的な方法とし
ては例えば、特許公報第２５５９８３３号に記載されて
いる様に、重合体ラテックスを凝折した後に溶剤を加え
て粒子を融着させる方法などが知られているが、この方
法では、有機溶剤を使用するためにその処理が必要であ
ると共に、架橋重合体粒子は加熱による融着が起こりに
くく集合体としにくいという問題がある。As a general method for producing a fine particle aggregate, for example, as described in Japanese Patent Publication No. 2559833, there is a method in which a polymer latex is coagulated and then a solvent is added to fuse the particles. As is known, this method has a problem that the treatment is necessary because an organic solvent is used, and the cross-linked polymer particles are less likely to be fused by heating and difficult to form an aggregate.
【０００４】一方、架橋重合体微粒子を集合体とする方
法は、例えば、特開平２−７０７４１号公報に記載され
ている様に、不飽和カルボン酸を含む重合体を中和膨潤
させ種粒子として用い、それと異なる組成の重合体を第
２段階として乳化重合することにより集合体を得る方法
などが知られている。しかし、この方法では第２段階の
重合において新粒子が生成しない条件を選択する必要が
あり重合組成や重合条件に限りがあると共に、集合体の
強度が弱く破壊されやすいという問題がある。On the other hand, a method of forming fine particles of a crosslinked polymer into an aggregate is, for example, as described in JP-A-2-70741, neutralizing and swelling a polymer containing an unsaturated carboxylic acid into seed particles. There is known a method of obtaining an aggregate by using a polymer having a composition different from that as the second step and performing emulsion polymerization. However, this method has a problem that it is necessary to select conditions under which new particles are not formed in the second-stage polymerization, the polymerization composition and the polymerization conditions are limited, and the strength of the aggregate is weak and the aggregate is easily broken.
【０００５】以上の様に従来においては、架橋重合体微
粒子を容易に微粒子集合体とする方法および強度の高い
集合体は知られていなかった。As described above, hitherto, a method for easily forming crosslinked polymer fine particles into a fine particle aggregate and an aggregate having high strength have not been known.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の状況に
着目してなされたものであり、架橋重合体微粒子の集合
体を容易に製造する方法を提供することを目的とするも
のである。さらに、本発明の他の目的は、強度の高い微
粒子集合体を提供することである。The present invention has been made in view of the above situation, and an object thereof is to provide a method for easily producing an aggregate of crosslinked polymer fine particles. Still another object of the present invention is to provide a fine particle aggregate having high strength.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決した本発
明とは、ジビニルベンゼンと非架橋性単量体の重量比率
が２〜１０：９８〜９０であるビニル系単量体混合物、
または、トリメチロールプロパントリ（メタ）アクリレ
ートと非架橋性単量体の重量比率が５〜３０：９５〜７
０であるビニル系単量体を乳化重合して得られた架橋重
合体エマルションを噴霧式乾燥方法で乾燥させることを
要旨とするものである。Means for Solving the Problems The present invention, which has solved the above-mentioned problems, refers to a vinyl-based monomer mixture in which the weight ratio of divinylbenzene to the non-crosslinkable monomer is 2 to 10:98 to 90,
Alternatively, the weight ratio of trimethylolpropane tri (meth) acrylate to the non-crosslinkable monomer is 5 to 30:95 to 7.
The gist of the invention is to dry a crosslinked polymer emulsion obtained by emulsion polymerization of a vinyl-based monomer of 0 by a spray-type drying method.
【０００８】また、本発明の他の発明は、ジビニルベン
ゼンと非架橋性単量体の重量比率が２〜１０：９８〜９
０であるビニル系単量体混合物、または、トリメチロー
ルプロパントリ（メタ）アクリレートと非架橋性単量体
の重量比率が５〜３０：９５〜７０であるビニル系単量
体混合物を重合して得られた粒子径０．０１〜１μｍの
架橋微粒子が相互に連結してなる平均粒子径が２〜２０
０μｍである微粒子集合体を要旨とするものである。In another invention of the present invention, the weight ratio of divinylbenzene to the non-crosslinking monomer is 2 to 10:98 to 9.
0 or a vinyl monomer mixture in which the weight ratio of trimethylolpropane tri (meth) acrylate and non-crosslinking monomer is 5 to 30:95 to 70 is polymerized. The average particle size obtained by interconnecting the obtained crosslinked fine particles having a particle size of 0.01 to 1 μm is 2 to 20.
The gist is a fine particle aggregate having a size of 0 μm.
【０００９】[0009]
【発明の実施の形態】本発明者らは、ある特定範囲の組
成のビニル系単量体混合物を重合して得られる架橋微粒
子を、噴霧式乾燥方法によって乾燥させることにより、
耐熱性や強度が高く、原料微粒子の形状を保持した比表
面積の大きい微粒子集合体を得ることができることを見
いだし、本発明に到達した。BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have dried cross-linked fine particles obtained by polymerizing a vinyl-based monomer mixture having a composition in a specific range by a spray-type drying method,
The inventors have found that it is possible to obtain a fine particle aggregate having a high specific surface area that has high heat resistance and strength and retains the shape of the raw material fine particles, and has reached the present invention.
【００１０】本発明の微粒子集合体の原料となる架橋重
合体微粒子は、ジビニルベンゼンまたはトリメチロール
プロパントリ（メタ）アクリレートを特定範囲で含むビ
ニル系単量体の混合物を、従来公知の方法で乳化重合す
ることにより製造することが可能である。これらの架橋
性単量体と混合しうる非架橋性単量体とは、１分子内に
１個の重合性不飽和結合を有する単量体のことであり、
例えば、スチレンやαメチルスチレンなどの芳香族ビニ
ル化合物、（メタ）アクリル酸、（メタ）アクリル酸メ
チルや（メタ）アクリル酸エチルや（メタ）アクリル酸
ブチルなどの（メタ）アクリル酸エステル類、酢酸ビニ
ルやプロピオン酸ビニルなどのビニルエステル類、（メ
タ）アクリロニトリルなどのビニルシアン化合物、塩化
ビニルや塩化ビニリデンなどのハロゲン化ビニル化合
物、ブタジエンなどの共役ジエン類などが用いられる。The crosslinked polymer fine particles used as the raw material of the fine particle aggregate of the present invention are obtained by emulsifying a mixture of vinyl monomers containing divinylbenzene or trimethylolpropane tri (meth) acrylate in a specific range by a conventionally known method. It can be produced by polymerization. The non-crosslinkable monomer that can be mixed with these crosslinkable monomers is a monomer having one polymerizable unsaturated bond in one molecule,
For example, aromatic vinyl compounds such as styrene and α-methylstyrene, (meth) acrylic acid, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, Vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyan compounds such as (meth) acrylonitrile, halogenated vinyl compounds such as vinyl chloride and vinylidene chloride, and conjugated dienes such as butadiene are used.
【００１１】ビニル系単量体混合物中の架橋性単量体の
比率が高いほど、得られる微粒子の耐熱性や強度が高く
なるので好ましいが、高すぎると粒子間の融着が起こり
にくく、集合体とするのが困難である。架橋性単量体と
してジビニルベンゼンを用いた場合には、ビニル系単量
体混合物中の重量比率は通常２から１０重量％の範囲で
あり、好ましくは３〜８重量％である。架橋性単量体と
してトリメチロールプロパントリ（メタ）アクリレート
を用いた場合には、ビニル系単量体混合物中の重量比率
は通常５〜３０重量％の範囲であり、好ましくは８〜２
０重量％の範囲である。The higher the ratio of the crosslinkable monomer in the vinyl-based monomer mixture, the higher the heat resistance and strength of the obtained fine particles, which is preferable, but if it is too high, fusion between the particles is less likely to occur and the particles are aggregated. It is difficult to make a body. When divinylbenzene is used as the crosslinkable monomer, the weight ratio in the vinyl monomer mixture is usually in the range of 2 to 10% by weight, preferably 3 to 8% by weight. When trimethylolpropane tri (meth) acrylate is used as the crosslinkable monomer, the weight ratio in the vinyl monomer mixture is usually in the range of 5 to 30% by weight, preferably 8 to 2
It is in the range of 0% by weight.
【００１２】架橋重合体のエマルションを乳化重合方法
により製造する方法は特に限定されるものではなく、一
般的には、界面活性剤を用い、固形分濃度が５から６０
重量％の範囲、開始剤として無機過酸化物あるいはレド
ックス系開始剤を使用し、重合温度２０から１００℃の
範囲で実施することが可能である。また、得られる粒子
径は通常０．０１から１μｍの範囲である。The method for producing the emulsion of the crosslinked polymer by the emulsion polymerization method is not particularly limited. Generally, a surfactant is used and the solid content concentration is 5 to 60.
It is possible to carry out the polymerization in the range of 20 to 100 ° C. using an inorganic peroxide or a redox type initiator as the initiator in the range of wt%. The particle size obtained is usually in the range of 0.01 to 1 μm.
【００１３】得られた架橋重合体微粒子を集合体とする
には、噴霧式乾燥方法によって乾燥して粒子間の融着を
起こす方法が、集合体の粒子径や形状の制御が容易であ
り推奨される。噴霧式乾燥方法とは、一般的にスプレー
ドライヤーや気流乾燥機を用いて、ガス気流と共に水分
散体を噴霧して粒子を乾燥させる方法のことである。In order to make the obtained crosslinked polymer fine particles into an aggregate, a method of drying by a spray drying method to cause fusion between particles is recommended because the particle diameter and shape of the aggregate can be easily controlled. To be done. The spray-type drying method is a method in which particles are dried by generally spraying an aqueous dispersion together with a gas stream using a spray dryer or a stream dryer.
【００１４】噴霧式乾燥における固形分濃度は通常５〜
６０重量％であり、より好ましくは１０〜５０重量％で
ある。乾燥温度は、噴霧入口温度が１００〜２００℃の
範囲、粉体の出口温度が３０〜１００℃の範囲である。
固形分濃度、供給速度、乾燥温度などを適宜に調節する
ことにより、粒子径、粒子形状、かさ比重などを調整す
ることが可能であり、特に上記の条件に限定する必要は
ない。The solid content concentration in spray drying is usually 5 to 5.
It is 60% by weight, and more preferably 10 to 50% by weight. The drying temperature is such that the spray inlet temperature is in the range of 100 to 200 ° C and the powder outlet temperature is in the range of 30 to 100 ° C.
The particle diameter, particle shape, bulk specific gravity, etc. can be adjusted by appropriately adjusting the solid content concentration, supply rate, drying temperature, etc., and it is not particularly limited to the above conditions.
【００１５】本発明の微粒子集合体は、架橋重合体微粒
子の形状を保持しながら該架橋重合体微粒子が相互に連
結した集合体であり、比表面積が大きくかさ比重が小さ
いという特長を有している。さらに、従来の微粒子集合
体に比べ、強度が高いという特長を有している。また、
本発明の微粒子集合体の平均粒子径は２〜２００μｍの
範囲とすることが好ましく、この範囲を外れた集合体で
は、表面処理剤等に用いた場合に効果が低下する傾向に
ある。The fine particle aggregate of the present invention is an aggregate in which the crosslinked polymer fine particles are connected to each other while maintaining the shape of the crosslinked polymer fine particles, and has a characteristic that the specific surface area is large and the bulk specific gravity is small. There is. Further, it has a feature that the strength is higher than that of the conventional fine particle aggregate. Also,
The average particle size of the aggregate of fine particles of the present invention is preferably in the range of 2 to 200 μm, and the aggregate outside this range tends to have a reduced effect when used as a surface treatment agent or the like.
【００１６】[0016]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例−１
撹拌機、温度計、還流冷却器付きの２Ｌセパラブルフラ
スコに、純水（４３３ｇ）とハイテノールＮ０８（第一
工業製薬製アニオン界面活性剤、０．９ｇ）を仕込み、
窒素置換を行いながら、撹拌下に７０℃まで昇温した。
７０℃に昇温後、メチルメタクリレート（５７ｇ）を添
加し、その５分後に、過硫酸カリウムの２％水溶液（７
０ｇ）を添加した。Example 1 Pure water (433 g) and Hitenol N08 (Daiichi Kogyo Seiyaku Co., Ltd. anionic surfactant, 0.9 g) were charged into a 2 L separable flask equipped with a stirrer, a thermometer, and a reflux condenser. ,
While purging with nitrogen, the temperature was raised to 70 ° C. with stirring.
After heating to 70 ° C., methyl methacrylate (57 g) was added, and 5 minutes later, a 2% aqueous solution of potassium persulfate (7
0 g) was added.
【００１８】予め調製しておいたプレエマルション（メ
チルメタクリレート：６０８ｇ、ジビニルベンゼン：３
５ｇ、純水：７５２ｇ、ハイテノールＮ０８：３４ｇ）
を、過硫酸カリウム添加の２０分後より７０℃にて等速
度で４時間かけて添加した。添加終了後、７５℃まで昇
温し２時間の熟成を行い、その後、４０℃まで冷却して
架橋重合体エマルションを得た。このエマルションの平
均粒子径を光散乱式粒度分布計で測定した所、０．２μ
ｍであった。Pre-emulsion prepared in advance (methyl methacrylate: 608 g, divinylbenzene: 3
5g, pure water: 752g, Hitenol N08: 34g)
Was added 20 minutes after the addition of potassium persulfate at 70 ° C. at a constant rate over 4 hours. After the addition was completed, the temperature was raised to 75 ° C., aging was carried out for 2 hours, and then cooled to 40 ° C. to obtain a crosslinked polymer emulsion. The average particle size of this emulsion was measured by a light scattering type particle size distribution analyzer and found to be 0.2 μm.
It was m.
【００１９】次いで、該エマルションをヤマト科学製の
スプレードライヤーで次の条件下にて乾燥して粉体を得
た。供給速度：１４ml/min、噴霧圧：２．３kg/cm2、風
量：０．３m3/min、入口温度：１５０℃、出口温度：６
０℃。Then, the emulsion was dried with a spray dryer manufactured by Yamato Scientific Co., Ltd. under the following conditions to obtain a powder. Supply rate: 14 ml / min, spray pressure: 2.3 kg / cm 2 , air volume: 0.3 m 3 / min, inlet temperature: 150 ° C, outlet temperature: 6
0 ° C.
【００２０】得られた該粉体をマルチサイザーII型（コ
ールター社製）で測定した所、平均粒子径は１４μｍで
あった。また、該粉体は電子顕微鏡（ＳＥＭ）観察によ
ると、架橋重合体微粒子からなる原料微粒子が形状を保
持したまま相互に連結してなる微粒子集合体であった。When the obtained powder was measured with a Multisizer II type (manufactured by Coulter Co.), the average particle diameter was 14 μm. Further, the powder was a fine particle aggregate formed by observing with electron microscope (SEM), raw material fine particles made of crosslinked polymer fine particles were connected to each other while maintaining their shapes.
【００２１】実施例−２
プレエマルション中のビニル系単量体をメチルメタクリ
レート（５３８ｇ）、トリメチロールプロパントリメタ
クリレート（１０５ｇ）とした以外は、実施例―１と同
様の操作を繰り返して粉体を得た。得られた粉体は平均
粒子径が１８μｍであり、原料微粒子が形状を保持した
まま相互に連結してなる微粒子集合体であった。Example-2 A powder was obtained by repeating the same procedure as in Example-1 except that methyl methacrylate (538 g) and trimethylolpropane trimethacrylate (105 g) were used as vinyl monomers in the pre-emulsion. Obtained. The obtained powder had an average particle diameter of 18 μm and was a fine particle aggregate in which raw material fine particles were interconnected while maintaining their shape.
【００２２】比較例―１
プレエマルション中のビニル系単量体をメチルメタクリ
レート（５３８ｇ）、ジビニルベンゼン（１０５ｇ）と
した以外は、実施例―１と同様の操作を繰り返した。し
かし、原料微粒子は集合体とならず、得られた乾燥粉体
の粒子径は１μｍ以下であった。Comparative Example-1 The same operation as in Example-1 was repeated except that the vinyl-based monomer in the pre-emulsion was methyl methacrylate (538 g) and divinylbenzene (105 g). However, the raw material fine particles did not form an aggregate, and the particle diameter of the obtained dry powder was 1 μm or less.
【００２３】比較例―２
プレエマルション中のビニル系単量体をメチルメタクリ
レート（６２２ｇ）、トリメチロールプロパントリメタ
クリレート（２１ｇ）とした以外は、実施例―１と同様
の操作を繰り返して比較用粉体を得た。得られた比較用
粉体の粒子径は１５μｍであった。しかし、電子顕微鏡
による観察では、原料微粒子が形状を保持しておらず、
風船状の１個の粒子であり比表面積も小さかった。Comparative Example-2 A powder for comparison was prepared by repeating the same procedure as in Example-1, except that the vinyl-based monomer in the pre-emulsion was methyl methacrylate (622 g) and trimethylolpropane trimethacrylate (21 g). Got the body The particle diameter of the obtained comparative powder was 15 μm. However, in observation with an electron microscope, the raw material fine particles do not retain their shape,
It was one balloon-shaped particle and had a small specific surface area.
【００２４】[0024]
【発明の効果】本発明の製造方法によれば、従来では困
難であった架橋重合体微粒子の集合体を容易な方法で製
造することが可能であり、得られる微粒子集合体は、微
粒子の形状を残しており、強度や耐熱性に優れた比表面
積の大きな集合体である。EFFECTS OF THE INVENTION According to the production method of the present invention, it is possible to produce an aggregate of crosslinked polymer fine particles, which has been difficult in the past, by an easy method, and the obtained fine particle aggregate has a fine particle shape. It is an aggregate having a large specific surface area with excellent strength and heat resistance.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 6/00 - 6/28 C08J 3/24 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) C08F 6/00-6/28 C08J 3/24
Claims (7)
量比率が２〜１０：９８〜９０であるビニル系単量体混
合物、または、トリメチロールプロパントリ（メタ）ア
クリレートと非架橋性単量体の重量比率が５〜３０：９
５〜７０であるビニル系単量体混合物を、乳化重合して
得られた架橋重合体エマルションを、噴霧入口温度が１
００〜２００℃の範囲、粉体の出口温度が３０〜１００
℃の範囲である噴霧式乾燥方法で乾燥させることを特徴
とする、平均粒子径０．０１〜１μｍの架橋重合体微粒
子が、形状を保持したまま、相互に連結してなる平均粒
子径が２〜２００μｍである微粒子集合体の製造方法。1. A vinyl-based monomer mixture having a weight ratio of divinylbenzene and a non-crosslinkable monomer of 2 to 10:98 to 90, or trimethylolpropane tri (meth) acrylate and a non-crosslinkable monomer. Body weight ratio is 5 to 30: 9
The cross-linked polymer emulsion obtained by emulsion polymerization of a vinyl-based monomer mixture of 5 to 70 has a spray inlet temperature of 1
In the range of 00 to 200 ° C, the outlet temperature of the powder is 30 to 100
Crosslinked polymer fine particles having an average particle diameter of 0.01 to 1 μm , characterized by being dried by a spray-type drying method in the range of ℃.
An average grain formed by the children connecting to each other while maintaining their shape.
A method for producing a fine particle aggregate having a child diameter of 2 to 200 µm .
後噴霧式乾燥方法で乾燥させることを特徴とする請求項
１記載の微粒子集合体の製造方法。 2. After the emulsion polymerization, aging is further performed,
A post-spray drying method is used for drying.
1. The method for producing a fine particle aggregate according to 1.
０．０１〜１μｍの架橋重合体微粒子の間に融着が起こ
り相互に連結した状態となっていることを特徴とする請
求項１または２記載の微粒子集合体の製造方法。 3. The average particle size according to the above spray drying method.
Fusion occurs between 0.01 to 1 μm crosslinked polymer particles.
A contract characterized by being connected to each other
The method for producing a fine particle aggregate according to claim 1 or 2.
０：９８〜９０であるビニル系単量体混合物、または、
トリメチロールプロパントリ（メタ）アクリレートと非
架橋性単量体の重量比率が５〜３０：９５〜７０である
ビニル系単量体混合物を、プレエマルジョンとして添加
して架橋重合体エマルションを得ることを特徴とする請
求項１〜３に記載の微粒子集合体の製造方法。 4. In the emulsion polymerization, the weight ratio of divinylbenzene and non-crosslinkable monomer is 2-1.
0: 98-90 vinyl-based monomer mixture, or
With trimethylolpropane tri (meth) acrylate
The weight ratio of the crosslinkable monomer is 5 to 30:95 to 70.
Add vinyl monomer mixture as pre-emulsion
To obtain a crosslinked polymer emulsion
The method for producing a fine particle aggregate according to claim 1.
活性剤を仕込んだ中に添加することによって、架橋重合
体エマルションを得ることを特徴とする請求項１〜４に
記載の微粒子集合体の製造方法。 5. In the emulsion polymerization, the pre-emulsion is previously interfaced with a non-crosslinkable monomer.
Cross-linking polymerization by adding the activator into the charged
Body emulsion is obtained, In Claims 1-4 characterized by the above-mentioned.
A method for producing the fine particle aggregate described.
比率が２〜１０：９８〜９０であるビニル系単量体混合
物、または、トリメチロールプロパントリ（メタ）アク
リレートと非架橋性単量体の重量比率が５〜３０：９５
〜７０であるビニル系単量体混合物を重合して得られた
平均粒子径０．０１〜１μｍの架橋重合体微粒子が、原
料粒子が形状を保持したまま、当該粒子の間に融着が起
こり相互に連結した状態となっている平均粒子径が２〜
２００μｍである微粒子集合体。6. A vinyl-based monomer mixture having a weight ratio of divinylbenzene to a non-crosslinkable monomer of 2 to 10:98 to 90, or trimethylolpropane tri (meth) acrylate and a non-crosslinkable monomer. Body weight ratio is 5 to 30:95
It is 70 cross-linked polymer particles having an average particle diameter 0.01~1μm obtained by polymerizing a vinyl monomer mixture, Hara
The material particles retain their shape, and fusion occurs between the particles.
The average particle size in the state of being connected to each other is 2 to
A fine particle aggregate having a size of 200 μm.
６記載の微粒子集合体。 7. A use as a paint or a surface treatment agent.
6. The fine particle assembly according to item 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22041898A JP3523075B2 (en) | 1998-08-04 | 1998-08-04 | Fine particle aggregate and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22041898A JP3523075B2 (en) | 1998-08-04 | 1998-08-04 | Fine particle aggregate and its manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| JP2000053720A JP2000053720A (en) | 2000-02-22 |
| JP3523075B2 true JP3523075B2 (en) | 2004-04-26 |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4907012B2 (en) * | 2000-05-12 | 2012-03-28 | 株式会社日本触媒 | Fine particle aggregate and method for producing the same |
| US6610405B2 (en) | 2000-05-12 | 2003-08-26 | Nippon Shokubai Co., Ltd. | Grain aggregate and producing method thereof, and light-diffusing agent |
| WO2003098724A1 (en) | 2002-05-22 | 2003-11-27 | Nippon Shokubai Co., Ltd. | Solid oxide type fuel cell-use electrode support substrate and production method therefor |
| US7829626B2 (en) * | 2006-03-15 | 2010-11-09 | Rohm And Haas Company | Aqueous compositions comprising polymeric duller particle |
| KR101588226B1 (en) | 2011-08-31 | 2016-01-25 | 세키스이가세이힝코교가부시키가이샤 | Resin particle aggregate, method for manufacturing same and application of same |
| KR101646649B1 (en) | 2014-08-28 | 2016-08-08 | 세키스이가세이힝코교가부시키가이샤 | Aggregate of polymeric particles |
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