JP2000053720A - Particulate aggregate and its production - Google Patents
Particulate aggregate and its productionInfo
- Publication number
- JP2000053720A JP2000053720A JP10220418A JP22041898A JP2000053720A JP 2000053720 A JP2000053720 A JP 2000053720A JP 10220418 A JP10220418 A JP 10220418A JP 22041898 A JP22041898 A JP 22041898A JP 2000053720 A JP2000053720 A JP 2000053720A
- Authority
- JP
- Japan
- Prior art keywords
- drying
- vinyl
- aggregate
- weight ratio
- meth
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000037396 body weight Effects 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- -1 aromatic vinyl compound Chemical class 0.000 abstract description 2
- 150000001993 dienes Chemical class 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101000879758 Homo sapiens Sjoegren syndrome nuclear autoantigen 1 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 102100037330 Sjoegren syndrome nuclear autoantigen 1 Human genes 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
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 Aggregates of fine particles are widely used in paints and various surface treatment agents, but aggregates of crosslinked polymer fine particles having higher heat resistance and higher 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, a method in which a polymer latex is coagulated and then a solvent is added to fuse the particles. Although known, this method has a problem that the treatment is necessary because an organic solvent is used, and that the crosslinked polymer particles are less likely to be fused by heating and are 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, as a method of forming crosslinked polymer fine particles into an aggregate, for example, as described in JP-A-2-70741, a polymer containing an unsaturated carboxylic acid is neutralized and swelled to obtain seed particles. A method is known in which a polymer having a composition different from that used is subjected to emulsion polymerization as a second step to obtain an aggregate. However, in this method, it is necessary to select conditions under which new particles are not generated in the polymerization in the second stage, and there are limitations on the polymerization composition and polymerization conditions, and there is a problem that 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, there has not been known a method of easily forming crosslinked polymer fine particles into a fine particle aggregate and an aggregate having high strength.
【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。SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and has as its object 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。According to the present invention, there is provided a vinyl monomer mixture in which the weight ratio of divinylbenzene to a non-crosslinkable monomer is from 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 present invention is to dry a crosslinked polymer emulsion obtained by emulsion polymerization of a vinyl monomer which is 0 by a spray 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 aspect of the present invention, the weight ratio of divinylbenzene to the non-crosslinkable monomer is from 2 to 10:98 to 9
0 or a vinyl monomer mixture in which the weight ratio of trimethylolpropane tri (meth) acrylate to the non-crosslinkable monomer is 5 to 30:95 to 70. The resulting crosslinked fine particles having a particle diameter of 0.01 to 1 μm have an average particle diameter of 2 to 20 which are interconnected.
The gist is a fine particle aggregate 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 present inventors dried crosslinked fine particles obtained by polymerizing a vinyl monomer mixture having a specific range of composition by a spray drying method,
The present inventors have found that it is possible to obtain a fine particle aggregate having high heat resistance and high strength and a large specific surface area while maintaining the shape of the raw material fine particles, and have 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 a raw material of the fine particle assembly of the present invention are prepared 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) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, Vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile, vinyl halide 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 proportion of the crosslinkable monomer in the vinyl-based monomer mixture, the higher the heat resistance and strength of the obtained fine particles, and therefore, it is preferable. Difficult to make 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%.
The range is 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.
The polymerization can be carried out at a polymerization temperature of 20 to 100 ° C. using an inorganic peroxide or a redox initiator as the initiator in the range of weight%. 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 the particles is preferred because the particle diameter and shape of the aggregate can be easily controlled. Is done. The spray drying method generally refers to a method in which particles are dried by spraying an aqueous dispersion together with a gas stream using a spray dryer or a flash 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
It is 60% by weight, 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, and the like can be adjusted by appropriately adjusting the solid concentration, the supply rate, the drying temperature, and the like, and it is not particularly necessary to limit 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 interconnected while maintaining the shape of the crosslinked polymer fine particles, and has a feature that the specific surface area is large and the bulk specific gravity is small. I have. Further, it has a feature that the strength is higher than that of a conventional fine particle aggregate. Also,
The average particle diameter of the fine particle aggregate of the present invention is preferably in the range of 2 to 200 μm. In the case where the average particle diameter is out of this range, the effect tends to decrease when used for 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 will be 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 A 2 L separable flask equipped with a stirrer, thermometer and reflux condenser was charged with pure water (433 g) and Hytenol N08 (Daiichi Kogyo Seiyaku anionic surfactant, 0.9 g). ,
The temperature was raised to 70 ° C. while stirring with nitrogen.
After the temperature was raised to 70 ° C., methyl methacrylate (57 g) was added, and 5 minutes later, a 2% aqueous solution of potassium persulfate (7%) was added.
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。A pre-emulsion (methyl methacrylate: 608 g, divinylbenzene: 3)
5 g, pure water: 752 g, Hytenol N08: 34 g)
Was added over 4 hours at 70 ° C. at a constant rate from 20 minutes after the addition of potassium persulfate. After the addition was completed, the temperature was raised to 75 ° C. and aging was performed for 2 hours, and then cooled to 40 ° C. to obtain a crosslinked polymer emulsion. When the average particle size of this emulsion was measured with a light scattering type particle size distribution analyzer, 0.2 μm was obtained.
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℃。Next, the emulsion was dried using a spray dryer manufactured by Yamato Scientific Co., Ltd. under the following conditions to obtain a powder. Supply speed: 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 (manufactured by Coulter Inc.), the average particle size was 14 μm. According to observation with an electron microscope (SEM), the powder was a fine particle aggregate in which raw material fine particles composed of crosslinked polymer fine particles were interconnected while maintaining the shape.
【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 operation as in Example 1 except that the vinyl monomers in the pre-emulsion were methyl methacrylate (538 g) and trimethylolpropane trimethacrylate (105 g). Obtained. The resulting powder had a mean particle size of 18 μm, and was a fine particle aggregate in which the raw material fine particles were interconnected while maintaining the 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 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 size 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 comparative powder was prepared by repeating the same operation as in Example 1 except that the vinyl monomers in the pre-emulsion were methyl methacrylate (622 g) and trimethylolpropane trimethacrylate (21 g). I got a body. The particle size of the obtained comparative powder was 15 μm. However, according to observation with an electron microscope, the raw material fine particles do not retain the shape,
It was a single 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。According to the production method of the present invention, it is possible to produce an aggregate of crosslinked polymer fine particles by an easy method, which has been difficult in the prior art. And an aggregate having a large specific surface area with excellent strength and heat resistance.
フロントページの続き Ｆターム(参考） 4J038 CA021 CC021 CC081 CD041 CD081 CF011 CF021 CG031 CG141 CG161 CH031 CJ051 CJ131 NA11 NA14 4J100 AB02P AB03P AB16Q AC03P AC04P AG02P AG04P AJ02P AL03P AL67Q AM02P AS02P FA20 JA01 Continued on the front page F-term (reference) 4J038 CA021 CC021 CC081 CD041 CD081 CF011 CF021 CG031 CG141 CG161 CH031 CJ051 CJ131 NA11 NA14 4J100 AB02P AB03P AB16Q AC03P AC04P AG02P AG04P AJ02P AL03P AL67P AM02 AS
Claims (2)
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式乾燥方法で乾燥
させることを特徴とする微粒子集合体の製造方法。1. A vinyl monomer mixture in which the weight ratio of divinylbenzene to a non-crosslinkable monomer is 2 to 10:98 to 90, or trimethylolpropane tri (meth) acrylate and a non-crosslinkable monomer Body weight ratio is 5-30: 9
A method for producing a fine particle aggregate, comprising drying a crosslinked polymer emulsion obtained by emulsion-polymerizing a vinyl monomer mixture of 5 to 70 by a spray drying method.
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。2. A vinyl monomer mixture in which the weight ratio of divinylbenzene to a non-crosslinkable monomer is 2 to 10:98 to 90, or trimethylolpropane tri (meth) acrylate and a non-crosslinkable monomer Body weight ratio is 5-30: 9
A fine particle aggregate having an average particle diameter of 2 to 200 μm formed by interconnecting crosslinked polymer fine particles of an average particle diameter of 0.01 to 1 μm obtained by polymerizing a vinyl monomer mixture of 5 to 70 μm; .
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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22041898A JP3523075B2 (en) | 1998-08-04 | 1998-08-04 | Fine particle aggregate and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000053720A true JP2000053720A (en) | 2000-02-22 |
| JP3523075B2 JP3523075B2 (en) | 2004-04-26 |
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ID=16750807
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22041898A Expired - Fee Related JP3523075B2 (en) | 1998-08-04 | 1998-08-04 | Fine particle aggregate and its manufacturing method |
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| Country | Link |
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| JP (1) | JP3523075B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030151A (en) * | 2000-05-12 | 2002-01-31 | Nippon Shokubai Co Ltd | 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 |
| JP2007262405A (en) * | 2006-03-15 | 2007-10-11 | Rohm & Haas Co | Aqueous composition comprising polymer dollar particles |
| US7351492B2 (en) | 2002-05-22 | 2008-04-01 | Nippon Shokubai Co., Ltd. | Solid oxide type fuel cell-use electrode support substrate and production method therefor |
| WO2013030977A1 (en) | 2011-08-31 | 2013-03-07 | 積水化成品工業株式会社 | Resin particle aggregate, method for manufacturing same and application of same |
| KR20160025738A (en) | 2014-08-28 | 2016-03-09 | 세키스이가세이힝코교가부시키가이샤 | Aggregate of polymeric particles |
-
1998
- 1998-08-04 JP JP22041898A patent/JP3523075B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030151A (en) * | 2000-05-12 | 2002-01-31 | Nippon Shokubai Co Ltd | 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 |
| US7351492B2 (en) | 2002-05-22 | 2008-04-01 | Nippon Shokubai Co., Ltd. | Solid oxide type fuel cell-use electrode support substrate and production method therefor |
| JP2007262405A (en) * | 2006-03-15 | 2007-10-11 | Rohm & Haas Co | Aqueous composition comprising polymer dollar particles |
| JP2011208160A (en) * | 2006-03-15 | 2011-10-20 | Rohm & Haas Co | Aqueous composition containing polymer duller particle |
| WO2013030977A1 (en) | 2011-08-31 | 2013-03-07 | 積水化成品工業株式会社 | Resin particle aggregate, method for manufacturing same and application of same |
| KR20140033233A (en) | 2011-08-31 | 2014-03-17 | 세키스이가세이힝코교가부시키가이샤 | Resin particle aggregate, method for manufacturing same and application of same |
| EP2754692A4 (en) * | 2011-08-31 | 2015-09-30 | Sekisui Plastics | AGGREGATE OF RESIN PARTICLES, ITS MANUFACTURING METHOD AND APPLICATION |
| US9499713B2 (en) | 2011-08-31 | 2016-11-22 | Sekisui Plastics Co., Ltd. | Resin particle aggregate, method for manufacturing same and application of same |
| KR20160025738A (en) | 2014-08-28 | 2016-03-09 | 세키스이가세이힝코교가부시키가이샤 | Aggregate of polymeric particles |
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|---|---|
| JP3523075B2 (en) | 2004-04-26 |
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