JPH11181037A - Production of flat heteromorphic microparticle and emulsion containing the same - Google Patents
Production of flat heteromorphic microparticle and emulsion containing the sameInfo
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- JPH11181037A JPH11181037A JP36555397A JP36555397A JPH11181037A JP H11181037 A JPH11181037 A JP H11181037A JP 36555397 A JP36555397 A JP 36555397A JP 36555397 A JP36555397 A JP 36555397A JP H11181037 A JPH11181037 A JP H11181037A
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- fine particles
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- monomer
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、塗料、紙、情報
記録紙または光拡散性フィルム等に用いられるコーティ
ング剤の添加剤、化粧品の添加剤等として有用な偏平状
異形微粒子の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing flat irregularly shaped fine particles useful as an additive for a coating agent used for paints, papers, information recording papers, light diffusing films and the like, an additive for cosmetics, and the like.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
乳化重合により粒子の形状をコントロールした高分子微
粒子を製造できることが知られており、そのような微粒
子は、コーティング剤の添加剤として使用されている。
例えば、ＵＳＰ４，４２７，８３６ではアルカリ膨潤性
のコア粒子に熱可塑性のシェルをつけた粒子を高温でア
ルカリ膨潤することにより、０．３〜０．６μｍの中空
粒子を製造できることが示されている。この方法により
製造された中空微粒子は、水系塗料中の酸化チタンの代
わりに高隠蔽性有機顔料として使用され、また紙コーテ
ィングの分野でも白色度および光沢の改良に使用されて
いる。2. Description of the Related Art In recent years,
It is known that polymer fine particles having a controlled particle shape can be produced by emulsion polymerization, and such fine particles are used as additives for coating agents.
For example, US Pat. No. 4,427,836 shows that hollow particles of 0.3 to 0.6 μm can be produced by alkali-swelling particles obtained by attaching a thermoplastic shell to alkali-swellable core particles at a high temperature. . The hollow fine particles produced by this method are used as high-concealment organic pigments instead of titanium oxide in water-based paints, and are also used for improving whiteness and gloss in the field of paper coating.
【０００３】また、特開平２−１４２２２号公報および
第１９回表面改質研究会講演要旨集１６〜２１頁（１９
９４年）では、赤血球に似た偏平面にくぼみのある偏平
状微粒子の製造法が示されている。すなわち、ビニル重
合体からなる種粒子を含むエマルジョンに水、重合開始
剤、単量体、有機溶剤を含む混合乳化物を連続的に添加
して重合する製造方法が開示されている。このような偏
平状微粒子を、塗料、化粧料、紙コーティング剤および
情報記録紙等に用いた場合、光沢、隠蔽力、白色度等に
優れた特性を有することが示されている。In addition, Japanese Patent Application Laid-Open No. Hei 2-14222 and the 19th Surface Modification Study Group Abstracts, pp. 16-21 (19)
(1994) discloses a method for producing flat fine particles having a concave in a flat surface similar to red blood cells. That is, there is disclosed a production method in which a mixed emulsion containing water, a polymerization initiator, a monomer, and an organic solvent is continuously added to an emulsion containing seed particles composed of a vinyl polymer to carry out polymerization. It has been shown that when such flat fine particles are used in paints, cosmetics, paper coating agents, information recording papers, and the like, they have excellent properties such as gloss, hiding power, and whiteness.
【０００４】しかし、この製造法の場合、イソオクタン
等の有機溶媒が種粒子内に存在しているため、重合後に
水蒸気蒸留を行って非水溶性有機溶剤を除去する必要が
あり、製造工程が煩雑になるという問題があった。ま
た、水蒸気蒸留を行わない場合には、塗工工程でエマル
ジョンの乾燥時に、水と一緒に非水溶性有機溶剤が大気
中に蒸散されるため環境上問題がある。However, in this production method, since an organic solvent such as isooctane is present in the seed particles, it is necessary to perform steam distillation after polymerization to remove the water-insoluble organic solvent, which complicates the production process. There was a problem of becoming. If steam distillation is not performed, the water-insoluble organic solvent evaporates into the atmosphere together with water when the emulsion is dried in the coating step, which is environmentally problematic.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、非水溶性
有機溶剤を使用することなく、内部にくぼみを有する凸
状のビニル系重合体異形微粒子を製造する方法について
鋭意検討した結果、重量平均分子量５，０００〜１５
０，０００のビニル系重合体粒子を種粒子とし、（メ
タ）アクリル酸エステル系単量体を主成分とし、かつ架
橋性ビニル系単量体を含む単量体混合物を種粒子に吸収
させ、水溶性重合開始剤を用いて、乳化重合することに
より、目的とする異形微粒子が得られることを見出し、
この発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method for producing irregular shaped fine particles of a vinyl polymer having depressions therein without using a water-insoluble organic solvent. Weight average molecular weight 5,000-15
000 vinyl polymer particles are used as seed particles, a monomer mixture containing a (meth) acrylate monomer as a main component and a crosslinkable vinyl monomer is absorbed by the seed particles, Using a water-soluble polymerization initiator, by emulsion polymerization, found that the desired irregular fine particles can be obtained,
The present invention has been completed.
【０００６】この発明における「偏平状異形微粒子」と
は、平面形状が略円形で、表面が凸状で、裏面（底部）
が凹状となった異形微粒子であって、底部の直径（Ｄ）
が０．３〜５μｍで、この直径（Ｄ）と底部から凸状表
面の先端までの厚み（Ｈ）との比（Ｄ／Ｈ）が１．５〜
４の範囲にあり、凸状表面に対応した内径０．１μｍ以
上の凹状内面を底部に有する微粒子を意味する。[0006] The term "flat irregular shaped fine particles" as used herein means that the planar shape is substantially circular, the front surface is convex, and the back surface (bottom portion).
Are irregular shaped fine particles having a concave shape, and the diameter at the bottom (D)
And the ratio (D / H) of the diameter (D) to the thickness (H) from the bottom to the tip of the convex surface is 1.5 to 5 μm.
4 means fine particles having a concave inner surface with an inner diameter of 0.1 μm or more corresponding to the convex surface at the bottom.
【０００７】[0007]
【発明の実施の形態】以下、この発明について詳細に説
明する。この発明で使用されるビニル系重合体粒子から
なる種粒子としては、スチレン、αーメチルスチレン等
の芳香族ビニル単量体、（メタ）アクリル酸メチル、
（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル
等の（メタ）アクリル酸エステル単量体、酢酸ビニル、
あるいは他の共重合可能な単量体の単独重合体またはこ
れらのブロック、ラムダム、グラフト共重合体が挙げら
れる。ここで、（メタ）アクリル酸とはアクリル酸およ
びメタクリル酸の双方を意味する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The seed particles composed of the vinyl polymer particles used in the present invention include styrene, aromatic vinyl monomers such as α-methylstyrene, methyl (meth) acrylate,
(Meth) acrylate monomers such as ethyl (meth) acrylate and butyl (meth) acrylate, vinyl acetate,
Alternatively, a homopolymer of another copolymerizable monomer or a block, ram dam, or graft copolymer thereof may be used. Here, (meth) acrylic acid means both acrylic acid and methacrylic acid.
【０００８】なお、種粒子を構成する単量体は、後述の
単量体混合物に含まれる単量体と同一であるか、または
同系列のものであれば、透明性の異形微粒子が得られや
すいので好ましい。種粒子の製造方法は特に限定されな
いが、乳化重合、ソープフリー乳化重合あるいは懸濁重
合などの方法を用いることができる。種粒子の粒径の均
一性や製造方法の簡便さを考慮すると、乳化重合および
ソープフリー乳化重合法が好ましい。If the monomers constituting the seed particles are the same as or the same as those contained in the monomer mixture described later, transparent irregular fine particles can be obtained. It is preferable because it is easy. The method for producing the seed particles is not particularly limited, but a method such as emulsion polymerization, soap-free emulsion polymerization, or suspension polymerization can be used. Considering the uniformity of the particle size of the seed particles and the simplicity of the production method, emulsion polymerization and soap-free emulsion polymerization are preferred.
【０００９】この発明で用いられる種粒子の重量平均分
子量は、ゲルパーミエーションクロマトグラフィーによ
る測定で、５，０００〜１５０，０００の範囲であり、
好ましくは１０，０００〜８０，０００、さらに好まし
くは１５，０００〜５０，０００である。重合開始剤の
使用量の加減あるいは分子量調整剤の添加などにより、
種粒子の重量平均分子量をこの範囲に調整することがで
きる。分子量調整剤としては、ｎ−オクチルメルカプタ
ン、ｔ−ドデシルメルカプタン等のメルカプタン類、四
塩化炭素等のハロゲン化炭化水素類が使用され得る。こ
れらの分子調整剤の添加量を加減することによっても、
種粒子の重量平均分子量を調整することができる。The weight average molecular weight of the seed particles used in the present invention is in the range of 5,000 to 150,000 as measured by gel permeation chromatography.
Preferably it is 10,000-80,000, More preferably, it is 15,000-50,000. By adjusting the amount of polymerization initiator used or adding a molecular weight regulator,
The weight average molecular weight of the seed particles can be adjusted to this range. As the molecular weight modifier, mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan, and halogenated hydrocarbons such as carbon tetrachloride can be used. By adjusting the amount of these molecular regulators,
The weight average molecular weight of the seed particles can be adjusted.
【００１０】種粒子の重量平均分子量が１５０，０００
より大きい場合には、得られる異形微粒子の偏平の度合
いが低下し、球状の微粒子が混入する。すなわち、種粒
子の重量平均分子量が１５０，０００より大きくなる
と、種粒子の単量体吸収能力が小さくなり、単量体混合
物の単量体が種粒子に吸収されないまま独自に重合する
ため、目的の形状とは異なる球状の微粒子が生成するも
のと思われる。The weight average molecular weight of the seed particles is 150,000.
If it is larger, the degree of flatness of the resulting irregularly shaped fine particles is reduced, and spherical fine particles are mixed. That is, if the weight average molecular weight of the seed particles is greater than 150,000, the monomer absorption capacity of the seed particles decreases, and the monomers of the monomer mixture are polymerized independently without being absorbed by the seed particles. It is thought that spherical fine particles having a shape different from the above-mentioned shape are generated.
【００１１】他方、種粒子の重量平均分子量が５，００
０より小さい場合には、多量の連鎖移動剤を使用して
も、所望の種粒子が得られ難いばかりでなく、最終的に
得られる偏平状異形微粒子の強度が低下するという問題
がある。なお、種粒子の大きさおよび形状は特に限定さ
れないが、通常０．１〜２μmの球状粒子が使用され
る。On the other hand, the seed particles have a weight average molecular weight of 5,000.
If it is less than 0, the desired seed particles are hardly obtained even when a large amount of the chain transfer agent is used, and the strength of the finally obtained flat irregular shaped fine particles is reduced. The size and shape of the seed particles are not particularly limited, but generally spherical particles of 0.1 to 2 μm are used.
【００１２】この発明で用いられる（メタ）アクリル酸
エステル系単量体としては、（メタ）アクリル酸メチ
ル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブ
チル等が挙げられる。偏平状異形微粒子として得られる
重合体のガラス転移温度は、粉体として取り扱う際の結
合、合着等の弊害を回避する上で５０℃以上が好まし
く、より好ましくは７０℃以上である。そのためには、
（メタ）アクリル酸メチルが好ましく、しかも（メタ）
アクリル酸メチルが単量体混合物中に５０〜９７重量％
程度含有されているのが好ましい。The (meth) acrylate monomers used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like. The glass transition temperature of the polymer obtained as the flat irregularly shaped fine particles is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, in order to avoid adverse effects such as bonding and coalescence when handling as a powder. for that purpose,
Methyl (meth) acrylate is preferred, and (meth)
50-97% by weight of methyl acrylate in the monomer mixture
To a certain extent.
【００１３】もう一方の単量体である架橋性ビニル系単
量体としては、例えば、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、トリメチロールプロパント
リメタクリレート等の、重合性ビニル基を１分子中に２
つ以上有する多官能性単量体が用いられる。この発明の
架橋性ビニル系単量体の使用量は、単量体混合物の全量
に対して３〜１５重量％に調整される。The crosslinkable vinyl monomer as the other monomer includes, for example, a polymerizable vinyl group such as divinylbenzene, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate in one molecule.
One or more multifunctional monomers are used. The amount of the crosslinkable vinyl monomer of the present invention is adjusted to 3 to 15% by weight based on the total amount of the monomer mixture.
【００１４】架橋性ビニル系単量体の比率が３重量％未
満であると、偏平化の度合いが小さく球状に近い粒子が
得られる。また、逆に架橋性ビニル系単量体の比率が１
５重量％より大きい場合も、同様の結果が得られる。な
お、所望により、上記以外の共重合可能な単量体を併用
することもできる。When the proportion of the crosslinkable vinyl monomer is less than 3% by weight, particles having a small degree of flattening and nearly spherical shape can be obtained. Conversely, when the ratio of the crosslinkable vinyl monomer is 1
Similar results are obtained with greater than 5% by weight. If desired, copolymerizable monomers other than those described above can be used in combination.
【００１５】そのような単量体としては、スチレン、α
ーメチルスチレン等の芳香族ビニル化合物、酢酸ビニ
ル、アクリロニトリル、（メタ）アクリル酸、（メタ）
アクリルアミド、２ーヒドロキシエチル（メタ）アクリ
レート、グリシジル（メタ）アクリレート等が挙げられ
る。この発明における単量体混合物の使用量は、種粒子
１重量部に対して３〜３０重量部であることが好まし
く、さらに好ましくは５〜２５重量部であり、特に好ま
しくは７〜１９重量部である。Such monomers include styrene, α
Aromatic vinyl compounds such as -methylstyrene, vinyl acetate, acrylonitrile, (meth) acrylic acid, (meth)
Acrylamide, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like can be mentioned. The amount of the monomer mixture used in the present invention is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, and particularly preferably 7 to 19 parts by weight based on 1 part by weight of the seed particles. It is.
【００１６】単量体混合物の使用量が種粒子１重量部に
対して３重量部未満であると、得られる偏平状異形微粒
子の偏平化の度合いが小さくなりやすい。逆に、この使
用量が３０重量部を越えると、種粒子の単量体吸収能力
が不充分となって、種粒子に吸収されない単量体が増
え、そのため目的とする形状以外の微小な粒子が生成し
やすい。If the amount of the monomer mixture is less than 3 parts by weight per 1 part by weight of the seed particles, the degree of flattening of the obtained flat irregular shaped fine particles tends to be small. Conversely, if the amount used exceeds 30 parts by weight, the monomer absorption capacity of the seed particles becomes insufficient, so that the amount of monomers not absorbed by the seed particles increases, and therefore, fine particles other than the target shape Is easy to generate.
【００１７】なお、単量体混合物の種粒子への添加方法
は特に限定されず、一度に、または分割して、あるいは
連続的に添加して、単量体を種粒子に吸収させることが
できる。この発明では、水溶性重合開始剤として、水溶
性のラジカル開始剤が用いられる。水溶性のラジカル開
始剤としては例えば、過硫酸カリウム、過硫酸アンモニ
ウム、過硫酸ナトリウム等の過硫酸塩類、ベンゾイルハ
イドロパーオキサイド等の有機過酸化物、４，４´−ア
ゾビス（４−シアノペンタン酸）等のアゾ系化合物類、
過硫酸カリウム−チオ硫酸ナトリウム、過酸化水素−ア
スコルビン酸等のレドックス系開始剤などが挙げられ
る。The method of adding the monomer mixture to the seed particles is not particularly limited, and the monomer can be absorbed by the seed particles by adding them all at once, in portions, or continuously. . In the present invention, a water-soluble radical initiator is used as the water-soluble polymerization initiator. Examples of the water-soluble radical initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; organic peroxides such as benzoyl hydroperoxide; and 4,4'-azobis (4-cyanopentanoic acid). Azo compounds such as
Redox initiators such as potassium persulfate-sodium thiosulfate and hydrogen peroxide-ascorbic acid are exemplified.
【００１８】なお、この発明の方法でベンゾイルパーオ
キシド，アゾイソビスブチロニトリル等の油溶性重合開
始剤を用いると、目的とする偏平状異形微粒子は得られ
ない。重合温度は、６５℃〜９０℃であることが好まし
く、さらに好ましくは７０℃〜８０℃である。重合温度
が６５℃未満では偏平化の度合いが小さくなりやすく、
逆に９０℃を越えると重合開始剤が分解しやすく、重合
開始剤の失活により重合が完結し難くなる。If an oil-soluble polymerization initiator such as benzoyl peroxide or azoisobisbutyronitrile is used in the method of the present invention, the desired flat irregular shaped fine particles cannot be obtained. The polymerization temperature is preferably from 65C to 90C, more preferably from 70C to 80C. If the polymerization temperature is less than 65 ° C., the degree of flattening tends to be small,
Conversely, if the temperature exceeds 90 ° C., the polymerization initiator is easily decomposed, and the polymerization is difficult to complete due to the deactivation of the polymerization initiator.
【００１９】重合に際して、界面活性剤を用いてもよ
く、好ましい界面活性剤としては、アルキルベンゼンス
ルホン酸ナトリウム、アルキルスルホン酸ナトリウム、
ジアルキルスルホコハク酸ナトリウム等のアニオン系界
面活性剤、ポリオキシエチレンアルキルエーテル、ポリ
オキシエチレンアルキルフェニルエーテル等のノニオン
系界面活性剤が挙げられ、これらの界面活性剤は単独
で、または２種以上のものを組み合わせて用いることが
できる。これらの界面活性剤を用いる場合、その使用量
は、臨界ミセル濃度以下であって、できるだけ少ない方
が好ましい。界面活性剤の使用量が多くなると、目的と
する粒子径の範囲外の粒子が生成しやすくなり、好まし
くない。In the polymerization, a surfactant may be used. Preferred surfactants include sodium alkylbenzenesulfonate, sodium alkylsulfonate, and the like.
Examples include anionic surfactants such as sodium dialkyl sulfosuccinate, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. These surfactants may be used alone or in combination of two or more. Can be used in combination. When these surfactants are used, the amount used is preferably not more than the critical micelle concentration and is preferably as small as possible. If the amount of the surfactant used is large, particles outside the target particle size range are likely to be generated, which is not preferable.
【００２０】また、この発明の方法では分散安定剤を用
いてもよく、好ましい分散安定剤としては、ポリビニル
アルコール、ヒドロキシエチルセルロース、カルボキシ
メチルセルロース等の水溶性高分子が挙げられる。この
ようにして得られる偏平状異形微粒子は、底部の直径
（Ｄ）が０．３〜５μｍであり、この直径（Ｄ）と底部
から凸状表面の頂点までの厚さ（Ｈ）との比（Ｄ／Ｈ）
が１．５〜４の範囲にあり、凸状表面に対応した内径
０．１μｍ以上の凹状内面を粒子の底部中央に有してい
る。In the method of the present invention, a dispersion stabilizer may be used. Preferred dispersion stabilizers include water-soluble polymers such as polyvinyl alcohol, hydroxyethyl cellulose and carboxymethyl cellulose. The flat irregular fine particles thus obtained have a bottom diameter (D) of 0.3 to 5 μm, and a ratio of the diameter (D) to the thickness (H) from the bottom to the top of the convex surface. (D / H)
Is in the range of 1.5 to 4, and has a concave inner surface having an inner diameter of 0.1 μm or more corresponding to the convex surface at the bottom center of the particle.
【００２１】なお、この発明の方法により偏平状異形微
粒子の得られるメカニズムは明確ではないが、次のよう
に推定される。まず、種粒子が単量体を吸収して膨潤し
た状態になる。次いで、水溶性重合開始剤で重合を行う
ため、水相で発生したラジカルが水相から単量体油滴に
浸入する。単量体油滴の表面で反応が開始されるが、架
橋性単量体を含有しているため、比較的低重合率の段階
で粒子の外形が定まる。そして、重合の進行に伴い、単
量体に溶解していた種粒子のポリマーが析出する。さら
に重合が進行して粒子内の重合収縮のひずみが増大す
る。析出した種粒子のポリマーと生成した架橋ポリマー
の相溶性が高く、架橋性単量体の量が比較的少ないた
め、空孔は形成されず、重合収縮により中央部にくぼみ
が形成される。Although the mechanism by which the method of the present invention produces flat irregular shaped fine particles is not clear, it is presumed as follows. First, the seed particles become swollen by absorbing the monomer. Next, in order to carry out polymerization with a water-soluble polymerization initiator, radicals generated in the aqueous phase enter the monomer oil droplets from the aqueous phase. The reaction starts on the surface of the monomer oil droplets, but since the crosslinkable monomer is contained, the outer shape of the particles is determined at a relatively low polymerization rate. Then, as the polymerization proceeds, the polymer of the seed particles dissolved in the monomer precipitates. Further, the polymerization proceeds, and the polymerization shrinkage strain in the particles increases. Since the compatibility between the polymer of the precipitated seed particles and the formed crosslinked polymer is high and the amount of the crosslinkable monomer is relatively small, no pores are formed, and a hollow is formed at the center due to polymerization shrinkage.
【００２２】この発明は、このようにして得られる偏平
状異形微粒子を含む水性エマルジョンをも提供するもの
である。このエマルジョンは、上記の重合反応により得
られる反応混合物そのままであってもよく、あるいは使
用目的に応じてエマルジョン中の固形成分の濃度を公知
の手段によって適宜調整したものであってもよい。The present invention also provides an aqueous emulsion containing the thus obtained flat irregularly shaped fine particles. This emulsion may be the reaction mixture obtained by the above-mentioned polymerization reaction as it is, or may be the one in which the concentration of the solid component in the emulsion is appropriately adjusted by a known means according to the purpose of use.
【００２３】さらに、該エマルジョンは、反応混合物か
ら一旦脱水、乾燥工程を経て単離された偏平状異形微粒
子を水中に分散させたものであってもよい。この場合に
は、必要に応じて、公知の乳化剤を添加してもよい。こ
の発明で得られる偏平状異形微粒子およびそれを含む水
性エマルジョンは、何れも有機溶剤を含むものでなく、
塗料、化粧品等の添加剤あるいは紙、情報記録紙、光拡
散性フィルム等のコーティング剤の添加剤などとして使
用され、作業環境や大気環境を改善するとともに、すぐ
れた光拡散効果を奏する。Further, the emulsion may be obtained by dispersing flat irregular shaped fine particles isolated from the reaction mixture through a dehydration and drying step once in water. In this case, a known emulsifier may be added as necessary. The flat irregularly shaped fine particles obtained in the present invention and the aqueous emulsion containing the same do not contain any organic solvent,
It is used as an additive for paints and cosmetics, or as an additive for coating agents such as paper, information recording paper, and light diffusing films. It improves the working environment and atmospheric environment, and has an excellent light diffusing effect.
【００２４】[0024]
【実施例】本発明の具体的な製造法を実施例により以下
に説明するが、この発明の方法はこれらの実施例に限定
されるものではない。なお、実施例における粒径、直
径、厚さ、長径、短径等の数値は、いずれも平均的な数
値である。EXAMPLES The specific production method of the present invention will be described below with reference to examples, but the method of the present invention is not limited to these examples. The numerical values of the particle diameter, diameter, thickness, major axis, minor axis, and the like in the examples are all average numerical values.
【００２５】また、実施例における重量平均分子量の測
定方法は、次の通りである。 測定機器：ゲルパーミエーションクロマトグラフィー 機種名：島津製作所（株）製 クロマトパック Ｃ−Ｒ
４Ａ 溶媒：ＴＨＦ 測定温度：４０℃ 以下に示す合成例１〜８により種粒子を作成した。The method for measuring the weight average molecular weight in the examples is as follows. Measuring instrument: Gel permeation chromatography Model name: Chromatopack CR manufactured by Shimadzu Corporation
4A Solvent: THF Measurement temperature: 40 ° C. Seed particles were prepared according to Synthesis Examples 1 to 8 shown below.
【００２６】（合成例１）攪拌機、温度計および還流コ
ンデンサーを備えたセパラブルフラスコに、水６００
g、メタクリル酸メチル１００ｇおよび連鎖移動剤とし
てｎ−オクチルメルカプタン（ｎ−ＯＭ）０．５ｇを仕
込み、攪拌下に窒素置換しながら７０℃まで昇温する。
内温を７０℃に保ち、重合開始剤として過硫酸カリウム
０．５ｇを添加した後、８時間重合反応させる。得られ
たエマルジョンは、固形分１４％を含有し、その固形成
分は粒径０．４μｍ、重量平均分子量45,000の真球状粒
子であった。(Synthesis Example 1) Water 600 was placed in a separable flask equipped with a stirrer, thermometer and reflux condenser.
g, 100 g of methyl methacrylate, and 0.5 g of n-octyl mercaptan (n-OM) as a chain transfer agent, and the temperature is raised to 70 ° C. while stirring and replacing with nitrogen.
After maintaining the internal temperature at 70 ° C. and adding 0.5 g of potassium persulfate as a polymerization initiator, the polymerization reaction is carried out for 8 hours. The obtained emulsion contained a solid content of 14%, and the solid component was spherical particles having a particle diameter of 0.4 μm and a weight average molecular weight of 45,000.
【００２７】（合成例２〜４）ｎ−ＯＭの添加量を表１
に示すように変えた以外は、合成例１と同様の方法で重
合を行った。(Synthesis Examples 2 to 4) Table 1 shows the amount of n-OM added.
The polymerization was carried out in the same manner as in Synthesis Example 1 except that the polymerization was changed as shown in Table 1.
【００２８】（合成例５）重合温度を８０℃とした以外
は、合成例１と同様の方法で重合を行った。(Synthesis Example 5) Polymerization was carried out in the same manner as in Synthesis Example 1 except that the polymerization temperature was 80 ° C.
【００２９】（合成例６）ｎ−ＯＭの添加量を２ｇとし
た以外は、合成例５と同様の方法で重合を行った。(Synthesis Example 6) Polymerization was carried out in the same manner as in Synthesis Example 5 except that the added amount of n-OM was changed to 2 g.
【００３０】（合成例７）ｎ−ＯＭの添加量を５ｇとし
た以外は、合成例５と同様の方法で重合を行った。(Synthesis Example 7) Polymerization was carried out in the same manner as in Synthesis Example 5 except that the amount of n-OM added was 5 g.
【００３１】（合成例８）攪拌機、温度計および還流コ
ンデンサーを備えたセパラブルフラスコに、水９００
ｇ、スチレン１００ｇおよび連鎖移動剤としｔ−ドデシ
ルメルカプタン（ｔ−ＤＭ）１ｇを仕込み、攪拌下に窒
素置換しながら７０℃まで昇温する。内温を７０℃に保
ち、重合開始剤として過硫酸カリウム１ｇを添加した
後、２４時間重合反応させる。得られたエマルジョンは
固形分１０％を含有し、その固形成分は粒径０．５μ
ｍ、重量平均分子量７５，０００の真球状粒子であっ
た。(Synthesis Example 8) Water 900 was placed in a separable flask equipped with a stirrer, a thermometer and a reflux condenser.
g, 100 g of styrene and 1 g of t-dodecylmercaptan (t-DM) as a chain transfer agent, and the temperature was raised to 70 ° C. while stirring and replacing with nitrogen. After maintaining the internal temperature at 70 ° C. and adding 1 g of potassium persulfate as a polymerization initiator, the polymerization reaction is carried out for 24 hours. The resulting emulsion contains 10% solids, and the solid component has a particle size of 0.5μ.
m and true spherical particles having a weight average molecular weight of 75,000.
【００３２】合成例１〜８により得られたポリマー微粒
子（種粒子）の粒径および重量平均分子量を表１に示
す。Table 1 shows the particle size and weight average molecular weight of the polymer fine particles (seed particles) obtained in Synthesis Examples 1 to 8.
【００３３】[0033]
【表１】 [Table 1]
【００３４】（実施例１）合成例１で製造したエマルジ
ョン７１．５ｇ（種粒子としての固形分換算１０ｇ）、
ラウリル硫酸ナトリウム０．１５ｇ、イオン交換水５０
０ｇ、メタクリル酸メチル９５ｇおよびエチレングリコ
ールジメタクリレート５ｇを混合し、３０℃で２時間攪
拌して、種粒子に単量体を吸収させた。次に、この混合
物を窒素気流下で７０℃に昇温し、重合開始剤として過
硫酸カリウム０．５ｇを溶解したイオン交換水５０ｇを
添加し、５時間重合を行った。その後、室温まで冷却
し、孔系０．８μｍの濾紙を用いて吸引濾過洗浄を行っ
た後、６０℃にて真空乾燥を行った。得られた重合体微
粒子は、走査型電子顕微鏡により観察したところ、底部
の直径が１．１μｍ、底部から凸状表面の頂点までの厚
さ（Ｈ）が０．６μｍで、粒子の底部中央に直径０．５
μｍの凹部を持つ偏平状異形微粒子であった。この実施
例で得られた微粒子の走査型電子顕微鏡写真を図１に示
す。Example 1 71.5 g of the emulsion produced in Synthesis Example 1 (10 g in terms of solid content as seed particles),
0.15 g of sodium lauryl sulfate, 50 ion-exchanged water
0 g, 95 g of methyl methacrylate and 5 g of ethylene glycol dimethacrylate were mixed and stirred at 30 ° C. for 2 hours to allow the seed particles to absorb the monomer. Next, this mixture was heated to 70 ° C. under a nitrogen stream, and 50 g of ion-exchanged water in which 0.5 g of potassium persulfate was dissolved as a polymerization initiator was added, and polymerization was carried out for 5 hours. Thereafter, the mixture was cooled to room temperature, washed by suction filtration using a filter paper having a pore size of 0.8 μm, and dried in vacuum at 60 ° C. Observation of the obtained polymer microparticles with a scanning electron microscope revealed that the diameter of the bottom was 1.1 μm, the thickness (H) from the bottom to the top of the convex surface was 0.6 μm, and the center of the bottom of the particle was 0.5 diameter
The particles were flat irregular shaped fine particles having a concave portion of μm. FIG. 1 shows a scanning electron micrograph of the fine particles obtained in this example.
【００３５】（実施例２）重合温度を８５℃とした以外
は、実施例１と同様の条件で重合を行った。得られた重
合体微粒子を走査型電子顕微鏡により観察したところ、
実施例１と同様の偏平状異形微粒子であった。(Example 2) Polymerization was carried out under the same conditions as in Example 1 except that the polymerization temperature was 85 ° C. Observation of the obtained polymer fine particles with a scanning electron microscope,
It was the same flat irregularly shaped fine particles as in Example 1.
【００３６】（実施例３）合成例２で製造した種粒子を
用いた以外は、実施例１と同様の条件で重合を行った。
得られた重合体微粒子は、走査型電子顕微鏡により観察
したところ、底部の直径が１μｍ、底部から凸状表面の
頂点までの厚さが０．５μｍで、粒子の底部中央部に直
径０．２μｍの凹部をもつ偏平状異形微粒子であった。Example 3 Polymerization was carried out under the same conditions as in Example 1 except that the seed particles produced in Synthesis Example 2 were used.
Observation with a scanning electron microscope revealed that the obtained polymer fine particles had a bottom diameter of 1 μm, a thickness from the bottom to the top of the convex surface of 0.5 μm, and a diameter of 0.2 μm at the bottom center of the particles. Were irregularly shaped fine particles having the following concave portions.
【００３７】（実施例４）メタクリル酸メチルの量を９
０ｇ、エチレングリコールジメタクリレートの量を１０
ｇとした以外は、実施例１と同様の条件で重合を行っ
た。得られた重合体微粒子は、走査型電子顕微鏡により
観察したところ、底部の直径が１μｍ、底部から凸状表
面の頂点までの厚さが０．５μｍで、粒子の中央部に直
径０．２μｍの凹部をもつ偏平状異形微粒子であった。Example 4 The amount of methyl methacrylate was 9
0 g, the amount of ethylene glycol dimethacrylate is 10
Polymerization was performed under the same conditions as in Example 1 except that the amount was changed to g. Observation with a scanning electron microscope showed that the obtained polymer fine particles had a bottom diameter of 1 μm, a thickness from the bottom to the top of the convex surface of 0.5 μm, and a diameter of 0.2 μm at the center of the particles. The particles were flat irregular shaped fine particles having concave portions.
【００３８】（実施例５）メタクリル酸メチルの量を８
５ｇ、エチレングリコールジメタクリレートの量を１５
ｇとした以外は、実施例１と同様の条件で重合を行っ
た。得られた重合体微粒子は、走査型電子顕微鏡により
観察したところ、底部の直径が１μｍ、底部から凸状表
面の頂点までの厚さが０．６μｍで、粒子の底部中央部
に直径０．１μｍの凹部をもつ偏平状異形微粒子であっ
た。Example 5 The amount of methyl methacrylate was changed to 8
5 g, the amount of ethylene glycol dimethacrylate was 15
Polymerization was performed under the same conditions as in Example 1 except that the amount was changed to g. Observation with a scanning electron microscope showed that the obtained polymer fine particles had a diameter of 1 μm at the bottom, a thickness of 0.6 μm from the bottom to the top of the convex surface, and a diameter of 0.1 μm at the center of the bottom of the particles. Were irregularly shaped fine particles having the following concave portions.
【００３９】（実施例６）合成例５で製造した種粒子を
固形分換算で３．３ｇ用いた以外は、実施例１と同様の
条件で重合を行った。得られた重合体微粒子は、走査型
電子顕微鏡により観察したところ、底部の直径が１．２
μｍ、底部から凸状表面の頂点までの厚さが０．６μｍ
で、粒子の底部中央に直径０．５μｍの凹部をもつ偏平
状異形微粒子であった。Example 6 Polymerization was carried out under the same conditions as in Example 1 except that 3.3 g of the seed particles produced in Synthesis Example 5 in terms of solid content was used. Observation of the obtained polymer fine particles with a scanning electron microscope revealed that the diameter of the bottom portion was 1.2.
μm, the thickness from the bottom to the top of the convex surface is 0.6 μm
The particles were flat irregularly shaped fine particles having a concave portion having a diameter of 0.5 μm at the bottom center of the particles.
【００４０】（実施例７）合成例１で製造した種粒子を
固形分換算で２０ｇ用いた以外は、実施例１と同様の条
件で重合を行った。得られた重合体微粒子は、走査型電
子顕微鏡により観察したところ、底部の直径が１．０μ
ｍ、底部から凸状表面の頂点までの厚さが０．６μｍ
で、粒子の底部中央に直径０．２μｍの凹部をもつ偏平
状異形微粒子であった。Example 7 Polymerization was carried out under the same conditions as in Example 1 except that 20 g of the seed particles produced in Synthesis Example 1 were used in terms of solid content. When the obtained polymer fine particles were observed with a scanning electron microscope, the diameter of the bottom was 1.0 μm.
m, the thickness from the bottom to the top of the convex surface is 0.6 μm
The particles were flat irregularly shaped fine particles having a concave portion having a diameter of 0.2 μm at the bottom center of the particles.
【００４１】（実施例８）合成例８で製造したポリスチ
レン粒子を種粒子として用いた以外は、実施例１と同様
の条件で重合を行った。得られた重合体微粒子は、走査
型電子顕微鏡により観察したところ、底部の直径が１．
２μｍ、底部から凸状表面の頂点までの厚さが０．５μ
ｍで、粒子の底部中央部に直径０．５μｍの凹部をもつ
偏平状異形微粒子であった。Example 8 Polymerization was carried out under the same conditions as in Example 1 except that the polystyrene particles produced in Synthesis Example 8 were used as seed particles. Observation of the obtained polymer fine particles with a scanning electron microscope showed that the diameter of the bottom was 1.
2 μm, the thickness from the bottom to the top of the convex surface is 0.5 μm
m, the particles were flat irregular shaped fine particles having a concave portion having a diameter of 0.5 μm in the center of the bottom of the particles.
【００４２】（実施例９）単量体として、メタクリル酸
メチル７５ｇ、メタクリル酸ノルマルブチル２０ｇおよ
びエチレングリコールジメタクリレート５ｇを用いた以
外は、実施例１と同様の条件で重合を行った。得られた
重合体微粒子は、走査型電子顕微鏡により観察したとこ
ろ、底部の直径が１．１μｍ、底部から凸状表面の頂点
までの厚さが０．６μｍで、粒子の底部中央に直径０．
５μｍの凹部をもつ偏平状異形微粒子であった。Example 9 Polymerization was carried out under the same conditions as in Example 1 except that 75 g of methyl methacrylate, 20 g of normal butyl methacrylate and 5 g of ethylene glycol dimethacrylate were used as monomers. Observation of the obtained polymer fine particles by a scanning electron microscope revealed that the bottom had a diameter of 1.1 μm, the thickness from the bottom to the top of the convex surface was 0.6 μm, and a diameter of 0.
It was a flat irregular shaped fine particle having a concave portion of 5 μm.
【００４３】（実施例１０）合成例６で製造した種粒子
を用いた以外は、実施例１と同様の条件で重合を行っ
た。得られた重合体微粒子は、走査型電子顕微鏡により
観察したところ、底部の直径が１．１μｍ、底部から凸
状表面の頂点まで厚さが０．５μｍで、粒子の中央部に
直径０．５μｍの凹部をもつ偏平状異形微粒子であっ
た。Example 10 Polymerization was carried out under the same conditions as in Example 1 except that the seed particles produced in Synthesis Example 6 were used. Observation with a scanning electron microscope showed that the obtained polymer fine particles had a diameter of 1.1 μm at the bottom, a thickness of 0.5 μm from the bottom to the top of the convex surface, and a diameter of 0.5 μm at the center of the particles. Were irregularly shaped fine particles having the following concave portions.
【００４４】（実施例１１）合成例７で製造した種粒子
を用いた以外は、実施例１と同様の条件で重合を行なっ
た。得られた重合体微粒子は、走査型電子顕微鏡により
観察したところ、底部の直径１．１μｍ、底部から凸部
の頂点まで厚さ０．５μｍで、粒子の中央部に直径０．
５μｍの凹部を持つ偏平状異形微粒子であった。Example 11 Polymerization was carried out under the same conditions as in Example 1 except that the seed particles produced in Synthesis Example 7 were used. Observation with a scanning electron microscope revealed that the obtained polymer fine particles had a diameter of 1.1 μm at the bottom, a thickness of 0.5 μm from the bottom to the apex of the projection, and a diameter of 0.5 μm at the center of the particles.
The flat irregular-shaped fine particles had a concave portion of 5 μm.
【００４５】（実施例１２）実施例１で得られた偏平状
異形微粒子１０ｇを、ラウリル硫酸ナトリウムを５００
ｐｐｍ含む水１００ｍｌに分散させてエマルジョンを得
た。(Example 12) 10 g of the flat irregularly shaped fine particles obtained in Example 1 were mixed with 500 g of sodium lauryl sulfate.
The emulsion was dispersed in 100 ml of water containing ppm.
【００４６】（比較例１）合成例３で製造した種粒子を
用いた以外は、実施例１と同様の条件で重合を行った。
得られた重合体微粒子は、走査型電子顕微鏡により観察
したところ、粒径０．９μｍのほぼ球状の微粒子であ
り、凹部は見られなかった。Comparative Example 1 Polymerization was carried out under the same conditions as in Example 1 except that the seed particles produced in Synthesis Example 3 were used.
Observation with a scanning electron microscope showed that the obtained polymer fine particles were substantially spherical fine particles having a particle size of 0.9 μm, and no concave portions were observed.
【００４７】（比較例２）実施例１における重合開始剤
としての過硫酸カリウムの代わりに、アゾイソビスブチ
ロニトリル（油溶性重合開始剤）をメタクリル酸メチル
に溶解したものを用いた以外は、実施例１と同様の条件
で重合を行った。得られた重合体微粒子を電子顕微鏡に
より観察したところ、粒径０．７μｍの真球状であっ
た。Comparative Example 2 The procedure of Example 1 was repeated except that azoisobisbutyronitrile (oil-soluble polymerization initiator) dissolved in methyl methacrylate was used instead of potassium persulfate as the polymerization initiator. Polymerization was carried out under the same conditions as in Example 1. Observation of the obtained polymer fine particles with an electron microscope revealed a true spherical shape with a particle size of 0.7 μm.
【００４８】（比較例３）メタクリル酸メチルの量を８
０ｇに変更し、エチレングリコールジメタクリレートの
量を２０ｇに変更した以外は、実施例１と同様の条件で
重合を行った。得られた重合体微粒子は、走査型電子顕
微鏡により観察したところ、長径０．９μｍ、短径０．
７μｍのいびつな形状をしていたが、直径が０．１μｍ
以上の凹部は認められなかった。Comparative Example 3 The amount of methyl methacrylate was 8
Polymerization was carried out under the same conditions as in Example 1 except that the amount was changed to 0 g and the amount of ethylene glycol dimethacrylate was changed to 20 g. Observation of the obtained polymer fine particles with a scanning electron microscope showed that the major axis was 0.9 μm and the minor axis was 0.1 μm.
It had an irregular shape of 7 μm, but the diameter was 0.1 μm
The above concave portions were not recognized.
【００４９】（比較例４）メタクリル酸メチルの量を９
９ｇに変更し、エチレングリコールジメタクリレートの
量を１ｇに変更した以外は、実施例１と同様の条件で重
合を行った。得られた重合体微粒子は、走査型電子顕微
鏡により観察したところ、長径０．９μｍ、短径０．７
μｍのいびつな形状をしていたが、凹部は認められなか
った。Comparative Example 4 The amount of methyl methacrylate was 9
Polymerization was carried out under the same conditions as in Example 1 except that the amount was changed to 9 g and the amount of ethylene glycol dimethacrylate was changed to 1 g. Observation of the obtained polymer fine particles with a scanning electron microscope revealed that the major axis was 0.9 μm and the minor axis was 0.7 μm.
It had an irregular shape of μm, but no concave portion was observed.
【００５０】（比較例５）合成例１で製造した種粒子を
固形分換算で１０ｇ、ラウリル硫酸ナトリウム０．１５
ｇ、イオン交換水５００ｇ、スチレン９５ｇおよびジビ
ニルベンゼン５ｇを混合し、３０℃で２時間攪拌して、
種粒子に単量体を吸収させた。この混合物を窒素気流下
で７０℃に昇温し、重合開始剤として過硫酸カリウム
０．５ｇを溶解したイオン交換水５０ｇを添加して、１
０時間重合を行った。得られた重合体微粒子を走査型電
子顕微鏡により観察したところ、粒径１．１μｍの真球
状微粒子であった。(Comparative Example 5) 10 g of the seed particles produced in Synthesis Example 1 was converted to a solid content, and 0.15 g of sodium lauryl sulfate was used.
g, 500 g of ion-exchanged water, 95 g of styrene and 5 g of divinylbenzene, and stirred at 30 ° C. for 2 hours.
The monomer was absorbed by the seed particles. The mixture was heated to 70 ° C. under a nitrogen stream, and 50 g of ion-exchanged water in which 0.5 g of potassium persulfate was dissolved as a polymerization initiator was added.
Polymerization was performed for 0 hours. Observation of the obtained polymer fine particles with a scanning electron microscope revealed that the fine particles were spherical particles having a particle size of 1.1 μm.
【００５１】[0051]
【発明の効果】この発明の方法によれば、非水溶性の有
機溶媒を用いることなく、偏平状異形微粒子を容易に製
造することができる。この発明の方法により得られる偏
平状異形微粒子およびこの微粒子を含むエマルジョン
は、塗料、化粧品等の添加剤あるいは紙、情報記録紙、
光拡散性フィルム等のコーティング剤の添加剤などとし
て使用することができ、特異な形状に由来する優れた光
拡散効果を奏する。According to the method of the present invention, flat irregular fine particles can be easily produced without using a water-insoluble organic solvent. Flat irregular shaped fine particles obtained by the method of the present invention and an emulsion containing the fine particles are used as a paint, an additive or paper for cosmetics, information recording paper,
It can be used as an additive for a coating agent such as a light diffusing film, etc., and exhibits an excellent light diffusing effect derived from a unique shape.
【図１】実施例１の方法で得られた偏平状異形微粒子の
走査型電子顕微鏡写真である。FIG. 1 is a scanning electron micrograph of the flat irregularly shaped fine particles obtained by the method of Example 1.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年１月３０日[Submission date] January 30, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】この発明で用いられる種粒子の重量平均分
子量は、ゲルパーミエーションクロマトグラフィーによ
る測定で、５，０００〜１５０，０００の範囲であり、
好ましくは１０，０００〜８０，０００、さらに好まし
くは１５，０００〜５０，０００である。重合開始剤の
使用量の加減あるいは分子量調整剤の添加などにより、
種粒子の重量平均分子量をこの範囲に調整することがで
きる。分子量調整剤としては、ｎ−オクチルメルカプタ
ン、ｔ−ドデシルメルカプタン等のメルカプタン類、四
塩化炭素等のハロゲン化炭化水素類が使用され得る。こ
れらの分子量調整剤の添加量を加減することによって
も、種粒子の重量平均分子量を調整することができる。The weight average molecular weight of the seed particles used in the present invention is in the range of 5,000 to 150,000 as measured by gel permeation chromatography.
Preferably it is 10,000-80,000, More preferably, it is 15,000-50,000. By adjusting the amount of polymerization initiator used or adding a molecular weight regulator,
The weight average molecular weight of the seed particles can be adjusted to this range. As the molecular weight modifier, mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan, and halogenated hydrocarbons such as carbon tetrachloride can be used. The weight average molecular weight of the seed particles can also be adjusted by adjusting the amount of the molecular weight modifier added.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】他方、種粒子の重量平均分子量が５，００
０より小さい場合には、多量の分子量調整剤を使用して
も、所望の種粒子が得られ難いばかりでなく、最終的に
得られる偏平状異形微粒子の強度が低下するという問題
がある。なお、種粒子の大きさおよび形状は特に限定さ
れないが、通常０．１〜２μmの球状粒子が使用され
る。On the other hand, the seed particles have a weight average molecular weight of 5,000.
When it is smaller than 0, even if a large amount of the molecular weight modifier is used, not only is it difficult to obtain desired seed particles, but also the problem is that the strength of the finally obtained flat irregular shaped fine particles is reduced. The size and shape of the seed particles are not particularly limited, but generally spherical particles of 0.1 to 2 μm are used.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２６[Correction target item name] 0026
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２６】（合成例１）攪拌機、温度計および還流コ
ンデンサーを備えたセパラブルフラスコに、水６００
ｇ、メタクリル酸メチル１００ｇおよび分子量調整剤と
してｎ−オクチルメルカプタン（ｎ−ＯＭ）０．５ｇを
仕込み、攪拌下に窒素置換しながら７０℃まで昇温す
る。内温を７０℃に保ち、重合開始剤として過硫酸カリ
ウム０．５ｇを添加した後、８時間重合反応させる。得
られたエマルジョンは、固形分１４％を含有し、その固
形成分は粒径０．４μｍ、重量平均分子量45,000の真球
状粒子であった。(Synthesis Example 1) Water 600 was placed in a separable flask equipped with a stirrer, thermometer and reflux condenser.
g, 100 g of methyl methacrylate and 0.5 g of n-octyl mercaptan (n-OM) as a molecular weight modifier, and the temperature was raised to 70 ° C. while stirring and replacing with nitrogen. After maintaining the internal temperature at 70 ° C. and adding 0.5 g of potassium persulfate as a polymerization initiator, the polymerization reaction is carried out for 8 hours. The obtained emulsion contained a solid content of 14%, and the solid component was spherical particles having a particle diameter of 0.4 μm and a weight average molecular weight of 45,000.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３１[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３１】（合成例８）攪拌機、温度計および還流コ
ンデンサーを備えたセパラブルフラスコに、水９００
ｇ、スチレン１００ｇおよび分子量調整剤としてｔ−ド
デシルメルカプタン（ｔ−ＤＭ）１ｇを仕込み、攪拌下
に窒素置換しながら７０℃まで昇温する。内温を７０℃
に保ち、重合開始剤として過硫酸カリウム１ｇを添加し
た後、２４時間重合反応させる。得られたエマルジョン
は固形分１０％を含有し、その固形成分は粒径０．５μ
ｍ、重量平均分子量７５，０００の真球状粒子であっ
た。(Synthesis Example 8) Water 900 was placed in a separable flask equipped with a stirrer, a thermometer and a reflux condenser.
g, were charged styrene 100g and molecular weight modifier and to t- dodecylmercaptan (t-DM) 1g, the temperature is raised to 70 ° C. with a nitrogen substituted with stirring. 70 ° C internal temperature
After adding 1 g of potassium persulfate as a polymerization initiator, the polymerization reaction is carried out for 24 hours. The resulting emulsion contains 10% solids, and the solid component has a particle size of 0.5μ.
m and true spherical particles having a weight average molecular weight of 75,000.
Claims (2)
００のビニル系重合体粒子からなる種粒子の存在下に、
（メタ）アクリル酸エステル系単量体を主成分とし、か
つ架橋性ビニル系単量体３〜１５重量％を含む単量体混
合物を、水溶性重合開始剤を用いて、水性媒体中で乳化
重合させることを特徴とする偏平状異形微粒子の製造方
法。1. A weight average molecular weight of 5,000 to 150,0.
In the presence of seed particles comprising a vinyl polymer particle of No. 00,
A monomer mixture containing a (meth) acrylate monomer as a main component and containing 3 to 15% by weight of a crosslinkable vinyl monomer is emulsified in an aqueous medium using a water-soluble polymerization initiator. A method for producing flat irregularly shaped fine particles, characterized by polymerizing.
微粒子が、水性媒体中に分散されてなる水性エマルジョ
ン。2. An aqueous emulsion comprising fine particles produced by the method according to claim 1 dispersed in an aqueous medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36555397A JP3440197B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing flat irregular shaped fine particles and emulsion containing the fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36555397A JP3440197B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing flat irregular shaped fine particles and emulsion containing the fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11181037A true JPH11181037A (en) | 1999-07-06 |
| JP3440197B2 JP3440197B2 (en) | 2003-08-25 |
Family
ID=18484547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36555397A Expired - Fee Related JP3440197B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing flat irregular shaped fine particles and emulsion containing the fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3440197B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197588A (en) * | 2006-01-27 | 2007-08-09 | Jsr Corp | Deformed particle, deformed particle composition and its production method, and light diffusion molded product |
| JP2007308634A (en) * | 2006-05-19 | 2007-11-29 | Soken Chem & Eng Co Ltd | Light diffusion polymer particle, method for producing the same, and light diffusion sheet containing the light diffusion polymer particle |
| JP2008111132A (en) * | 2007-12-11 | 2008-05-15 | Soken Chem & Eng Co Ltd | Method for manufacturing cluster of acrylic anti-blocking particles |
| JP2010222444A (en) * | 2009-03-23 | 2010-10-07 | Sekisui Plastics Co Ltd | Globular composite particle, method for manufacturing the same, and cosmetic containing the same |
| JP2011105909A (en) * | 2009-11-20 | 2011-06-02 | Sekisui Plastics Co Ltd | Method for producing irregular-shaped resin particle, irregular-shaped resin particle, and light-diffusing material |
| JP2011219744A (en) * | 2010-03-23 | 2011-11-04 | Sekisui Plastics Co Ltd | Deformed particle and production method therefor |
-
1997
- 1997-12-22 JP JP36555397A patent/JP3440197B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197588A (en) * | 2006-01-27 | 2007-08-09 | Jsr Corp | Deformed particle, deformed particle composition and its production method, and light diffusion molded product |
| JP2007308634A (en) * | 2006-05-19 | 2007-11-29 | Soken Chem & Eng Co Ltd | Light diffusion polymer particle, method for producing the same, and light diffusion sheet containing the light diffusion polymer particle |
| JP2008111132A (en) * | 2007-12-11 | 2008-05-15 | Soken Chem & Eng Co Ltd | Method for manufacturing cluster of acrylic anti-blocking particles |
| JP2010222444A (en) * | 2009-03-23 | 2010-10-07 | Sekisui Plastics Co Ltd | Globular composite particle, method for manufacturing the same, and cosmetic containing the same |
| JP2011105909A (en) * | 2009-11-20 | 2011-06-02 | Sekisui Plastics Co Ltd | Method for producing irregular-shaped resin particle, irregular-shaped resin particle, and light-diffusing material |
| JP2011219744A (en) * | 2010-03-23 | 2011-11-04 | Sekisui Plastics Co Ltd | Deformed particle and production method therefor |
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| Publication number | Publication date |
|---|---|
| JP3440197B2 (en) | 2003-08-25 |
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