JPH0699493B2 - Method for producing monodisperse vinyl polymer fine particles - Google Patents
Method for producing monodisperse vinyl polymer fine particlesInfo
- Publication number
- JPH0699493B2 JPH0699493B2 JP2253387A JP2253387A JPH0699493B2 JP H0699493 B2 JPH0699493 B2 JP H0699493B2 JP 2253387 A JP2253387 A JP 2253387A JP 2253387 A JP2253387 A JP 2253387A JP H0699493 B2 JPH0699493 B2 JP H0699493B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- particle size
- polymer fine
- polymerization
- vinyl polymer
- 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
- 239000010419 fine particle Substances 0.000 title claims description 23
- 229920002554 vinyl polymer Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- -1 vinyl aromatic compounds Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- KMNONFBDPKFXOA-UHFFFAOYSA-N prop-2-enamide;styrene Chemical compound NC(=O)C=C.C=CC1=CC=CC=C1 KMNONFBDPKFXOA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、単分散ビニル重合体微粒子の製造法に関し、
特に、粒径が揃った比較的大粒径の単分散ビニル重合体
微粒子の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing monodisperse vinyl polymer fine particles,
In particular, it relates to a method for producing monodisperse vinyl polymer fine particles having a relatively large particle size and a uniform particle size.
従来の技術 従来の乳化重合においては、粒径の揃った単分散ラテッ
クスを得る場合、その最大粒径は、一般的には0.5μｍ
程度であった。従来、乳化重合よって得られる重合体微
粒子の粒径を大きくするための手段としては、（１）乳
化剤の量を少なくすること、（２）重合開始剤の量を少
なくすること、及び（３）無機電界質を添加することが
知られている。これらの方法では、乳化重合安定性が低
下すること、又、たとえ大粒径の重合体微粒子が得られ
たとしても、粒度が多分散になるなどの欠点を有してい
る。これらの欠点を改善する手段として、例えば、特開
昭59−22904号公報に記載されているごとく、無機電解
質の濃度を制御する方法、あるいは、高分子学界予稿集
Vol.34に記載されているように、溶剤を水と併用してス
チレン−アクリルアミド共重合体のラテックスを得る方
法などが提案されている。Conventional technology In conventional emulsion polymerization, when obtaining monodisperse latex with uniform particle size, the maximum particle size is generally 0.5 μm.
It was about. Conventionally, as means for increasing the particle size of polymer fine particles obtained by emulsion polymerization, (1) decrease the amount of emulsifier, (2) decrease the amount of polymerization initiator, and (3) It is known to add an inorganic electrolyte. These methods have the drawbacks that the emulsion polymerization stability is reduced, and that even if polymer fine particles having a large particle size are obtained, the particle size becomes polydisperse. As means for improving these drawbacks, for example, as described in JP-A-59-22904, a method of controlling the concentration of an inorganic electrolyte, or a collection of abstracts in polymer science
As described in Vol.34, there has been proposed a method of obtaining a latex of a styrene-acrylamide copolymer by using a solvent in combination with water.
発明が解決しようとする問題点 しかしながら、上記の無機電界質の濃度を制御する方法
においては、粒径１μ以上のものを得ることはできなか
った。また、溶剤を水と併用してスチレン−アクリルア
ミド共重合体のラテックスを得る方法は、粒径１μ以上
のものが得られるが、重合に用いる単量体がスチレンと
アクリルアミド以外のものには適用できず、多種多様の
用途には対応できないものであった。Problems to be Solved by the Invention However, in the above method for controlling the concentration of the inorganic electrolyte, it was not possible to obtain particles having a particle size of 1 μm or more. Further, the method of obtaining a latex of styrene-acrylamide copolymer by using a solvent in combination with water gives particles having a particle size of 1 μm or more, but is applicable to monomers other than styrene and acrylamide used for the polymerization. Therefore, it could not be used for various purposes.
本発明者等は、以上のような状況に鑑み、粒径１μ以上
の、且つ、極めて粒度分布の狭い重合体微粒子の製造法
について鋭意検討した結果、本発明を完成するに至っ
た。In view of the above situation, the inventors of the present invention have made extensive studies on a method for producing polymer fine particles having a particle size of 1 μm or more and having an extremely narrow particle size distribution, and as a result, have completed the present invention.
従って、本発明の目的は、大粒径、且つ、粒度分布の極
めて狭い、単分散のビニル重合体微粒子の製造方法を提
供することにある。Therefore, an object of the present invention is to provide a method for producing monodisperse vinyl polymer particles having a large particle size and an extremely narrow particle size distribution.
本発明の他の目的は、原料として用いられる単量体の種
類に大きな制限を受けることなく、重合体微粒子を製造
する方法を提供することにある。Another object of the present invention is to provide a method for producing polymer fine particles without being greatly restricted by the type of monomer used as a raw material.
問題点を解決するための手段及び作用 本発明者等は、粒径を大きくし、且つ、単分散性を保つ
ためには、重合開始剤の種類及び濃度、電解質の種類及
び濃度、及び重合温度等と共に、重合時に用いる界面活
性剤も重要な要因であることを見出だし、鋭意検討した
結果、下記一般式（Ｉ）で示される化合物を用い、特定
の条件下で重合を行うと、上記目的が達成されることを
見出だし、本発明を完成するに至った。Means and Actions for Solving Problems In order to increase the particle size and maintain monodispersity, the present inventors have found that the type and concentration of the polymerization initiator, the type and concentration of the electrolyte, and the polymerization temperature. In addition, it was found that the surfactant used at the time of polymerization is also an important factor, and as a result of diligent studies, it was found that when the compound represented by the following general formula (I) is used and the polymerization is carried out under specific conditions, The present invention has been completed and the present invention has been completed.
即ち、本発明の単分散ビニル重合体微粒子の製造法は、
ビニル芳香族化合物、アクリル酸エステル及びメタクリ
ル酸エステルよりなる群から選ばれた一種以上の単量体
を乳化重合するに際して、界面活性剤として下記一般式
（Ｉ）で示される化合物の存在下、重合開始剤として過
硫酸塩10-1〜10-3モル／及び電解質として二価金属硫
酸塩10-2〜10-4モル／を使用して重合を行うことを特
徴とする。それにより数平均粒径1.0〜10.0μｍ及びコ
ールターカウンターによる標準偏差1.25以下の粒度分布
を有する単分散ビニル重合体微粒子を得ることができ
る。That is, the method for producing monodisperse vinyl polymer fine particles of the present invention,
In emulsion-polymerizing one or more monomers selected from the group consisting of vinyl aromatic compounds, acrylic acid esters and methacrylic acid esters, polymerization is carried out in the presence of a compound represented by the following general formula (I) as a surfactant. The polymerization is carried out by using 10 -1 to 10 -3 mol / persulfate as an initiator and 10 -2 to 10 -4 mol / divalent metal sulfate as an electrolyte. As a result, monodisperse vinyl polymer fine particles having a number average particle size of 1.0 to 10.0 μm and a particle size distribution with a standard deviation of 1.25 or less by a Coulter counter can be obtained.
（式中、R1及びR2は、同一でも異なっていてもよく、そ
れぞれ炭素数４〜８のアルキル基、置換又は非置換のフ
ェニル基、又は、置換又は非置換のシクロヘキシル基を
表わし、Ｍはアルカリ金属を表わす） 以下、本発明について詳細に説明する。 (In the formula, R 1 and R 2, which may be the same or different, each represents an alkyl group having 4 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group, and M Represents an alkali metal) Hereinafter, the present invention will be described in detail.
本発明において、乳化重合において使用するビニル単量
体は、スチレン等のビニル芳香族化合物、アクリル酸エ
ステル及びメタクリル酸エステルよりなる群から選択さ
れる一種又はそれ以上のものであり、所望により、他の
共単量体例えば、アクリロニトリル、メタクリロニトリ
ル等を少量成分として使用してもよい。In the present invention, the vinyl monomer used in the emulsion polymerization is one or more selected from the group consisting of vinyl aromatic compounds such as styrene, acrylic acid esters and methacrylic acid esters, and if desired, other A comonomer of, for example, acrylonitrile or methacrylonitrile may be used as a minor component.
本発明において、重合は一段階で行ってもよいが、二段
階で行うこともできる。例えば、まず、スチレンのみを
重合させ、引続いてスチレンと他のビニル単量体を添加
して重合反応を継続する方法、あるいは、メチルメタク
リレートのごとき親水性単量体を使用する場合には、ま
ず、スチレン、２−エチルヘキシルアクリレート等を重
合し、粒径／電位のバランスが平行に達した後に、メチ
ルメタクリレート及び他のビニル単量体を添加して重合
を行う等の方法が採用できる。In the present invention, the polymerization may be carried out in one step, but it may be carried out in two steps. For example, first, a method in which only styrene is polymerized, and then styrene and another vinyl monomer are added to continue the polymerization reaction, or when a hydrophilic monomer such as methyl methacrylate is used, First, a method of polymerizing styrene, 2-ethylhexyl acrylate, etc. and, after reaching a parallel particle size / potential balance, adding methyl methacrylate and another vinyl monomer to carry out polymerization can be employed.
乳化重合反応は、上記一般式（Ｉ）で示される化合物の
存在下で行われるが、具体的には次のものが例示され
る。The emulsion polymerization reaction is carried out in the presence of the compound represented by the above general formula (I), and specific examples include the following.
それ等の添加量は任意に設定できるが、特に水溶液濃度
0.04〜0.80g/dlの範囲で使用するのが望ましい。 The amount of such addition can be set arbitrarily, but especially the aqueous solution concentration
It is desirable to use it in the range of 0.04 to 0.80 g / dl.
乳化重合において、粒径を大きくし、且つ、単分散性を
保つために要求される界面活性剤の性質として、１）通
常用いられるドデシル硫酸ナトリウム等より高表面張力
をもつこと、２）エマルジョンの生成／消失の繰返し極
力が少ないこと、３）十分な表面電荷を有しているこ
と、の各条件があげられる。上記１）は、粒径を大きく
するための条件の生成による多分散化（微少粒子の発
生）の制御のための条件であり、３）は粒子間の結合防
止による多分散化（粗大粒子の生成）の制御のための条
件である。本発明において用いる上記一般式（Ｉ）で示
される界面活性剤は、上記の条件を満足する。即ち、従
来用いられているドデシル硫酸ナトリウムのごとき、直
鎖状の活性剤に比べて、エマルジョンの生成−消失の繰
返しが少なく、更に、アルキル基の炭素数を４〜８にす
ることによって粒径と表面電位のバランスが取りやすい
物となる。In emulsion polymerization, the surfactant properties required to increase the particle size and maintain monodispersity are 1) have a higher surface tension than commonly used sodium dodecyl sulfate, etc. The conditions are that the number of repetitions of generation / disappearance is as small as possible, and 3) the surface charge is sufficient. The above 1) is a condition for controlling polydispersion (generation of fine particles) by generating conditions for increasing the particle size, and 3) is polydispersion by preventing interparticle bonding (for coarse particles). This is a condition for controlling (generation). The surfactant represented by the general formula (I) used in the present invention satisfies the above conditions. That is, compared with a conventional linear activator such as sodium dodecylsulfate, the generation-disappearance of the emulsion is less repeated, and the carbon number of the alkyl group is 4 to 8 And the surface potential can be easily balanced.
本発明おいて、重合開始剤としては、過硫酸塩系開始剤
が使用され、例えば、過硫酸カリウム、過硫酸アンモニ
ウム等が最も好ましく用いられる。その場合、水溶液濃
度として、10-1〜10-3モル／の範囲で用いることが必
要である。この範囲を逸脱すると、所定の粒径及び標準
偏差の単分散ビニル重合体微粒子は得られなくなる。In the present invention, a persulfate-based initiator is used as the polymerization initiator, and for example, potassium persulfate, ammonium persulfate and the like are most preferably used. In this case, it is necessary to use the aqueous solution in the concentration range of 10 -1 to 10 -3 mol /. If it deviates from this range, monodisperse vinyl polymer fine particles having a predetermined particle size and standard deviation cannot be obtained.
又、電解質としては、本発明においては、硫酸第一銅
（CuSO4）、硫酸第一鉄（FeSO4）などの二価金属硫酸塩
が使用され、それにより、重合体微粒子の平均粒径が大
きくなると共に、粒度分布もシャープになる。電解質の
濃度は、10-2〜10-4モル／の範囲で用いることが必要
である。この範囲を逸脱すると、所定の粒径及び平均偏
差の単分散ビニル重合体微粒子は得られなくなる。Further, in the present invention, as the electrolyte, divalent metal sulfate such as cuprous sulfate (CuSO 4 ) and ferrous sulfate (FeSO 4 ) is used, whereby the average particle size of the polymer fine particles is The larger the particle size, the sharper the particle size distribution. The concentration of the electrolyte needs to be in the range of 10 −2 to 10 −4 mol /. Outside this range, monodisperse vinyl polymer fine particles having a predetermined particle size and average deviation cannot be obtained.
更に、前記一般式（Ｉ）で示される界面活性剤と共に、
アクリル酸−マレイン酸共重合体等の水溶性高分子を分
散安定剤として使用してもよい。その場合表面張力は40
〜75ダイン/cmであるのがよい。Further, together with the surfactant represented by the general formula (I),
A water-soluble polymer such as an acrylic acid-maleic acid copolymer may be used as a dispersion stabilizer. In that case, the surface tension is 40
It should be ~ 75 dynes / cm.
重合温度は、40〜90℃、好ましくは45〜75℃の範囲で行
われる。The polymerization temperature is 40 to 90 ° C, preferably 45 to 75 ° C.
実施例 以下、本発明を実施例によって説明する。以下の実施例
はすべて、N2導入口、いかり型撹拌翼、温度調節計を備
えた５グラスライニング製オートクレーブによって実
施した。Examples Hereinafter, the present invention will be described with reference to Examples. All of the following examples were carried out in a 5 glass-lined autoclave equipped with a N 2 inlet, anchor type stirring blade, and temperature controller.
実施例１ 蒸溜水3.2を反応器に入れ、窒素ガスで置換した後、
温度を50℃まで昇温した。これに、下記化合物（花王
（株）製ペレックスCS）4.32g及びアクリル酸−マレイ
ン酸共重合体（花王（株）製ポイズ520）0.72gを0.2
の水に溶解して得た水溶液を添加した。Example 1 3.2 distilled water was put into a reactor, and after being replaced with nitrogen gas,
The temperature was raised to 50 ° C. To this, 4.32 g of the following compound (Perex CS manufactured by Kao Corporation) and 0.72 g of acrylic acid-maleic acid copolymer (Poise 520 manufactured by Kao Corporation) were added.
An aqueous solution obtained by dissolving the same in water was added.
次いで、過硫酸アンモニウム28.8gを0.2の水に溶解し
て得た水溶液を添加した。更に、スチレン400ml及び硫
酸第一銅（CuSO4）0.6gを加え、重合温度を50℃に保ち
ながら、４時間重合を行った。４時間経過した後、スチ
レン400ml及びｔ−ドデシルメルカプタン12gの混合液を
滴下ロートに入れ、約２時間で滴下した。更に60℃で20
時間重合を継続させ、重合を完結させた。得られた重合
体微粒子のついて走査型電子顕微鏡によって粒径を観察
したところ、粒径は、2.8μｍであり、単分散粒子集合
体が得られていることが確認された。コールターカウン
ターによる粒度分布の標準偏差は1.16であった。又、重
合体微粒子の重量平均分子量は72000、数平均分子量は1
4000、ガラス転移点は98.5℃であった。（収率84％） 実施例２ 単量体としてスチレン1080ml及び２−エチルヘキシルア
クリレート120mlを用い、実施例１におけると同様に、
二段階添加によって重合を実施した。但し過硫酸アンモ
ニウムの代わりに過硫酸カリウム46.8gを用い、又、硫
酸第一銅を0.72g用いて反応を行った。重合反応は、50
℃で24時間、次いで65℃で12時間行った。得られた重合
体微粒子のついて、実施例１におけると同様に粒径を観
察したところ、粒径は、5.9μｍであり、単分散粒子集
合体が得られていることが確認された。コールターカウ
ンターによる粒度分布の標準偏差は1.17であった。又、
重合体微粒子の重量平均分子量は220400、数平均分子量
は30200、ガラス転移点は61.5℃であった。（収率78
％） 実施例３ 実施例１におけるペレックスCSの代わりに下記化合物
（花王（株）製ペレックスBB）5.40gを用い、過硫酸ア
ンモニウムの代わりに過硫酸カリウム46.8gを用い、
又、硫酸銅（CuSO4）を0.72g用いた以外は同様にしてス
チレンの重合を行った。 Then, an aqueous solution obtained by dissolving 28.8 g of ammonium persulfate in 0.2 water was added. Further, 400 ml of styrene and 0.6 g of cuprous sulfate (CuSO 4 ) were added and polymerization was carried out for 4 hours while maintaining the polymerization temperature at 50 ° C. After 4 hours, a mixed solution of 400 ml of styrene and 12 g of t-dodecyl mercaptan was placed in a dropping funnel and added dropwise in about 2 hours. 20 at 60 ° C
The polymerization was continued for an hour to complete the polymerization. When the particle size of the obtained polymer fine particles was observed by a scanning electron microscope, the particle size was 2.8 μm, and it was confirmed that a monodisperse particle aggregate was obtained. The standard deviation of the particle size distribution measured by a Coulter counter was 1.16. The weight average molecular weight of the polymer fine particles is 72,000 and the number average molecular weight is 1
The glass transition point was 4000 and the glass transition point was 98.5 ° C. (Yield 84%) Example 2 As in Example 1, using styrene 1080 ml and 2-ethylhexyl acrylate 120 ml as monomers,
Polymerization was carried out by two-step addition. However, the reaction was performed using 46.8 g of potassium persulfate instead of ammonium persulfate and 0.72 g of cuprous sulfate. The polymerization reaction is 50
It was carried out at 24 ° C for 24 hours and then at 65 ° C for 12 hours. When the particle size of the obtained polymer fine particles was observed in the same manner as in Example 1, the particle size was 5.9 μm, and it was confirmed that a monodisperse particle aggregate was obtained. The standard deviation of the particle size distribution measured by a Coulter counter was 1.17. or,
The polymer fine particles had a weight average molecular weight of 220400, a number average molecular weight of 30,200, and a glass transition point of 61.5 ° C. (Yield 78
%) Example 3 5.40 g of the following compound (Perex BB manufactured by Kao Corporation) was used in place of Perex CS in Example 1, and 46.8 g of potassium persulfate was used in place of ammonium persulfate.
Further, styrene was polymerized in the same manner except that 0.72 g of copper sulfate (CuSO 4 ) was used.
但し、重合反応は、50℃で24時間、次いで65℃で12時間
行った。得られた重合体微粒子のついて、実施例１にお
けると同様に粒径を観察したところ、粒径は、1.5μｍ
であり、単分散粒子集合体が得られていることが確認さ
れた。コールターカウンターによる粒度分布の標準偏差
は1.14であった。又、重合体微粒子の重量平均分子量は
27600、数平均分子量は49000、ガラス転移点は99.5℃で
あった。（収率81％） 比較例１ 実施例１におけるペレックスCSの代わりに下記化合物を
用いた以外は同様にして操作を行ったところ、得られた
重合体微粒子の数平均粒径は0.25μｍであった。 However, the polymerization reaction was carried out at 50 ° C. for 24 hours and then at 65 ° C. for 12 hours. The particle size of the obtained polymer fine particles was observed in the same manner as in Example 1. The particle size was 1.5 μm.
It was confirmed that a monodisperse particle aggregate was obtained. The standard deviation of the particle size distribution measured by a Coulter counter was 1.14. The weight average molecular weight of the polymer particles is
27,600, the number average molecular weight was 49000, and the glass transition point was 99.5 ° C. (Yield 81%) Comparative Example 1 When a similar operation was performed except that the following compound was used instead of Perex CS in Example 1, the number average particle diameter of the obtained polymer fine particles was 0.25 μm. It was
比較例２ 実施例１におけるペレックスCSの代わりにドデシル硫酸
ナトリウムを用いた以外は同様にして操作を行ったとこ
ろ、得られた重合体微粒子の数平均粒径は0.40μｍであ
った。 Comparative Example 2 When a similar operation was performed except that sodium dodecyl sulfate was used instead of Perex CS in Example 1, the number average particle diameter of the obtained polymer fine particles was 0.40 μm.
発明の効果 本発明によれば、乳化重合法によって、数平均粒径1.0
〜10.0μｍ程度の極めて大きな粒径を持ち、且つ、標準
偏差が1.25以下の狭い粒度分布を有する単分散性の重合
体微粒子が、複雑な工程を要することなく容易に得られ
る。EFFECTS OF THE INVENTION According to the present invention, the number average particle size is 1.0 by the emulsion polymerization method.
Monodisperse polymer particles having an extremely large particle size of about 10.0 μm and a narrow particle size distribution with a standard deviation of 1.25 or less can be easily obtained without requiring complicated steps.
又、本発明によって得られた重合体微粒子は、生物学的
担体、固定化酵素担体、免疫血清学的診断薬担体、医薬
投与用担体、イオン交換樹脂、結晶表示用スペーサー、
カラム充填剤、電子写真現像剤、塗料等への応用が可能
であり、特に着色した重合体微粒子は、そのままの状態
で電子写真現像剤として使用することができるので、有
利である。Further, the polymer fine particles obtained by the present invention include a biological carrier, an immobilized enzyme carrier, an immunoserological diagnostic drug carrier, a drug administration carrier, an ion exchange resin, a crystal display spacer,
It can be applied to a column filler, an electrophotographic developer, a paint, and the like, and in particular, colored polymer fine particles can be used as an electrophotographic developer as they are, which is advantageous.
Claims (1)
及びメタクリル酸エステルよりなる群から選ばれた一種
以上の単量体を乳化重合するに際して、界面活性剤とし
て下記一般式（Ｉ）で示される化合物の存在下、重合開
始剤として過硫酸塩10-1〜10-3モル／及び電解質とし
て二価金属硫酸塩10-2〜10-4モル／のを用いて重合を
行うことを特徴とする単分散ビニル重合体微粒子の製造
法。 （式中、R1及びR2は、同一でも異なっていてもよく、そ
れぞれ炭素数４〜８のアルキル基、置換又は非置換のフ
ェニル基、又は、置換又は非置換のシクロヘキシル基を
表わし、Ｍはアルカリ金属を表わす。）1. A compound represented by the following general formula (I) as a surfactant when emulsion-polymerizing one or more monomers selected from the group consisting of vinyl aromatic compounds, acrylic acid esters and methacrylic acid esters. In the presence of a persulfate of 10 -1 to 10 -3 mol / as a polymerization initiator and a divalent metal sulfate of 10 -2 to 10 -4 mol / m as an electrolyte. Method for producing fine particles of dispersed vinyl polymer. (In the formula, R 1 and R 2, which may be the same or different, each represents an alkyl group having 4 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group, and M Represents an alkali metal.)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2253387A JPH0699493B2 (en) | 1987-02-04 | 1987-02-04 | Method for producing monodisperse vinyl polymer fine particles |
| US07/152,003 US4935469A (en) | 1987-02-04 | 1988-02-03 | Process for producing monodispersed vinyl polymer fine particles |
| US07/735,768 US5219943A (en) | 1987-02-04 | 1991-07-29 | Process for producing monodispersed vinyl polymer fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2253387A JPH0699493B2 (en) | 1987-02-04 | 1987-02-04 | Method for producing monodisperse vinyl polymer fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63191808A JPS63191808A (en) | 1988-08-09 |
| JPH0699493B2 true JPH0699493B2 (en) | 1994-12-07 |
Family
ID=12085436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2253387A Expired - Fee Related JPH0699493B2 (en) | 1987-02-04 | 1987-02-04 | Method for producing monodisperse vinyl polymer fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699493B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0745527B2 (en) * | 1987-04-13 | 1995-05-17 | 富士ゼロックス株式会社 | Method for producing monodisperse vinyl polymer fine particles |
| JP6269671B2 (en) * | 2013-07-18 | 2018-01-31 | 旭硝子株式会社 | Method for producing fluoropolymer aqueous dispersion, fluoropolymer aqueous dispersion, and fluoropolymer |
-
1987
- 1987-02-04 JP JP2253387A patent/JPH0699493B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63191808A (en) | 1988-08-09 |
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