JPS62209106A - Vinyl chloride polymer latex and production thereof - Google Patents
Vinyl chloride polymer latex and production thereofInfo
- Publication number
- JPS62209106A JPS62209106A JP5307586A JP5307586A JPS62209106A JP S62209106 A JPS62209106 A JP S62209106A JP 5307586 A JP5307586 A JP 5307586A JP 5307586 A JP5307586 A JP 5307586A JP S62209106 A JPS62209106 A JP S62209106A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- latex
- water
- weight
- polymerization
- 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
- 239000004816 latex Substances 0.000 title claims abstract description 91
- 229920000126 latex Polymers 0.000 title claims abstract description 91
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229920000642 polymer Polymers 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 230000005484 gravity Effects 0.000 abstract description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 abstract description 6
- 239000004641 Diallyl-phthalate Substances 0.000 abstract description 5
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001900 immune effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- -1 sodium alkyl sulfate Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 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
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000002331 protein detection Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012926 reference standard material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
ｌの３細な晋゛口
（産業上の利用分野）
本発明は、均一な粒径を有し乳化剤を含まない塩化ビニ
ル重合体ラテックスおよびその製造方法に関する。Detailed Description of the Invention The present invention relates to a vinyl chloride polymer latex having a uniform particle size and containing no emulsifier, and a method for producing the same.
（従来の技術）
免疫試薬用担体として、あるいは電子顕微鏡の比較標準
物質の長さを測定するための標準品として、ラテックス
が利用されている。このようなラテックスとしては、１
１製が容易であることなどからポリスチレンラテックス
が好適に用いられる。(Prior Art) Latex is used as a carrier for immunoreagents or as a standard product for measuring the length of a reference standard material for electron microscopy. As such latex, 1
Polystyrene latex is preferably used because it is easy to make.
しかし、ポリスチレンの比重は比較的小さいため。However, since the specific gravity of polystyrene is relatively small.
例えばラテックス試薬と検体との反応指標である凝集反
応に長時間を要する。したがって、ラテックスの用途に
よっては、高比重であることが望ましい。このような用
途の高比重ラテックスとしては塩化ビニル重合体が考え
られる。塩化ビニル重合体ラテックスは２通常、アルキ
ル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリ
ウム、脂肪酸ナトリウムなどのアニオン系界面活性剤や
非イオン系界面活性剤を乳化剤として乳化重合すること
により得られる。しかし、このような方法では粒径の揃
ったラテックスが得られにくい。For example, the agglutination reaction, which is an indicator of the reaction between a latex reagent and a specimen, takes a long time. Therefore, depending on the use of the latex, it is desirable that the latex has a high specific gravity. A vinyl chloride polymer can be considered as a high-density latex for such uses. Vinyl chloride polymer latex is usually obtained by emulsion polymerization using an anionic surfactant or nonionic surfactant such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, or sodium fatty acid as an emulsifier. However, with such a method, it is difficult to obtain latex with uniform particle size.
粒径の均一な塩化ビニル重合体ラテックスを得る方法は
２例えば特公昭４０−１０５８６ 、特開昭６０−９４
４０４および特開昭６０−９４４０５号公報に開示され
ている。そこには、使用される乳化剤の種類や乳化剤の
反応系への添加工程に改良を加えることにより、比較的
均一なラテックスが得られることが示されている。しか
し、いずれも界面活性剤などの乳化剤の使用が必須要件
であるため、得られるラテックスには乳化剤が残留する
。そのため、そのラテックスを長期間保存するとラテッ
クス粒子同士が凝集し沈澱することがあり、安定性に欠
ける。There are two methods for obtaining vinyl chloride polymer latex with uniform particle size, for example, Japanese Patent Publication No. 40-10586 and Japanese Patent Publication No. 60-94.
404 and Japanese Patent Application Laid-Open No. 60-94405. It is shown that a relatively uniform latex can be obtained by making improvements to the type of emulsifier used and the process of adding the emulsifier to the reaction system. However, since both require the use of an emulsifier such as a surfactant, the emulsifier remains in the resulting latex. Therefore, if the latex is stored for a long period of time, the latex particles may aggregate and precipitate, resulting in a lack of stability.
（発明が解決しようとする問題点） 本発明は上記従来の欠点を解決するものであり。(Problem that the invention attempts to solve) The present invention solves the above-mentioned conventional drawbacks.
その目的とするところは２粒径が均一であり長期間安定
に保存しうる高比重で高品質のラテックスを提供するこ
とにある。本発明の他の目的は、上記価れた性質を有す
る塩化ビニル重合体ラテックスを提供することにある。The purpose is to provide a high-quality latex with a high specific gravity that has uniform particle diameters and can be stored stably for a long period of time. Another object of the present invention is to provide a vinyl chloride polymer latex having the above-mentioned excellent properties.
本発明のさらに他の目的は、上記価れた性質を有する塩
化ビニル重合体ラテックスを乳化剤を使用せずに製造す
る方法を提供することにある。Still another object of the present invention is to provide a method for producing a vinyl chloride polymer latex having the above-mentioned excellent properties without using an emulsifier.
（問題点を解決するための手段および作用）本発明の塩
化ビニル重合体ラテックスは、水１００重量部、塩化ビ
ニル３０重量部以下、そして多官能性単量体を該塩化ビ
ニルに対して０．１〜１０重量％の割合で含有する混合
液を、乳化剤の不存在下で水溶性重合開始剤を用い２重
合反応に供して得られ、そのことにより上記目的が達成
される。(Means and effects for solving the problems) The vinyl chloride polymer latex of the present invention contains 100 parts by weight of water, 30 parts by weight or less of vinyl chloride, and 0.0 parts by weight of a polyfunctional monomer based on the vinyl chloride. A mixed solution containing 1 to 10% by weight is subjected to a double polymerization reaction using a water-soluble polymerization initiator in the absence of an emulsifier, thereby achieving the above object.
本発明の塩化ビニル重合体ラテックスの製造方法は、水
１００重量部、塩化ビニル３０重量部以下。The method for producing vinyl chloride polymer latex of the present invention uses 100 parts by weight of water and 30 parts by weight or less of vinyl chloride.
そして多官能性単量体を該塩化ビニルに対して０．１〜
１０重量％の割合で含有する混合液を、乳化剤の不存在
下で水溶性重合開始剤を用い１重合反応に供し、そのこ
とにより上記目的が達成される。And the polyfunctional monomer is 0.1 to 0.1 to the vinyl chloride.
The above object is achieved by subjecting a mixed solution containing 10% by weight to a single polymerization reaction using a water-soluble polymerization initiator in the absence of an emulsifier.
発明者らは、乳化剤を全く使用しない場合でも塩化ビニ
ルの仕込量や反応条件を調整することにより高品質の塩
化ビニル重合体ラテックスが得られるのではないかと考
え２種々の実験を行った。The inventors conducted two various experiments with the idea that a high-quality vinyl chloride polymer latex could be obtained by adjusting the amount of vinyl chloride charged and the reaction conditions even when no emulsifier was used at all.
まず２重合反応時の分散媒である水と塩化ビニ）ルとの
配合割合を検討した。水溶性の重合開始剤である後述の
過硫酸塩を用い、水１００重量部に対する塩化ビニルの
配合割合を種々に変化させてラテックスの調製を試みた
。塩化ビニルの量が１０重量部以下であるときには攪拌
により塩化ビニルが水中に微細に分散し粒径が０．１〜
０．５μｌの均一なラテックスが生成した。このときの
ラテックスの粒径は塩化ビニルの量が増加するのにつれ
て大きくなるのが観察された。塩化ビニルの量が約１５
重量部に達するとラテックスの粒径は約１．０μｍとな
った。塩化ビニルの仕込量をさらに増加させてもラテッ
クスの粒径は平均的には大きくならなかった。塩化ビニ
ルの量が２０重量部を越えると反応容器壁面にスケール
が認められるようになり。First, the mixing ratio of water and vinyl chloride as a dispersion medium during the double polymerization reaction was investigated. Latex preparation was attempted using a water-soluble polymerization initiator, a persulfate salt described below, and varying the blending ratio of vinyl chloride to 100 parts by weight of water. When the amount of vinyl chloride is 10 parts by weight or less, the vinyl chloride is finely dispersed in water by stirring and the particle size is 0.1~
0.5 μl of homogeneous latex was produced. It was observed that the particle size of the latex at this time increased as the amount of vinyl chloride increased. The amount of vinyl chloride is approximately 15
When the weight part was reached, the particle size of the latex was approximately 1.0 μm. Even if the amount of vinyl chloride charged was further increased, the average particle size of the latex did not increase. When the amount of vinyl chloride exceeds 20 parts by weight, scale becomes visible on the walls of the reaction vessel.
ラテックス粒子のなかに、誤差範囲内ではあるが。Inside the latex particles, although within the margin of error.
均一粒径のラテックス粒子よりも大きな粒径の粒子が認
められるようになった。３０重量部になるとスケールの
付着がやや多くなった。３０重量部を越えると２反応時
の内温に対応する塩化ビニルの飽和蒸気圧に達した時に
、塩化ビニル単量体が反応容器上部の温度の低い壁面で
凝縮する傾向が強まる。凝縮・液化した塩化ビニルはこ
の部分でも重合反応を起こしスケールとなって壁面へ付
着したり９反応液内へ入り込む。あるいは、液化した塩
化ビニルが反応液内で重合・固化し大きな粒子を形成す
る。このように塩化ビニルの量が３０重量部を越えると
ラテックス粒子の粒径や形状が著しく不均一になる。さ
らに、塩化ビニル量が増加すると形成された重合体粒子
同士がお互いに付着して大粒子となりラテックスを形成
しなくなる。全体がブロック状態となることもある。上
記特徴は３０〜５０重量％の塩化ビニルを乳化剤の存在
下にて水中で重合させる一般の乳化重合法の反応状況と
は極めて異なる。Particles with a larger particle size than latex particles with a uniform particle size were observed. When the amount was 30 parts by weight, there was a slight increase in scale adhesion. When the amount exceeds 30 parts by weight, when the saturated vapor pressure of vinyl chloride corresponding to the internal temperature during the second reaction is reached, the vinyl chloride monomer tends to condense on the lower temperature wall of the upper part of the reaction vessel. The condensed and liquefied vinyl chloride also undergoes a polymerization reaction in this area, becomes scale, and adheres to the wall surface or enters the reaction solution. Alternatively, liquefied vinyl chloride polymerizes and solidifies in the reaction solution to form large particles. As described above, when the amount of vinyl chloride exceeds 30 parts by weight, the particle size and shape of the latex particles become significantly non-uniform. Furthermore, when the amount of vinyl chloride increases, the formed polymer particles adhere to each other and become large particles, making it impossible to form latex. The entire system may become blocked. The above characteristics are extremely different from the reaction conditions of the general emulsion polymerization method in which 30 to 50% by weight of vinyl chloride is polymerized in water in the presence of an emulsifier.
このように、水１００重量部に対して塩化ビニルの仕込
量を３０重量部以下、好ましくは２０重量部以下の割合
とし、水溶性重合開始剤を用いて攪拌下で重合反応を行
うと均一な粒径のラテックスが得られることが基本的に
Ｎ認された。発明者らはこれをもとに検討を重ね１本発
明を完成するに至った。、
本発明では、上記重合時にさらに多官能性単量体が加え
られる。多官能性単量体としては、ジアリルフタレート
、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など２分子末端の２ケ所
以上に重合性の基を有する単量体が用いられる。塩化ビ
ニルの重合時に多官能性単量体が存在すると架橋構造を
有する塩化ビニル重合体が形成される。架橋構造を有す
ることにより長期間保存してもラテックス粒子同士が合
着したり変形するのが抑制される。このような架橋構造
の導入によるラテックス粒子の合着変形の抑制効果は上
記化合物のうちジアリルフタレートを用いたときに最も
効果的である。このような多官能性単量体は塩化ビニル
に対して０．１〜１０重量％、好ましくは０．１〜５重
量％の割合で加えられる。過少であるとラテックスの保
存安定性に劣り、過剰であると不揃いなラテックス粒子
となる。In this way, if the amount of vinyl chloride charged is 30 parts by weight or less, preferably 20 parts by weight or less, per 100 parts by weight of water, and the polymerization reaction is carried out under stirring using a water-soluble polymerization initiator, a uniform result can be obtained. It was basically confirmed that a latex of particle size could be obtained. The inventors have conducted repeated studies based on this and have completed the present invention. In the present invention, a polyfunctional monomer is further added during the polymerization. As the polyfunctional monomer, a monomer having polymerizable groups at two or more positions at two molecular ends, such as diallyl phthalate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate, is used. If a polyfunctional monomer is present during polymerization of vinyl chloride, a vinyl chloride polymer having a crosslinked structure is formed. Having a crosslinked structure prevents latex particles from coalescing or deforming even after long-term storage. The effect of suppressing the cohesive deformation of latex particles by introducing such a crosslinked structure is most effective when diallylphthalate is used among the above compounds. Such polyfunctional monomers are added in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on vinyl chloride. If it is too small, the storage stability of the latex will be poor, and if it is too large, the latex particles will be irregular.
重合時には上記塩化ビニルおよび多官能性単量体の他に
共重合成分として他の単量体が加えられていてもよい。During polymerization, other monomers may be added as copolymerization components in addition to the above vinyl chloride and polyfunctional monomers.
このような単量体としては、酢酸ビニル、エチレン、プ
ロピレン、各種（メタ）アクリル酸エステル、塩化ビニ
リデンなど１通常。Examples of such monomers include vinyl acetate, ethylene, propylene, various (meth)acrylic acid esters, vinylidene chloride, and the like.
塩化ビニルと共重合されうる単量体が使用される。Monomers that can be copolymerized with vinyl chloride are used.
これら他の単量体は塩化ビニルに対し１０重量％以下の
割合で加えられる。These other monomers are added in a proportion of 10% by weight or less based on vinyl chloride.
本発明に使用される重合開始剤としては、塩化ビニルの
エマルジョン重合に通常使用される水溶性重合開始剤が
使用され得、それには１例えば。As the polymerization initiator used in the present invention, water-soluble polymerization initiators commonly used for emulsion polymerization of vinyl chloride can be used, including, for example, one.
過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩が
ある。油溶性の有機過酸化物は、生成した塩化ビニル重
合体の粒子同士が合着したり反応器の内壁にスケールが
大量に付着するため、好ましくない。重合開始剤は塩化
ビニル１００重量部に対して０．５〜０．０５重量部、
好ましくは０．３〜０．１重量部の割合で反応系に加え
られる。There are persulfates such as potassium persulfate and ammonium persulfate. Oil-soluble organic peroxides are not preferred because they cause particles of the vinyl chloride polymer produced to coalesce and a large amount of scale to adhere to the inner walls of the reactor. The polymerization initiator is 0.5 to 0.05 parts by weight per 100 parts by weight of vinyl chloride,
It is preferably added to the reaction system in a proportion of 0.3 to 0.1 parts by weight.
本発明方法により塩化ビニル重合体ラテックスを得るに
は２例えば、まず、攪拌装置と冷却・加熱装置とを備え
た耐圧の反応容器を準備する。このような反応容器に水
および重合開始剤を入れ。To obtain a vinyl chloride polymer latex by the method of the present invention 2 For example, first, a pressure-resistant reaction vessel equipped with a stirring device and a cooling/heating device is prepared. Put water and a polymerization initiator into such a reaction vessel.
反応器内を水の蒸気圧に達するまで排気する０次に塩化
ビニル、多官能性単量体および必要に応じて他の単量体
を容器内に加え、攪拌下加温して重合反応を開始させる
。重合反応が始まると昇温するので加温をやめ反応系を
適度に冷却して、所定温度で重合反応を行うとラテック
スが形成される。The inside of the reactor is evacuated until it reaches the vapor pressure of water. Next, vinyl chloride, a polyfunctional monomer, and other monomers as necessary are added to the container, and the polymerization reaction is carried out by heating with stirring. Let it start. When the polymerization reaction begins, the temperature rises, so the heating is stopped, the reaction system is appropriately cooled, and the polymerization reaction is carried out at a predetermined temperature to form latex.
本発明では、塩化ビニルの量を所定量以下としたため１
反応器内での塩化ビニルの凝縮・液化に起因する不揃い
な、ラテックス粒子の生成が少ない。In the present invention, since the amount of vinyl chloride is set to below a predetermined amount, 1
Less irregular latex particles are produced due to condensation and liquefaction of vinyl chloride in the reactor.
また、ブロッキングも生じない。Moreover, blocking does not occur.
重合反応が進行すると単量体が消費されるため。Because monomers are consumed as the polymerization reaction progresses.
反応途中で塩化ビニル単量体や多官能性単量体を仕込時
の割合に応じて追加してもよい。このような方法を用い
ると一回の重合反応で通常の量以上のラテックスが調製
されうる。During the reaction, a vinyl chloride monomer or a polyfunctional monomer may be added depending on the ratio at the time of charging. By using such a method, more than the usual amount of latex can be prepared in a single polymerization reaction.
さらに大きな粒径のラテックスを得たい場合には、得ら
れたラテックスを上記塩化ビニル重合時に同時に反応系
に加え、これを核（シード）としてさらに重合を行う。If it is desired to obtain a latex with an even larger particle size, the obtained latex is added to the reaction system at the same time as the above-mentioned vinyl chloride polymerization, and further polymerization is carried out using this as a nucleus (seed).
このようにシード重合を行うことにより粒径が均一で、
かつ大粒径のラテックスが生成する。加えられるシード
重合体ラテックスは固形分重量換算で塩化ビニル単量体
の０．０５〜０．２倍量が適当である。過少であると大
粒径ラテックスが得られず、過剰であると新たな重合体
粒子が生成するため、シードから大きくなった粒子と微
小粒子が混在するラテックスとなる。By performing seed polymerization in this way, the particle size is uniform,
Also, latex with large particle size is produced. The amount of seed polymer latex added is suitably 0.05 to 0.2 times the amount of vinyl chloride monomer in terms of solid content weight. If it is too small, a large particle size latex will not be obtained, and if it is too large, new polymer particles will be produced, resulting in a latex containing a mixture of particles grown from seeds and fine particles.
このように９本発明によれば、均一な粒径を有する塩化
ビニル重合体ラテックスが得られる。ラテックスの粒径
のコントロールも容易であり、塩化ビニルの仕込量に応
じて０．１〜１．０μｍの所望の粒径のラテックスが容
易に調製されうる。塩化ビニルの量が１５重量部以上の
場合はラテックスの粒径が約１．０μとなる。従来の技
術の項に記載された各公報の方法はいずれも比較的大粒
径のラテックスを調製しうる方法ではあるが１例えば特
公昭４０−１０５８６号公報に記載された方法では２粒
径のコントロールが難しく、かつ得られるラテックスの
粒径はせいぜい０．５μｍである。これに比べても本発
明の優れていることがわかる。As described above, according to the present invention, a vinyl chloride polymer latex having a uniform particle size can be obtained. The particle size of the latex can be easily controlled, and a latex with a desired particle size of 0.1 to 1.0 μm can be easily prepared depending on the amount of vinyl chloride charged. If the amount of vinyl chloride is 15 parts by weight or more, the particle size of the latex will be about 1.0 microns. All of the methods in the publications described in the prior art section are methods that can prepare latex with relatively large particle sizes. Control is difficult, and the particle size of the obtained latex is at most 0.5 μm. It can be seen that the present invention is superior compared to this.
本発明方法ではラテックスの調製時に乳化剤を使用しな
いため、得られたラテックスは比較的安定であり、さら
に架橋構造を有するため長期間保存してもラテックス粒
子同士が合着したり粒子が変形することが極めて少ない
。さらに、生成したラテックス粒子中の残存単量体は非
常に少ないため、懸濁重合の場合に見られるような９反
応器を開放したときに未反応の塩化ビニル単量体が激し
く蒸発して重合体粒子が多孔質となるというようなこと
が抑制され、高品質のラテックスが得られる。塩化ビニ
ル重合体は比重が１．４と比較的大きいため免疫試薬用
担体など多くの分野に利用されうる。Since the method of the present invention does not use an emulsifier when preparing the latex, the obtained latex is relatively stable, and since it has a crosslinked structure, the latex particles will not coalesce or deform even if stored for a long period of time. are extremely rare. Furthermore, since the amount of residual monomer in the latex particles produced is very small, unreacted vinyl chloride monomers will violently evaporate and become heavy when the reactor is opened, as occurs in suspension polymerization. Porousness of the combined particles is suppressed, and high-quality latex can be obtained. Vinyl chloride polymers have a relatively high specific gravity of 1.4, so they can be used in many fields such as carriers for immunoreagents.
（実施例） 以下に本発明を実施例につき説明する。(Example) The invention will be explained below with reference to examples.
去上斑上
反応容器として直径２５ｃｍ、深さ４５ｃｍ、内容積２
０１で２回転数２０Ｏｒｐｍ 、直径２，５ｃｎ＋、直
径３ ｃｍの攪拌羽根と幅２．５ｃｍの仮バッフル１本
を取り付けたジャケント付重合器を用いた。重合器の内
面および攪拌軸の表面をメチレンクロライドを用いで洗
浄し、さらによく水洗してスケールなどの付着物を落と
した後１重合器を組立てた。Diameter 25 cm, depth 45 cm, internal volume 2 as epidermis reaction container
A polymerization vessel equipped with a jacket was used, which was equipped with a stirring blade of 2.5 cn+ diameter, 3 cm diameter, and one temporary baffle of 2.5 cm width. The inner surface of the polymerization vessel and the surface of the stirring shaft were washed with methylene chloride and thoroughly washed with water to remove deposits such as scale, and then one polymerization vessel was assembled.
この重合器にイオン交換水１２Ａと重合開始剤として過
硫酸カリウム１．２ｇとを仕込んだ後、真空ポンプによ
って器内に残存する空気を仕込水の蒸気圧に達するまで
排気した。これに撹拌しながら塩化ビニル単量体１００
０ ｇおよびジアリルフタレート３０ｇを加えた。常温
でしばらく攪拌した後、ジャケットに熱水を通して７０
℃に昇温した。重合反応が開始されたらジャケットを冷
却水に切り替え。After charging 12 A of ion-exchanged water and 1.2 g of potassium persulfate as a polymerization initiator into this polymerization vessel, the air remaining in the vessel was evacuated using a vacuum pump until the vapor pressure of the charged water was reached. Add 100% of vinyl chloride monomer to this while stirring.
0 g and 30 g of diallyl phthalate were added. After stirring for a while at room temperature, hot water was passed through the jacket and heated to 70℃.
The temperature was raised to ℃. Once the polymerization reaction has started, switch the jacket to cooling water.
温度を約７０℃に保ちながら重合反応を行なった。The polymerization reaction was carried out while maintaining the temperature at about 70°C.
重合反応の進行状況は重合器の内圧の変化によって推定
し、適当な重合率に達したと思われる４、２時間後に反
応系を冷却し重合器内温を３０℃以下に低下させた。未
反′応の塩化ビニル単量体を蒸発させ、さらに窒素ガス
を吹き込んで完全に除去した。The progress of the polymerization reaction was estimated by the change in the internal pressure of the polymerization vessel, and after 4 to 2 hours when an appropriate polymerization rate was thought to have been reached, the reaction system was cooled to lower the internal temperature of the polymerization vessel to 30° C. or less. Unreacted vinyl chloride monomer was evaporated and completely removed by blowing in nitrogen gas.
生成した重合体ラテックスを透過型電子顕微鏡で観察し
たところ、はぼ均一の粒子径を有することが確認された
。このラテックスの粒子径および生成量（重合率）を測
定した。粒子径はラテックスを透過型電子顕微鏡写真に
逼り、 １００個の粒子の直径を測定し、その平均値と
した。重合率はラテックスの一部を蒸発乾固し固形分を
計量して算出した。さらにこの固形分をテトラハイドロ
フラン（ＴＨＦ）に溶解したところ不溶解成分が残留し
、架橋されていることが確認された。重合度は不溶解成
分が多いため測定できなかった。それぞれの結果を下表
に示す。When the produced polymer latex was observed with a transmission electron microscope, it was confirmed that it had a fairly uniform particle size. The particle size and production amount (polymerization rate) of this latex were measured. To determine the particle size, the latex was photographed using a transmission electron microscope, the diameters of 100 particles were measured, and the average value was used. The polymerization rate was calculated by evaporating a portion of the latex to dryness and measuring the solid content. Furthermore, when this solid content was dissolved in tetrahydrofuran (THF), it was confirmed that insoluble components remained and crosslinking occurred. The degree of polymerization could not be measured due to the large amount of insoluble components. The respective results are shown in the table below.
得られたラテックスを２０℃に放置したところ。The obtained latex was left at 20°C.
４０日後に粒子の沈澱が生じた。７８日後にはさらに進
行して沈澱が増加したがポイントミキサーで３分間分散
させたところ均一に再分散した。このように１本発明の
塩化ビニル重合体ラテックスは保存安定性に優れること
がわかる。Particle precipitation occurred after 40 days. After 78 days, the precipitation progressed further and the amount of precipitate increased, but after 3 minutes of dispersion using a point mixer, it was uniformly redispersed. Thus, it can be seen that the vinyl chloride polymer latex of the present invention has excellent storage stability.
大旌炎主
多官能性単量体としてトリメチロールプロパントリメタ
クリレートを用いｉこと以外は実施例１と同様にラテッ
クスの調製を行ったところ均一粒径のラテックスが得ら
れた。このラテックスの各測定・結果を下表に示す。A latex was prepared in the same manner as in Example 1 except that trimethylolpropane trimethacrylate was used as the main polyfunctional monomer, and a latex with uniform particle size was obtained. The results of each measurement of this latex are shown in the table below.
得られたラテックスを２０℃に放置したところ。The obtained latex was left at 20°C.
３７日後に粒子沈澱が生じた。７３日後にはさらに進行
して沈澱が増加したが、ポイントミキサーで３分間分散
させたところ均一に分散した。ラテックス５０μｍｌを
ガラス板に取り、ゆるやかに前後左右に３分間揺り動か
したが凝集は認められなかった。このように１本発明の
塩化ビニル重合体ラテックスは保存安定性に優れること
がわかる。Particle precipitation occurred after 37 days. After 73 days, the precipitation progressed further and the amount of precipitate increased, but when dispersed for 3 minutes using a point mixer, it was uniformly dispersed. 50 μml of latex was placed on a glass plate and gently rocked back and forth and left and right for 3 minutes, but no aggregation was observed. Thus, it can be seen that the vinyl chloride polymer latex of the present invention has excellent storage stability.
次上斑主
過硫酸カリウムを５．０ｇ、塩化ビニルを３ 、０ ｋ
ｇ 。5.0g of potassium persulfate, 3.0k of vinyl chloride
g.
そしてジアリルフタレートを８０ｇとし１反応時間を６
．８時間としたこと以外は実施例１と同様にラテックス
の調製を行ったところ、均一粒径のラテックスが得られ
た。このラテックスの各測定結果を下表に示す。得られ
たラテックスを２０℃で保存したところ実施例１と同様
の結果が得られた。Then, 80g of diallyl phthalate was used, and 1 reaction time was 6.
．． A latex was prepared in the same manner as in Example 1 except that the heating time was 8 hours, and a latex with a uniform particle size was obtained. The measurement results for this latex are shown in the table below. When the obtained latex was stored at 20°C, the same results as in Example 1 were obtained.
（以下余白）
此土日生り
塩化ビニル単量体を４．２ｋｇ （水１００重量部に対
し塩化ビニル単量体３５重量部）、そして過硫酸カリウ
ムを４．２ｇ用いたこと以外は実施例１と同様に重合反
応を行なった。重合反応は４時間を要したが１ｍ重合応
開始後約３時間は重合器の内圧が重合温度（７０℃）に
おける飽和蒸気圧を示し、その後圧力が低くなるのが認
められた。反応終了後。(Left below) Example 1 except that 4.2 kg of vinyl chloride monomer (35 parts by weight of vinyl chloride monomer per 100 parts by weight of water) and 4.2 g of potassium persulfate were used. The polymerization reaction was carried out in the same manner. The polymerization reaction took 4 hours, but the internal pressure of the polymerization vessel showed the saturated vapor pressure at the polymerization temperature (70° C.) for about 3 hours after the start of the 1m polymerization reaction, and then it was observed that the pressure decreased. After the reaction is complete.
重合器内壁および攪拌軸に付着したスケール量を測定し
たところ９８０ｇであった。これは全重合体量の約３０
パーセントであり、全体がブロッキング寸前であった。The amount of scale attached to the inner wall of the polymerization vessel and the stirring shaft was measured and found to be 980 g. This is about 30% of the total polymer content.
%, and the whole thing was on the verge of blocking.
得られた重合体う、テックスは不均一であり、多数の大
粒子が認められた。The obtained polymer texture was non-uniform and many large particles were observed.
得られたラテックスを２０℃に放置したところ１８日後
に粒子が凝集し沈澱が生じた。２５日後にはさらに進行
して沈澱が増加した。ポイントミキサーで５分間°分散
させたが均一には分散せず、大きい凝集の塊が多数比め
られた。When the obtained latex was left at 20° C., particles agglomerated and precipitated after 18 days. After 25 days, the precipitation progressed further and the amount of precipitation increased. Although the mixture was dispersed for 5 minutes using a point mixer, it was not uniformly dispersed and many large aggregates were observed.
ル較炎１
実施例１と同様の重合器に水１０ρ、過硫酸カリウム３
．０ｇおよび非イオン界面活性剤としてポリオキシエチ
レンノニルフェニルエーテル４．０ｇを仕込んだあと、
真空ポンプによって器内に残存する空気を仕込水の蒸気
圧に達するまで排気した。Comparative flame 1 In a polymerization vessel similar to Example 1, water 10ρ, potassium persulfate 3
．． After charging 0 g and 4.0 g of polyoxyethylene nonylphenyl ether as a nonionic surfactant,
The air remaining in the vessel was evacuated using a vacuum pump until it reached the vapor pressure of the charged water.
撹拌しながら塩化ビニル単量体３ 、 Ｏｋｇを仕込み
。While stirring, add 3 kg of vinyl chloride monomer.
常温で攪拌を続けた後、ジャケットに熱水を通して６５
℃に昇温した。重合反応が開始されたらジャケットを冷
却水に切り替え２重合部度を６５℃に保ちながら３．８
時間反応させた。次に１重合器内温を３０℃以下に低下
させ、未反応の塩化ビニル単量体を蒸発させ、さらに窒
素ガスを吹き込んで、完全に除去した。生成したラテッ
クス粒子の平均粒径は０．６５μｍであり２重合率は７
５％であった。After continuing to stir at room temperature, hot water was passed through the jacket at 65°C.
The temperature was raised to ℃. Once the polymerization reaction has started, switch the jacket to cooling water and add 3.8 degrees of polymerization while keeping the degree of polymerization at 65℃.
Allowed time to react. Next, the internal temperature of the polymerization reactor was lowered to 30° C. or lower to evaporate unreacted vinyl chloride monomer, and nitrogen gas was further blown into the reactor to completely remove it. The average particle size of the latex particles produced was 0.65 μm, and the dipolymerization rate was 7.
It was 5%.
このラテックスを２０℃で放置したところ２５日後に粒
子が′ａ集し沈澱が生じた。さらに３４日後（５９日後
）には、さらに進行して全体が沈澱するに至った。ポイ
ントミキサーで５分間分散させたが均一には分散せず、
大きい凝集のかたまりが多数比められた。When this latex was left to stand at 20°C, particles were collected and precipitated after 25 days. After a further 34 days (59 days), the reaction progressed further and the entire substance precipitated. I tried dispersing it for 5 minutes with a point mixer, but it was not dispersed uniformly.
Many large aggregates were compared.
（発明の効果）
本発明によれば、このように２粒径が均一で高品質の塩
化ビニル重合体ラテックスが得られる。(Effects of the Invention) According to the present invention, a high-quality vinyl chloride polymer latex having two uniform particle sizes can be obtained.
ラテックスの調製時に乳化剤を全く使用しないため乳化
剤に起因するラテックスの凝集や沈澱が生じにり（、か
つラテックス粒子が架橋構造を有するため、長期間安定
に保存されうる。塩化ビニルの配合割合を変えることに
より所望の粒径のラテックスが得られる。従来、調製の
難しかった大粒径のラテックスも容易に調製されうる。Since no emulsifier is used during latex preparation, latex agglomeration and precipitation due to emulsifiers does not occur (and since the latex particles have a crosslinked structure, they can be stored stably for a long period of time. Changing the blending ratio of vinyl chloride As a result, a latex with a desired particle size can be obtained. Latex with a large particle size, which has been difficult to prepare in the past, can also be easily prepared.
このような大粒径・高品質のラテックスは１例えば、各
種抗原、抗体などを吸着させ免疫試薬とした場合。Such large particle size, high quality latex can be used, for example, as an immunoreagent by adsorbing various antigens, antibodies, etc.
これを抗原抗体反応に用いると凝、集が短時間で起こる
ため、測定が短時間でなされうる。そのためリウマチの
検査、妊娠の診断、蛋白質の検出など各種検査に好適に
用いられうる。大粒径のラテックスは、このほか電子顕
微鏡２粒子計数器、光散乱モデルなどに用いられる比較
標準物質の測定のための標準品；濾過・透析膜等のフィ
ルタ一孔径測定用標準品などに好適に用いられる。本発
明のラテックスはまた。高比重であることを利用して細
胞などの分離コロイドの研究や拡散の研究などにも用い
られる。When this is used for antigen-antibody reactions, aggregation and aggregation occur in a short time, so measurements can be made in a short time. Therefore, it can be suitably used for various tests such as rheumatism tests, pregnancy diagnosis, and protein detection. The large particle size latex is also suitable as a standard product for measuring comparative standard substances used in electron microscope two-particle counters, light scattering models, etc.; a standard product for measuring the pore size of filters such as filtration and dialysis membranes, etc. used for. The latex of the present invention also includes: Due to its high specific gravity, it is also used to study separated colloids such as cells and to study diffusion.
以上that's all
Claims (1)
て多官能性単量体を該塩化ビニルに対して０．１〜１０
重量％の割合で含有する混合液を、乳化剤の不存在下で
水溶性重合開始剤を用い、重合反応に供して得られる塩
化ビニル重合体ラテックス。 ２、前記水溶性重合開始剤が過硫酸塩である特許請求の
範囲第１項に記載のラテックス。 ３、粒径が０．１〜１．０μｍである特許請求の範囲第
１項に記載のラテックス。 ４、水１００重量部、塩化ビニル３０重量部以下、そし
て多官能性単量体を該塩化ビニルに対して０．１〜１０
重量％の割合で含有する混合液を、乳化剤の不存在下で
水溶性重合開始剤を用い、重合反応に供する塩化ビニル
重合体ラテックスの製造方法。 ５、前記水溶性重合開始剤が過硫酸塩である特許請求の
範囲第４項に記載の製造方法。[Claims] 1. 100 parts by weight of water, 30 parts by weight or less of vinyl chloride, and a polyfunctional monomer of 0.1 to 10 parts by weight based on the vinyl chloride.
A vinyl chloride polymer latex obtained by subjecting a mixed solution containing % by weight to a polymerization reaction using a water-soluble polymerization initiator in the absence of an emulsifier. 2. The latex according to claim 1, wherein the water-soluble polymerization initiator is a persulfate. 3. The latex according to claim 1, which has a particle size of 0.1 to 1.0 μm. 4. 100 parts by weight of water, 30 parts by weight or less of vinyl chloride, and a polyfunctional monomer of 0.1 to 10 parts by weight based on the vinyl chloride.
A method for producing vinyl chloride polymer latex, in which a mixed solution containing % by weight is subjected to a polymerization reaction using a water-soluble polymerization initiator in the absence of an emulsifier. 5. The manufacturing method according to claim 4, wherein the water-soluble polymerization initiator is a persulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053075A JPH0745524B2 (en) | 1986-03-11 | 1986-03-11 | Vinyl chloride polymer latex for diagnostic reagent and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053075A JPH0745524B2 (en) | 1986-03-11 | 1986-03-11 | Vinyl chloride polymer latex for diagnostic reagent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62209106A true JPS62209106A (en) | 1987-09-14 |
| JPH0745524B2 JPH0745524B2 (en) | 1995-05-17 |
Family
ID=12932687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61053075A Expired - Lifetime JPH0745524B2 (en) | 1986-03-11 | 1986-03-11 | Vinyl chloride polymer latex for diagnostic reagent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745524B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011071031A1 (en) * | 2009-12-10 | 2011-06-16 | 東ソー株式会社 | Vinyl chloride resin latex, process for producing same, and thermal transfer image-receiving sheet obtained using same |
| JP2011121274A (en) * | 2009-12-10 | 2011-06-23 | Tosoh Corp | Thermal transfer image receiving sheet |
| JP2011126972A (en) * | 2009-12-16 | 2011-06-30 | Tosoh Corp | Vinyl chloride resin latex and method for producing the same |
-
1986
- 1986-03-11 JP JP61053075A patent/JPH0745524B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011071031A1 (en) * | 2009-12-10 | 2011-06-16 | 東ソー株式会社 | Vinyl chloride resin latex, process for producing same, and thermal transfer image-receiving sheet obtained using same |
| JP2011121274A (en) * | 2009-12-10 | 2011-06-23 | Tosoh Corp | Thermal transfer image receiving sheet |
| US8932985B2 (en) | 2009-12-10 | 2015-01-13 | Tosoh Corporation | Vinyl chloride-based resin latexes, processes for producing the same, and thermal transfer image-receiving sheet obtained using the same |
| JP2011126972A (en) * | 2009-12-16 | 2011-06-30 | Tosoh Corp | Vinyl chloride resin latex and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745524B2 (en) | 1995-05-17 |
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