JPH0873520A - Production of coagulated particle from polymer latex - Google Patents
Production of coagulated particle from polymer latexInfo
- Publication number
- JPH0873520A JPH0873520A JP23236694A JP23236694A JPH0873520A JP H0873520 A JPH0873520 A JP H0873520A JP 23236694 A JP23236694 A JP 23236694A JP 23236694 A JP23236694 A JP 23236694A JP H0873520 A JPH0873520 A JP H0873520A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- particles
- coagulated
- particle size
- coagulated particles
- 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.)
- Withdrawn
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- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高分子ラテックスより
凝固粒子を製造する方法に関し、更に詳しくは、凝固剤
を使用せずにラテックスを凝固させ、粒度分布がシャー
プで、ほぼ球形の凝固粒子を得るとともに、洗浄液量を
低減し得る凝固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 coagulated particles from a polymer latex, more specifically, coagulating latex without using a coagulant, which has a sharp particle size distribution and substantially spherical coagulated particles. And a method for producing coagulated particles capable of reducing the amount of cleaning liquid.
【０００２】[0002]
【従来の技術】一般に乳化重合法により製造された高分
子ラテックスから粉末状重合体を回収するにあたって
は、ラテックス中に無機塩類、酸類等の凝固剤水溶液を
添加し、または逆に凝固剤水溶液中にラテックスを投入
し液相中で凝固させ、熱処理等の操作によりスラリー状
にした後、脱水工程、乾燥工程を経て粉末状重合体を回
収している。この際、形成されるラテックスの凝固体は
形状が不定形であり粒径の調整が困難であるため、凝固
体の粒度分布が広くなり微粉の発生量が多くなる傾向が
ある。その結果、微粉の飛散に基づく樹脂の損失、目詰
まりによる工程上のトラブルの頻発、粉塵発生による作
業環境の悪化、粉塵爆発による危険性の増大等の問題点
が生じている。また、脱水性、乾燥性、流動性、耐ブロ
ッキング性等が悪いため、高価な脱水、乾燥設備を必要
とする。2. Description of the Related Art Generally, when recovering a powdery polymer from a polymer latex produced by an emulsion polymerization method, an aqueous solution of a coagulant such as an inorganic salt or an acid is added to the latex, or vice versa. The latex is charged into the above to coagulate in a liquid phase, and after being made into a slurry by an operation such as heat treatment, a powdery polymer is recovered through a dehydration step and a drying step. At this time, the coagulated body of the latex to be formed has an indefinite shape and it is difficult to adjust the particle size. Therefore, the particle size distribution of the coagulated body tends to be broad and the amount of fine powder generated tends to increase. As a result, there are problems such as loss of resin due to scattering of fine powder, frequent process troubles due to clogging, deterioration of working environment due to dust generation, and increased risk of dust explosion. Further, since the dehydration property, drying property, fluidity, blocking resistance and the like are poor, expensive dehydration and drying equipment is required.
【０００３】また乳化重合法では重合時に乳化剤を用い
ており、凝固時に用いられる凝固剤と共に、残存すれば
製品品質を著しく低下させる場合があるため、乳化剤、
凝固剤の洗浄が不可欠となり多量の洗浄液が必要であ
る。近年では、この洗浄液の排出による環境破壊が大き
な問題となっている。In the emulsion polymerization method, an emulsifier is used at the time of polymerization, and if it remains together with the coagulant used at the time of coagulation, the product quality may be significantly deteriorated.
Cleaning of the coagulant is indispensable and a large amount of cleaning liquid is required. In recent years, environmental damage due to the discharge of the cleaning liquid has become a serious problem.
【０００４】これらの問題を解決するため、これまで種
々の方法が提案されている。例えばラテックスを凝固性
雰囲気中へ噴霧して球状凝固粒子として回収する方法
や、水相に分散した有機溶剤中へ凝固粒子を吸収し、溶
剤の除去と凝固粒子の固化をすることで球状凝固粒子を
回収する方法等が提案されている。前者の方法では５０
０μｍ以上の粒子の製造や軟化温度が８０℃以上である
高耐熱性高分子の製造に関しては工業的には困難である
し、また後者の方法では溶剤の除去、夾雑物の除去の困
難さに加え、高分子の種類によっては利用できる有機溶
剤がないなど、コスト面、品質面、適用範囲、粒子特性
等の問題が提起されている。In order to solve these problems, various methods have been proposed so far. For example, a method of collecting latex as spherical coagulated particles by spraying into a coagulating atmosphere, or absorbing coagulated particles in an organic solvent dispersed in an aqueous phase, removing the solvent and solidifying the coagulated particles to form spherical coagulated particles. A method of recovering the waste has been proposed. 50 in the former method
It is industrially difficult to produce particles of 0 μm or more and a high heat-resistant polymer having a softening temperature of 80 ° C. or more, and the latter method makes it difficult to remove solvents and contaminants. In addition, depending on the type of polymer, there are problems such as cost, quality, range of application, and particle characteristics, such as no usable organic solvent.
【０００５】一方では、ラテックスを直接乾燥するスプ
レー乾燥や真空造粒乾燥があり、数多くの装置上の工夫
が試されている。しかし、これらの方法ではラテックス
中の夾雑物の除去が困難であること、大きい粒子を製造
するには設備が大型化するのに加え、低濃度のラテック
スでは大量の熱エネルギーが必要であることから処理費
がかかるなど、品質面、コスト面での制約が大きくなっ
ている。また従来の方法における共通の課題として、夾
雑物の除去、また夾雑物除去のために使用した洗浄液排
出による環境問題が依然未解決のままである。On the other hand, there are spray drying for directly drying the latex and vacuum granulation drying, and many device ideas have been tried. However, it is difficult to remove impurities in the latex by these methods, large equipment is required for producing large particles, and a large amount of heat energy is required for low-concentration latex. There are significant restrictions in terms of quality and cost, such as processing costs. Further, as a common problem in the conventional methods, the environmental problem due to the removal of impurities and the discharge of the cleaning liquid used for removing the impurities remains unsolved.
【０００６】[0006]
【発明が解決しようとする課題】本発明は高分子ラテッ
クスより凝固粒子を製造する方法において、微粉の発生
量を減少させ、その結果、凝固粒子の粒度分布がシャー
プになり、且つ粒径の調整が可能で、更に洗浄液量を低
減させ得る方法を提供する。DISCLOSURE OF THE INVENTION The present invention is a method for producing coagulated particles from polymer latex, which reduces the amount of fine powder generated, resulting in a sharp particle size distribution of coagulated particles and adjustment of the particle size. And a method capable of further reducing the amount of cleaning liquid.
【０００７】[0007]
【課題を解決するための手段】本発明者らは乳化重合法
で得られた高分子ラテックスの凝固操作において、任意
の攪拌下でラテックス粒子周辺の比誘電率を、有機溶剤
の水溶液を用いて調整しラテックス粒子間反発力を低下
させることにより、凝固剤を用いることなく、粒度分布
のシャープさを表す指標であるロジンラムラー式の傾き
が２以上であるシャープな粒度分布を持つほぼ球形の凝
固粒子を形成できることを見いだした。更に、凝固時の
攪拌レイノルズ数を操作することにより凝固粒子の粒径
が調整可能であることを見いだした。Means for Solving the Problems In the coagulation operation of a polymer latex obtained by an emulsion polymerization method, the present inventors have used an aqueous solution of an organic solvent to determine the relative dielectric constant around the latex particles under arbitrary stirring. By adjusting the repulsive force between latex particles to reduce the repulsive force between latex particles, a substantially spherical coagulated particle having a sharp particle size distribution with a slope of 2 or more of the Rosin-Rammler formula, which is an index showing the sharpness of the particle size distribution, without using a coagulant. I found that I can form. Further, it was found that the particle size of the solidified particles can be adjusted by manipulating the stirring Reynolds number during solidification.
【０００８】即ち、本発明の第１は、乳化重合法で得ら
れたラテックス液に含まれるラテックス基本粒子周辺の
比誘電率を、有機溶剤の水溶液を用いて凝固時の温度下
で１０〜７０に調整することを特徴とする、高分子ラテ
ックスより凝固粒子を製造する方法を、That is, the first aspect of the present invention is that the relative dielectric constant around the latex basic particles contained in the latex liquid obtained by the emulsion polymerization method is 10 to 70 at a temperature at the time of coagulation using an aqueous solution of an organic solvent. A method for producing coagulated particles from a polymer latex, which is characterized in that
【０００９】本発明の第２は、上記の方法において、攪
拌レイノルズ数を１０００〜１００００の範囲内で操作
することにより凝固粒子の粒径をコントロールすること
を特徴とする、高分子ラテックスより凝固粒子を製造す
る方法を、それぞれ内容とするものである。The second aspect of the present invention is that in the above method, the particle size of the coagulated particles is controlled by operating the stirring Reynolds number within the range of 1,000 to 10,000, and the coagulated particles are made from polymer latex. The method for producing the above is respectively described.
【００１０】以下に本発明を更に詳細に説明する。本発
明に用いる高分子ラテックスは、特に限定されないが、
例えば、スチレン、モノクロロスチレン、ジクロロスチ
レン、α−メチルスチレン等のビニル芳香族、アクリロ
ニトリル、メタクリロニトリル等のビニルシアン化物、
メチルアクリレート、エチルアクリレート、ブチルアク
リレート等のアクリルエステル、メチルメタクリレー
ト、エチルメタクリレート、ブチルメタクリレート等の
メタクリルエステル、塩化ビニル、臭化ビニル、弗化ビ
ニル等のハロゲン化ビニル、塩化ビニリデン、臭化ビニ
リデン等のハロゲン化ビニリデン、アクリル酸、メタク
リル酸、イタコン酸、マレイン酸、酢酸ビニル、エチレ
ン、プロピレン、ブチレン、ブタジエン、イソプレン、
クロロプレン、アリルメタクリレート、ジアリルフタレ
ート、トリアリルシアヌレート、モノエチレングリコー
ルジメタクリレート、テトラエチレングリコールジメタ
クリレート、ジビニルベンゼン、グリシジルメタクリレ
ート等の架橋モノマーが挙げられ、それらのホモ重合
体、共重合体またはそれら重合体のラテックスの混合物
にも適用できる。The present invention will be described in more detail below. The polymer latex used in the present invention is not particularly limited,
For example, vinyl aromatic such as styrene, monochlorostyrene, dichlorostyrene and α-methylstyrene, vinyl cyanide such as acrylonitrile and methacrylonitrile,
Acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride, vinylidene chloride and vinylidene bromide. Vinylidene halide, acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl acetate, ethylene, propylene, butylene, butadiene, isoprene,
Examples include cross-linking monomers such as chloroprene, allyl methacrylate, diallyl phthalate, triallyl cyanurate, monoethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, divinylbenzene, and glycidyl methacrylate, and their homopolymers, copolymers or their polymers. It can also be applied to a mixture of coalesced latices.
【００１１】この場合、重合時に用いた乳化剤が有機溶
媒の水溶液に溶解するものである場合は、凝固時に乳化
剤の洗浄効果がある上に、本凝固法では凝固剤を使用し
ないため、洗浄工程での洗浄液量が減少でき排水量が低
減できるので極めて好都合である。なお、高分子ラテッ
クスの固形分濃度は２０〜５０重量％が好ましい。固形
分が２０重量％未満では凝固粒子製造時に微粉が発生し
やすくなり、５０重量％を越えるとラテックスの安定性
が悪くなる傾向がある。本発明に用いる水溶性の有機溶
剤は、特に限定されないが、例えば、メタノール、エタ
ノール、ｎ−プロパノール、イソプロパノール、ｎ−ブ
タノール、イソブタノール、２−ブタノール、ｔ−ブタ
ノール等のアルコール類、プロピレンオキシド、ジオキ
サン、トリオキサン、フルフラール等のアセタール類、
アセトン、メチルアセトン、メチルエチルケトン等のケ
トン類、ギ酸メチル、ギ酸エチル、酢酸メチル、酢酸エ
チル等のエステル類、エチレングリコール、エチレング
リコールモノメチルエーテルアセテート、エチレングリ
コールモノエチルエーテル等の多価アルコール類、ギ
酸、酢酸、プロピオン酸等の脂肪酸類、フェノール、ク
レゾール等のフェノール類、ニトロベンゼン、ジエチル
アミン、トリエチルアミン等の窒素化合物が挙げられ、
これらは単独あるいは２種以上の混合物で使用すること
ができる。なお、比誘電率を調整した有機溶剤の水溶液
に樹脂が溶解してはならない。In this case, when the emulsifier used in the polymerization is soluble in an aqueous solution of an organic solvent, it has a washing effect on the emulsifier during coagulation and, in the coagulation method, no coagulant is used. This is extremely convenient because the amount of cleaning liquid can be reduced and the amount of drainage can be reduced. The solid content concentration of the polymer latex is preferably 20 to 50% by weight. If the solid content is less than 20% by weight, fine powder tends to be generated during the production of coagulated particles, and if it exceeds 50% by weight, the stability of the latex tends to deteriorate. The water-soluble organic solvent used in the present invention is not particularly limited, but for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, t-butanol, propylene oxide, Acetals such as dioxane, trioxane and furfural,
Acetone, methylacetone, ketones such as methylethylketone, methyl formate, ethyl formate, methyl acetate, esters such as ethyl acetate, ethylene glycol, ethylene glycol monomethyl ether acetate, polyhydric alcohols such as ethylene glycol monoethyl ether, formic acid, Acetic acid, fatty acids such as propionic acid, phenol, phenols such as cresol, nitrogen compounds such as nitrobenzene, diethylamine and triethylamine,
These can be used alone or as a mixture of two or more kinds. The resin should not be dissolved in an aqueous solution of an organic solvent whose relative dielectric constant is adjusted.
【００１２】本発明において、ラテックス粒子周辺の比
誘電率は、凝固時の温度下で１０〜７０、好ましくは２
０〜６０に調整される。比誘電率が１０より低くなる
と、凝集速度が速すぎ粒子が成長するという現象が見ら
れず、粒子形状が不定形になり微粉の発生量が多くな
る。逆に比誘電率が７０より高くなると、凝集速度が遅
すぎ凝固粒子の形成に時間がかかりすぎ生産性が低下す
る。In the present invention, the relative dielectric constant around the latex particles is 10 to 70, preferably 2 at the temperature during solidification.
It is adjusted to 0-60. When the relative dielectric constant is lower than 10, the phenomenon that the aggregation speed is too fast and particles grow is not seen, and the particle shape becomes irregular and the amount of fine powder generated increases. On the other hand, when the relative dielectric constant is higher than 70, the aggregation speed is too slow and it takes too long to form the solidified particles, so that the productivity is lowered.
【００１３】次に、比誘電率の測定方法を説明する。比
誘電率は水溶液の電気容量を測定し、その測定値から算
出する。電気容量を測定する電極には金メッキを施した
真鍮性の二重円筒管を用い、外部電極と内部電極の間に
有機溶剤の水溶液を仕込み、ＬＣＲメーターを使用し交
流電流により水溶液の電気容量を測定する。本発明にお
いて、凝固温度は０〜１２０℃が好ましく、温度により
比誘電率が変化するので調整が必要である。Next, a method for measuring the relative dielectric constant will be described. The relative dielectric constant is calculated from the measured value by measuring the electric capacity of the aqueous solution. A gold-plated brass double cylindrical tube is used as an electrode for measuring the electric capacity, an aqueous solution of an organic solvent is charged between the external electrode and the internal electrode, and the electric capacity of the aqueous solution is measured by an alternating current using an LCR meter. taking measurement. In the present invention, the solidification temperature is preferably 0 to 120 ° C., and the relative dielectric constant changes depending on the temperature, so that adjustment is necessary.
【００１４】本発明において、有機溶剤の水溶液中にお
ける粒子濃度は、好ましくは２〜１０重量％、更に好ま
しくは４〜８重量％の条件下で凝固操作を行う。粒子濃
度が２重量％より低くなると、粒子同士の衝突回数が減
少することにより凝固体の形成に時間がかかる。逆に粒
子濃度が１０重量％より高くなると、凝固初期に起こる
粘度の上昇により攪拌を均一に加えることができず凝固
体の粒度分布がブロードになる。本発明において、攪拌
レイノルズ数を操作することにより、凝固粒子の粒径を
コントロールすることができる。攪拌レイノルズ数は１
０００〜１００００の範囲で操作するのが好ましい。攪
拌レイノルズ数が１０００未満では凝固粒子の粒径を揃
えることが難しく、粒度分布がブロードになり、１００
００を越えると微粉しか製造できず各工程での操作性の
低下、作業環境の悪化を引き起こす原因となる。In the present invention, the coagulation operation is performed under the condition that the particle concentration in the aqueous solution of the organic solvent is preferably 2 to 10% by weight, more preferably 4 to 8% by weight. If the particle concentration is lower than 2% by weight, the number of collisions between particles is reduced and thus it takes time to form a solidified body. On the other hand, if the particle concentration is higher than 10% by weight, the increase in the viscosity that occurs at the initial stage of solidification makes it impossible to uniformly add stirring, and the particle size distribution of the solidified product becomes broad. In the present invention, the particle size of the solidified particles can be controlled by manipulating the stirring Reynolds number. Stirring Reynolds number is 1
It is preferable to operate in the range of 000 to 10,000. If the stirring Reynolds number is less than 1000, it is difficult to make the particle sizes of the solidified particles uniform, and the particle size distribution becomes broad, and
If it exceeds 00, only fine powder can be produced, which causes deterioration of operability in each step and deterioration of working environment.
【００１５】[0015]
【実施例】以下実施例により本発明を更に詳細に説明す
るが、本発明はかかる実施例のみに限定されるものでは
ない。 実施例１ ラテックス粒子周辺の比誘電率が２４．６（７５℃）に
なるようにイソプロパノール水溶液を調整し、内径７５
mmφの円筒形の凝固槽内に３００cm3 仕込んだ。同温に
昇温したアクリロニトリルと塩化ビニルを共重合させた
ラテックス（乳化剤としてラウリル硫酸ナトリウムを使
用）であって、アクリロニトリル５０重量％、塩化ビニ
ル５０重量％よりなり、軟化点が９０℃で固形分濃度３
１重量％のラテックスを、攪拌羽根として角度付き４枚
プロペラ（２段）を使用し攪拌レイノルズ数５４７０の
攪拌下にある上記のイソプロパノール水溶液中に粒子濃
度６重量％になるように投入し、３０分攪拌を行った。
以上の条件によりラテックスを凝固し、平均粒径９３μ
ｍ、ロジンラムラー式の傾き４．５である、図１に示す
粒度分布を持ち、図５の顕微鏡写真に示す概ね球形の凝
固粒子を得た。なお、乳化剤は、仕込み乳化剤量の６
３．６％が凝固粒子の外部に除去されていた。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 An isopropanol aqueous solution was adjusted so that the relative dielectric constant around the latex particles was 24.6 (75 ° C.), and the inner diameter was 75.
300 cm 3 was charged in a cylindrical coagulation tank of mmφ. A latex obtained by copolymerizing acrylonitrile and vinyl chloride heated to the same temperature (using sodium lauryl sulfate as an emulsifier), which comprises 50% by weight of acrylonitrile and 50% by weight of vinyl chloride and has a softening point of 90 ° C. and a solid content of 90 ° C. Concentration 3
1% by weight of latex was added to the above isopropanol aqueous solution under stirring with a stirring Reynolds number of 5470 using an angled 4-blade propeller (2 stages) as a stirring blade so that the particle concentration would be 6% by weight. It was stirred for a minute.
The latex was coagulated under the above conditions, and the average particle size was 93μ.
m and a Rosin-Rammler slope of 4.5, the particle size distribution shown in FIG. 1 and substantially spherical coagulated particles shown in the micrograph of FIG. 5 were obtained. In addition, the emulsifier is 6 times the amount of the charged emulsifier.
3.6% was removed outside the solidified particles.
【００１６】実施例２ 次の各条件を変更した他は、実施例１と同様にして凝固
粒子を得た。即ち、比誘電率が５１．１（３０℃）にな
るようにｔ−ブタノール水溶液を調整し凝固槽に仕込
み、同温に昇温したメチルメタクリレート、ブチルアク
リレートを共重合させたラテックス（乳化剤としてオレ
イン酸カリウムを使用）であって、メチルメタクリレー
ト３０重量％、ブチルアクリレート７０重量％よりな
り、軟化点が６５℃であり固形分濃度３２重量％のラテ
ックスを、攪拌レイノルズ数８２００の攪拌下にある上
記のｔ−ブタノール水溶液中に粒子濃度６重量％になる
ように投入した。以上の条件によりラテックスを凝固
し、平均粒径４００μｍ、ロジンラムラー式の傾き５．
１である、図２に示す粒度分布を持ち、図６の顕微鏡写
真に示す概ね球形の凝固粒子を得た。なお、乳化剤は、
仕込み乳化剤量の５６．３％が凝固粒子の外部に除去さ
れていた。Example 2 Coagulated particles were obtained in the same manner as in Example 1 except that the following conditions were changed. That is, a latex prepared by adjusting an aqueous t-butanol solution to a relative dielectric constant of 51.1 (30 ° C.), charging it in a coagulation tank, and copolymerizing methyl methacrylate and butyl acrylate heated to the same temperature (olein as an emulsifier). (A potassium acidate is used), which comprises 30% by weight of methyl methacrylate and 70% by weight of butyl acrylate, has a softening point of 65 ° C. and a solid content concentration of 32% by weight, and is subjected to stirring with stirring Reynolds number 8200. Was added to the t-butanol aqueous solution so that the particle concentration would be 6% by weight. 4. The latex was coagulated under the above conditions, the average particle size was 400 μm, and the slope of the Rosin-Rammler formula was 5.
2 was obtained, and the substantially spherical solidified particles shown in the micrograph of FIG. 6 were obtained. The emulsifier is
56.3% of the charged emulsifier amount was removed to the outside of the coagulated particles.
【００１７】実施例３ 次の各条件を変更した他は、実施例１と同様にして凝固
粒子を得た。即ち、比誘電率が６０．５（３０℃）にな
るようにｎ−プロパノール水溶液を調整し凝固槽に仕込
み、同温に昇温したメチルメタクリレート、ブタジエ
ン、スチレンを共重合させたラテックス（乳化剤として
オレイン酸カリウムを使用）であって、メチルメタクリ
レート１０重量％、ブタジエン６０重量％、スチレン３
０重量％よりなり、軟化点が５０℃であり固形分濃度３
０重量％のラテックスを、攪拌レイノルズ数８２００の
攪拌下にある上記のｎ−プロパノール水溶液中に粒子濃
度６重量％になるように投入した。以上の条件によりラ
テックスを凝固し、平均粒径１７５μｍ、ロジンラムラ
ー式の傾き３．２である、図３に示す粒度分布を持ち、
図７の顕微鏡写真に示す概ね球形の凝固粒子を得た。な
お、乳化剤は、仕込み乳化剤量の６５．９％が凝固粒子
の外部に除去されていた。Example 3 Coagulated particles were obtained in the same manner as in Example 1 except that the following conditions were changed. That is, a latex prepared by adjusting an n-propanol aqueous solution so as to have a relative dielectric constant of 60.5 (30 ° C.), charging it in a coagulation tank, and copolymerizing methyl methacrylate, butadiene, and styrene heated to the same temperature (as an emulsifier, Potassium oleate), which is 10% by weight of methyl methacrylate, 60% by weight of butadiene, and 3 of styrene.
0% by weight, softening point of 50 ° C, solid content of 3
0% by weight of latex was added to the above-mentioned aqueous solution of n-propanol under stirring with Reynolds number of 8200 so as to have a particle concentration of 6% by weight. The latex is coagulated under the above conditions, and has a particle size distribution shown in FIG. 3, which has an average particle size of 175 μm and a Rosin-Rammler slope of 3.2.
The substantially spherical solidified particles shown in the micrograph of FIG. 7 were obtained. As for the emulsifier, 65.9% of the charged emulsifier was removed to the outside of the coagulated particles.
【００１８】実施例４ 次の各条件を変更した他は、実施例１と同様にして凝固
粒子を得た。即ち、比誘電率が２３．８（７０℃）にな
るようにエタノール水溶液を調整し凝固槽に仕込み、同
温に昇温した実施例１と同様のラテックスを攪拌レイノ
ルズ数２７３０、４１００、５４７０、６８３０、８２
００のそれぞれの攪拌下にある上記のエタノール水溶液
中に粒子濃度６．２重量％になるように投入した。以上
の条件によりラテックスを凝固し、各攪拌条件により、
それぞれ図４に示すような粒径の異なるシャープな粒度
分布を持つ凝固粒子を得た。Example 4 Coagulated particles were obtained in the same manner as in Example 1 except that the following conditions were changed. That is, an aqueous ethanol solution was adjusted so that the relative dielectric constant was 23.8 (70 ° C.), the mixture was charged in a coagulation tank, and the same latex as in Example 1 heated to the same temperature was stirred and Reynolds number 2730, 4100, 5470, 6830, 82
Into each of the above-mentioned ethanol aqueous solutions of No. 00 under stirring, they were added so as to have a particle concentration of 6.2% by weight. The latex is coagulated under the above conditions, and by each stirring condition,
Coagulated particles having sharp particle size distributions having different particle sizes as shown in FIG. 4 were obtained.
【００１９】比較例１ 次の条件を変更した他は、実施例１と同様にして凝固体
を得た。即ち、比誘電率が８．４（８５℃）になるよう
にｔ−ブタノール水溶液を調整し凝固槽に仕込み、同温
に昇温した実施例１と同様のラテックスを攪拌下にある
上記のｔ−ブタノールの水溶液中に投入した。以上の条
件によりラテックスを凝固したところ、非常にブロード
な粒度分布を持ち、形状が不定形である凝固体を得た。Comparative Example 1 A coagulated product was obtained in the same manner as in Example 1 except that the following conditions were changed. That is, t-butanol aqueous solution was adjusted so that the relative dielectric constant was 8.4 (85 ° C.), the t-butanol aqueous solution was charged into the coagulation tank, and the same latex as in Example 1 heated to the same temperature was stirred under the above t. Thrown into an aqueous solution of butanol. When the latex was coagulated under the above conditions, a coagulum having a very broad particle size distribution and an irregular shape was obtained.
【００２０】比較例２ 次の条件を変更した他は、実施例１と同様に実施した。
即ち、比誘電率が７２．６（２０℃）になるようにエタ
ノール水溶液を調整し凝固槽に仕込み、同温に昇温した
実施例１と同様のラテックスを攪拌下にある上記のエタ
ノール水溶液中に投入した。以上の条件によりラテック
スを凝固したところ、１時間経過しても凝固粒子の形成
は見られず、ラテックスは分散したままの状態であっ
た。Comparative Example 2 The procedure of Example 1 was repeated except that the following conditions were changed.
That is, an aqueous ethanol solution was adjusted so that the relative dielectric constant was 72.6 (20 ° C.), charged into a coagulation tank, and the same latex as in Example 1 heated to the same temperature was stirred in the above aqueous ethanol solution. I put it in. When the latex was coagulated under the above conditions, formation of coagulated particles was not observed even after 1 hour, and the latex remained in a dispersed state.
【００２１】[0021]
【発明の効果】叙上のとおり、本発明によれば、ほぼ球
形で、シャープな粒度分布を有する凝固粒子を得ること
ができ、また粒径をコントロールして所望の粒径の凝固
粒子を得ることができる。かくして、微粉の発生が抑え
られ、製造工程での操作性、工程安定性、作業環境の向
上に貢献するものである。更に、凝固の際に乳化剤を洗
浄できるとともに、凝固剤を使用しないため、洗浄工程
における洗浄液量を減少させることができるので、排水
量が少なくてすみ環境を汚染したり破壊したりする虞れ
が小さい。As described above, according to the present invention, it is possible to obtain coagulated particles having a substantially spherical shape and a sharp particle size distribution, and controlling the particle size to obtain coagulated particles having a desired particle size. be able to. Thus, generation of fine powder is suppressed, which contributes to improvement of operability in the manufacturing process, process stability, and working environment. Furthermore, since the emulsifier can be washed during coagulation and the coagulant is not used, the amount of cleaning liquid in the cleaning step can be reduced, so the amount of drainage is small and there is little risk of contaminating or destroying the environment. .
【図１】実施例１で得られた凝固粒子の粒度分布を示す
グラフである。FIG. 1 is a graph showing a particle size distribution of coagulated particles obtained in Example 1.
【図２】実施例２で得られた凝固粒子の粒度分布を示す
グラフである。FIG. 2 is a graph showing the particle size distribution of coagulated particles obtained in Example 2.
【図３】実施例３で得られた凝固粒子の粒度分布を示す
グラフである。FIG. 3 is a graph showing a particle size distribution of coagulated particles obtained in Example 3.
【図４】実施例４で得られた凝固粒子の粒度分布を示す
グラフである。FIG. 4 is a graph showing a particle size distribution of coagulated particles obtained in Example 4.
【図５】実施例１で得られた凝固粒子の粒子構造を示す
顕微鏡写真である。5 is a micrograph showing the particle structure of the solidified particles obtained in Example 1. FIG.
【図６】実施例２で得られた凝固粒子の粒子構造を示す
顕微鏡写真である。6 is a micrograph showing the particle structure of the solidified particles obtained in Example 2. FIG.
【図７】実施例３で得られた凝固粒子の粒子構造を示す
顕微鏡写真である。7 is a micrograph showing the particle structure of the solidified particles obtained in Example 3. FIG.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年１月５日[Submission date] January 5, 1995
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図５[Name of item to be corrected] Figure 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図５】 [Figure 5]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図６[Name of item to be corrected] Figure 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図６】 [Figure 6]
【手続補正３】[Procedure 3]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図７[Name of item to be corrected] Figure 7
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図７】 [Figure 7]
Claims (2)
まれるラテックス基本粒子周辺の比誘電率を、有機溶剤
の水溶液を用いて凝固時の温度下で１０〜７０の範囲内
に調整することによりラテックスを凝固させることを特
徴とする、高分子ラテックスより凝固粒子を製造する方
法。1. The relative dielectric constant around the latex basic particles contained in the latex liquid obtained by the emulsion polymerization method is adjusted within the range of 10 to 70 at a temperature during coagulation using an aqueous solution of an organic solvent. A method for producing coagulated particles from a polymer latex, which comprises coagulating the latex by means of:
ノルズ数を１０００〜１００００の範囲内で操作するこ
とにより凝固粒子の粒径をコントロールすることを特徴
とする、高分子ラテックスより凝固粒子を製造する方
法。2. The method according to claim 1, wherein the particle size of the coagulated particles is controlled by operating the stirring Reynolds number in the range of 1,000 to 10,000 to produce coagulated particles from polymer latex. how to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23236694A JPH0873520A (en) | 1994-08-31 | 1994-08-31 | Production of coagulated particle from polymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23236694A JPH0873520A (en) | 1994-08-31 | 1994-08-31 | Production of coagulated particle from polymer latex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0873520A true JPH0873520A (en) | 1996-03-19 |
Family
ID=16938097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23236694A Withdrawn JPH0873520A (en) | 1994-08-31 | 1994-08-31 | Production of coagulated particle from polymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0873520A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031245A1 (en) | 2011-08-29 | 2013-03-07 | ハイモ株式会社 | Pulverulent hydrophilic polymer, method for producing same, and flocculation treatment agent using same |
| JP2020084079A (en) * | 2018-11-28 | 2020-06-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Manufacturing method of rubber-like polymer |
| WO2023210819A1 (en) * | 2022-04-28 | 2023-11-02 | ダイキン工業株式会社 | Method for producing fluoropolymer |
-
1994
- 1994-08-31 JP JP23236694A patent/JPH0873520A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031245A1 (en) | 2011-08-29 | 2013-03-07 | ハイモ株式会社 | Pulverulent hydrophilic polymer, method for producing same, and flocculation treatment agent using same |
| JP2020084079A (en) * | 2018-11-28 | 2020-06-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Manufacturing method of rubber-like polymer |
| WO2023210819A1 (en) * | 2022-04-28 | 2023-11-02 | ダイキン工業株式会社 | Method for producing fluoropolymer |
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