JP3063222B2 - Method for producing vinyl polymer particles and expandable vinyl polymer particles - Google Patents
Method for producing vinyl polymer particles and expandable vinyl polymer particlesInfo
- Publication number
- JP3063222B2 JP3063222B2 JP3109054A JP10905491A JP3063222B2 JP 3063222 B2 JP3063222 B2 JP 3063222B2 JP 3109054 A JP3109054 A JP 3109054A JP 10905491 A JP10905491 A JP 10905491A JP 3063222 B2 JP3063222 B2 JP 3063222B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer particles
- weight
- particle size
- particles
- 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.)
- Expired - Lifetime
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は狭い粒径分布をもち、か
つ品質に優れるビニル系重合体粒子の製造法および発泡
性ビニル系重合体粒子の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing vinyl polymer particles having a narrow particle size distribution and excellent quality, and a method for producing expandable vinyl polymer particles.
【０００２】[0002]
【従来の技術】従来スチレン等の重合性モノマーを水性
媒体中で懸濁重合する際にはポリビニルアルコール、ポ
リビニルピロリドン、メチルセルロース等の水溶性高分
子又は陰イオン界面活性剤を併用する難溶性無機塩微粉
末が懸濁安定化剤として使用されていた。しかしながら
前者を懸濁安定化剤として使用した場合、重合排液のＣ
ＯＤ負荷が増大するため排水処理を必要とする欠点があ
り、後者を懸濁安定化剤として使用した場合、得られる
重合体粒子の粒径分布が広くなるという欠点があった。2. Description of the Related Art Conventionally, when a polymerizable monomer such as styrene is subjected to suspension polymerization in an aqueous medium, a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, or an anionic surfactant is used in combination with a hardly soluble inorganic salt. Fine powder has been used as suspension stabilizer. However, when the former is used as a suspension stabilizer, C
There is a disadvantage that wastewater treatment is required due to an increase in OD load, and when the latter is used as a suspension stabilizer, there is a disadvantage that the particle size distribution of the obtained polymer particles is widened.
【０００３】発泡性ポリスチレン用重合体粒子は粒子径
によりその用途が異なり、粒子径３００μｍ〜７００μ
ｍのものはインスタント食品のカップ用に、粒子径７０
０μｍ〜１８００μｍのものは各種梱包用および魚箱用
に、粒子径１５００μｍ〜３０００μｍのものは建材用
ボードに使用される。[0003] The use of polymer particles for expandable polystyrene varies depending on the particle size, and the particle size ranges from 300 µm to 700 µm.
m for a cup of instant food, particle size 70
Those having a particle size of 0 μm to 1800 μm are used for various packings and fish boxes, and those having a particle size of 1500 μm to 3000 μm are used for building material boards.
【０００４】難溶性無機塩微粉末及び陰イオン界面活性
剤を懸濁安定化剤とする懸濁重合で得られる重合体の粒
子径は１００μｍ〜３０００μｍの広範囲にあり、粒径
分布が幅広いために上記用途に使用する発泡性ポリスチ
レン用重合体粒子は篩分けすることにより各種用途別に
提供されてきた。しかしながら現在用途の違いにより発
泡性ポリスチレン用重合体粒子に要求される性質も多種
多様になってきており、用途別に重合体粒子を製造する
必要に迫られている。したがって所望の粒径の重合体粒
子を高収率で得られる懸濁重合法が強く望まれている。
また同時に微小粒子の発生が少ない懸濁重合法も強く望
まれている。微小粒子が多く生成すると、脱水処理、篩
分けによっても微小粒子を完全に除去するのが困難であ
り、目的とする粒径の粒子間に微小粒子が混入した場合
成形不良の原因となる。加えて排水中に混入した微小粒
子の回収も容易な作業ではない。[0004] The particle size of the polymer obtained by suspension polymerization using a hardly soluble inorganic salt fine powder and an anionic surfactant as a suspension stabilizer is in a wide range of 100 µm to 3000 µm, and the particle size distribution is wide. The polymer particles for expandable polystyrene used in the above applications have been provided for various applications by sieving. However, the properties required for the polymer particles for expandable polystyrene are now becoming various due to the difference in applications, and it is necessary to produce polymer particles for each application. Therefore, there is a strong demand for a suspension polymerization method capable of obtaining polymer particles having a desired particle size in high yield.
At the same time, a suspension polymerization method in which generation of fine particles is small is strongly desired. If a large number of fine particles are generated, it is difficult to completely remove the fine particles even by dehydration treatment and sieving, and if the fine particles are mixed between particles having a target particle diameter, it causes molding failure. In addition, collecting fine particles mixed in the wastewater is not an easy task.
【０００５】難溶性無機塩と陰イオン界面活性剤とを懸
濁安定化剤とする懸濁重合において、上記問題点を改善
し、狭い粒径分布をもつスチレン系重合体粒子を得るこ
とを目的として各種添加剤を使用する方法が提案されて
いる。例えば特公昭５５−５００４２号公報にはペルオ
キソ二硫酸塩を添加する方法が開示されている。その他
中性を示す水溶性無機塩、例えば塩化ナトリウムや硫酸
ナトリウムを添加する方法も知られている。また難溶性
無機塩と各種界面活性剤の組み合せからなる懸濁化安定
剤も多数開示されている（特開昭５３−１２６０９４号
公報、特開昭５９−１７６３０９号公報、特開昭６０−
１４７４０６号公報、特公昭５８−１０４０６号公報、
特公昭５９−４１４４８号公報など）。In suspension polymerization using a poorly soluble inorganic salt and an anionic surfactant as a suspension stabilizer, an object of the present invention is to improve the above problems and obtain styrene-based polymer particles having a narrow particle size distribution. A method using various additives has been proposed. For example, Japanese Patent Publication No. 55-50042 discloses a method of adding peroxodisulfate. In addition, a method of adding a neutral water-soluble inorganic salt such as sodium chloride or sodium sulfate is also known. Also, a large number of suspension stabilizers comprising a combination of a hardly soluble inorganic salt and various surfactants have been disclosed (JP-A-53-126094, JP-A-59-176309, JP-A-60-176309).
No. 147406, Japanese Patent Publication No. 58-10406,
JP-B-59-41448, etc.).
【０００６】特公昭４２−１７４９７号公報には、分散
効果の増大を目的に懸濁安定化剤として酸化亜鉛を使用
し、懸濁液の水相を少なくともｐＨ９．３に保ち重合を
開始する方法、特公昭４５−３９５４９号公報には粒径
の揃った透明な重合体粒子を得るために懸濁系にけい酸
ナトリウムを使用する方法、特公昭６２−５１９６１号
公報には粒径の揃った重合体粒子を得るために分散媒で
ある水相の水素イオン濃度を水溶性の緩衝剤を用いてｐ
Ｈ７〜ｐＨ５の範囲に保つ方法が開示されている。また
特開昭６４−７０５０８号公報には粒径の揃った重合体
粒子を得るために有機保護コロイドおよび無機懸濁安定
剤の存在下水相に５０ｐｐｍ〜５００ｐｐｍの炭酸塩ま
たは重炭酸塩を添加する方法が開示されている。[0006] Japanese Patent Publication No. 42-17497 discloses a method in which zinc oxide is used as a suspension stabilizer to increase the dispersing effect, and the aqueous phase of the suspension is kept at least at pH 9.3 to initiate polymerization. Japanese Patent Publication No. 45-39549 discloses a method in which sodium silicate is used in a suspension system to obtain transparent polymer particles having a uniform particle diameter. In order to obtain polymer particles, the hydrogen ion concentration of the aqueous phase as a dispersion medium is adjusted using a water-soluble buffer.
A method for maintaining the pH in the range of H7 to pH 5 is disclosed. JP-A-64-70508 discloses that 50 ppm to 500 ppm of a carbonate or bicarbonate is added to an aqueous phase in the presence of an organic protective colloid and an inorganic suspension stabilizer in order to obtain polymer particles having a uniform particle size. A method is disclosed.
【０００７】[0007]
【発明が解決しようとする課題】特開昭５５−５００４
２号公報に示される方法は微小粒子の発生が少なく、従
来法より粒径分布の幅の狭い重合体粒子が得られるが、
用途別に見た場合、尚必要粒径範囲外の重合体粒子が多
い問題点を有する。Problems to be Solved by the Invention
In the method disclosed in JP-A No. 2 (1994), polymer particles having a smaller particle size distribution and a narrower particle size distribution than those of the conventional method can be obtained.
When viewed by application, there is a problem that many polymer particles are out of the required particle size range.
【０００８】特公昭４５−３９５４９号公報に示される
方法はけい酸ソーダと有機の高分子化合物を併用する必
要があるため重合排液のＣＯＤ負荷を増大させる問題点
がある。The method disclosed in JP-B-45-39549 has a problem that the COD load of the polymerization effluent is increased because it is necessary to use sodium silicate and an organic polymer compound in combination.
【０００９】特公昭４２−１７４９７号公報は沈殿防止
剤としての酸化亜鉛を多量に必要とするため、これが重
合体粒子中に含まれるので品質が低下する問題点があ
る。また得られる重合体粒子の粒径分布も幅広い欠点が
ある。Japanese Patent Publication No. Sho 42-17497 requires a large amount of zinc oxide as a suspending agent, and the zinc oxide is contained in polymer particles. Further, the particle size distribution of the obtained polymer particles also has a wide disadvantage.
【００１０】特公昭６２−５１９６１に示される方法
は、懸濁化剤として水溶性高分子を用いた場合、重合排
液のＣＯＤ負荷を増大させるため、排水処理を必要とす
る問題点があり、難溶性無機塩を用いた場合、多量の懸
濁化剤を必要とするため、これが重合体粒子中に含まれ
品質が低下する問題点と再現可能な操作範囲が狭い欠点
がある。The method disclosed in JP-B-62-51961 has a problem that when a water-soluble polymer is used as a suspending agent, the COD load of the polymerization effluent is increased, so that wastewater treatment is required. When a poorly soluble inorganic salt is used, a large amount of a suspending agent is required, and therefore, there is a problem in that it is contained in the polymer particles to deteriorate the quality and a drawback that the reproducible operation range is narrow.
【００１１】特開昭６４−７０５０８号公報に示される
方法は懸濁安定剤として有機保護コロイドと水不溶性無
機粉末を使用するため、やはり重合排液のＣＯＤ負荷を
増大させる問題点があり、また重合体粒子中の水分含有
量が多く気泡構造が不均一になる問題点がある。The method disclosed in JP-A-64-70508 uses an organic protective colloid and a water-insoluble inorganic powder as suspension stabilizers, and thus has the problem of increasing the COD load of the polymerization effluent. There is a problem that the water content in the polymer particles is large and the cell structure becomes non-uniform.
【００１２】発泡ポリスチレン用重合体粒子は粒径が均
一で微小粒子が少ないことが要求されるが、この他品質
面では重合体粒子を予備発泡し、成形したとき発泡粒子
間の間隙がなく、発泡粒子が十分に融着し、成形品とし
て十分に強度をもつことが要求される。この要求を満足
させるためには重合体粒子中の水、懸濁剤等の不純物含
有量が少ないことが好ましい。また懸濁重合時に乳化重
合が併発すると乳化物自体が不純物として作用する他
水、懸濁剤等が重合体粒子中に取り込まれやすくなるた
め乳化重合の併発は抑制するのが好ましい。これらの不
純物は粒子の発泡時に影響を及ぼし、気泡構造を乱すた
めに上記要求特性を満足させることができない。したが
って従来の懸濁重合法では粒径が均一で微小粒子が少な
く、かつ品質に優れた重合体粒子を提供することができ
ない。本発明は排水処理、品質の問題がなく、かつ微小
粒子を減少させた狭い粒径分布をもつビニル系重合体粒
子が得られる製造法を提供する。[0012] The polymer particles for expanded polystyrene are required to have a uniform particle size and a small number of fine particles. However, from the viewpoint of quality, there is no gap between the expanded particles when the polymer particles are pre-expanded and molded. It is required that the expanded particles be sufficiently fused and have sufficient strength as a molded product. In order to satisfy this requirement, the content of impurities such as water and a suspending agent in the polymer particles is preferably small. When emulsion polymerization occurs concurrently with suspension polymerization, the emulsion itself acts as an impurity, and water, a suspending agent, and the like are easily incorporated into the polymer particles. Therefore, it is preferable to suppress the concurrent occurrence of emulsion polymerization. These impurities affect the expansion of the particles and disturb the cell structure, so that the above required characteristics cannot be satisfied. Therefore, conventional suspension polymerization cannot provide polymer particles having a uniform particle size, a small number of fine particles, and excellent quality. The present invention provides a method for producing vinyl polymer particles having a narrow particle size distribution with reduced fine particles without wastewater treatment and quality problems.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、懸濁安定
化剤として難溶性リン酸塩と陰イオン界面活性剤を用い
る懸濁重合において、ビニル系単量体に脂肪族ジアミド
化合物を添加し水性媒体中の水素イオン濃度を制御する
ことにより、品質の問題がなく、かつ微小粒子が少な
く、狭い粒径分布をもつビニル系重合体粒子を再現性よ
く製造できることを見出し本発明を完成するに至った。Means for Solving the Problems In the suspension polymerization using a sparingly soluble phosphate and an anionic surfactant as a suspension stabilizer, the present inventors used an aliphatic diamide compound as a vinyl monomer. Completed the present invention by finding that by adding and controlling the hydrogen ion concentration in the aqueous medium, it is possible to produce vinyl polymer particles having a small particle size and a narrow particle size distribution with good reproducibility without quality problems. I came to.
【００１４】すなわち本発明はビニル系単量体を難溶性
リン酸塩及び陰イオン界面活性剤の存在下、水性媒体中
で懸濁重合するのに際し、ビニル系単量体に脂肪族ジア
ミド化合物を添加しかつビニル系単量体の重合転化率が
０重量％〜３０重量％の期間内に塩基性金属水酸化物を
用いて水性媒体中の水素イオン濃度をｐＨ１０〜ｐＨ１
３とすることを特徴とするビニル系重合体粒子の製造法
及び、該製造法において重合途中又は重合後に発泡剤を
含浸させる発泡性ビニル系重合体粒子の製造法に関す
る。That is, in the present invention, when a vinyl monomer is subjected to suspension polymerization in an aqueous medium in the presence of a sparingly soluble phosphate and an anionic surfactant, an aliphatic diamide compound is added to the vinyl monomer. The hydrogen ion concentration in the aqueous medium is adjusted to pH 10 to pH 1 using a basic metal hydroxide while the polymerization conversion of the vinyl monomer is 0% to 30% by weight.
The present invention also relates to a method for producing vinyl-based polymer particles, which is characterized by No. 3, and a method for producing expandable vinyl-based polymer particles in which a foaming agent is impregnated during or after polymerization in the production method.
【００１５】本発明において、ビニル系単量体の重合転
化率が０重量％〜３０重量％の期間内に水性媒体中の水
素イオン濃度はｐＨ１０〜ｐＨ１３とするが、水系イオ
ン濃度がｐＨ１０未満であると粒径分布を狭くする効果
が不十分であり、ｐＨ１３を超えると重合体粒子の粒径
分布が幅広くなる。また水素イオン濃度をｐＨ１０〜ｐ
Ｈ１３にする期間は重合性単量体の重合転化率が０重量
％〜３０重量％の期間内、好ましくは重合転化率が５重
量％〜１５重量％の期間内である。重合転化率が３０重
量％を超えると、油滴の粘度が著しく上昇するために、
本発明の効果は得難く、狭い粒径分布をもつ重合体粒子
が得られない。In the present invention, the hydrogen ion concentration in the aqueous medium is adjusted to pH 10 to pH 13 while the polymerization conversion of the vinyl monomer is 0 to 30% by weight. If it is, the effect of narrowing the particle size distribution is insufficient, and if the pH exceeds 13, the particle size distribution of the polymer particles becomes wide. Further, the hydrogen ion concentration is adjusted to pH 10 to p.
The period during which H13 is set is within the period where the polymerization conversion of the polymerizable monomer is 0% to 30% by weight, preferably within the period where the polymerization conversion is 5% to 15% by weight. If the polymerization conversion exceeds 30% by weight, the viscosity of the oil droplets increases significantly,
The effect of the present invention is difficult to obtain, and polymer particles having a narrow particle size distribution cannot be obtained.
【００１６】本発明において水性媒体中の水素イオン濃
度を上記範囲にする手段としては乳化重合の併発による
品質の低下が少ない水酸化ナトリウム、水酸化カリウ
ム、水酸化リチウム等の塩基性金属（アルカリ金属）水
酸化物を添加する。炭酸ナトリウム、炭酸カリウム、炭
酸リチウム、炭酸水素ナトリウム等の可溶性塩基性金属
炭酸塩の添加は乳化重合を著しく併発する。また、水酸
化カルシウムの添加は系を不安定化させ、粒子の集塊現
象をもたらす。さらに炭酸カルシウム、炭酸マグネシウ
ム、炭酸亜鉛、炭酸バリウム及び炭酸銅などの不溶性ま
たは難溶性の炭酸塩では目的とする水素イオン濃度が得
られず粒径分布を狭くする効果が全く認められない。In the present invention, as a means for controlling the hydrogen ion concentration in the aqueous medium to the above range, a basic metal (such as an alkali metal) such as sodium hydroxide, potassium hydroxide, lithium hydroxide or the like, which causes little deterioration in quality due to concurrent emulsion polymerization, is used. ) Add hydroxide. Addition of a soluble basic metal carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogencarbonate, etc. significantly causes emulsion polymerization. Also, the addition of calcium hydroxide destabilizes the system and causes the agglomeration of particles. Further, insoluble or hardly soluble carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate and copper carbonate, the desired hydrogen ion concentration cannot be obtained and the effect of narrowing the particle size distribution is not recognized at all.
【００１７】本発明において、重合するビニル系単量体
としては、スチレンやα−メチルスチレン、クロルスチ
レン、ビニルトルエン等のスチレン誘導体、アクリロニ
トリル、ビニルピロリドン、ビニルピリジン、ビニルカ
ルバゾール、ポリブタジエン、炭素数１〜８のアルコー
ルとアクリル酸またはメタクリル酸のエステル等を用い
ることができるが、スチレンまたはスチレン誘導体を５
０重量％以上使用するのが好ましい。In the present invention, the vinyl monomers to be polymerized include styrene, α-methylstyrene, chlorostyrene, styrene derivatives such as vinyltoluene, acrylonitrile, vinylpyrrolidone, vinylpyridine, vinylcarbazole, polybutadiene, and carbon atoms having 1 carbon atom. Esters of acrylic acid or methacrylic acid, etc. can be used.
It is preferable to use 0% by weight or more.
【００１８】重合開始剤としては、ビニル系単量体に可
溶なベンゾイルパーオキサイド、ラウロイルパーオキサ
イド、ｔ−ブチルパーベンゾエート、ジ−ｔ−ブチルパ
ーオキサイド等の有機過酸化物、アゾビスイソブチロニ
トリル等のアゾ化合物などを使用することができるが、
有機過酸化物を使用するのが好ましい。Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate and di-t-butyl peroxide which are soluble in a vinyl monomer, and azobisisobutyrate. Although azo compounds such as lonitrile can be used,
Preferably, an organic peroxide is used.
【００１９】難溶性リン酸塩としては、リン酸三カルシ
ウム、ヒドロキシアパタイト、リン酸マグネシウム、リ
ン酸バリウム、リン酸ストロンチウム、リン酸アルミニ
ウム、リン酸鉄、リン酸コバルト、ピロリン酸カルシウ
ム等を使用することができるが、リン酸三カルシウム、
ヒドロキシアパタイトが好ましい。添加量は重合性単量
体に対して０．１〜０．８重量％が好ましく、特に好ま
しくは０．１５重量％〜０．４０重量％である。As the poorly soluble phosphate, tricalcium phosphate, hydroxyapatite, magnesium phosphate, barium phosphate, strontium phosphate, aluminum phosphate, iron phosphate, cobalt phosphate, calcium pyrophosphate and the like can be used. Can be, but tricalcium phosphate,
Hydroxyapatite is preferred. The addition amount is preferably 0.1 to 0.8% by weight, particularly preferably 0.15% to 0.40% by weight, based on the polymerizable monomer.
【００２０】陰イオン界面活性剤としては、ドデシルベ
ンゼンスルホン酸ナトリウム、スチレンスルホン酸ナト
リウム、ドデシルスルホン酸ナトリウム、ジオクチルス
ルホコハク酸ナトリウム等を使用することができる。添
加量は重合性単量体に対して０．０００１重量％〜０．
０１重量％が好ましい。As the anionic surfactant, sodium dodecylbenzenesulfonate, sodium styrenesulfonate, sodium dodecylsulfonate, sodium dioctylsulfosuccinate and the like can be used. The addition amount is 0.0001% by weight to 0.1% based on the polymerizable monomer.
01% by weight is preferred.
【００２１】懸濁重合の重合温度は７０℃〜１４０℃が
好ましく、重合性単量体と水性媒体の重量比は前者／後
者で０．８／１〜１．２／１程度が好ましい。The polymerization temperature of the suspension polymerization is preferably 70 ° C. to 140 ° C., and the weight ratio of the polymerizable monomer to the aqueous medium is preferably about 0.8 / 1 to 1.2 / 1 in the former / latter.
【００２２】本発明においては、ビニル系単量体に乳化
重合を抑制する効果のある脂肪族ジアミド化合物を添加
する。該ジアミド化合物としては、エチレンビスステア
リルアミド又はメチレンビスステアリルアミドを添加す
るのが好ましい。添加量はビニル系単量体に対して０．
０１重量％〜０．２重量％が好ましい。In the present invention, an aliphatic diamide compound having an effect of suppressing emulsion polymerization is added to the vinyl monomer. As the diamide compound, it is preferable to add ethylenebisstearylamide or methylenebisstearylamide. The amount of addition is 0.1 to the vinyl monomer.
It is preferably from 01% to 0.2% by weight.
【００２３】本発明において、発泡性ビニル系重合体粒
子を製造する場合、前記重合途中又は重合後にプロパ
ン、ブタン、ペンタン、ヘキサン、シクロペンタン、シ
クロヘキサン等の炭化水素、メチレンクロリド、ジクロ
ルジフルオルメタン、トリフルオルフロルメタンのよう
なハロゲン化炭化水素またはこれらの混合物などを発泡
剤として公知の方法により含浸させて発泡性ビニル系重
合体粒子とすることができる。In the present invention, when producing expandable vinyl polymer particles, hydrocarbons such as propane, butane, pentane, hexane, cyclopentane and cyclohexane, methylene chloride, and dichlorodifluoromethane are used during or after the polymerization. A halogenated hydrocarbon such as trifluoromethane or a mixture thereof is impregnated with a known method as a foaming agent to obtain foamable vinyl polymer particles.
【００２４】[0024]
【作用】本発明では重合性単量体の重合転化率が０重量
％〜３０重量％の期間内に水性媒体中の水素イオン濃度
をｐＨ１０〜ｐＨ１３にすることにより、この期間内に
おける油滴の分散と合一の頻度を抑制できるため粒径分
布が幅広くなることを防止することができる。また、脂
肪族ジアミド化合物は、乳化重合を抑制する効果があ
り、乳化物と一緒に油滴内部に取り込まれる水や懸濁化
剤が減少するので気泡構造が均一でかつ表面平滑性の優
れる発泡成形品が得られる。According to the present invention, the hydrogen ion concentration in the aqueous medium is adjusted to pH 10 to pH 13 within a period in which the polymerization conversion of the polymerizable monomer is 0% by weight to 30% by weight, so that the oil droplets in this period are reduced. Since the frequency of dispersion and coalescence can be suppressed, it is possible to prevent the particle size distribution from broadening. In addition, the aliphatic diamide compound has an effect of suppressing emulsion polymerization, and reduces the amount of water and a suspending agent taken into the oil droplets together with the emulsion, so that the foam has a uniform cell structure and excellent surface smoothness. A molded article is obtained.
【００２５】[0025]
【実施例】以下本発明を実施例により説明する。ここで
重合体粒子の粒径分布と平均粒径についてはそれぞれ偏
差係数Ｃｖとメディアン径で示す。すなわち累積重量分
布曲線を基にして累積重量が１５％、５０％、８５％と
なる粒径をそれぞれｄ15、ｄ50、ｄ85とし偏差係数Ｃｖ
を次式で求め粒径分布の広狭を判断した。 Ｃｖ＝（ｄ85−ｄ15）／ｄ50 Ｃｖ値が大きい程粒径分布は広く、小さい程粒径分布は
狭くなる。平均径は前述のｄ50で代表されるメディアン
径を採用した。The present invention will be described below with reference to examples. Here, the particle size distribution and the average particle size of the polymer particles are represented by a deviation coefficient Cv and a median diameter, respectively. That is, based on the cumulative weight distribution curve, the particle diameters at which the cumulative weight becomes 15%, 50%, and 85% are d 15 , d 50 , and d 85 , respectively, and the deviation coefficient Cv
Was determined by the following equation, and the width of the particle size distribution was determined. Cv = (d 85 -d 15) / d 50 Cv value is greater Hodotsubu size distribution is wide, small Hodotsubu size distribution is narrow. The average diameter was adopted median diameter represented by d 50 described above.
【００２６】また、成形品の表面平滑率を示す尺度を次
の方法で求め表面平滑率とした。すなわち成形品表面に
印刷用黒インクをローラーで薄く塗布すると、平滑な部
分にはインクが塗られるが、発泡粒子間の間隙は白く残
る。全表面積に対する黒色部の面積の比率を画像処理装
置で計算して表面平滑率とした。Further, a scale indicating the surface smoothness of the molded article was obtained by the following method and was defined as the surface smoothness. That is, when the printing black ink is thinly applied to the surface of the molded article by a roller, the ink is applied to the smooth portion, but the gap between the foam particles remains white. The ratio of the area of the black portion to the total surface area was calculated by an image processing apparatus and defined as the surface smoothness.
【００２７】実施例１ ４ｌオートクレーブに１０％第３リン酸カルシウム分散
液（日本化学工業社製、スーパタイト１０）２４ｇ、ド
デシルベンゼンスルホン酸ナトリウム（和光純薬工業社
製）０．０４８ｇ、イオン交換水１１７６ｇを入れてよ
く撹拌し均一な混合溶液とした。次いでベンゾイルパー
オキサイド（昭光化学社製）３．０ｇ、ｔ−ブチルパー
ベンゾエート（日本油脂社製）０．１ｇ及びエチレンビ
スステアリルアミド（日本化成社製）１．２ｇを溶解し
たスチレン（電気化学工業社製）１２００ｇを撹拌しな
がら添加し、９０℃に昇温して重合を開始した。重合転
化率（比重法により測定）が１０重量％に達した時点で
水酸化ナトリウム（和光純薬工業社製）の１０％水溶液
３．０ｇを添加した。添加直後の水素イオン濃度はｐＨ
１１．８であった。さらに重合転化率が３５重量％に達
した時点で１０％第３リン酸カルシウム分散液６ｇを加
え、そのまま重合を進めた。重合転化率が９５重量％に
達した時点でさらに１０％第３リン酸カルシウム分散液
１２ｇを加えた後、シクロヘキサン２４ｇとブタン８４
ｇを１時間要して導入した。その後１２０℃に２時間要
して昇温し、１２０℃に５時間保った後、室温まで冷却
して目的とする発泡性ポリスチレン重合体粒子を得た。
得られた重合体粒子を篩分けした結果、平均粒径ｄ50は
９３０μｍで、偏差係数Ｃｖ値は０．３０と非常に狭い
粒径分布であった。３００μｍ以下の微小粒子量は１．
４重量％であった。得られた重合体粒子中の水及び懸濁
剤含有量は表１に示すように少なく、重合体粒子を５０
ｍｌ／ｇに予備発泡した後、予備発泡粒子の切断面を観
察したところ均一な気泡構造が認められた。予備発泡粒
子を２４時間熟成した後成形を行った。得られた成形品
は発泡粒子間の間隙が少なく表面平滑率は９２％であっ
た。Example 1 In a 4 l autoclave, 24 g of 10% tribasic calcium phosphate dispersion (Superitite 10 manufactured by Nippon Chemical Industry Co., Ltd.), 0.048 g of sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 1176 g of ion-exchanged water were placed. The mixture was stirred well to form a uniform mixed solution. Then, styrene containing 3.0 g of benzoyl peroxide (manufactured by Shoko Chemical Co., Ltd.), 0.1 g of t-butyl perbenzoate (manufactured by NOF Corporation) and 1.2 g of ethylenebisstearylamide (manufactured by Nippon Kasei Co., Ltd.) (Manufactured by the company) was added with stirring, and the temperature was raised to 90 ° C. to initiate polymerization. When the polymerization conversion (measured by the specific gravity method) reached 10% by weight, 3.0 g of a 10% aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The hydrogen ion concentration immediately after addition is pH
It was 11.8. When the polymerization conversion reached 35% by weight, 6 g of a 10% tribasic calcium phosphate dispersion was added, and the polymerization was allowed to proceed as it was. When the polymerization conversion reached 95% by weight, 12 g of a 10% tribasic calcium phosphate dispersion was further added, and then 24 g of cyclohexane and 84 g of butane 84 were added.
g was introduced over 1 hour. Thereafter, the temperature was raised to 120 ° C. for 2 hours, kept at 120 ° C. for 5 hours, and then cooled to room temperature to obtain target expandable polystyrene polymer particles.
As a result of sieving the obtained polymer particles, the average particle diameter d 50 was 930 μm, and the coefficient of variation Cv was 0.30, which was a very narrow particle size distribution. The amount of fine particles of 300 μm or less is 1.
It was 4% by weight. The content of water and suspending agent in the obtained polymer particles was small as shown in Table 1,
After prefoaming to a ml / g, the cut surface of the prefoamed particles was observed, and a uniform cell structure was observed. After aging the pre-expanded particles for 24 hours, molding was performed. The resulting molded article had a small gap between the foamed particles and a surface smoothness of 92%.
【００２８】比較例１ 実施例１において水酸化ナトリウムの１０％水溶液３ｇ
を炭酸ナトリウム（和光純薬工業社製）の１０％水溶液
３．６ｇに変更した以外は実施例１と同様にして懸濁重
合を行い、重合体粒子を得た。炭酸ナトリウム添加直後
の水素イオン濃度はｐＨ１０．９であった。得られた重
合体粒子の平均粒径ｄ50は９３０μｍで、偏差係数Ｃｖ
値は０．３１と非常に狭い粒径分布であった。３００μ
ｍ以下の微小粒子は１．６重量％であった。重合体粒子
中の水及び懸濁剤含有量が多く、予備発泡粒子の気泡構
造は不均一であった。予備発泡粒子を成形したところ、
成形品の表面平滑率は８５％であった。Comparative Example 1 In Example 1, 3 g of a 10% aqueous solution of sodium hydroxide was used.
Was changed to 3.6 g of a 10% aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) in the same manner as in Example 1 to obtain polymer particles. The hydrogen ion concentration immediately after the addition of sodium carbonate was pH 10.9. The average particle diameter d 50 of the obtained polymer particles is 930 μm, and the deviation coefficient Cv
The value was a very narrow particle size distribution of 0.31. 300μ
The fine particles having a particle size of m or less were 1.6% by weight. The content of water and the suspending agent in the polymer particles was large, and the cell structure of the pre-expanded particles was not uniform. After molding the pre-expanded particles,
The surface smoothness of the molded product was 85%.
【００２９】比較例２ 実施例１においてエチレンビスステアリルアミドを除い
た他は実施例１と同様に懸濁重合を行い、重合体粒子を
得た。水酸化ナトリウム添加直後の水素イオン濃度はｐ
Ｈ１１．５であった。得られた重合体粒子の平均粒径ｄ
50は９２０μｍで、偏差係数Ｃｖ値は０．３０と非常に
狭い粒径分布であった。３００μｍ以下の微小粒子は
１．５重量％であった。また重合体粒子中の水及び懸濁
剤含有量が増加し、予備発泡粒子の気泡構造はやや不均
一であった。予備発泡粒子を成形したところ、成形品の
表面平滑率は８７％であった。Comparative Example 2 A suspension polymerization was carried out in the same manner as in Example 1 except that ethylenebisstearylamide was omitted, to obtain polymer particles. The hydrogen ion concentration immediately after adding sodium hydroxide is p
H11.5. Average particle size d of polymer particles obtained
50 was 920 μm, and the coefficient of deviation Cv was 0.30, which was a very narrow particle size distribution. The fine particles having a size of 300 μm or less were 1.5% by weight. Further, the content of water and the suspending agent in the polymer particles increased, and the cell structure of the pre-expanded particles was slightly non-uniform. When the pre-expanded particles were molded, the molded article had a surface smoothness of 87%.
【００３０】比較例３ 比較例１においてエチレンビスステアリルアミドを除い
た他は比較例１と同様にして重合体粒子を得た。炭酸ナ
トリウム添加直後水素イオン濃度はｐＨ１０．８であっ
た。得られた重合体粒子の平均粒径ｄ50は９１０μｍ
で、偏差係数Ｃｖ値は０．３２と狭い粒径分布であっ
た。３００μｍ以下の微小粒子は１．６重量％であっ
た。また重合体粒子中の水及び懸濁剤含有量が増加し、
予備発泡粒子の気泡構造は不均一で粒子表面近くの気泡
がかなり小さくなった。予備発泡粒子を成形したとこ
ろ、成形品の表面平滑率は８４％であった。Comparative Example 3 Polymer particles were obtained in the same manner as in Comparative Example 1 except that ethylene bisstearylamide was omitted. Immediately after the addition of sodium carbonate, the hydrogen ion concentration was pH 10.8. The average particle size d 50 of the obtained polymer particles is 910 μm
, And the particle diameter distribution was as narrow as 0.32. The fine particles having a size of 300 μm or less were 1.6% by weight. In addition, the content of water and suspending agent in the polymer particles increases,
The cell structure of the pre-expanded particles was non-uniform and the cells near the particle surface were considerably smaller. When the pre-expanded particles were molded, the molded article had a surface smoothness of 84%.
【００３１】比較例４ 実施例１において水酸化ナトリウムの１０％水溶液３ｇ
を炭酸カルシウム微粉末（和光純薬工業社製）０．４８
ｇに変更した以外は実施例１と同様にして懸濁重合を行
い、重合体粒子を得た。炭酸カルシウム添加直後の水素
イオン濃度はｐＨ７．８であった。得られた重合体粒子
の平均粒径ｄ50は８８０μｍで、偏差係数Ｃｖ値は０．
６１と幅広い粒径分布であった。３００μｍ以下の微小
粒子は３．６重量％であった。重合体粒子中の水及び懸
濁剤含有量は少なく、予備発泡粒子の気泡構造は均一で
あった。予備発泡粒子を成形したところ、成形品の表面
平滑率は９１％であった。Comparative Example 4 In Example 1, 3 g of a 10% aqueous solution of sodium hydroxide was used.
To calcium carbonate fine powder (manufactured by Wako Pure Chemical Industries, Ltd.) 0.48
The suspension polymerization was carried out in the same manner as in Example 1 except that the amount was changed to g, to obtain polymer particles. The hydrogen ion concentration immediately after the addition of calcium carbonate was pH 7.8. The average particle diameter d 50 of the obtained polymer particles is 880 μm, and the coefficient of deviation Cv is 0.5.
The particle size distribution was as wide as 61. The fine particles having a diameter of 300 μm or less accounted for 3.6% by weight. The content of water and the suspending agent in the polymer particles was small, and the cell structure of the pre-expanded particles was uniform. When the pre-expanded particles were molded, the molded article had a surface smoothness of 91%.
【００３２】比較例５ 実施例１において水酸化ナトリウムの１０％水溶液３ｇ
を塩化ナトリウム（和光純薬工業社製）の１０％水溶液
６ｇに変更した以外は実施例１と同様にして懸濁重合を
行い、重合体粒子を得た。塩化ナトリウム添加直後の水
素イオン濃度はｐＨ７．５であった。得られた重合体粒
子の平均粒径ｄ50は９４０μｍで、偏差係数Ｃｖ値は
０．４３であった。３００μｍ以下の微粒子は３．１重
量％であった。重合体粒子中の水及び懸濁剤含有量は少
なく、予備発泡粒子の気泡構造は均一であった。予備発
泡粒子を成形したところ、成形品の表面平滑率は９２％
であった。Comparative Example 5 In Example 1, 3 g of a 10% aqueous solution of sodium hydroxide was used.
Was changed to 6 g of a 10% aqueous solution of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), and suspension polymerization was carried out in the same manner as in Example 1 to obtain polymer particles. The hydrogen ion concentration immediately after the addition of sodium chloride was pH 7.5. The average particle diameter d 50 of the obtained polymer particles was 940 μm, and the coefficient of deviation Cv was 0.43. Fine particles having a size of 300 μm or less accounted for 3.1% by weight. The content of water and the suspending agent in the polymer particles was small, and the cell structure of the pre-expanded particles was uniform. When the pre-expanded particles were molded, the surface smoothness of the molded product was 92%.
Met.
【００３３】比較例６ 実施例１において水酸化ナトリウムの１０％水溶液３．
０ｇを水酸化カルシウム０．３ｇに変更した以外は実施
例１と同様にして懸濁重合を行ったが、水酸化カルシウ
ム添加直後に連続相と分散相が逆転し、重合体粒子を得
ることができなかった。Comparative Example 6 A 10% aqueous solution of sodium hydroxide in Example 1
The suspension polymerization was carried out in the same manner as in Example 1 except that 0 g was changed to 0.3 g of calcium hydroxide. However, immediately after the addition of calcium hydroxide, the continuous phase and the dispersed phase were reversed to obtain polymer particles. could not.
【００３４】実施例２ ４ｌオートクレーブに１０％第３リン酸カルシウム水溶
液２１ｇ、ドデシルベンゼンスルホン酸ナトリウム０．
０６０ｇ、イオン交換水１１７９ｇを入れてよく撹拌し
均一な混合溶液とした。次いでベンゾイルパーオキサイ
ド３．２ｇ、ｔ−ブチルパーベンゾエート０．１ｇ及び
エチレンビスステアリルアミド０．６ｇを溶解したスチ
レン１２００ｇをよく撹拌しながら添加し、９０℃に昇
温して重合を開始した。重合転化率が７重量％に達した
時点で水酸化カリウム（和光純薬工業社製）の１０％水
溶液３．６ｇを添加した。添加直後の水素イオン濃度は
ｐＨ１１．８であった。さらに重合転化率が４０重量％
に達した時点で１０％第３リン酸カルシウム水溶液９ｇ
を加え、そのまま重合を進めた。重合転化率が９５重量
％に達した時点で１０％第３リン酸カルシウム水溶液１
２ｇを加えた後、シクロヘキサン２４ｇとブタン８４ｇ
を１時間要して導入した。その後１２０℃に２時間要し
て昇温し、１２０℃に５時間保った後、室温まで冷却し
て発泡ポリスチレン重合体粒子を得た。得られた重合体
粒子の平均粒径ｄ50は９３０μｍで、偏差係数Ｃｖ値は
０．３０と非常に狭い粒径分布であった。３００μｍ以
下の微小粒子量は１．５重量％であった。重合体粒子中
の水及び懸濁剤含有量は少なく、予備発泡粒子の気泡構
造は均一であった。予備発泡粒子を成形したところ、成
形品の表面平滑率は９２％であった。Example 2 In a 4 l autoclave, 21 g of a 10% aqueous solution of tribasic calcium phosphate, 0.1 g of sodium dodecylbenzenesulfonate were added.
060 g and 1179 g of ion-exchanged water were added and stirred well to form a uniform mixed solution. Next, 3.2 g of benzoyl peroxide, 0.1 g of t-butyl perbenzoate and 1200 g of styrene in which 0.6 g of ethylenebisstearylamide were dissolved were added with good stirring, and the temperature was raised to 90 ° C. to initiate polymerization. When the polymerization conversion reached 7% by weight, 3.6 g of a 10% aqueous solution of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The hydrogen ion concentration immediately after the addition was pH 11.8. Further, the polymerization conversion rate is 40% by weight.
9% of 10% tribasic calcium phosphate aqueous solution
And the polymerization was allowed to proceed. When the polymerization conversion reaches 95% by weight, a 10% tribasic calcium phosphate aqueous solution 1
After adding 2 g, 24 g of cyclohexane and 84 g of butane
Was introduced for 1 hour. Thereafter, the temperature was raised to 120 ° C. for 2 hours, kept at 120 ° C. for 5 hours, and then cooled to room temperature to obtain expanded polystyrene polymer particles. The resulting average particle size d 50 of the polymer particles in 930Myuemu, deviation coefficient Cv value was very narrow particle size distribution 0.30. The amount of the fine particles having a size of 300 μm or less was 1.5% by weight. The content of water and the suspending agent in the polymer particles was small, and the cell structure of the pre-expanded particles was uniform. When the pre-expanded particles were molded, the molded article had a surface smoothness of 92%.
【００３５】比較例７ 実施例２において水酸化カリウムの１０％水溶液３．６
ｇを炭酸カリウム（和光純薬工業社製）の１０％水溶液
４．０ｇに変更した以外は実施例１と同様に懸濁重合を
行い、重合体粒子を得た。炭酸カリウム添加直後の水素
イオン濃度はｐＨ１０．９であった。得られた重合体粒
子の平均粒径ｄ50は９３０μｍで、偏差係数Ｃｖ値は
０．３１と非常に狭い粒径分布であった。３００μｍ以
下の微小粒子は１．５重量％であった。重合体粒子中の
水及び懸濁剤含有量が多く、予備発泡粒子の気泡構造は
不均一であった。予備発泡粒子を成形したところ、成形
品の表面平滑率は８４％であった。Comparative Example 7 In Example 2, a 10% aqueous solution of potassium hydroxide 3.6 was used.
The suspension polymerization was carried out in the same manner as in Example 1 except that g was changed to 4.0 g of a 10% aqueous solution of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain polymer particles. The hydrogen ion concentration immediately after the addition of potassium carbonate was pH 10.9. The resulting average particle size d 50 of the polymer particles in 930Myuemu, deviation coefficient Cv value was very narrow particle size distribution 0.31. The fine particles having a size of 300 μm or less were 1.5% by weight. The content of water and the suspending agent in the polymer particles was large, and the cell structure of the pre-expanded particles was not uniform. When the pre-expanded particles were molded, the molded article had a surface smoothness of 84%.
【００３６】実施例３ 実施例１においてエチレンビスステアリルアミドをメチ
レンビスステアリルアミドに変更した以外は実施例１と
同様に懸濁重合を行い、重合体粒子を得た。水酸化ナト
リウム添加直後の水素イオン濃度はｐＨ１１．７濃度で
あった。得られた重合体粒子の平均粒径ｄ50は９２０μ
ｍで、偏差係数Ｃｖ値は０．３０と非常に狭い粒径分布
であった。３００μｍ以下の微小粒子は１．５重量％で
あった。重合体粒子中の水及び懸濁剤含有量は少なく、
予備発泡粒子の気泡構造は均一であった。予備発泡粒子
を成形したところ、成形品の表面平滑率は９２％であっ
た。Example 3 Suspension polymerization was carried out in the same manner as in Example 1 except that ethylene bisstearylamide was changed to methylene bisstearylamide to obtain polymer particles. The hydrogen ion concentration immediately after the addition of sodium hydroxide was pH 11.7. The average particle diameter d 50 of the obtained polymer particles is 920 μm.
m, the coefficient of variation Cv was 0.30 and the particle size distribution was very narrow. The fine particles having a size of 300 μm or less were 1.5% by weight. Water and suspending agent content in the polymer particles is small,
The cell structure of the pre-expanded particles was uniform. When the pre-expanded particles were molded, the molded article had a surface smoothness of 92%.
【００３７】以上の各実施例及び比較例の配合と特性を
まとめて表１に示す。なお、重合体粒子中の含水率は重
合体粒子をメタノールで洗浄後、風乾し、カールフィッ
シャー法により求めた。また重合体粒子中の懸濁剤リン
酸カルシウム（ＴＣＰ）の含有量は重合体粒子をクロロ
ホルムで溶解し、１０％塩酸水溶液で抽出し、水溶液中
のカルシウムイオン濃度を原子吸光光度計で求めて算出
した。Table 1 shows the compositions and characteristics of the above Examples and Comparative Examples. The water content in the polymer particles was determined by washing the polymer particles with methanol, air-drying, and Karl Fischer method. The content of the suspending agent calcium phosphate (TCP) in the polymer particles was calculated by dissolving the polymer particles in chloroform, extracting the solution with a 10% hydrochloric acid aqueous solution, and calculating the calcium ion concentration in the aqueous solution with an atomic absorption spectrophotometer. .
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】以上から明らかなように本発明によれば
粒径分布が狭く、品質の優れたビニル系重合体粒子を提
供することができる。また本発明の発泡性ビニル系重合
体粒子の製造法は特に微小粒子生成量も少なく、不良生
成品を減少できるので、生産性及び品質の面から工業上
極めて有益である。As is clear from the above, according to the present invention, vinyl polymer particles having a narrow particle size distribution and excellent quality can be provided. In addition, the method for producing expandable vinyl polymer particles of the present invention is particularly industrially useful in terms of productivity and quality, since the amount of produced fine particles is particularly small and defective products can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 ▲吉▼川 徹 茨城県日立市東町四丁目13番１号 日立 化成工業株式会社 茨城研究所内 (72)発明者 国武 和彦 千葉県市原市五井南海岸14番地 日立化 成工業株式会社 五井工場内 (72)発明者 日比野 信吾 千葉県市原市五井南海岸14番地 日立化 成工業株式会社 五井工場内 (56)参考文献 特開 昭50−53487（ＪＰ，Ａ) 特開 昭48−48588（ＪＰ，Ａ) 特開 平２−147602（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/00 - 2/18 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor ▲ Yoshi ▼ Tohru 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd., Ibaraki Research Laboratory (72) Inventor Kazuhiko Kunitake Goi Minami Coast, Ichihara City, Chiba Prefecture No. 14 in the Goi Plant, Hitachi Chemical Co., Ltd. (72) Inventor Shingo Hibino No. 14, Goi South Coast, Ichihara City, Chiba Prefecture In the Goi Plant of Hitachi Chemical Co., Ltd. (56) References JP-A-50-53487 (JP, A) JP-A-48-48588 (JP, A) JP-A-2-147602 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 2/00-2/18
Claims (4)
イオン界面活性剤の存在下水性媒体中で懸濁重合するの
に際し、ビニル系単量体に脂肪族ジアミド化合物を添加
し、かつビニル系単量体の重合転化率が０重量％〜３０
重量％の期間内に、塩基性金属水酸化物を用いて水性媒
体中の水素イオン濃度をｐＨ１０〜ｐＨ１３とすること
を特徴とするビニル系重合体粒子の製造法。When a vinyl monomer is subjected to suspension polymerization in an aqueous medium in the presence of a sparingly soluble phosphate and an anionic surfactant, an aliphatic diamide compound is added to the vinyl monomer. And the polymerization conversion of the vinyl monomer is 0% by weight to 30%.
A method for producing vinyl polymer particles, wherein a hydrogen ion concentration in an aqueous medium is adjusted to pH 10 to pH 13 using a basic metal hydroxide within a period of weight%.
テアリルアミド又はメチレンビスステアリルアミドであ
る請求項１記載のビニル系重合体粒子の製造法。2. The method for producing vinyl polymer particles according to claim 1, wherein the aliphatic diamide compound is ethylenebisstearylamide or methylenebisstearylamide.
ル系単量体に対して０．０１重量％〜０．２重量％であ
る請求項１又は２記載のビニル系重合体粒子の製造法。3. The method for producing vinyl polymer particles according to claim 1, wherein the amount of the aliphatic diamide compound is 0.01% by weight to 0.2% by weight based on the vinyl monomer. .
体粒子の製造法において、重合途中又は重合後にさらに
発泡剤を含浸させる発泡性ビニル系重合体粒子の製造
法。4. The process for producing expandable vinyl polymer particles according to claim 1, 2 or 3, wherein a foaming agent is further impregnated during or after polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3109054A JP3063222B2 (en) | 1990-05-31 | 1991-05-14 | Method for producing vinyl polymer particles and expandable vinyl polymer particles |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14279290 | 1990-05-31 | ||
| JP2-142792 | 1991-01-17 | ||
| JP392891 | 1991-01-17 | ||
| JP3-3928 | 1991-01-17 | ||
| JP3109054A JP3063222B2 (en) | 1990-05-31 | 1991-05-14 | Method for producing vinyl polymer particles and expandable vinyl polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04279602A JPH04279602A (en) | 1992-10-05 |
| JP3063222B2 true JP3063222B2 (en) | 2000-07-12 |
Family
ID=27276038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3109054A Expired - Lifetime JP3063222B2 (en) | 1990-05-31 | 1991-05-14 | Method for producing vinyl polymer particles and expandable vinyl polymer particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3063222B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100367184B1 (en) * | 1997-12-26 | 2003-11-22 | 제일모직주식회사 | Method for preparing foamable polystyrene resin particles |
-
1991
- 1991-05-14 JP JP3109054A patent/JP3063222B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04279602A (en) | 1992-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5290819A (en) | Preparation of bead-form expandable styrene polymers | |
| JP3168882B2 (en) | Styrene-based expandable resin particles and method for producing the same | |
| JP3097170B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| JP3063222B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| JP3063223B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| JP2998216B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| EP0234705A2 (en) | Process for producing expandable polystyrene beads | |
| JP3265246B2 (en) | Method for producing styrene resin particles | |
| JP2907068B2 (en) | Method for producing expandable styrene polymer particles | |
| RU2307845C2 (en) | Granules of foamable vinylaromatic polymers and a process for manufacture thereof | |
| JP3265247B2 (en) | Method for producing styrene resin particles | |
| JP2002053605A (en) | Method of producing styrene foaming resin particle | |
| JPH04339811A (en) | Production of vinyl polymer particle and expandable vinyl polymer particle | |
| JPH04339805A (en) | Production of vinyl polymer particle and expandable vinyl polymer particle | |
| JPH04339806A (en) | Production of vinyl polymer particle and expandable vinyl polymer particle | |
| JP2636400B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| JP2684740B2 (en) | Method for producing vinyl polymer particles | |
| JP3494249B2 (en) | Method for producing vinyl polymer particles | |
| JP3125418B2 (en) | Method for producing expandable vinyl resin particles | |
| JPH0826083B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| EP1994085A1 (en) | Process for preparing expandable styrene polymers | |
| JPS587407A (en) | Manufacture of styrol suspension polymer | |
| JPS6312481B2 (en) | ||
| JPH0826084B2 (en) | Method for producing vinyl polymer particles and expandable vinyl polymer particles | |
| JPH03258807A (en) | Production of vinylic polymer particle and expandable vinylic polymer particle |