JP2013018974A - Vinyl chloride-based copolymer latex, and method for producing the same - Google Patents
Vinyl chloride-based copolymer latex, and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、塩化ビニル系共重合体ラテックスおよびその製造方法に関する。 The present invention relates to a vinyl chloride copolymer latex and a method for producing the same.
塩化ビニル系樹脂は安価でかつ品質バランスに優れているため、繊維処理、塗料など種々の分野で利用されている。塩化ビニル系樹脂からなる水性塗工液は、溶剤系と比較し有機溶剤を使用しないため大気汚染の問題、作業者の安全衛生の問題、火災の問題等がなく、近年利用が広がっている。その際、塩化ビニル樹脂の高機能化を目的とし、様々な単量体を塩化ビニル単量体と共重合している。特に、ガラス転移温度（Ｔｇ）の低下のため塩化ビニル単量体に、不飽和カルボン酸エステル単量体を共重合するが、これらエステル類は加水分解しやすく、加水分解防止のため重合系内のｐＨを概ね３〜７に保つようにｐＨ緩衝剤の添加が行われている（非特許文献１、特許文献１、特許文献２）。 Since vinyl chloride resin is inexpensive and excellent in quality balance, it is used in various fields such as fiber treatment and paint. The aqueous coating liquid made of a vinyl chloride resin does not use an organic solvent as compared with a solvent system, and therefore has no problem of air pollution, safety and health of workers, fire, etc. At that time, various monomers are copolymerized with a vinyl chloride monomer for the purpose of enhancing the functionality of the vinyl chloride resin. In particular, an unsaturated carboxylic acid ester monomer is copolymerized with a vinyl chloride monomer in order to lower the glass transition temperature (Tg), but these esters are easily hydrolyzed. A pH buffering agent is added so as to keep the pH at 3 to 7 (Non-patent Document 1, Patent Document 1, and Patent Document 2).
ところが従来一般的に使用されている重炭酸ナトリウム、炭酸ナトリウム、酢酸ナトリウム、一価又は二価のリン酸カリウム、クエン酸ナトリウム、酒石酸ナトリウム、安息香酸ナトリウム等のｐＨ緩衝剤を添加して塩化ビニルとビニルエステルを共重合すると、重合中のラテックス溶液のｐＨ低下は防止できるものの、重合中にスケールが多く発生する問題があった。 However, vinyl chloride is added by adding a pH buffer such as sodium bicarbonate, sodium carbonate, sodium acetate, monovalent or divalent potassium phosphate, sodium citrate, sodium tartrate, sodium benzoate and the like generally used conventionally. When vinyl ester and vinyl ester are copolymerized, the pH of the latex solution during polymerization can be prevented from decreasing, but there is a problem that a large amount of scale is generated during polymerization.
また、平均粒径０．１５μｍのラテックスを得る方法が記載されているが（特許文献３）、このラテックスはシードミクロ懸濁重合法に使用されるものであり、貯蔵安定性が十分でなかった。 Moreover, although the method of obtaining the latex of average particle diameter 0.15 micrometer is described (patent document 3), this latex is used for a seed micro suspension polymerization method, and its storage stability was not enough. .
本発明は、上記課題に鑑みてなされたものであり、貯蔵安定性に優れるラテックス、および重合中に発生するスケールが少なく、ｐＨが３〜８であるラテックスの製造方法を提供するものである。 The present invention has been made in view of the above problems, and provides a latex having excellent storage stability and a method for producing a latex having a small scale generated during polymerization and having a pH of 3-8.
本発明者らは、上記の課題について鋭意検討を重ねた結果、塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０〜１０．０重量部及び高級脂肪酸塩０．０５〜３．０重量部となるように、重合中にスルホン酸塩又は硫酸エステル塩、脂肪酸塩を添加することで、重合中に発生するスケールが少なく、重合後に得られるラテックスのｐＨの低下を防止できることを見出した。すなわち、本発明は、塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０〜１０．０重量部及び高級脂肪酸塩０．０５〜３．０重量部を含有し、ｐＨ３〜８である塩化ビニル系共重合体ラテックス、並びにその製造方法である。 As a result of intensive studies on the above problems, the present inventors have found that an organic compound having a sulfonate or sulfate ester salt of 0.20 to 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer. By adding sulfonate, sulfate ester salt or fatty acid salt during polymerization so that 10.0 parts by weight and higher fatty acid salt 0.05-3.0 parts by weight, the scale generated during polymerization is reduced. The present inventors have found that a decrease in pH of the latex obtained after polymerization can be prevented. That is, in the present invention, 0.20 to 10.0 parts by weight of an organic compound having a sulfonate salt or a sulfate ester salt and 0.1 part by weight of a higher fatty acid salt with respect to 100 parts by weight of a vinyl chloride-unsaturated carboxylic acid ester copolymer. This is a vinyl chloride copolymer latex containing 0.5 to 3.0 parts by weight and having a pH of 3 to 8, and a method for producing the same.
以下に本発明について詳細に説明する。 The present invention is described in detail below.
本発明の塩化ビニル系共重合体ラテックスは、塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０〜１０．０重量部及び高級脂肪酸塩０．０５〜３．０重量部を含有するものである。 The vinyl chloride copolymer latex of the present invention is 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. And 0.05 to 3.0 parts by weight of a higher fatty acid salt.
塩化ビニル−不飽和カルボン酸エステル共重合体は、塩化ビニル単量体と不飽和カルボン酸エステル単量体を共重合させたものである。 The vinyl chloride-unsaturated carboxylic acid ester copolymer is obtained by copolymerizing a vinyl chloride monomer and an unsaturated carboxylic acid ester monomer.
不飽和カルボン酸エステルとしては、例えば、アクリル酸のメチル，エチル，ブチル等のエステル、メタクリル酸のメチル，エチル，ブチル等のエステル、マレイン酸エステル、フマル酸エステル、桂皮酸エステル等を挙げることができ、これらは２種類以上でも用いることができる。 Examples of the unsaturated carboxylic acid ester include esters of acrylic acid such as methyl, ethyl, and butyl, esters of methyl methacrylate such as methyl, ethyl, and butyl, maleic acid esters, fumaric acid esters, and cinnamic acid esters. Two or more of these can be used.
塩化ビニルと不飽和カルボン酸エステルを共重合させる方法としては、例えば、乳化重合、溶液重合、気相重合等が挙げられる。 Examples of the method of copolymerizing vinyl chloride and unsaturated carboxylic acid ester include emulsion polymerization, solution polymerization, and gas phase polymerization.
スルホン酸塩を有する化合物としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸アンモニウム等のアルキルベンゼンスルホン酸塩；ジオクチルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウム等のジアルキルスルホコハク酸塩類；アルキルナフタレンスルフォン酸ナトリウム等のアルキルナフタレンスルフォン酸塩類；アルキルジフェニルエーテルジスルフォン酸ナトリウム等のアルキルジフェニルエーテルジスルフォン酸塩類等が挙げられ、硫酸エステル塩を有する有機化合物としては、例えば、ラウリル硫酸エステルナトリウム、ミリスチル硫酸エステルナトリウム等のアルキル硫酸エステル塩類；ポリオキシエチレンアルキル硫酸エステル塩類、ポリオキシエチレンアルキルアリール硫酸エステル塩類等が挙げられる。スルホン酸塩又は硫酸エステル塩を有する有機化合物の含有量としては、０．２０〜１０．０重量部である。０．２０重量部未満の場合は、貯蔵安定性に劣り、ラテックスが不安定となり、１０．０重量部を超える場合は、塩化ビニル系共重合体の不純物となる。好ましくは、１．０〜５．０重量部である。 Examples of the compound having a sulfonate include alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; sodium alkylnaphthalenesulfonate Alkyl naphthalene sulfonates such as alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether. Examples of organic compounds having a sulfate ester salt include sodium lauryl sulfate and sodium myristyl sulfate. Alkyl sulfates; polyoxyethylene alkyl sulfates, polyoxyethylene alkyl esters Lumpur sulfate ester salts, and the like. The content of the organic compound having a sulfonate or a sulfate ester salt is 0.20 to 10.0 parts by weight. When the amount is less than 0.20 parts by weight, the storage stability is inferior, and the latex becomes unstable. When the amount exceeds 10.0 parts by weight, it becomes an impurity of the vinyl chloride copolymer. Preferably, it is 1.0-5.0 weight part.
高級脂肪酸塩としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸等とアルカリとの塩が挙げられる。入手のしやすさから、ナトリウム、カリウム、アンモニア、トリエタノールアミンとの塩が好ましい。高級脂肪酸塩の含有量は０．０５〜３．０重量部である。０．０５重量部未満の場合は、ｐＨが３より低くなり、３．０重量部を超える場合は、ｐＨが８より高くなる。好ましくは、０．１〜１．０重量部である。 Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. From the viewpoint of availability, a salt with sodium, potassium, ammonia, or triethanolamine is preferable. The content of the higher fatty acid salt is 0.05 to 3.0 parts by weight. When it is less than 0.05 parts by weight, the pH is lower than 3, and when it exceeds 3.0 parts by weight, the pH is higher than 8. Preferably, it is 0.1-1.0 weight part.
本発明の塩化ビニル系共重合体ラテックス中の塩化ビニル−不飽和カルボン酸エステル共重合体の平均粒子径は、０．１４μｍ以下であることが好ましい。平均粒子径が０．１４μｍを超えると長期貯蔵後に沈殿物が発生するおそれがある。平均粒子径は、さらに好ましくは０．１２μｍ以下であり、特に好ましくは０．１０μｍ以下であり、最も好ましくは０．０５〜０．１０μｍである。 The average particle size of the vinyl chloride-unsaturated carboxylic acid ester copolymer in the vinyl chloride copolymer latex of the present invention is preferably 0.14 μm or less. If the average particle size exceeds 0.14 μm, a precipitate may be generated after long-term storage. The average particle diameter is more preferably 0.12 μm or less, particularly preferably 0.10 μm or less, and most preferably 0.05 to 0.10 μm.
本発明の塩化ビニル系共重合体ラテックスは、ｐＨが３〜８である。ｐＨが３〜８を外れると、塩化ビニル−不飽和カルボン酸エステル共重合体の加水分解が進行しラテックスの品質が低下する。 The vinyl chloride copolymer latex of the present invention has a pH of 3-8. If the pH deviates from 3 to 8, hydrolysis of the vinyl chloride-unsaturated carboxylic acid ester copolymer proceeds and the quality of the latex is lowered.
本発明の塩化ビニル系共重合体ラテックスは、連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩以外の乳化剤等を含有してもよい。 The vinyl chloride copolymer latex of the present invention may contain a chain transfer agent, a reducing agent, a buffering agent, an emulsifier other than alkylbenzene sulfonate, and the like.
本発明の塩化ビニル系共重合体ラテックスは、水を分散媒とし、塩化ビニル単量体と不飽和カルボン酸エステル単量体を共重合する際に、塩化ビニル単量体及び不飽和カルボン酸エステル単量体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．０５〜３．０重量部及び高級脂肪酸塩０．０５〜１．０重量部を使用して、乳化重合することによって得られる。スルホン酸塩又は硫酸エステル塩を有する有機化合物が０．０５重量部未満の場合は、重合が不安定となり、得られるラテックスの平均粒子径が０．１４μｍを超えるおそれがある。３．０重量部を超える場合は、あわ立ちが問題となる。高級脂肪酸塩が０．０５重量部未満の場合は、重合中のｐＨが低くなり、1．０重量部を超えて添加しても効果が少ない。スルホン酸塩又は硫酸エステル塩を有する有機化合物は、重合開始前、重合中、重合終了後に適時添加する。高級脂肪酸塩は、重合の開始前、重合中、重合終了後のいずれでいれても問題なく、重合中に高級脂肪酸塩を逐次又は分割添加で添加することも可能である。このなかでも高級脂肪酸塩を逐次又は分割添加で添加することが、少ない量でラテックスのｐＨを３〜８とすることが可能で好ましい。 When the vinyl chloride copolymer latex of the present invention is copolymerized with a vinyl chloride monomer and an unsaturated carboxylic acid ester monomer using water as a dispersion medium, the vinyl chloride monomer and the unsaturated carboxylic acid ester are used. Emulsion polymerization using 0.05 to 3.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 1.0 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the monomer It is obtained by doing. When the organic compound having a sulfonate salt or a sulfate ester salt is less than 0.05 parts by weight, the polymerization becomes unstable, and the average particle size of the resulting latex may exceed 0.14 μm. If it exceeds 3.0 parts by weight, foaming becomes a problem. When the higher fatty acid salt is less than 0.05 parts by weight, the pH during the polymerization is lowered, and even if added over 1.0 part by weight, the effect is small. The organic compound having a sulfonate salt or a sulfate ester salt is added as appropriate before, during or after the polymerization. The higher fatty acid salt may be added before the start of polymerization, during the polymerization, or after the completion of the polymerization, and it is possible to add the higher fatty acid salt sequentially or by divided addition during the polymerization. Among these, it is preferable to add higher fatty acid salts sequentially or in divided additions because the pH of the latex can be adjusted to 3 to 8 in a small amount.
重合開始剤は、例えば、過硫酸カリウム、過硫酸アンモニウム等の水溶性開始剤、２、２’−アゾビスイソブチロニトリル、２、２’−アゾビス−２−メチルブチロニトリル、ラウロイルパーオキサイド、ｔ−ブチルペルオキシピバレート、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネート等の油溶性開始剤等を挙げることができる。 Examples of the polymerization initiator include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2, 2′-azobisisobutyronitrile, 2, 2′-azobis-2-methylbutyronitrile, lauroyl peroxide, Examples thereof include oil-soluble initiators such as t-butyl peroxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate.
重合温度は、特に限定するものではないが、３０〜１００℃が好ましく、４０〜８０℃がさらに好ましい。 The polymerization temperature is not particularly limited, but is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.
重合時間は、特に限定するものではないが、３〜２４時間が好ましい。 The polymerization time is not particularly limited, but is preferably 3 to 24 hours.
塩化ビニル単量体と不飽和カルボン酸エステル単量体の重合率は、全単量体に対して８０〜９７重量％であることが好ましい。 The polymerization rate of the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer is preferably 80 to 97% by weight based on the total monomers.
重合の終了は、容器内の圧力を常圧、さらに減圧し、モノマーを回収することにより行う。重合禁止剤を添加して重合を終了させてもよい。 The polymerization is terminated by recovering the monomer by reducing the pressure in the vessel to normal pressure and further reducing the pressure. A polymerization inhibitor may be added to terminate the polymerization.
必要に応じ、重合終了後のラテックスに、塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対して０．２０〜１０．０重量部を含有するように、アルキルベンゼンスルホン酸スルホン酸塩を追加添加することができる。また、塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対して、０．０５〜３．０重量部を含有するように、高級脂肪酸塩を追加添加することができる。 If necessary, an alkylbenzene sulfonic acid sulfonate is added to the latex after completion of polymerization so as to contain 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. Additional additions can be made. Further, a higher fatty acid salt can be additionally added so as to contain 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer.
本発明の塩化ビニル系共重合体ラテックスを製造する際に、重合の安定化やスケール発生量の低減を目的として連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩以外の乳化剤等を添加することもできる。 When producing the vinyl chloride copolymer latex of the present invention, a chain transfer agent, a reducing agent, a buffering agent, an emulsifier other than alkylbenzene sulfonate is added for the purpose of stabilizing the polymerization and reducing the amount of scale generated. You can also.
本発明の塩化ビニル系共重合体ラテックスは、貯蔵安定性に優れ、本発明の塩化ビニル系共重合体ラテックスの製造方法は、重合中に発生するスケールが少なく、重合後に得られるラテックスのｐＨを３〜８とする方法を提供することができる。 The vinyl chloride copolymer latex of the present invention is excellent in storage stability, and the production method of the vinyl chloride copolymer latex of the present invention has a small scale generated during the polymerization, and the pH of the latex obtained after the polymerization is reduced. A method of 3 to 8 can be provided.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
平均粒子径、固形分濃度、ｐＨ、スケール発生量、ラテックス貯蔵安定性は、以下の通りである。 The average particle diameter, solid content concentration, pH, scale generation amount, and latex storage stability are as follows.
＜平均粒子径＞
塩化ビニル樹脂ラテックスをレーザー透過率が８４〜８６％となるように水を添加して濃度調整を行った測定用試料を、レーザー回折／散乱式粒径測定装置（商品名ＬＡ−９２０、堀場製作所（株）製）を用いて、メジアン径を測定し、平均粒子径とした。
<Average particle size>
A measurement sample prepared by adding water to a vinyl chloride resin latex so that the laser transmittance is 84 to 86% and adjusting the concentration is used as a laser diffraction / scattering particle size measuring device (trade name LA-920, HORIBA, Ltd.). Was used to measure the median diameter, and the average particle diameter was determined.
＜固形分濃度＞
塩化ビニル系共重合体ラテックス５ｇをアルミ皿にとり、重量を測定後、４０℃の乾燥機で２４ｈｒ乾燥して水分を蒸発させた。その後、乾燥物の重量を測定し、重量比から固形分濃度を算出した。
<Concentration of solid content>
5 g of vinyl chloride copolymer latex was placed in an aluminum dish and weighed, and then dried for 24 hours with a dryer at 40 ° C. to evaporate water. Thereafter, the weight of the dried product was measured, and the solid content concentration was calculated from the weight ratio.
＜ｐＨ＞
ｐＨメーター（商品名Ｄ−１２、堀場製作所（株）製）を用いて、濃度調整をせず室温にて塩化ビニル系共重合体ラテックスのｐＨを測定した。
<PH>
Using a pH meter (trade name D-12, manufactured by Horiba, Ltd.), the pH of the vinyl chloride copolymer latex was measured at room temperature without adjusting the concentration.
＜スケール発生量＞
２．５Ｌオートクレーブ壁面及び攪拌翼への樹脂付着物と、得られた塩化ビニル系共重合体ラテックスを６０メッシュの金網でろ過した後の樹脂捕集物を、４０℃の乾燥機で７２ｈｒ乾燥して水分を蒸発させた。その後、乾燥物の重量を測定し、この重量のオートクレーブに仕込んだ混合単量体重量に対する割合を、百分率で表し、スケール発生量とした。
<Scale generation amount>
Resin adhering matter to the wall of 2.5 L autoclave and stirring blade, and the resulting vinyl chloride copolymer latex filtered through a 60-mesh wire mesh were dried for 72 hr in a 40 ° C. dryer. The water was evaporated. Thereafter, the weight of the dried product was measured, and the ratio of this weight to the weight of the mixed monomer charged in the autoclave was expressed as a percentage and used as the scale generation amount.
＜ラテックスの貯蔵安定性＞
塩化ビニル系共重合体ラテックスを水で希釈し、固形分を３０重量％に調整した。そのうち５００ｇを透明なガラス瓶に入れ、室温下２週間静置し、ラテックス中の沈降物発生の有無を目視で確認し、以下の通り評価した。
<Storage stability of latex>
The vinyl chloride copolymer latex was diluted with water to adjust the solid content to 30% by weight. Of these, 500 g was placed in a transparent glass bottle and allowed to stand at room temperature for 2 weeks. The presence or absence of precipitates in the latex was visually confirmed and evaluated as follows.
○：沈降物の発生全くない。 ○: No sediment is generated.
△：僅かに発生が見られた。 Δ: Slight occurrence was observed.
×：多量の沈降物発生が見られた。 X: A large amount of sediment was observed.
実施例１
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４４重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 1
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The amount of latex scale generation was as small as 0.44% by weight, and it was in the range of pH 6.7 and pH 3-8, and the average particle diameter was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例２
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後すぐにブチルアクリレート単量体６０ｇを３００分間かけて連続添加し、重合開始６０分後より５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４７重量％と少なく、ｐＨ６．９とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 2
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 5.4 g of 3 wt% potassium persulfate and 60 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. While maintaining the temperature at 66 ° C., 60 g of butyl acrylate monomer was continuously added over 300 minutes immediately after the start of polymerization, and 105.6 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution was added 60 minutes after the start of polymerization. 0.88 parts by weight) and 38.4 g of a 5% by weight aqueous potassium laurate solution (0.32 parts by weight with respect to the monomer) were continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The scale generation amount of latex was as small as 0.47% by weight, and it was in the range of pH 6.9 and pH 3-8, and the average particle size was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例３
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液８４ｇ（単量体に対して０．７０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後すぐに、５重量％ラウリン酸カリウム水溶液２４ｇ（単量体に対して０．２０重量部）を３００分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム１３８ｇ（単量体に対して１．１５重量部）、５重量％ラウリン酸カリウム水溶液３６ｇ（単量体に対して０．３０重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４９重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 3
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 84 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and immediately after the start of polymerization, 24 g of a 5 wt% potassium laurate aqueous solution (0.20 parts by weight based on the monomer) was continuously added over 300 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 138 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.15 parts by weight based on the monomer) and 36 g of a 5% by weight aqueous potassium laurate solution (0.30 parts by weight based on the monomer). And a vinyl chloride copolymer latex was obtained (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). ). The amount of latex scale generation was as small as 0.49% by weight and was in the range of pH 6.7 and pH 3 to 8. The average particle diameter was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例４
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液８４ｇ（単量体に対して０．７０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後すぐに、ブチルアクリレート単量体６０ｇ、５重量％ラウリン酸カリウム水溶液２４ｇ（単量体に対して０．２０重量部）を３００分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム１３８ｇ（単量体に対して１．１５重量部）、５重量％ラウリン酸カリウム水溶液３６ｇ（単量体に対して０．３０重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４９重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 4
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 5.4 g of 3 wt% potassium persulfate and 84 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution (0.70 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. While maintaining the temperature at 66 ° C., immediately after the start of polymerization, 60 g of a butyl acrylate monomer and 24 g of a 5 wt% aqueous potassium laurate solution (0.20 parts by weight based on the monomer) were continuously added over 300 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 138 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.15 parts by weight based on the monomer) and 36 g of a 5% by weight aqueous potassium laurate solution (0.30 parts by weight based on the monomer). And a vinyl chloride copolymer latex was obtained (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). ). The amount of latex scale generation was as small as 0.49% by weight and was in the range of pH 6.7 and pH 3 to 8. The average particle diameter was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例５
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：０．５６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．７０重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１１μｍであった。
Example 5
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C. and 60 minutes after the start of polymerization, 38.4 g of a 5 wt% aqueous potassium laurate solution (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 21.6 g of potassium laurate having a concentration of 5% by weight (0.18 parts by weight based on the monomer) was additionally added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 0.56 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the copolymer). The scale generation amount of latex was as small as 0.70% by weight, and it was in the range of pH 6.7 and pH 3-8, and the average particle diameter was measured to be 0.11 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例６
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに１５重量％濃度のドデシルベンゼンスルホン酸ナトリウム２６４．８ｇ（単量体に対して６．６２重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：８．８９重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４８重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 6
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 264.8 g of sodium dodecylbenzenesulfonate at a concentration of 15% by weight (6.62 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Part by weight) was added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 8.89 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The amount of latex scale generation was as small as 0.48% by weight and was in the range of pH 6.7 and pH 3 to 8. The average particle size was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例７
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液２２．８ｇ（単量体に対して０．１９重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム６ｇ（単量体に対して０．０５重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．２７重量部）。ラテックスのスケール発生量０．４６重量％と少なく、ｐＨ６．１とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 7
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of the polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 22.8 g of 5% by weight potassium laurate aqueous solution. (0.19 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 6 g of potassium laurate having a concentration of 5% by weight (0.05 parts by weight based on the monomer) ) Was added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0. 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer). 27 parts by weight). The scale generation amount of latex was as small as 0.46% by weight, and it was in the range of pH 6.1 and pH 3 to 8. When the average particle size was measured, it was 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例８
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液６０．０ｇ（単量体に対して０．５０重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム１５６ｇ（単量体に対して１．３０重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：２．００重量部）。ラテックスのスケール発生量０．４１重量％と少なく、ｐＨ７．５とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 8
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of the polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight based on the monomer) and 60.0 g of 5% by weight potassium laurate aqueous solution (0.50 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 156 g of potassium laurate having a concentration of 5% by weight (1.30 parts by weight based on the monomer) ) Was further added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight and potassium laurate: 100 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). 00 parts by weight). The scale generation amount of latex was as small as 0.41% by weight, and it was in the range of pH 7.5 and pH 3 to 8. When the average particle size was measured, it was 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例９
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルメタクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルメタクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．３８重量％と少なく、ｐＨ６．４とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 9
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl methacrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl methacrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The amount of latex scale generation was as low as 0.38% by weight, and it was in the range of pH 6.4 and pH 3-8, and the average particle diameter was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例１０
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルメタクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルメタクリレート単量体を回収した。これに１５重量％濃度のドデシルベンゼンスルホン酸ナトリウム２６４．８ｇ（単量体に対して６．６２重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：８．８９重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．４３重量％と少なく、ｐＨ６．５とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 10
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl methacrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl methacrylate monomer were recovered. To this, 264.8 g of sodium dodecylbenzenesulfonate at a concentration of 15% by weight (6.62 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Part by weight) was added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 8.89 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The scale generation amount of latex was as small as 0.43% by weight, and it was in the range of pH 6.5 and pH 3 to 8. When the average particle size was measured, it was 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例１１
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、エチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびエチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．５４重量％と少なく、ｐＨ６．６とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 11
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of ethyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and ethyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The amount of latex scale generation was as small as 0.54% by weight, and it was in the range of pH 6.6 and pH 3-8, and the average particle size was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
実施例１２
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、アクリル酸２−エチルヘキシル単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびアクリル酸２−エチルヘキシル単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．６１重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。
Example 12
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of 2-ethylhexyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (single The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and 2-ethylhexyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The scale generation amount of latex was as small as 0.61% by weight, and it was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured to be 0.1 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例１
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１３０ｇ（単量体に対して１．０８重量部）と５重量％ラウリン酸カリウム水溶液２．４ｇ（単量体に対して０．０２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム３２ｇ（単量体に対して０．２７重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．０２重量部）。ラテックスのスケール発生量０．５２重量％と少なく、平均粒子径を測定したところ０．１μｍであったが、ｐＨ２．２と低い結果であった。
Comparative Example 1
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 130 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight based on the monomer) and 2.4 g of a 5 wt% potassium laurate aqueous solution ( 0.02 part by weight based on the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 32 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) was added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.02 parts by weight based on 100 parts by weight of the copolymer). The amount of latex generated was as small as 0.52% by weight, and the average particle diameter was measured to be 0.1 μm, but the result was low at pH 2.2.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例２
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１３０ｇ（単量体に対して１．０８重量部）と５重量％ラウリン酸カリウム水溶液１８４ｇ（単量体に対して１．５３重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム３２ｇ（単量体に対して０．２７重量部）、５重量％濃度のラウリン酸カリウム１８４ｇ（単量体に対して１．５３重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：３．４１重量部）。ラテックスのスケール発生量０．８３重量％と少なく、平均粒子径を測定したところ０．１μｍであったが、ｐＨ８．４と高い結果であった。
Comparative Example 2
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 130 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight with respect to the monomer) and 184 g of a 5 wt% potassium laurate aqueous solution (single amount) 1.53 parts by weight based on the body) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 32 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) and 184 g of potassium laurate having a concentration of 5% by weight (1.53 parts by weight based on the monomer) were added. Additional addition was performed to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 3.41 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylate copolymer). Part). The amount of latex scale generation was as small as 0.83% by weight, and the average particle size was measured to be 0.1 μm, but the result was high at pH 8.4.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例３
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２．４ｇ（単量体に対して０．０２重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：０．０２重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．５３重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１５μｍであった。
Comparative Example 3
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 2.4 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (single amount) 0.02 part by weight based on the body) was added, the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 38.4 g of a 5 wt% aqueous potassium laurate solution (0.32 parts by weight based on the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 21.6 g of potassium laurate having a concentration of 5% by weight (0.18 parts by weight based on the monomer) was additionally added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 0.02 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the copolymer). The scale generation amount of latex was as small as 0.53% by weight, and it was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured to be 0.15 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物が多量に発生し（×）、劣った結果であった。 When the storage stability of the latex was evaluated, a large amount of sediment was generated (x), which was an inferior result.
比較例４
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）、２５重量％の重炭酸カリウム３．２ｇ（単量体に対して０．１３重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１３０ｇ（単量体に対して１．０８重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム３２ｇ（単量体に対して０．２７重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、重炭酸カリウム：０．１５重量部）。ｐＨ４．１とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであったが、ラテックスのスケール発生量２．１重量％と多い結果であった。
Comparative Example 4
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution 0.50 part by weight) and 3.2 g of potassium bicarbonate of 25% by weight (0.13 part by weight with respect to the monomer) were added, the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 130 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 32 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) was added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium bicarbonate: 0.15 parts by weight based on 100 parts by weight of the copolymer). It was in the range of pH 4.1 and pH 3 to 8, and the average particle diameter was measured to be 0.1 μm, but the result was as large as 2.1% by weight of latex scale generation.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例５
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）、２５重量％の酢酸ナトリウム３．２ｇ（単量体に対して０．１３重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１３０ｇ（単量体に対して１．０８重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム３２ｇ（単量体に対して０．２７重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、酢酸ナトリウム：０．１５重量部）。ｐＨ３．９とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであったが、ラテックスのスケール発生量２．２重量％と多い結果であった。
Comparative Example 5
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution 0.50 parts by weight) and 3.2 g of sodium acetate of 25% by weight (0.13 parts by weight with respect to the monomer) were added, the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 130 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 32 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) was added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, sodium acetate: 0.15 parts by weight based on 100 parts by weight of the copolymer). It was in the range of pH 3.9 and pH 3-8, and the average particle diameter was measured to be 0.1 μm, but the result was as large as 2.2% by weight of latex scale.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例６
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）、２５重量％のりん酸二水素ナトリウム３．２ｇ（単量体に対して０．１３重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１３０ｇ（単量体に対して１．０８重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム３２ｇ（単量体に対して０．２７重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、りん酸二水素ナトリウム：０．１５重量部）。ｐＨ３．２とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１μｍであったが、ラテックスのスケール発生量１．９重量％と多い結果であった。
Comparative Example 6
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution 0.50 parts by weight) and 25% by weight of sodium dihydrogen phosphate 3.2 g (0.13 parts by weight with respect to the monomer) were charged, the temperature was raised to 66 ° C., and emulsion polymerization was started. . The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 130 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 32 g of sodium dodecylbenzenesulfonate having a concentration of 5% by weight (0.27 parts by weight based on the monomer) was added to obtain a vinyl chloride copolymer latex (vinyl chloride-unsaturated carboxylic acid ester). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, sodium dihydrogen phosphate: 0.15 parts by weight based on 100 parts by weight of the copolymer). It was in the range of pH 3.2 and pH 3-8, and the average particle diameter was measured to be 0.1 μm, but the result was as large as 1.9% by weight of latex scale generation.
ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（○）、良好な結果であった。 When the storage stability of the latex was evaluated, no precipitate was generated (◯), and the result was good.
比較例７
２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２．４ｇ（単量体に対して０．０２重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム２１９．６ｇ（単量体に対して１．８３重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル−不飽和カルボン酸エステル共重合体１００重量部に対するドデシルベンゼンスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのスケール発生量０．５５重量％と少なく、ｐＨ６．７とｐＨ３〜８の範囲に入っており、平均粒子径を測定したところ０．１５μｍであった。
Comparative Example 7
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 2.4 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (single amount) 0.02 part by weight based on the body) was added, the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C. and 60 minutes after the start of polymerization, 38.4 g of a 5 wt% aqueous potassium laurate solution (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 219.6 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.83 parts by weight based on the monomer), and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer). Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). The amount of latex scale generation was as small as 0.55% by weight and was in the range of pH 6.7 and pH 3 to 8. The average particle diameter was measured to be 0.15 μm.
ラテックスの貯蔵安定性を評価したところ、沈降物が発生し(×)、劣った結果であった。 When the storage stability of the latex was evaluated, sediment was generated (x), which was inferior.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163799A (en) * | 2012-01-13 | 2013-08-22 | Tosoh Corp | Vinyl chloride resin latex, and method for production thereof |
| JP2014173002A (en) * | 2013-03-08 | 2014-09-22 | Tosoh Corp | Vinyl chloride polymer latex composition and method for manufacturing the same as well as adhesion adjuvant, adhesive treatment liquid for a rubber composition-fiber composite, and rubber composition-fiber composite |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656915A (en) * | 1992-08-10 | 1994-03-01 | Tosoh Corp | Production of polyvinyl chloride resin for paste processing |
| JP2001040012A (en) * | 1999-07-27 | 2001-02-13 | Tosoh Corp | Vinyl chloride resin for paste, method for producing the same and vinyl chloride resin composition used for paste and comprising the same |
| JP2003301083A (en) * | 2002-04-12 | 2003-10-21 | Tosoh Corp | Vinyl chloride-based resin latex, vinyl chloride-based resin for paste processing and production method thereof, and vinyl chloride-based resin composition for paste processing and use thereof |
| JP2004035850A (en) * | 2002-07-08 | 2004-02-05 | Tosoh Corp | Particle diameter-controlling agent for vinyl chloride based resin latex, method for producing vinyl chloride based resin latex and vinyl chloride based resin for paste processing using the same |
| JP2006096947A (en) * | 2004-09-30 | 2006-04-13 | Tosoh Corp | Vinyl chloride-based resin for paste processing and method for producing the same, vinyl chloride-based resin composition for paste processing and its use |
| JP2010031169A (en) * | 2008-07-30 | 2010-02-12 | Tosoh Corp | Polyol composition with vinyl chloride polymer particle and/or vinyl chloride-unsaturated vinyl copolymer particle being dispersed |
-
2012
- 2012-06-14 JP JP2012134827A patent/JP6047937B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656915A (en) * | 1992-08-10 | 1994-03-01 | Tosoh Corp | Production of polyvinyl chloride resin for paste processing |
| JP2001040012A (en) * | 1999-07-27 | 2001-02-13 | Tosoh Corp | Vinyl chloride resin for paste, method for producing the same and vinyl chloride resin composition used for paste and comprising the same |
| JP2003301083A (en) * | 2002-04-12 | 2003-10-21 | Tosoh Corp | Vinyl chloride-based resin latex, vinyl chloride-based resin for paste processing and production method thereof, and vinyl chloride-based resin composition for paste processing and use thereof |
| JP2004035850A (en) * | 2002-07-08 | 2004-02-05 | Tosoh Corp | Particle diameter-controlling agent for vinyl chloride based resin latex, method for producing vinyl chloride based resin latex and vinyl chloride based resin for paste processing using the same |
| JP2006096947A (en) * | 2004-09-30 | 2006-04-13 | Tosoh Corp | Vinyl chloride-based resin for paste processing and method for producing the same, vinyl chloride-based resin composition for paste processing and its use |
| JP2010031169A (en) * | 2008-07-30 | 2010-02-12 | Tosoh Corp | Polyol composition with vinyl chloride polymer particle and/or vinyl chloride-unsaturated vinyl copolymer particle being dispersed |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163799A (en) * | 2012-01-13 | 2013-08-22 | Tosoh Corp | Vinyl chloride resin latex, and method for production thereof |
| JP2014173002A (en) * | 2013-03-08 | 2014-09-22 | Tosoh Corp | Vinyl chloride polymer latex composition and method for manufacturing the same as well as adhesion adjuvant, adhesive treatment liquid for a rubber composition-fiber composite, and rubber composition-fiber composite |
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| JP6047937B2 (en) | 2016-12-21 |
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