JP2013163799A - Vinyl chloride resin latex, and method for production thereof - Google Patents
Vinyl chloride resin latex, and method for production thereof Download PDFInfo
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Abstract
Description
本発明は、塩化ビニル樹脂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 resin 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。 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.
塩化ビニル樹脂ラテックスは、必要に応じて水酸化ナトリウム、水酸化カリウム、アンモニア水等のアルカリでｐＨを６〜１０に調整するが、ｐＨが低下していく問題がある（非特許文献１）。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緩衝剤を添加することで、ｐＨ低下を抑制することが可能であるが、ラテックスの機械安定性が低下する問題点があった。 The vinyl chloride resin latex is adjusted to pH 6 to 10 with an alkali such as sodium hydroxide, potassium hydroxide, or aqueous ammonia as necessary, but there is a problem that the pH decreases (Non-patent Document 1). By adding a pH buffer such as sodium bicarbonate, sodium carbonate, sodium acetate, monovalent or divalent potassium phosphate, sodium citrate, sodium tartrate, sodium benzoate, it is possible to suppress the pH drop. However, there is a problem that the mechanical stability of the latex is lowered.
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１）、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、機械安定性については十分でなかった。 Moreover, although the method of obtaining latex with an average particle diameter of 0.15 micrometer is described (patent document 1), this latex is used for a seed micro suspension polymerization method, and it is not enough about mechanical stability. It was.
本発明は、上記課題に鑑みてなされたものであり、ラテックスの機械安定性が良好であり、アルカリ中和後のｐＨ低下が抑制された、ｐＨが３．２〜１０であるラテックスおよびそ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, latex having good mechanical stability, pH reduction after alkali neutralization being suppressed, and latex having a pH of 3.2 to 10 and its production A method is provided.
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、塩化ビニルホモポリマー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０．０５〜２．５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を有する有機化合物、高級脂肪酸塩を添加することで、ラテックスのｐＨ低下を防止できることを見出した。すなわち、本発明は、塩化ビニルホモポリマー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０．０５〜２．５重量部を含有し、塩化ビニルホモポリマーの平均粒子径が０．１２μｍ以下であり、ｐＨ３．２〜１０である塩化ビニル樹脂ラテックス、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 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or a sulfate ester salt and 100% by weight of the vinyl chloride homopolymer It has been found that the addition of an organic compound having a sulfonate or a sulfate ester salt or a higher fatty acid salt during the polymerization can prevent a decrease in pH of the latex so that the fatty acid salt is 0.05 to 2.5 parts by weight. . That is, the present invention relates to 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2.5 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride homopolymer. The vinyl chloride homopolymer has a mean particle size of 0.12 μm or less and a pH of 3.2 to 10, 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樹脂ラテックスは、塩化ビニルホモポリマー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０．０５〜２．５重量部を含有するものである。 The vinyl chloride resin latex of the present invention comprises 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2% of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride homopolymer. It contains 5 parts by weight.
塩化ビニルホモポリマーは、塩化ビニル単量体を単独で重合させたものである。 The vinyl chloride homopolymer is obtained by polymerizing a vinyl chloride monomer alone.
塩化ビニル単量体を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 for polymerizing the vinyl chloride monomer 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、ラテックスが不安定となり、１０．０重量部を超える場合は、塩化ビニル樹脂の不純物となる。好ましくは、１．０〜５．０重量部である。 Examples of the compound having a sulfonate include alkylbenzene sulfonates 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. If it is less than 0.20 parts by weight, the latex becomes unstable, and if it exceeds 10.0 parts by weight, it becomes an impurity of the vinyl chloride resin. 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０．０５〜２．５重量部である。０．０５重量部未満の場合は、アルカリ中和後のｐＨ変化が大きく、２．５重量部を超える場合は、ｐＨが１０より高くなる。好ましくは、０．１〜２．３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 2.5 parts by weight. When the amount is less than 0.05 parts by weight, the pH change after alkali neutralization is large. When the amount exceeds 2.5 parts by weight, the pH is higher than 10. Preferably, it is 0.1 to 2.3 parts by weight.
本発明の塩化ビニル樹脂ラテックス中の塩化ビニルホモポリマーの平均粒子径は、０．１２μｍ以下である。平均粒子径が０．１２μｍを超えると機械安定性に劣る。好ましくは０．１１μｍ以下であり、さらに好ましくは０．１０μｍ以下である。 The average particle diameter of the vinyl chloride homopolymer in the vinyl chloride resin latex of the present invention is 0.12 μm or less. When the average particle diameter exceeds 0.12 μm, the mechanical stability is poor. Preferably it is 0.11 micrometer or less, More preferably, it is 0.10 micrometer or less.
本発明の塩化ビニル樹脂ラテックスは、ｐＨ３．２〜１０である。ｐＨ３．２未満であるとアルカリ中和後のｐＨが低下し、１０を超えると高級脂肪酸塩が多量に添加する必要があり塩化ビニル樹脂の不純物となる。好ましくは、ｐＨ４〜９.８である。 The vinyl chloride resin latex of the present invention has a pH of 3.2 to 10. When the pH is less than 3.2, the pH after alkali neutralization decreases, and when it exceeds 10, a higher amount of higher fatty acid salt needs to be added, which becomes an impurity of the vinyl chloride resin. Preferably, the pH is 4 to 9.8.
本発明の塩化ビニル樹脂ラテックスは、連鎖移動剤、還元剤、緩衝剤、乳化剤（スルホン酸塩又は硫酸エステル塩を有する有機化合物、及び高級脂肪酸塩以外のもの）等を含有してもよい。 The vinyl chloride resin latex of the present invention may contain a chain transfer agent, a reducing agent, a buffering agent, an emulsifier (an organic compound having a sulfonate or sulfate ester salt, and a higher fatty acid salt).
本発明の塩化ビニル樹脂ラテックスは、水を分散媒とし、塩化ビニル単量体を重合する際に、塩化ビニル単量体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０．２０〜１０．０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０．２０重量部未満の場合は、重合が不安定となり、１０．０重量部を超える場合は、あわ立ちが問題となる。スルホン酸塩又は硫酸エステル塩を有する有機化合物は、重合開始前、重合中に適時添加する。高級脂肪酸塩は、重合の開始前、重合中のいずれで添加しても問題なく、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。ただし、高級脂肪酸塩を重合の開始前に全量添加すると、平均粒子径が０．１２μｍを超え、得られたラテックスが機械安定性に劣る。高級脂肪酸塩を添加する場合は、得られたラテックスのアルカリ中和後のｐＨ変化をより抑制するために、塩化ビニル単量体１００重量部に対して、高級脂肪酸塩０．０５〜２．５重量部を添加することが好ましい。 The vinyl chloride resin latex of the present invention is an organic compound having a sulfonate or sulfate ester salt with respect to 100 parts by weight of vinyl chloride monomer when water is used as a dispersion medium and the vinyl chloride monomer is polymerized. It is obtained by emulsion polymerization using 20 to 10.0 parts by weight. When the amount of the organic compound having a sulfonate or sulfate ester salt is less than 0.20 parts by weight, the polymerization becomes unstable. The organic compound having a sulfonate salt or a sulfate ester salt is added as needed during the polymerization before the polymerization is started. The higher fatty acid salt may be added either before or during the polymerization, during the polymerization, and the higher fatty acid salt may be added sequentially or in divided portions during the polymerization. However, when the total amount of the higher fatty acid salt is added before the start of polymerization, the average particle diameter exceeds 0.12 μm, and the resulting latex is inferior in mechanical stability. In the case of adding a higher fatty acid salt, in order to further suppress the pH change after alkali neutralization of the obtained latex, the higher fatty acid salt is 0.05 to 2.5 to 100 parts by weight of the vinyl chloride monomer. It is preferable to add parts by weight.
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 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、単量体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 completed by recovering the monomer by reducing the pressure in the container 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、塩化ビニルホモポリマー１００重量部に対して０．２０〜１０．０重量部を含有するように、スルホン酸塩又は硫酸エステル塩を有する有機化合物を追加添加することができる。また、必要に応じ、重合終了後のラテックスに、塩化ビニルホモポリマー１００重量部に対して、０．０５〜２．５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, add an organic compound having a sulfonate or sulfate ester salt to the latex after completion of polymerization so that it contains 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride homopolymer. can do. Further, if necessary, a higher fatty acid salt can be additionally added to the latex after completion of polymerization so as to contain 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the vinyl chloride homopolymer.
本発明の塩化ビニル樹脂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、乳化剤（スルホン酸塩又は硫酸エステル塩を有する有機化合物、及び高級脂肪酸塩以外のもの）等を添加することもできる。 When producing the vinyl chloride resin latex of the present invention, a chain transfer agent, a reducing agent, a buffering agent, an emulsifier (an organic compound having a sulfonate or a sulfate ester salt, for the purpose of stabilizing polymerization and reducing the amount of scale generated) And other than higher fatty acid salts).
本発明では、機械安定性が良好であり、ｐＨ低下が抑制された塩化ビニル樹脂ラテックスを提供することができる。 In the present invention, it is possible to provide a vinyl chloride resin latex having good mechanical stability and suppressed pH decrease.
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、ラテックスの機械安定性、アルカリ中和後のラテックスｐＨ変化の測定は、以下の通りである。 Measurement of average particle diameter, solid content concentration, pH, latex mechanical stability, and latex pH change after alkali neutralization 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＞
塩化ビニル樹脂ラテックス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 resin latex was put on 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樹脂ラテックスの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 resin latex was measured at room temperature without adjusting the concentration.
＜ラテックスの機械安定性＞
ラテックス２５０ｇにクロロホルム１．２５ｇ、消泡剤３ｇを入れ、ホモジナイザー（ＩＫＡ社製ＵＬＴＲＡ−ＴＵＲＲＡＸ Ｔ−５０ Ｔ−５０ ｂａｓｉｃ）で６４００ｒｐｍ撹拌し、ラテックス全体が増粘するまでの時間を測定する。
<Mechanical stability of latex>
1.25 g of chloroform and 3 g of antifoaming agent are added to 250 g of latex, and stirred at 6400 rpm with a homogenizer (ULTRA-TURRAX T-50 T-50 basic manufactured by IKA), and the time until the latex is thickened is measured.
＜アルカリ中和後のラテックスｐＨ変化＞
塩化ビニル樹脂ラテックスを１ｗｔ％の水酸化ナトリウム水溶液でｐＨ１０に調整し、さらに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、４０℃で２ヶ月間静置し、ラテックスのｐＨを測定した。
<Latex pH change after alkali neutralization>
The vinyl chloride resin latex was adjusted to pH 10 with a 1 wt% sodium hydroxide aqueous solution and further diluted with water to adjust the solid content to 30 wt%. Of these, 500 g was placed in a transparent glass bottle and allowed to stand at 40 ° C. for 2 months, and the pH of the latex was measured.
実施例１
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム１５ｇ（単量体に対して０．１重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：０．１１重量部）。ラテックスのｐＨは４．２、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 15 g of 5 wt% potassium laurate (0.1 part by weight based on the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.11 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 4.2, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは８．５とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the change in latex pH after neutralization with alkali was evaluated, the pH was 8.5 and the decrease in pH was slight.
実施例２
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム７５ｇ（単量体に対して０．５重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのｐＨは８．３、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 75 g of 5 wt% potassium laurate (0.5 parts by weight based on the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 8.3, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは９．０とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the latex pH change after alkali neutralization was evaluated, the pH was 9.0 and the decrease in pH was slight.
実施例３
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、１５重量％ラウリン酸カリウム１００ｇ（単量体に対して２．０重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：２．２２重量部）。ラテックスのｐＨは９．６、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 100 g of 15 wt% potassium laurate (2.0 parts by weight with respect to the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 2.22 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 9.6, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは９．２とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the change in latex pH after neutralization with alkali was evaluated, the pH was 9.2 and the decrease in pH was slight.
実施例４
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ステアリン酸カリウム７５ｇ（単量体に対して０．５重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ステアリン酸カリウム：０．５６重量部）。ラテックスのｐＨは８．３、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 75 g of 5 wt% potassium stearate (0.5 parts by weight based on the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium stearate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 8.3, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは９．０とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the latex pH change after alkali neutralization was evaluated, the pH was 9.0 and the decrease in pH was slight.
実施例５
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム７５ｇ（単量体に対して０．５重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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ｐＨは８．２、平均粒子径を測定したところ０．１μｍであった。
Example 5
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 75 g of 5 wt% potassium laurate (0.5 parts by weight based on the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 0.56 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 8.2, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは８．９とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the latex pH change after alkali neutralization was evaluated, the pH was 8.9 and the decrease in pH was slight.
実施例６
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム７５ｇ（単量体に対して０．５重量部）、１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１２５ｇ（単量体に対して２．５０重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：５．３３重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのｐＨは８．４、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 75 g of 5 wt% potassium laurate (0.5 wt part relative to the monomer), 15 A 125% by weight aqueous sodium dodecylbenzenesulfonate solution (2.50 parts by weight) was added to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride homopolymer: 5 .33 parts by weight, potassium laurate: 0.56 parts by weight). The pH of the latex was 8.4, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは９．１とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the latex pH change after alkali neutralization was evaluated, the pH was 9.1 and the decrease in pH was slight.
実施例７
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム７．５ｇ（単量体に対して０．０５重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：０．０６重量部）。ラテックスのｐＨは３．３、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 7.5 g of 5% by weight potassium laurate (0.05 parts by weight based on the monomer) Was added to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.06 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 3.3, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。１ｗｔ％水酸化ナトリウムでラテックスのｐＨを１０に調整し、ｐＨ変化を測定したところ、ｐＨは７．８とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the pH of the latex was adjusted to 10 with 1 wt% sodium hydroxide and the change in pH was measured, the pH was 7.8, which was a slight decrease in pH.
実施例８
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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１６２ｇ（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５７ｇ（単量体に対して０．３８重量部）を２９０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０．７ＭＰａまで低下した後、未反応の塩化ビニ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４０．５ｇ（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１３．５ｇ（単量体に対して０．０９重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：０．５３重量部）。ラテックスのｐＨは８．４、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, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 162 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.08 parts by weight based on the monomer) and 57 g of a 5 wt% potassium laurate aqueous solution (single amount) 0.38 parts by weight based on the body) was continuously added over 290 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered. To this, 40.5 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.27 parts by weight based on the monomer) and 13.5 g of potassium laurate at a concentration of 5% by weight (0.09% relative to the monomer) Part by weight) was added to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.53 parts by weight with respect to 100 parts by weight of vinyl chloride homopolymer). The pH of the latex was 8.4, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。１ｗｔ％水酸化ナトリウムでラテックスのｐＨを１０に調整し、ｐＨ変化を測定したところ、ｐＨは７．７とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the pH of the latex was adjusted to 10 with 1 wt% sodium hydroxide and the change in pH was measured, the pH was 7.7, showing a slight decrease in pH.
比較例１
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部）。ラテックスのｐＨは３．０、平均粒子径を測定したところ０．１μｍであった。
Comparative Example 1
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride homopolymer: 2.56 parts by weight). The pH of the latex was 3.0, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは４．１と大幅にｐＨが低下した。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the change in latex pH after alkali neutralization was evaluated, the pH was drastically reduced to 4.1.
比較例２
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム３ｇ（単量体に対して０．０２重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：０．０２重量部）。ラテックスのｐＨは３．１、平均粒子径を測定したところ０．１μｍであった。
Comparative Example 2
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, the unreacted vinyl chloride monomer was recovered, and 3 g of 5 wt% potassium laurate (0.02 parts by weight with respect to the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 0.02 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 3.1, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、２０分以上であり良好な結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは４．７と大幅にｐＨが低下した。 When the mechanical stability of the latex was evaluated, it was 20 minutes or more, which was a good result. When the latex pH change after alkali neutralization was evaluated, the pH was drastically lowered to 4.7.
比較例３
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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１５ｇ（単量体に対して０．１０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。６６℃におけるオートクレーブ内の圧力が０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、５重量％ラウリン酸カリウム７５ｇ（単量体に対して０．５０重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：０．１１重量部、ラウリン酸カリウム：０．５６重量部）。ラテックスのｐＨは８．２、平均粒子径を測定したところ０．１４μｍであった。
Comparative Example 3
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 15 g of 5% by weight aqueous sodium dodecylbenzenesulfonate (0.10 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered and 75 g of 5 wt% potassium laurate (0.50 parts by weight based on the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 0.11 parts by weight, potassium laurate: 0.56 parts by weight with respect to 100 parts by weight of the vinyl chloride homopolymer). The latex was found to have a pH of 8.2 and an average particle diameter of 0.14 μm.
ラテックスの機械安定性を評価したところ、３分と非常に劣った結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは８．９と低下は僅かであった。 When the mechanical stability of the latex was evaluated, the result was very inferior at 3 minutes. When the pH change of the latex after neutralization with alkali was evaluated, the pH was 8.9 and the decrease was slight.
比較例４
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、１０重量％炭酸カリウム７．５ｇ（単量体に対して０．１０重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、炭酸カリウム：０．１１重量部）。ラテックスのｐＨは６．２、平均粒子径を測定したところ０．１μｍであった。
Comparative Example 4
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 7.5 g of 10 wt% potassium carbonate (0.10 parts by weight with respect to the monomer) was recovered. Additional addition was performed to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium carbonate: 0.11 parts by weight with respect to 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 6.2, and the average particle size was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ、１０分と劣った結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは９．０とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was inferior to 10 minutes. When the latex pH change after alkali neutralization was evaluated, the pH was 9.0 and the decrease in pH was slight.
比較例５
２．５Ｌオートクレーブ中に脱イオン水８３０ｇ、塩化ビニル単量体７５０ｇ、３重量％過硫酸カリウム６．８ｇ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７５ｇ（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２７０ｇ（単量体に対して１．８０重量部）を３６０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０．７ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収し、１５重量％ラウリン酸カリウム１５０ｇ（単量体に対して３．０重量部）を追加添加し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：２．５６重量部、ラウリン酸カリウム：３．３３重量部）。ラテックスのｐＨは１０．５とｐＨ１０を超えていた。平均粒子径を測定したところ０．１μｍであった。
Comparative Example 5
In a 2.5 L autoclave, 830 g of deionized water, 750 g of vinyl chloride monomer, 6.8 g of 3% by weight potassium persulfate and 75 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution (0.50 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 270 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.80 parts by weight with respect to the monomer) was continuously added over 360 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer was recovered, and 150 g of 15 wt% potassium laurate (3.0 parts by weight with respect to the monomer) was added. By addition, a vinyl chloride resin latex was obtained (sodium dodecylbenzenesulfonate: 2.56 parts by weight, potassium laurate: 3.33 parts by weight based on 100 parts by weight of the vinyl chloride homopolymer). The pH of the latex was 10.5 and above pH 10. The average particle diameter was measured and found to be 0.1 μm.
ラテックスの機械安定性を評価したところ２０分以上と良好な結果であったが、上記したように、得られたラテックスのｐＨが１０を超えていた。 When the mechanical stability of the latex was evaluated, the result was as good as 20 minutes or longer. However, as described above, the pH of the obtained latex exceeded 10.
比較例６
１ｍ3オートクレーブ中に脱イオン水４００ｋｇ、塩化ビニル単量体３５０ｋｇ、１６重量％ラウリン酸カリウム水溶液２ｋｇ（単量体に対して０．０９重量部）及び１６重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５ｋｇ（単量体に対して０．２３重量部）を仕込み、温度を５４℃に上げて重合反応を開始した。そして、圧力が低下した後、未反応塩化ビニル単量体を回収し、塩化ビニル樹脂ラテックスを得た（塩化ビニルホモポリマー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：０．２５重量部、ラウリン酸カリウム：０．１０重量部）。ラテックスのｐＨは４．１、平均粒子径を測定したところ０．１５μｍであった。
Comparative Example 6
In a 1 m 3 autoclave, 400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of 16 wt% potassium laurate aqueous solution (0.09 parts by weight with respect to the monomer) and 5 kg of 16 wt% sodium dodecylbenzenesulfonate aqueous solution ( The polymerization reaction was started by raising the temperature to 54 ° C. After the pressure dropped, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex (sodium dodecylbenzenesulfonate: 0.25 parts by weight, potassium laurate with respect to 100 parts by weight of vinyl chloride homopolymer) : 0.10 parts by weight). The pH of the latex was 4.1, and the average particle diameter was measured and found to be 0.15 μm.
ラテックスの機械安定性を評価したところ、７分と劣った結果であった。アルカリ中和後のラテックスｐＨ変化を評価したところ、ｐＨは８．３とｐＨの低下はわずかであった。 When the mechanical stability of the latex was evaluated, it was inferior to 7 minutes. When the latex pH change after alkali neutralization was evaluated, the pH was 8.3, and the decrease in pH was slight.
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