JP6848227B2 - Vinyl chloride resin for paste processing and its manufacturing method - Google Patents
Vinyl chloride resin for paste processing and its manufacturing method Download PDFInfo
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Description
本発明はペースト加工用塩化ビニル系樹脂及びその製造方法に関するものであり、さらに詳細には、ペースト加工用塩化ビニル系樹脂を可塑剤に分散させて調製したペースト加工用塩化ビニル系樹脂ゾルの高せん断粘度が高くスプレー加工性が良好で、粘度の経時変化が少なく、低温での機械的強度に優れ、コート剤、特に自動車アンダーボディコート用、自動車シーラント用として優れた特性を有するペースト加工用塩化ビニル系樹脂及びその製造方法に関するものである。 The present invention relates to a vinyl chloride resin for paste processing and a method for producing the same. More specifically, the height of the vinyl chloride resin sol for paste processing prepared by dispersing the vinyl chloride resin for paste processing in a plasticizer. Chloride for paste processing, which has high shear viscosity, good spray workability, little change in viscosity over time, excellent mechanical strength at low temperatures, and excellent properties for coating agents, especially for automobile underbody coats and automobile sealants. It relates to a vinyl resin and a method for producing the same.
ペースト加工用塩化ビニル系樹脂（以下、ペースト塩ビと略記する場合もある。）は、一般に可塑剤、充填剤、安定剤又はその他の配合剤などと共に混練することにより、ペースト加工用塩化ビニル系樹脂ゾル（以下、ペースト塩ビゾルと略記する場合もある。）を調製し、該ペースト塩ビゾルを使用し種々の成形加工法により壁紙、タイルカーペット、手袋などの様々な成形加工品に用いられている。また、加工温度の低い用途用として、比較的低温でも機械的強度が得られるゲル化溶融性に優れた特性を持つペースト塩ビとして、塩化ビニルに酢酸ビニルを共重合させた塩化ビニル／酢酸ビニル共重合樹脂が知られている。せん断速度の高い加工方法であるコーティングやスプレー加工においては、高せん断速度領域での粘度レベルが適切な範囲であることが求められる。 The vinyl chloride resin for paste processing (hereinafter, may be abbreviated as PVC) is generally a vinyl chloride resin for paste processing by kneading with a plasticizer, a filler, a stabilizer, or other compounding agent. A sol (hereinafter, may be abbreviated as paste PVC sol) is prepared and used for various molded products such as wallpaper, tile carpet, gloves, etc. by various molding processing methods using the paste PVC sol. .. In addition, for applications with low processing temperature, vinyl chloride / vinyl acetate, which is a copolymer of vinyl acetate with vinyl acetate, is used as a paste vinyl chloride that can obtain mechanical strength even at a relatively low temperature and has excellent gelling meltability. Polymerized resins are known. In coating and spray processing, which are processing methods with a high shear rate, the viscosity level in the high shear rate region is required to be in an appropriate range.
そして、高せん断粘度領域の粘度を変える方法として、配合中の液状成分である可塑剤量、希釈剤量を調整する方法が知られている（例えば非特許文献１参照）。 Then, as a method of changing the viscosity of the high shear viscosity region, a method of adjusting the amount of the plasticizer and the amount of the diluent which are liquid components in the compounding is known (see, for example, Non-Patent Document 1).
また、高せん断粘度領域の粘度を調整する別の方法として、粒子径分布において複数の極大値を有する塩化ビニル系重合体を用いることが提案されている（例えば特許文献１参照）。 Further, as another method for adjusting the viscosity in the high shear viscosity region, it has been proposed to use a vinyl chloride polymer having a plurality of maximum values in the particle size distribution (see, for example, Patent Document 1).
しかし、非特許文献１に記載されているような配合中の可塑剤量を変えて高せん断粘度を調整する場合、最終製品に含まれる可塑剤量の違いから柔軟性や機械強度が変化するという課題が発生する。また、配合中の希釈剤量を変えて高せん断粘度を調整する場合、柔軟性や機械強度は大きく変わらないものの、加工時に希釈剤が揮発してしまい作業環境が悪化するという新たな課題が発生する。 However, when the high shear viscosity is adjusted by changing the amount of plasticizer in the formulation as described in Non-Patent Document 1, the flexibility and mechanical strength change due to the difference in the amount of plasticizer contained in the final product. Challenges arise. In addition, when adjusting the high shear viscosity by changing the amount of diluent in the formulation, although the flexibility and mechanical strength do not change significantly, a new problem arises that the diluent volatilizes during processing and the working environment deteriorates. To do.
また、特許文献１に提案の方法で高せん断粘度を調整する場合、０．４μｍ以下の小さな粒子を多量に含むため、粘度の経時変化が大きくなるという課題が発生する。 Further, when the high shear viscosity is adjusted by the method proposed in Patent Document 1, since a large amount of small particles of 0.4 μm or less are contained, there arises a problem that the viscosity changes with time.
そこで、本発明は、ペースト加工用塩化ビニル系樹脂を可塑剤に分散させて調製した際のペースト塩ビゾルの高せん断粘度が高くスプレー加工性が良好で、粘度の経時変化が極めて少なく、低温加工時の機械的強度にも優れ、コート剤、特に自動車アンダーボディコート剤、自動車用シーラント剤として優れた特性を有するペースト塩ビゾルとすることが可能となるペースト塩ビ及びその製造方法を提供することにある。 Therefore, according to the present invention, when a vinyl chloride resin for paste processing is dispersed in a plasticizer and prepared, the paste PVC sol has a high high shear viscosity and good spray processability, the viscosity does not change with time, and the paste is processed at a low temperature. To provide a paste PVC having excellent mechanical strength at the time and capable of producing a paste PVC having excellent properties as a coating agent, particularly an automobile underbody coating agent and an automobile sealant, and a method for producing the same. is there.
本発明者は、上記の課題について鋭意検討を重ねた結果、特定の重合度と特定量の酢酸ビニル残基単位を有する塩化ビニル−酢酸ビニル共重合体、特定の化合物、アルキル硫酸エステル塩及びポリビニルアルコールを含有するペースト加工用塩化ビニル系樹脂が、ペースト塩ビゾルの高せん断粘度に優れ、機械的強度に優れ、粘度の経時変化が極めて少ないものとなることを見出し、本発明を完成させるに至った。 As a result of diligent studies on the above-mentioned problems, the present inventor has made a vinyl chloride-vinyl acetate residue unit having a specific degree of polymerization and a specific amount of vinyl acetate residue units, a specific compound, an alkyl sulfate ester salt and polyvinyl acetate. We have found that an alcohol-containing vinyl chloride resin for paste processing has excellent high shear viscosity of paste vinyl chloride sol, excellent mechanical strength, and extremely little change in viscosity with time, leading to the completion of the present invention. It was.
即ち、本発明は、平均重合度が１５００を越えて２５００以下、酢酸ビニル残基単位を６〜１０重量％有する塩化ビニル−酢酸ビニル共重合体、下記一般式（Ｉ）で表される化合物１００〜３０００ｐｐｍ、アルキル硫酸エステル塩２０００〜１００００ｐｐｍ及びポリビニルアルコール５００〜２００００ｐｐｍを含有することを特徴とするペースト加工用塩化ビニル系樹脂に関するものである。 That is, the present invention is a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of more than 1500 and 2500 or less and a vinyl acetate residue unit of 6 to 10% by weight, and the compound 100 represented by the following general formula (I). The present invention relates to a vinyl chloride resin for paste processing, which comprises ~ 3000 ppm, an alkyl sulfate ester salt 2000 to 10000 ppm, and polyvinyl alcohol 500 to 20000 ppm.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明のペースト加工用塩化ビニル系樹脂は、平均重合度が１５００を越えて２５００以下、酢酸ビニル残基単位を６〜１０重量％有する塩化ビニル−酢酸ビニル共重合体、上記一般式（Ｉ）で表される化合物１００〜３０００ｐｐｍ、アルキル硫酸エステル塩２０００〜１００００ｐｐｍ及びポリビニルアルコール５００〜２００００ｐｐｍを含有するものである。 The vinyl chloride resin for paste processing of the present invention is a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of more than 1500 and 2500 or less and a vinyl acetate residue unit of 6 to 10% by weight. It contains a compound represented by (1) (100 to 3000 ppm), an alkyl sulfate ester salt (2000 to 10000 ppm), and polyvinyl alcohol (500 to 20000 ppm).
該塩化ビニル−酢酸ビニル共重合体としては、平均重合度が１５００を越えて２５００以下であり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、平均重合度１６００〜２４００であることが好ましい。ここで、平均重合度が、１５００以下である場合、低温加工での機械的強度に劣るものとなる。一方、平均重合度が２５００を越える場合、ペースト塩ビゾルとした際の粘度の経時変化が大きなものとなる。なお、本発明における平均重合度は、例えばＪＩＳ−Ｋ６７２１に準拠した方法により求めることができる。 The vinyl chloride-vinyl acetate copolymer has an average degree of polymerization of more than 1500 and 2500 or less, and is particularly excellent for an automobile underbody coat and an automobile sealant. Therefore, the average degree of polymerization is 1600 to 1600. It is preferably 2400. Here, when the average degree of polymerization is 1500 or less, the mechanical strength in low-temperature processing is inferior. On the other hand, when the average degree of polymerization exceeds 2500, the change in viscosity with time when the paste PVC sol is used becomes large. The average degree of polymerization in the present invention can be determined by, for example, a method based on JIS-K6721.
また、該塩化ビニル−酢酸ビニル共重合体は、酢酸ビニル残基単位を６〜１０重量％共重合したものであり、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから６〜８重量％であることが好ましい。ここで、酢酸ビニル残基単位含有量が６重量％未満のものである場合、ペースト塩ビを低温加工に供した際の成形品は機械的強度の低いものとなる。一方、酢酸ビニル残基単位含有量が１０重量％を超えるものである場合、ゾルとした際の粘度の経時変化が大きいものとなる。 Further, the vinyl chloride-vinyl acetate copolymer is obtained by copolymerizing 6 to 10% by weight of vinyl acetate residue units, and in particular, the mechanical strength in low-temperature processing and the aging of viscosity when made into a paste vinyl chloride bisol. It is preferably 6 to 8% by weight because both changes are extremely excellent, and particularly excellent for an automobile underbody coat and an automobile sealant. Here, when the vinyl acetate residue unit content is less than 6% by weight, the molded product when the paste PVC is subjected to low-temperature processing has low mechanical strength. On the other hand, when the vinyl acetate residue unit content exceeds 10% by weight, the viscosity of the sol changes significantly with time.
本発明のペースト加工用塩化ビニル系樹脂は、上記一般式（Ｉ）で示される化合物を１００〜３０００ｐｐｍで含有するものである。なお、該化合物の含有量が１００ｐｐｍ未満である場合、ペースト塩ビゾルを調製した際の粘度の経時変化が大きいものとなる。一方、３０００ｐｐｍを超える場合、製造時の塩化ビニル−酢酸ビニル共重合体の重合反応が遅くなり、実質上本発明のペースト加工用塩化ビニル系樹脂を得ることが困難となる。 The vinyl chloride resin for paste processing of the present invention contains the compound represented by the above general formula (I) at 100 to 3000 ppm. When the content of the compound is less than 100 ppm, the change in viscosity with time when the paste PVC sol is prepared becomes large. On the other hand, if it exceeds 3000 ppm, the polymerization reaction of the vinyl chloride-vinyl acetate copolymer at the time of production becomes slow, and it becomes practically difficult to obtain the vinyl chloride-based resin for paste processing of the present invention.
ここで、Ｒ１は炭素数６〜１８のアルキル基、アルケニル基又はアラルキル基を示し、Ｒ２は水素又は炭素数６〜１８のアルキル基、アルケニル基若しくはアラルキル基を示し、Ｒ３は水素又はプロペニル基を示し、Ａは炭素数２〜４のアルキレン基を示し、ｎは１〜２００の整数を示し、Ｍはアルカリ金属、アンモニウムイオン又はアルカノールアミン残基を示し、中でも、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、Ｒ１の炭素数は７〜１１、Ｒ２及びＲ３は水素、Ａは炭素数２〜３のアルキレン基、ｎは１〜４０であることが好ましい。そして、該一般式（Ｉ）で示される化合物としては、例えばノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩、ノニルプロペニルフェノールエチレンオキシド２０モル付加体硫酸エステルアンモニウム塩、オクチルジプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩、オクチルジプロペニルフェノールエチレンオキシド１００モル付加体硫酸エステルアンモニウム塩、ドデシルプロペニルフェノールエチレンオキシド２０モルランダム付加体硫酸エステルナトリウム塩、ドデシルプロペニルフェノールプロピレンオキシド１０モルランダム付加体硫酸エステルナトリウム塩、ドデシルプロペニルフェノールブチレンオキシド４モルブロック付加体硫酸エステルナトリウム塩、ドデシルプロペニルフェノールエチレンオキシド３０モルブロック付加体硫酸エステルナトリウム塩等が挙げられ、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩、ノニルプロペニルフェノールエチレンオキシド２０モル付加体硫酸エステルアンモニウム塩であることが好ましい。 Here, R 1 represents an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R 2 represents hydrogen or an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R 3 represents hydrogen or an aralkyl group. It represents a propenyl group, A represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 200, M represents an alkali metal, ammonium ion or alkanolamine residue, among others, especially in low temperature processing. The mechanical strength and the change in viscosity over time when made into a paste vinyl chloride are both extremely excellent, and in particular, they are excellent for automobile underbody coats and automobile sealants. Therefore, the number of carbon atoms in R 1 is 7. It is preferable that ~ 11, R 2 and R 3 are hydrogen, A is an alkylene group having 2 to 3 carbon atoms, and n is 1 to 40. Examples of the compound represented by the general formula (I) include addition of 10 mol of nonylpropenylphenol ethylene oxide, 10 mol of nonylpropenylphenol ethylene oxide, 20 mol of nonylpropenylphenol ethylene oxide, and 10 mol of octyldipropenylphenolethylene oxide. Body Sulfate Ammonium Salt, Octyldipropenylphenol Ethylene Oxide 100 Mol Random Additive Sulfate Ammonium Salt, Dodecylpropenylphenol Ethylene Oxide 20 Mol Random Additive Sulfate Sodium Salt, Dodecylpropenylphenol Propoxide 10 Mol Random Additive Sulfate Sodium Salt, Dodecyl Examples thereof include propenylphenol butylene oxide 4 molblock adduct sulfate sodium salt, dodecylpropenylphenol ethylene oxide 30 molblock adduct sodium sulfate, etc., which are particularly excellent for automobile underbody coats and automobile sealants. Therefore, it is preferable that it is a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ammonium salt and a nonylpropenylphenol ethylene oxide 20 mol adduct sulfate ammonium salt.
該一般式（Ｉ）で示される化合物は、ペースト加工用塩化ビニル系樹脂を製造する際には、界面活性剤としても作用するものであるが、本発明のペースト加工用塩化ビニル系樹脂においては、ペースト塩ビゾルとした際の保存安定性、粘度経時変化の抑制にもその効果を発現するものであり、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、５００〜２０００ｐｐｍを含有するものであることが好ましい。 The compound represented by the general formula (I) also acts as a surfactant when producing a vinyl chloride resin for paste processing, but in the vinyl chloride resin for paste processing of the present invention. , The effect is also exhibited in the storage stability when made into a paste PVC bisole and the suppression of the change in viscosity with time. In particular, the mechanical strength in low-temperature processing and the change in viscosity with time when made into a paste PVC bisol are both exhibited. It is extremely excellent, and particularly excellent for automobile underbody coats and automobile sealants. Therefore, it is preferably contained in an amount of 500 to 2000 ppm.
本発明のペースト加工用塩化ビニル系樹脂は、アルキル硫酸エステル塩を２０００〜１００００ｐｐｍ含有するものであり、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、２０００〜８０００ｐｐｍであることが好ましい。また、炭素数が１０〜１４のアルキル硫酸エステル塩であることが好ましい。そして、アルキル硫酸エステル塩としては、例えばラウリル硫酸ナトリウム、ミリスチル硫酸ナトリウム、オレイル硫酸ナトリウム、ラウリル硫酸アンモニウムなどのアルキル硫酸エステル塩類等が挙げられる。ここで、アルキル硫酸エステル塩の含有量が２０００ｐｐｍ未満である場合、ペースト加工用塩化ビニル系重合体とする際の重合が不安定となり、安定して本発明のペースト加工用塩化ビニル系樹脂を得ることが困難となる。一方、１００００ｐｐｍを超える場合、ペースト塩ビゾルとした際の粘度の経時変化が大きいものとなる。 The vinyl chloride resin for paste processing of the present invention contains 2000 to 10000 ppm of an alkyl sulfate ester salt, and is extremely excellent in both mechanical strength especially in low temperature processing and change in viscosity with time when it is made into a paste vinyl chloride resin. It is preferably 2000 to 8000 ppm because it is particularly excellent for an automobile underbody coat and an automobile sealant. Further, it is preferably an alkyl sulfate ester salt having 10 to 14 carbon atoms. Examples of the alkyl sulfate ester salt include alkyl sulfate ester salts such as sodium lauryl sulfate, sodium myristyl sulfate, sodium oleyl sulfate, and ammonium lauryl sulfate. Here, when the content of the alkyl sulfate ester salt is less than 2000 ppm, the polymerization becomes unstable when the vinyl chloride polymer for paste processing is used, and the vinyl chloride resin for paste processing of the present invention is stably obtained. Becomes difficult. On the other hand, when it exceeds 10000 ppm, the change in viscosity with time when the paste PVC sol is used becomes large.
本発明のペースト加工用塩化ビニル系樹脂は、ポリビニルアルコールを５００〜２００００ｐｐｍ含有するものであり、特に高せん断粘度が高くスプレー加工性が極めて優れたものとなり、特に自動車アンダーボディコート剤、自動車用シーラント剤として優れたものとなることから１０００〜１００００ｐｐｍであることが好ましい。ここで、ポリビニルアルコール含有量が５００ｐｐｍ未満のものである場合、ペースト塩ビゾルとした際の高せん断粘度が低く、スプレーパターンが広がりすぎて加工性が劣る。一方、ポリビニルアルコール含有量が２００００ｐｐｍを超える場合、高せん断粘度が高く、スプレーパターンが狭すぎて加工性が劣る。そして、該ポリビニルアルコールとしては、重合度２００〜３０００、ケン化度５０〜９９モル％のポリビニルアルコールであることが好ましい。 The vinyl chloride resin for paste processing of the present invention contains polyvinyl alcohol at 500 to 20000 ppm, and has a particularly high shear viscosity and extremely excellent spray processability. In particular, an automobile underbody coating agent and a sealant for automobiles. It is preferably 1000 to 10000 ppm because it is an excellent agent. Here, when the polyvinyl alcohol content is less than 500 ppm, the high shear viscosity when the paste vinyl chloride is used is low, the spray pattern spreads too much, and the processability is poor. On the other hand, when the polyvinyl alcohol content exceeds 20000 ppm, the high shear viscosity is high and the spray pattern is too narrow, resulting in poor processability. The polyvinyl alcohol is preferably a polyvinyl alcohol having a degree of polymerization of 200 to 3000 and a degree of saponification of 50 to 99 mol%.
本発明のペースト塩ビは、特にペースト塩ビゾルとした際の高せん断粘度が高くスプレー加工性が良好で、特に自動車アンダーボディコート剤、自動車用シーラント剤として優れたものとなることから、高せん断粘度７００〜１２００ｍＰａ・ｓとなるものであることが好ましい。その際の高せん断粘度の測定方法としては、例えば、ペースト塩ビ１００重量部、フタル酸ジイソノニル１００重量部、脂肪酸塩表面処理炭酸カルシウム７０重量部、希釈剤１５重量部を配合し、ペースト塩ビゾルを調製し、２３℃、２４時間保管後にキャピラリー粘度計を用いて、せん断速度１０５００ｓｅｃ−１での粘度を測定する方法を挙げることができる。その際のキャピラリー粘度計は所定のせん断速度下での粘度測定が可能であればいかなるものでもよい。なお、脂肪酸塩表面処理炭酸カルシウムとしては、例えば脂肪酸ナトリウム塩又は脂肪酸カリウム塩を含む表面処理剤等で表面処理した炭酸カルシウムを挙げることができ、市販品としては、例えば（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ（白石カルシウム株式会社製）を挙げることができる。また、希釈剤としては、例えばノルマルパラフィン系炭化水素系溶剤、イソパラフィン系炭化水素溶剤、ナフテン系炭化水素溶剤、芳香族系炭化水素溶剤等を挙げることができ、市販品としては、例えば（商品名）Ｅｘｘｓｏｌ Ｄ４０(東燃ゼネラル石油株式会社製）を挙げることができる。 The paste vinyl chloride of the present invention has a high high shear viscosity especially when it is made into a paste vinyl chloride sol and has good spray workability, and is particularly excellent as an automobile underbody coating agent and an automobile sealant. Therefore, it has a high shear viscosity. It is preferably 700 to 1200 mPa · s. As a method for measuring the high shear viscosity at that time, for example, 100 parts by weight of paste vinyl chloride, 100 parts by weight of diisononyl phthalate, 70 parts by weight of fatty acid salt surface-treated calcium carbonate, and 15 parts by weight of a diluent are blended to prepare a paste PVC bisole. A method of measuring the viscosity at a shear rate of 10500 sec -1 using a capillary viscometer after preparation and storage at 23 ° C. for 24 hours can be mentioned. At that time, the capillary viscometer may be any viscometer as long as it can measure the viscosity under a predetermined shear rate. Examples of the fatty acid salt surface-treated calcium carbonate include calcium carbonate surface-treated with a surface treatment agent containing a fatty acid sodium salt or a fatty acid potassium salt, and examples of a commercially available product include (trade name) Viscolite-OS. (Manufactured by Shiraishi Calcium Co., Ltd.) can be mentioned. Examples of the diluent include a normal paraffin-based hydrocarbon solvent, an isoparaffin-based hydrocarbon solvent, a naphthen-based hydrocarbon solvent, an aromatic hydrocarbon solvent, and the like, and examples of commercially available products include (trade name). ) Exxsol D40 (manufactured by Tonen General Petroleum Co., Ltd.) can be mentioned.
本発明のペースト加工用塩化ビニル系樹脂は、特にペースト塩ビゾルとした際の粘度の経時変化が極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、増粘率が１００％未満となるペースト加工用塩化ビニル系樹脂であることが好ましい。その際の増粘率の測定方法としては、例えば、ペースト加工用塩化ビニル系樹脂１００重量部に対し、フタル酸ジイソノニル１００重量部、該脂肪酸塩表面処理炭酸カルシウム７０重量部、該希釈剤１５重量部を配合し、ペースト塩ビゾルを調製し、２３℃、２時間保管後の粘度（Ａ）とその後、４０℃、７日間保管後の粘度（Ｂ）をＢ８Ｈ型回転粘度計を用い回転数２０ｒｐｍの条件にて測定し、下記式により増粘率を求めることができる。
増粘率（％）＝１００×（粘度（Ｂ）−粘度（Ａ））／粘度（Ａ）
また、本発明のペースト加工用塩化ビニル系樹脂は、特に低温加工での機械的強度に優れるものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、引張強度が９．０ＭＰａ以上となるペースト加工用塩化ビニル系樹脂であることが好ましい。その際の引張強度の測定方法としては、例えば、ペースト加工用塩化ビニル系樹脂１００重量部に対し、フタル酸ジイソノニル６０重量部、安定剤２重量部を配合し、ペースト塩ビゾルを調製し、０．５ｍｍ厚に塗布したシートから、ＪＩＳ３号ダンベル試験片を用い、２３℃、２００ｍｍ／ｍｉｎの条件で測定し、引張強度を求めることができる。なお、安定剤としては、塩化ビニル用安定剤を挙げることができ、例えば鉛、バリウム、亜鉛、カルシウム、銅などの金属石鹸、それらの混合物を挙げることができる。そして、市販品としては、例えば（商品名）ＳＣ３２（ＡＤＥＫＡ社製）を挙げることができる。
The vinyl chloride-based resin for paste processing of the present invention has an extremely excellent change in viscosity with time, especially when it is made into a paste PVC sol, and is particularly excellent for an automobile underbody coat and an automobile sealant. A vinyl chloride resin for paste processing having a viscosity thickening rate of less than 100% is preferable. As a method for measuring the viscosity at that time, for example, 100 parts by weight of diisononyl phthalate, 70 parts by weight of the fatty acid salt surface-treated calcium carbonate, and 15 parts by weight of the diluent are used with respect to 100 parts by weight of a vinyl chloride resin for paste processing. Parts are mixed to prepare a paste vinyl chloride sol, and the viscosity (A) after storage at 23 ° C. for 2 hours and the viscosity (B) after storage at 40 ° C. for 7 days are measured at 20 rpm using a B8H type rotational viscometer. The viscosity can be calculated by the following formula.
Thickening rate (%) = 100 x (viscosity (B) -viscosity (A)) / viscosity (A)
Further, the vinyl chloride-based resin for paste processing of the present invention has excellent mechanical strength especially in low-temperature processing, and is particularly excellent for an automobile underbody coat and an automobile sealant, so that the tensile strength is high. It is preferably a vinyl chloride resin for paste processing having a pressure of 9.0 MPa or more. As a method for measuring the tensile strength at that time, for example, 60 parts by weight of diisononyl phthalate and 2 parts by weight of a stabilizer are mixed with 100 parts by weight of a vinyl chloride resin for paste processing to prepare a paste vinyl chloride resin, and 0 Tensile strength can be determined from a sheet coated to a thickness of .5 mm by measuring with a JIS No. 3 dumbbell test piece under the conditions of 23 ° C. and 200 mm / min. Examples of the stabilizer include a stabilizer for vinyl chloride, and examples thereof include metal soaps such as lead, barium, zinc, calcium, and copper, and mixtures thereof. As a commercially available product, for example, (trade name) SC32 (manufactured by ADEKA Corporation) can be mentioned.
本発明のペースト加工用塩化ビニル系樹脂は、平均粒子径を特に制限するものではなく、中でも、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから、平均粒子径０．８〜２．０μｍであることが好ましく、特に１．０〜１．７μｍであることがさらに好ましい。 The vinyl chloride-based resin for paste processing of the present invention does not particularly limit the average particle size, and among them, the mechanical strength especially in low-temperature processing and the change in viscosity with time when made into a paste PVC sol are extremely excellent. The average particle size is preferably 0.8 to 2.0 μm, and particularly 1.0 to 1.7 μm, because it is particularly excellent for automobile underbody coats and automobile sealants. Is even more preferable.
本発明のペースト加工用塩化ビニル系樹脂は、本発明の目的を奏する限りペースト加工用塩化ビニル系樹脂を製造する際に用いられる連鎖移動剤、架橋剤、脂肪族高級アルコール、緩衝剤、水溶性開始剤、還元剤等を含有してもよい。 The vinyl chloride resin for paste processing of the present invention is a chain transfer agent, a cross-linking agent, an aliphatic higher alcohol, a buffer, and a water-soluble agent used in producing the vinyl chloride resin for paste processing as long as the object of the present invention is achieved. It may contain an initiator, a reducing agent and the like.
本発明のペースト加工用塩化ビニル系樹脂の製造方法としては、該ペースト加工用塩化ビニル系樹脂を得ることが可能であれば如何なる方法であってもよく、例えば、塩化ビニル単量体／酢酸ビニル単量体＝９４／６〜８５／１５（重量％）よりなる混合単量体を、重合開始剤の存在下において水性媒体中で重合を行い、ペースト加工用塩化ビニル系樹脂を製造するに際し、重合開始前及び／又は重合開始後に前記一般式（Ｉ）で示される化合物及び該アルキル硫酸エステル塩を添加し、重合終了後に該ポリビニルアルコールを添加するペースト加工用塩化ビニル系樹脂の製造方法を挙げることができる。 The method for producing the vinyl chloride resin for paste processing of the present invention may be any method as long as the vinyl chloride resin for paste processing can be obtained, for example, vinyl chloride monomer / vinyl acetate. When a mixed monomer consisting of monomer = 94/6 to 85/15 (% by weight) is polymerized in an aqueous medium in the presence of a polymerization initiator to produce a vinyl chloride resin for paste processing. A method for producing a vinyl chloride resin for paste processing, in which the compound represented by the general formula (I) and the alkyl sulfate ester salt are added before and / or after the start of polymerization, and the polyvinyl alcohol is added after the completion of polymerization. be able to.
該製造方法においては、酢酸ビニル残基単位を６〜１０重量％含有する塩化ビニル−酢酸ビニル共重合体を効率的に製造することが可能となることから、塩化ビニル単量体／酢酸ビニル単量体＝９４／６〜８５／１５（重量％）よりなる混合単量体を用いてなることが好ましく、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れるものを効率的に製造することが可能となることから、塩化ビニル単量体／酢酸ビニル単量体＝９２．５／７．５〜９０／１０（重量％）よりなることが好ましい。 In the production method, a vinyl chloride-vinyl acetate copolymer containing 6 to 10% by weight of a vinyl acetate residue unit can be efficiently produced. Therefore, a vinyl chloride monomer / vinyl acetate simpler can be produced. It is preferable to use a mixed monomer having a dimer of 94/6 to 85/15 (% by weight), and both the mechanical strength in low-temperature processing and the change in viscosity with time when made into a paste vinyl chloride sol are both. It is extremely excellent, and in particular, it is possible to efficiently produce excellent products for automobile underbody coats and automobile sealants. Therefore, vinyl chloride monomer / vinyl acetate monomer = 92.5 / It is preferably composed of 7.5 to 90/10 (% by weight).
その際の重合開始剤としては、重合開始剤の範疇に属するものであれば如何なるものであってもよく、例えば過硫酸カリウム、過硫酸アンモニウム等の水溶性重合開始剤；アゾビスイソブチロニトリル等のアゾ化合物，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、パーオキシジカボネート等の過酸化物，等の油溶性重合開始剤等を挙げることができる。また、後述するシードミクロ懸濁重合法の際には、油溶性開始剤を含む種粒子（シード）であってもよい。 The polymerization initiator at that time may be any one that belongs to the category of the polymerization initiator, for example, a water-soluble polymerization initiator such as potassium persulfate or ammonium persulfate; azobisisobutyronitrile or the like. Examples thereof include oil-soluble polymerization initiators such as azo compounds, lauroyl peroxide, t-butyl peroxypivalate, diacyl peroxide, peroxy ester, and peroxides such as peroxy dicarbonate. Further, in the case of the seed microsuspension polymerization method described later, seed particles (seed) containing an oil-soluble initiator may be used.
該製造方法においては、重合開始前及び／又は重合開始後に前記一般式（Ｉ）で表される化合物を界面活性剤として添加するものであり、該一般式（Ｉ）で表される化合物の添加方法としては、機械的強度、ペースト塩ビゾルとした際の粘度の経時変化の小さいペースト加工用塩化ビニル系樹脂を効率よく製造することが可能となることから、重合開始前及び／又は重合開始後の重合中に連続又は一括で仕込むことが好ましく、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れるものを効率的に製造することが可能となることから、重合開始後から重合転化率が８５％に達するまでに連続又は一括で仕込むことが好ましい。 In the production method, the compound represented by the general formula (I) is added as a surfactant before and / or after the start of polymerization, and the compound represented by the general formula (I) is added. As a method, since it is possible to efficiently produce a vinyl chloride-based resin for paste processing in which the mechanical strength and the viscosity of the paste PVC sol do not change with time, it is possible to efficiently produce the vinyl chloride resin before the start of polymerization and / or after the start of polymerization. It is preferable to prepare continuously or collectively during the polymerization of the above, and in particular, the mechanical strength at low temperature processing and the change over time in the viscosity when made into a paste PVC sol are extremely excellent, especially for automobile underbody coats and automobiles. Since it is possible to efficiently produce excellent products for sealants, it is preferable to charge them continuously or collectively from the start of polymerization until the polymerization conversion rate reaches 85%.
また、該製造方法においては、重合開始前及び／又は重合開始後に該アルキル硫酸エステル塩を添加するものであり、該アルキル硫酸エステル塩の添加方法は、機械的強度、ペースト塩ビゾルとした際の粘度の経時変化の小さいペースト加工用塩化ビニル系樹脂を効率よく製造することが可能となることから、重合開始前及び／又は重合開始後の重合中に連続又は一括で仕込むことが好ましく、特に低温加工での機械的強度、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート用、自動車用シーラント用として優れるものを効率的に製造することが可能となることから、重合開始後から重合転化率が８５％に達するまでに連続又は一括で仕込むことが好ましい。 Further, in the production method, the alkyl sulfate ester salt is added before the start of the polymerization and / or after the start of the polymerization, and the method of adding the alkyl sulfate ester salt is based on the mechanical strength and the paste vinyl chloride bisol. Since it is possible to efficiently produce a vinyl chloride resin for paste processing having a small change in viscosity with time, it is preferable to charge the resin continuously or collectively before the start of the polymerization and / or during the polymerization after the start of the polymerization, especially at a low temperature. Both the mechanical strength during processing and the change in viscosity over time when made into a paste PVC sol are extremely excellent, and it is possible to efficiently manufacture products that are particularly excellent for automobile underbody coats and automobile sealants. Therefore, it is preferable to charge continuously or collectively from the start of polymerization until the polymerization conversion rate reaches 85%.
さらに、該製造方法においては、重合終了後、つまり塩化ビニル−酢酸ビニル共重合体ラテックスに、ポリビニルアルコールを添加するものであり、その際のポリビニルアルコールとしては、前記ポリビニルアルコールを挙げることができ、該ポリビニルアルコールのまま、水溶液、有機溶媒溶液等のいずれの形態でも添加することができる。 Further, in the production method, polyvinyl alcohol is added after the completion of the polymerization, that is, to the vinyl chloride-vinyl acetate copolymer latex, and the polyvinyl alcohol at that time can be mentioned as the polyvinyl alcohol. The polyvinyl alcohol can be added as it is in any form such as an aqueous solution or an organic solvent solution.
そして、該製造方法においては、塩化ビニル単量体、酢酸ビニル単量体の仕込み時期として、重合開始前に１段目仕込みとして、酢酸ビニル単量体全量と塩化ビニル単量体のうちの１５〜８０重量％を仕込み、重合を開始し、残りの塩化ビニル単量体を２段階以上に分割して追加仕込みを行い、それぞれの追加仕込みはそれまでに仕込まれた単量体の重合転化率が８０を超えて９５重量％に達する前の期間に開始する製造方法とすることもできる。このような仕込み、特に重合開始前に酢酸ビニル単量体の全量の仕込みを行うことにより、機械的強度、ペースト塩ビゾルとした際の粘度の経時変化の小さいペースト加工用塩化ビニル系樹脂を効率よく製造することが可能となるものである。そして、重合開始後に、残りの塩化ビニル単量体を２段階以上に分割して追加仕込みを行い、それぞれの追加仕込みはそれまでに仕込まれた単量体の重合転化率が８０を超えて９５重量％に達する前の期間に開始する、このような追加仕込みを行うことにより、機械的強度、ペースト塩ビゾルとした際の粘度の経時変化の小さいペースト加工用塩化ビニル系樹脂を効率よく製造することが可能となるものである。 Then, in the production method, as the preparation time of the vinyl chloride monomer and the vinyl acetate monomer, as the first stage preparation before the start of the polymerization, the total amount of the vinyl acetate monomer and 15 of the vinyl chloride monomer are charged. ~ 80% by weight was charged, polymerization was started, and the remaining vinyl chloride monomer was divided into two or more stages to perform additional charging, and each additional charging was the polymerization conversion rate of the monomers charged so far. It is also possible to use a manufacturing method that starts in a period before the amount exceeds 80 and reaches 95% by weight. By charging the entire amount of the vinyl acetate monomer before the start of polymerization, such preparation, in particular, the vinyl chloride resin for paste processing, which has a small change in mechanical strength and viscosity when made into a paste PVC sol, can be efficiently produced. It can be manufactured well. Then, after the start of polymerization, the remaining vinyl chloride monomer is divided into two or more stages and additional charges are made, and in each additional charge, the polymerization conversion rate of the monomers charged up to that point exceeds 80 and 95. By performing such additional preparation starting in the period before reaching% by weight, a vinyl chloride resin for paste processing with a small change in mechanical strength and viscosity when made into a paste PVC sol with time is efficiently produced. Is possible.
該製造方法における重合法としては、例えば塩化ビニル系単量体、界面活性剤、油溶性重合開始剤、必要に応じて脂肪族高級アルコール等の乳化補助剤を脱イオン水に添加しホモジナイザー等で混合分散した後、緩やかな攪拌下で重合を行うミクロ懸濁重合法；ミクロ懸濁重合法で得られた油溶性重合開始剤を含む種粒子（シード）を用いて行うシードミクロ懸濁重合法；塩化ビニル系単量体を脱イオン水、界面活性剤、水溶性重合開始剤とともに緩やかな攪拌下で重合を行う乳化重合法で得られた粒子をシードとして用いて乳化重合を行うシード乳化重合法等があげられ、その際に、例えば、重合温度は３０〜８０℃とし、塩化ビニル−酢酸ビニル共重合体ラテックスとして得ることができる。これらの重合により製造された塩化ビニル−酢酸ビニル共重合体ラテックスを噴霧乾燥し、必要に応じて粉砕することにより本発明のペースト加工用塩化ビニル系樹脂を得ることができる。 As a polymerization method in the production method, for example, a vinyl chloride-based monomer, a surfactant, an oil-soluble polymerization initiator, and an emulsifying aid such as an aliphatic higher alcohol are added to deionized water as needed, and a homogenizer or the like is used. Microsuspension polymerization method in which polymerization is carried out under gentle stirring after mixing and dispersing; Seed microsuspension polymerization method in which seed particles containing an oil-soluble polymerization initiator obtained by the microsuspension polymerization method are used. Seed emulsion polymerization using particles obtained by the emulsion polymerization method in which a vinyl chloride-based monomer is polymerized with deionized water, a surfactant, and a water-soluble polymerization initiator under gentle stirring as a seed. Legal and the like can be mentioned, and at that time, for example, the polymerization temperature is set to 30 to 80 ° C., and a vinyl chloride-vinyl acetate copolymer latex can be obtained. The vinyl chloride-vinyl acetate copolymer latex produced by these polymerizations is spray-dried and pulverized if necessary to obtain the vinyl chloride-based resin for paste processing of the present invention.
以下に、該製造方法のより好ましい態様としてのシードミクロ懸濁重合法による製造方法を示す。 The production method by the seed microsuspension polymerization method as a more preferable embodiment of the production method is shown below.
シードミクロ懸濁重合法としては、例えば塩化ビニル単量体／酢酸ビニル単量体よりなる混合単量体を、脱イオン水、前記一般式（Ｉ）で表される化合物、アルキル硫酸エステル塩、油溶性開始剤を含む種粒子、緩衝剤、必要に応じて油溶性開始剤を含まない種粒子、他の界面活性剤、連鎖移動剤、架橋剤としての多官能性単量体、水溶性開始剤、還元剤、脂肪族高級アルコールの存在下で、緩やかに攪拌しながら重合器内の温度を上げて重合反応を開始し、所定の転化率に達するまで重合を行う方法を挙げることができ、この際の重合温度としては、例えば３０〜７０℃である。また、塩化ビニル単量体を２段階以上に分割追加仕込みする際には、分割追加仕込みに合わせて、重合温度の低下を行うことが好ましい。界面活性剤としては、前記一般式（Ｉ）で表される化合物、アルキル硫酸エステル塩の他、必要に応じて他の界面活性剤等を更に用いてもよい。 As a seed microsuspension polymerization method, for example, a mixed monomer composed of a vinyl chloride monomer / vinyl acetate monomer is prepared by deionizing water, a compound represented by the general formula (I), an alkyl sulfate ester salt, and the like. Seed particles with oil-soluble initiator, buffer, seed particles without oil-soluble initiator, other surfactants, chain transfer agents, polyfunctional monomer as cross-linking agent, water-soluble initiator In the presence of an agent, a reducing agent, and an aliphatic higher alcohol, a method can be mentioned in which the temperature inside the polymerizer is raised while gently stirring to start the polymerization reaction, and the polymerization is carried out until a predetermined conversion rate is reached. The polymerization temperature at this time is, for example, 30 to 70 ° C. Further, when the vinyl chloride monomer is separately and additionally charged in two or more stages, it is preferable to lower the polymerization temperature in accordance with the divided and additional preparation. As the surfactant, in addition to the compound represented by the general formula (I) and the alkyl sulfate ester salt, other surfactants and the like may be further used if necessary.
また、油溶性開始剤を含む種粒子、油溶性開始剤を含まない種粒子、連鎖移動剤、架橋剤、脂肪族高級アルコール、緩衝剤、水溶性開始剤、還元剤としては、特開２０１４−１２９４７１号公報、特開２００９−２２１３３５号公報、特開２００３−０１２８１１号公報等の記載を参照することもでき、これらは単独又は２種類以上を混合しても用いることができる。 Further, as seed particles containing an oil-soluble initiator, seed particles not containing an oil-soluble initiator, a chain transfer agent, a cross-linking agent, an aliphatic higher alcohol, a buffer, a water-soluble initiator, and a reducing agent, Japanese Patent Application Laid-Open No. 2014- The description of JP-A-129471, JP-A-2009-221335, JP-A-2003-012811 and the like can also be referred to, and these can be used alone or in combination of two or more.
そして、得られた塩化ビニル−酢酸ビニル共重合体ラテックスをペースト加工用塩化ビニル系樹脂とする際に用いる乾燥機は一般的に使用されているものでよく、例えば、噴霧乾燥機等が挙げられる（具体例としては、「ＳＰＲＡＹ ＤＲＹＩＮＧ ＨＡＮＤＢＯＯＫ」（Ｋ．Ｍａｓｔｅｒｓ著、３版、１９７９年、ＧｅｏｒｇｅｇｏｄｗｉｎＬｉｍｉｔｅｄより出版）の１２１頁第４．１０図に記載されている各種の噴霧乾燥機）。乾燥用空気入口温度、乾燥用空気出口温度に特に制限はなく、乾燥用空気入口温度は８０〜２００℃、乾燥用空気出口温度は４５〜７５℃が一般的に用いられる。乾燥用空気入口温度は１００〜１７０℃、乾燥用空気出口温度は５０〜７０℃が更に好ましい。乾燥後に得られたペースト加工用塩化ビニル樹脂は、塩化ビニル−酢酸ビニル共重合体ラテックスを構成する粒子の集合体であり、通常１０〜１００μｍの顆粒状である。乾燥出口温度が５５℃を超える場合には、得られた顆粒状ペースト加工用塩化ビニル樹脂を粉砕した方が可塑剤への分散の点から好ましく、乾燥出口温度が５５℃以下の場合には、顆粒状のままでも粉砕して使用してもどちらでも良い。 The dryer used when the obtained vinyl chloride-vinyl acetate copolymer latex is used as a vinyl chloride resin for paste processing may be generally used, and examples thereof include a spray dryer. (As a specific example, various spray dryers described in FIG. 4.10 on page 121 of "SPRAY DRYING HANDBOOK" (written by K. Masters, 3rd edition, published by Georgegodwin Limited, 1979)). The drying air inlet temperature and the drying air outlet temperature are not particularly limited, and the drying air inlet temperature is generally 80 to 200 ° C. and the drying air outlet temperature is 45 to 75 ° C. The drying air inlet temperature is more preferably 100 to 170 ° C., and the drying air outlet temperature is more preferably 50 to 70 ° C. The vinyl chloride resin for paste processing obtained after drying is an aggregate of particles constituting the vinyl chloride-vinyl acetate copolymer latex, and is usually in the form of granules having a size of 10 to 100 μm. When the drying outlet temperature exceeds 55 ° C, it is preferable to pulverize the obtained vinyl chloride resin for processing granular paste from the viewpoint of dispersion in a plasticizer, and when the drying outlet temperature is 55 ° C or less, it is preferable. It may be used in the form of granules or crushed.
本発明のペースト加工用塩化ビニル樹脂は、可塑剤に分散させて調製したペースト塩ビゾルの高せん断粘度が高くスプレー加工性が良好で、粘度の経時変化が少なく、低温加工時の機械的強度に優れ、コート剤、特に自動車アンダーボディコート用、自動車用シーラント用として優れた特性を有するものである。 The vinyl chloride resin for paste processing of the present invention has a high shear viscosity of a paste PVC sol prepared by dispersing it in a plasticizer, has good spray processability, has little change in viscosity with time, and has a mechanical strength during low temperature processing. It is excellent and has excellent properties as a coating agent, particularly for an automobile underbody coat and an automobile sealant.
以下に、本発明を実施例により、さらに詳細に説明するが本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
以下に実施例より得られたペースト加工用塩化ビニル系樹脂の評価方法を示す。 The evaluation method of the vinyl chloride resin for paste processing obtained from the examples is shown below.
＜高せん断粘度の測定方法＞
ペースト加工用塩化ビニル系樹脂１００重量部、フタル酸ジイソノニル１００重量部（株式会社ジェイプラス製）、脂肪酸塩表面処理炭酸カルシウム（（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ 白石工業株式会社製）７０重量部、ナフテン系炭化水素溶剤（（商品名）Ｅｘｘｓｏｌ Ｄ４０ 東燃ゼネラル石油株式会社製）１５重量部からなるペースト塩ビゾルを２３℃にて２４時間保管し、キャピラリーレオメーター（（商品名）Ｒｈｅｏｓｓｏｌ−ＣＲ１００（ＵＢＭ社製））にてせん断速度１０５００ｓｅｃ−１の条件にて粘度を測定した。
<Measurement method of high shear viscosity>
100 parts by weight of vinyl chloride resin for paste processing, 100 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd.), 70 parts by weight of fatty acid salt surface-treated calcium carbonate ((trade name) Viscolite-OS Shiraishi Kogyo Co., Ltd.), naphthenic acid Hydrocarbon solvent ((trade name) Exsol D40 manufactured by Tonen General Petroleum Co., Ltd.) A paste vinyl chloride solution consisting of 15 parts by weight was stored at 23 ° C. for 24 hours, and a capillary rheometer ((trade name) Rheossol-CR100 (UBM)) was stored. The viscosity was measured under the condition of a shear rate of 10500 sec -1.
＜増粘率の測定方法＞
ペースト加工用塩化ビニル系樹脂１００重量部、フタル酸ジイソノニル１００重量部（株式会社ジェイプラス製）、脂肪酸塩表面処理炭酸カルシウム（（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ 白石工業株式会社製）７０重量部、ナフテン系炭化水素溶剤（（商品名）Ｅｘｘｓｏｌ Ｄ４０ 東燃ゼネラル石油株式会社製）１５重量部からなるペースト塩ビゾルの２３℃にて保管した際の、混練２時間後のＢ８Ｈ型回転粘度計で２０ｒｐｍ条件にて測定した粘度をＡとし、該ゾルを２時間後の測定後に４０℃にて保管し混練から７日間経過後に４０℃下にて測定した粘度をＢとした際に、下記式にて求めた。
増粘率（％）＝１００×（Ｂ−Ａ）／Ａ
＜引張強度の測定方法＞
ペースト加工用塩化ビニル系樹脂１００重量部、フタル酸ジイソノニル６０重量部（株式会社ジェイプラス製）、Ｃａ／Ｚｎ系安定剤２重量部（（商品名）ＳＣ３２ ＡＤＥＫＡ社製）からなるペースト塩ビゾルを脱泡した後、０．５ｍｍ厚に塗布し、１４０℃×１分間加熱して得られたシートから、ＪＩＳ３号ダンベルで作製された試験片を２３℃条件で２００ｍｍ／ｍｉｎの条件で測定した。
<Measurement method of thickening rate>
100 parts by weight of vinyl chloride resin for paste processing, 100 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd.), 70 parts by weight of fatty acid salt surface-treated calcium carbonate ((trade name) Viscolite-OS Shiraishi Kogyo Co., Ltd.), naphthen Hydrocarbon solvent ((trade name) Exsol D40 manufactured by Tonen General Petroleum Co., Ltd.) When stored at 23 ° C. in a paste PVC sol consisting of 15 parts by weight, the B8H type rotational viscometer after 2 hours of kneading was used under 20 rpm conditions. When the viscosity measured in the above was designated as A, the sol was stored at 40 ° C. after 2 hours of measurement, and the viscosity measured at 40 ° C. after 7 days from kneading was defined as B, it was calculated by the following formula. ..
Thickening rate (%) = 100 x (BA) / A
<Measurement method of tensile strength>
A paste PVC bisole consisting of 100 parts by weight of vinyl chloride resin for paste processing, 60 parts by weight of diisononyl phthalate (manufactured by J-PLUS Co., Ltd.), and 2 parts by weight of Ca / Zn-based stabilizer ((trade name) SC32 ADEKA). After defoaming, the mixture was applied to a thickness of 0.5 mm and heated at 140 ° C. for 1 minute. From the obtained sheet, a test piece prepared with a JIS No. 3 dumbbell was measured at 23 ° C. and 200 mm / min.
＜平均重合度の測定＞
ＪＩＳ−Ｋ６７２１に準拠し求めた。
<Measurement of average degree of polymerization>
Obtained in accordance with JIS-K6721.
＜酢酸ビニル残基単位重量％の測定方法＞
ペースト加工用塩化ビニル系樹脂中に含有する酢酸ビニル残基単位重量％（ＶＡｃ含量）は、ペースト加工用塩化ビニル系樹脂１００ｍｇと臭化カリウム１０ｍｇを混合し、すりつぶして成形した測定サンプルを、赤外分光光度計（島津社製、（商品名）ＦＴＩＲ−８１００Ａ）を使用して、赤外吸収スペクトル測定し、下記式より算出した。
ペースト加工用塩化ビニル系樹脂に含有する酢酸ビニル残基単位重量％（ＶＡｃ含量）
＝（３．７３×Ｂ／Ａ＋０．０２４）×１．０４
Ａ：１４３０ｃｍ−１付近のＣ−Ｈ面内変角による吸収ピークトップのＡｂｓ．値。
Ｂ：１７４０ｃｍ−１付近のＣ＝Ｏ伸縮による吸収ピークトップのＡｂｓ．値。
<Measurement method of vinyl acetate residue unit weight%>
The unit weight% (VAc content) of vinyl acetate residue contained in the vinyl chloride resin for paste processing is a measurement sample obtained by mixing 100 mg of vinyl chloride resin for paste processing and 10 mg of potassium bromide and grinding them into red. Infrared absorption spectrum was measured using an external spectrophotometer (manufactured by Shimadzu Corporation, (trade name) FTIR-8100A), and calculated from the following formula.
Vinyl acetate residue unit weight% (VAc content) contained in vinyl chloride resin for paste processing
= (3.73 x B / A + 0.024) x 1.04
A: 1430cm -1 C-H in-plane absorption peak top by bending Abs near. value.
B: Abs at the top of the absorption peak due to C = O expansion and contraction near 1740 cm -1. value.
合成例１（重合開始剤等含有シードの製造例）
１ｍ３オートクレーブ中に脱イオン水３６０ｋｇ、塩化ビニル単量体３００ｋｇ、過酸化ラウロイル６ｋｇ及び１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液３０ｋｇを仕込み、該重合液をホモジナイザーを用いて２時間循環し、均質化処理後、温度を４５℃に上げて、重合を進めた。４５℃における塩化ビニルの飽和蒸気圧より０．２ＭＰａ圧力が低下した後、未反応の塩化ビニル単量体を回収した。得られた開始剤等含有シードラテックス（以下、シード１と略記する）の平均粒子径は０．６０μｍ、固形分濃度は３２％であった。
Synthesis Example 1 (Production example of seed containing polymerization initiator, etc.)
1 m 3 into the autoclave deionized water 360 kg, vinyl monomers 300kg chloride was charged lauroyl peroxide 6kg and 15 wt% aqueous solution of sodium dodecylbenzenesulfonate 30kg, and 2 hours circulation using a homogenizer the polymer solution, homogenized After the treatment, the temperature was raised to 45 ° C. to proceed with the polymerization. After the pressure dropped by 0.2 MPa from the saturated vapor pressure of vinyl chloride at 45 ° C., the unreacted vinyl chloride monomer was recovered. The obtained seed latex containing an initiator and the like (hereinafter abbreviated as seed 1) had an average particle size of 0.60 μm and a solid content concentration of 32%.
実施例１
１ｍ３オートクレーブ中に脱イオン水３２５ｋｇ、１段目仕込み単量体として塩化ビニル単量体を１４４ｋｇ（混合単量体の全仕込み量に対して３６重量％）と酢酸ビニル単量体を３６ｋｇ（混合単量体の全仕込み量に対して９重量％）、ラウリル硫酸ナトリウムを１０００ｐｐｍ（混合単量体１００重量部に対して）、シード１を６３ｋｇ、硫酸銅を５ｐｐｍ仕込み、その後、この反応混合物の温度を４５℃に上げて１段目重合を開始するとともに、０．２重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が８５％となったところで、２段目仕込み単量体として、塩化ビニル単量体１４４ｋｇ（混合単量体の全仕込み量に対して３６重量％）を１５分間で１ｍ３オートクレーブに仕込み、重合温度４２．５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が８７％となったところで、３段目仕込み単量体として、塩化ビニル単量体７６ｋｇ（混合単量体の全仕込み量に対して１９重量％）を１５分間で１ｍ３オートクレーブに仕込み、重合温度４０℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了した。
Example 1
1 m 3 into the autoclave deionized water 325 kg, 1 stage (36% by weight relative to the total charged amount of monomer mixture) was charged 144kg vinyl chloride monomer as monomer and 36kg of vinyl acetate monomer ( 9% by weight based on the total amount of the mixed monomer charged), 1000 ppm of sodium lauryl sulfate (relative to 100 parts by weight of the mixed monomer), 63 kg of seed 1, 5 ppm of copper sulfate, and then this reaction mixture. The temperature of the above was raised to 45 ° C. to start the first-stage polymerization, and a 0.2 wt% ascorbic acid aqueous solution was continuously added so as to maintain the polymerization temperature throughout the entire polymerization time. When the polymerization conversion rate reached 85%, 144 kg of vinyl chloride monomer (36% by weight based on the total amount of mixed monomer charged) was added to 1 m 3 autoclave as the second-stage charged monomer in 15 minutes. The preparation was carried out, and the second-stage polymerization was continued at a polymerization temperature of 42.5 ° C. Further, when the polymerization conversion rate was 87% with respect to the total of the first-stage charged monomer and the second-stage charged monomer, 76 kg of vinyl chloride monomer (mixed) was used as the third-stage charged monomer. 19 wt%) relative to the total charged amount of the monomers were charged to the 1 m 3 autoclave for 15 minutes, to continue the 3-stage polymerization at a polymerization temperature of 40 ° C., the polymerization conversion rate with respect to the total monomer mixture The polymerization was terminated when the value reached 90%.
なお、重合開始してから重合終了までの間、ラウリル硫酸ナトリウム６０００ｐｐｍ（混合単量体１００重量部に対して）とノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩水溶液（第一工業製薬製：（商品名）アクアロンＨＳ−１０）１０００ｐｐｍ（混合単量体１００重量部に対して）を連続的に添加した。 From the start of the polymerization to the end of the polymerization, 6000 ppm of sodium lauryl sulfate (relative to 100 parts by weight of the mixed monomer) and 10 mol of nonylpropenylphenol ethylene oxide adducted ammonium sulfate aqueous solution (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: (Product name) Aqualon HS-10) 1000 ppm (relative to 100 parts by weight of the mixed monomer) was continuously added.
そして、未反応単量体を回収してペースト加工用塩化ビニル系樹脂ラテックスとし、重合度６００、ケン化度９３モル％のポリビニルアルコール（（商品名）ゴーセノールＡＬ−０６Ｒ、日本合成化学社製）を塩化ビニル−酢酸ビニル共重合体に対する含有量が３０００ｐｐｍとなるように添加した。スプレードライヤーにて、熱風入口１６０℃、出口温度５５℃で噴霧乾燥を行って、ペースト加工用塩化ビニル系樹脂を得た。得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 Then, the unreacted monomer was recovered to obtain a vinyl chloride resin latex for paste processing, which was a polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% ((trade name) Gosenol AL-06R, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Was added so that the content with respect to the vinyl chloride-vinyl acetate copolymer was 3000 ppm. A vinyl chloride resin for paste processing was obtained by spray drying with a spray dryer at a hot air inlet of 160 ° C. and an outlet temperature of 55 ° C. The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例２
重合度６００、ケン化度９３モル％のポリビニルアルコールの添加量を１００００ｐｐｍとした以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 2
A vinyl chloride-based resin for paste processing was obtained in the same manner as in Example 1 except that the amount of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% was 10000 ppm.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例３
重合度６００、ケン化度９３モル％のポリビニルアルコールの添加量を１５０００ｐｐｍとしたこと以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 3
A vinyl chloride-based resin for paste processing was obtained in the same manner as in Example 1 except that the amount of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% was 15,000 ppm.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例４
重合度６００、ケン化度９３モル％のポリビニルアルコールの添加量を１０００ｐｐｍとし、噴霧乾燥時の熱風出口温度を５０℃としたこと以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 4
The same procedure as in Example 1 was carried out except that the amount of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% was 1000 ppm and the hot air outlet temperature during spray drying was 50 ° C. A resin was obtained.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例５
重合度６００、ケン化度９３モル％のポリビニルアルコールの代わりに、重合度２５０、ケン化度６５モル％のポリビニルアルコールを添加した以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 5
The same procedure as in Example 1 was carried out except that polyvinyl alcohol having a degree of polymerization of 250 and a degree of saponification of 65 mol% was added instead of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol%. A resin was obtained.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例６
重合度６００、ケン化度９３モル％のポリビニルアルコールの代わりに、重合度２７００、ケン化度９８モル％のポリビニルアルコールを添加した以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 6
The same procedure as in Example 1 was carried out except that polyvinyl alcohol having a degree of polymerization of 2700 and a degree of saponification of 98 mol% was added instead of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol%. A resin was obtained.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例７
重合度６００、ケン化度９３モル％のポリビニルアルコールの代わりに、重合度１０００、ケン化度９８モル％のポリビニルアルコールを添加したこと以外は、実施例１と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 7
The same procedure as in Example 1 was carried out except that polyvinyl alcohol having a degree of polymerization of 1000 and a degree of saponification of 98 mol% was added instead of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol%. A based resin was obtained.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
実施例８
１段目仕込み単量体として塩化ビニル単量体を２２０ｋｇ（混合単量体の全仕込み量に対して５５重量％）と酢酸ビニル単量体を３６ｋｇ（混合単量体の全仕込み量に対して９重量％）を仕込み、重合転化率が８５％となったところで、２段目仕込み単量体として、塩化ビニル単量体１４４ｋｇ（混合単量体の全仕込み量に対して３６重量％）を１５分間で１ｍ３オートクレーブに仕込み、重合温度４０℃にて２段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了したこと以外は実施例1と同様に行い、ペースト加工用塩化ビニル系樹脂を得た。
Example 8
As the first-stage charged monomer, 220 kg of vinyl chloride monomer (55% by weight based on the total amount of mixed monomer charged) and 36 kg of vinyl acetate monomer (based on the total amount of mixed monomer charged). When the polymerization conversion rate reached 85%, 144 kg of vinyl chloride monomer (36% by weight based on the total amount of mixed monomer charged) was charged as the second-stage charged monomer. Was charged into a 1 m 3 autoclave for 15 minutes, the second stage polymerization was continued at a polymerization temperature of 40 ° C., and the polymerization was terminated when the polymerization conversion rate was 90% of the total of the mixed monomers. The same procedure as in Example 1 was carried out to obtain a vinyl chloride-based resin for paste processing.
得られたペースト加工用塩化ビニル系樹脂は、平均重合度１６５０、酢酸ビニル残基単位の含有量６．７重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られたペースト加工用塩化ビニル系樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 The obtained vinyl chloride resin for paste processing was a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1650 and a vinyl acetate residue unit content of 6.7% by weight, and a nonylpropenylphenol ethylene oxide 10 mol adduct sulfate ester. It contained 1111 ppm of ammonium salt and 7778 ppm of sodium lauryl sulfate. In addition, a paste vinyl chloride resin was prepared using the obtained vinyl chloride resin for paste processing, and its physical properties were evaluated. The results are shown in Table 1.
重合度６００、ケン化度９３モル％のポリビニルアルコールを添加しなかったこと以外は、実施例１と同様に行い、塩化ビニル系樹脂を得た。
A vinyl chloride resin was obtained in the same manner as in Example 1 except that polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% was not added.
得られた塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られた塩化ビニル系樹脂を用いて塩ビゾルを作製し、物性を評価した。その結果を表２に示す。得られた塩ビゾルは、高せん断粘度が劣るものであった。 The obtained vinyl chloride resin is a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and nonylpropenylphenol ethylene oxide 10 mol adduct, ammonium sulfate 1111 ppm. , Sodium lauryl sulfate 7778 ppm. In addition, a vinyl chloride resin was prepared using the obtained vinyl chloride resin, and its physical properties were evaluated. The results are shown in Table 2. The obtained PVC sol was inferior in high shear viscosity.
比較例２
重合度６００、ケン化度９３モル％のポリビニルアルコールの添加量を３００００ｐｐｍとした以外は、実施例１と同様に行い、塩化ビニル系樹脂を得た。
Comparative Example 2
A vinyl chloride resin was obtained in the same manner as in Example 1 except that the amount of polyvinyl alcohol having a degree of polymerization of 600 and a degree of saponification of 93 mol% was set to 30,000 ppm.
得られた塩化ビニル系樹脂は、平均重合度１７００、酢酸ビニル残基単位の含有量７．３重量％の塩化ビニル−酢酸ビニル共重合体、ノニルプロペニルフェノールエチレンオキシド１０モル付加体硫酸エステルアンモニウム塩１１１１ｐｐｍ、ラウリル硫酸ナトリウム７７７８ｐｐｍを含むものであった。また、得られた塩化ビニル系樹脂を用いて塩ビゾルを作製し、物性を評価した。その結果を表２に示す。得られた塩ビゾルは、高せん断粘度が劣るものであった。 The obtained vinyl chloride resin is a vinyl chloride-vinyl acetate copolymer having an average degree of polymerization of 1700 and a vinyl acetate residue unit content of 7.3% by weight, and nonylpropenylphenol ethylene oxide 10 mol adduct, ammonium sulfate 1111 ppm. , Sodium lauryl sulfate 7778 ppm. In addition, a vinyl chloride resin was prepared using the obtained vinyl chloride resin, and its physical properties were evaluated. The results are shown in Table 2. The obtained PVC sol was inferior in high shear viscosity.
本発明のペースト加工用塩化ビニル系樹脂は、可塑剤に分散させて調製したペースト塩ビゾルの高せん断粘度が高くスプレー加工性が良好で、粘度の経時変化が少なく、低温加工した際の機械的強度に優れ、コート剤、特に自動車アンダーボディコート用、自動車用シーラント用として優れた特性を有するものであり、その産業上の利用価値は高いものである。 The vinyl chloride resin for paste processing of the present invention has a high shear viscosity of a paste PVC sol prepared by dispersing it in a plasticizer, has good spray processability, has little change in viscosity with time, and is mechanical when processed at a low temperature. It has excellent strength and excellent properties as a coating agent, particularly for an automobile underbody coat and an automobile sealant, and its industrial utility value is high.
Claims (5)
条件１；ペースト加工用塩化ビニル系樹脂を水に超音波分散し、遠心分離器により２０００ｒｐｍ、３０分の条件で遠心分離を行い、回収した上澄みを乾燥することにより、得られる微小粒子が２重量％以下。
条件２；条件１により得られる微小粒子の酢酸ビニル残基含量が、ペースト加工用塩化ビニル系樹脂の酢酸ビニル残基含量より少ない。）
Condition 1: The vinyl chloride resin for paste processing is ultrasonically dispersed in water, centrifuged at 2000 rpm for 30 minutes with a centrifuge, and the recovered supernatant is dried to obtain 2 weights of fine particles. %the following.
Condition 2: The vinyl acetate residue content of the fine particles obtained under Condition 1 is smaller than the vinyl acetate residue content of the vinyl chloride resin for paste processing. )
高せん断粘度の測定方法；ペースト加工用塩化ビニル系樹脂組成物１００重量部、フタル酸ジイソノニル１００重量部、脂肪酸塩表面処理炭酸カルシウム７０重量部、希釈剤１５重量部を配合し、ペースト加工用塩化ビニル系樹脂ゾルを調製し、２３℃、２４時間保管後にキャピラリー粘度計を用いて、せん断速度１０５００ｓｅｃ−１での粘度を測定する。 Claim 1 or 2 paste for processing the vinyl chloride resin composition according to wherein the high shear viscosity by the following method is paste processing vinyl chloride resin composition in the range of 700~1200mPa · s.
Method for measuring high shear viscosity; 100 parts by weight of vinyl chloride resin composition for paste processing, 100 parts by weight of diisononyl phthalate, 70 parts by weight of calcium carbonate surface-treated fatty acid salt, and 15 parts by weight of diluent are blended to form chloride for paste processing. A vinyl resin sol is prepared, stored at 23 ° C. for 24 hours, and then the viscosity is measured at a shear rate of 10500 sec -1 using a capillary viscometer.
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| JPH07126608A (en) * | 1993-10-29 | 1995-05-16 | Aisin Chem Co Ltd | Plastisol composition for sealing |
| JPH09176423A (en) * | 1995-12-27 | 1997-07-08 | Tosoh Corp | Production of vinyl chloride polymer |
| JP3998762B2 (en) * | 1997-07-23 | 2007-10-31 | 新第一塩ビ株式会社 | Vinyl chloride resin granules for paste processing and method for producing the same |
| JP5169344B2 (en) * | 2008-03-14 | 2013-03-27 | 東ソー株式会社 | Method for producing vinyl chloride resin for paste processing |
| EP2305752B1 (en) * | 2008-06-18 | 2016-08-24 | Kuraray Co., Ltd. | Polyvinyl chloride resin composition and manufacturing method thereof |
| KR20110008881A (en) * | 2009-07-21 | 2011-01-27 | 주식회사 엘지화학 | Method for preparing poly vinyl chloride based resin having transparency, low-high shear viscosity and a molded article of the same resin |
| JP6047940B2 (en) * | 2012-06-20 | 2016-12-21 | 東ソー株式会社 | Vinyl chloride copolymer latex and process for producing the same |
| JP6115133B2 (en) * | 2012-12-28 | 2017-04-19 | 東ソー株式会社 | Vinyl chloride resin for paste processing and method for producing the same |
| JP6638456B2 (en) * | 2016-02-18 | 2020-01-29 | 東ソー株式会社 | Vinyl chloride resin for paste processing and its production method |
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