JP3576351B2 - Method for producing polyvinyl chloride paste resin and blend resin for paste - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、ポリ塩化ビニル系ペースト樹脂及びペーストブレンド樹脂の製造方法に関する。更に詳しくは、可塑剤、化学発泡剤、安定剤等と混練してプラスチゾルとした後、加熱成型した時のケミカルエンボス性が優れたポリ塩化ビニル系ペースト樹脂及びペースト用ブレンド樹脂の製造方法に関する。
【０００２】
【従来の技術】
ポリ塩化ビニル系ペースト樹脂（以下、ペースト樹脂という）は、可塑剤、希釈剤、安定剤、その他充填剤等の配合剤と共に攪拌混練してゾルとなし、これをディッピング、スラッシュ、ローテーションあるいはコーティング等の方法により成型した後、これを加熱ゲル化する加工法が採用される。この加工法における成型性はゾルの流動性に大きく支配されるが、特にコーティング用途ではゾルの粘度を低下させ、流動性を良くするために、ペーストブレンド樹脂（以下、ブレンド樹脂という）が併用される。
【０００３】
一般にペースト樹脂は、微細懸濁重合又は乳化重合で製造されており、前者の方法では０．１〜３μｍの多分散な粒子径分布をもち、後者では０．１〜３μｍの複数の単分散な粒子径分布をもつのが通常である。その重合体の形態は、乳濁したラテックス状であり、通常これをそのまま噴霧乾燥し、ペースト樹脂として製品化する。
【０００４】
一方、ゾルの流動性改良剤として用いられるブレンド樹脂の粒子径はペースト樹脂より大きく、通常の１００〜２００μｍのポリ塩化ビニル樹脂（以下、ＰＶＣ樹脂という）より小さい２０〜６０μｍの平均粒子径であり、その粒子形態はガラス状の低ポロシティ粒子で、滑らかな表面をもつ単一の球状粒子が良く、また、適度な可塑剤との親和性を持ち、加熱成型物の物性が優れていることが望ましく、この製造に際しては塩化ビニル系単量体の懸濁重合法が用いられるのが一般的である。そして、その重合後の形態はスラリー状であり、通常これを遠心脱水等により脱水処理した後に気流乾燥、流動乾燥等により乾燥処理してブレンド樹脂として製品化する。
【０００５】
ペースト樹脂及びブレンド樹脂は、その利便性から種々の用途に用いられているが、近年の生活様式の変化及び居住空間の快適性、利便性を求めるニーズの高まりにより、壁紙や床材用途に使用される比率が多くなりつつある状況にある。
【０００６】
この壁紙や床材分野においては、意匠性が重要視される傾向にあり、それを実現する手段として、その製品表面の図柄に沿って凹凸をつける方法が一般的になされるようになり、その技術的方法として化学発泡剤を用いるケミカルエンボス法や機械的手段で行うメカニカルエンボス法等が用いられる。
【０００７】
その中で、ケミカルエンボス法としては、ペースト樹脂（及びブレンド樹脂）、可塑剤、安定剤、化学発泡剤等を混練してプラスチゾルとし、これを予備ゲル化して原反を作り、その上にデザイン性を付与する印刷インキを塗布又は転写する。この印刷インキの中に発泡抑制剤を含有させておくことにより、その後加熱ゲル化した時、その図柄に沿って、製品表面の凹凸が発現される方法が利用される。そして発泡部と発泡抑制部との発泡倍率の差異が大きい程その凹凸差が顕著となり、商品価値の高いものとなる。
【０００８】
従って、その発泡倍率差を大きくする、即ちケミカルエンボス性を良好にするための技術的ポイントは、発泡部は充分発泡すると同時に、発泡抑制部においては発泡抑制剤が有効に機能してできるだけ発泡倍率を抑えることである。
【０００９】
しかしながら、これまでペースト樹脂市場での主要用途である壁紙、床材分野において、そのキー品質になるケミカルエンボス性について種々の検討がなされているが、充分でないのが実情であった。
【００１０】
【発明が解決しようとする課題】
本発明はかかる実情に鑑み、ケミカルエンボス性が優れているペースト樹脂及びペーストブレンド樹脂を提供することを目的とするものである。
【００１１】
【課題を解決するための手段】
本発明者らは、上記目的を達成するために鋭意研究を重ねた結果、ペースト樹脂及びブレンド樹脂の水分散液のｐＨを特定の範囲内に調整することにより、所期の目的を達成できることを見出し本発明を完成させたものである。
【００１２】
即ち、本発明は、乾燥した樹脂１重量部と純水２重量部とからなる水分散液のｐＨが２．５〜５．０の範囲になるように、ポリ塩化ビニル系重合体に酸性物質を含有させることを特徴とする、ポリ塩化ビニル系ペースト樹脂及びペースト用ブレンド樹脂の製造方法（但し、カルボン酸基を側鎖に有する水溶性高分子を含有する場合を除く）を内容とするものである。
尚、本発明において、乾燥した樹脂１重量部と純水２重量部とからなる水分散液のｐＨとは、乾燥した樹脂と純水とを１：２の割合で混合したリスラリーを３０℃で１時間静置した後ｐＨメーターで測定した値である。
【００１３】
本発明においては、乾燥した樹脂１重量部と純水２重量部とからなる水分散液のｐＨは、２．５〜５．０の範囲であることが必要である。該水分散液のｐＨが２．５より低いと成型体の発泡性及び耐熱性が著しく低下し、またｐＨが５．０より高くなると充分な効果が得られない。
【００１４】
酸性物質は特に限定されないが、無機酸性物質として、リン酸、亜リン酸、硫酸水素ナトリウム、硫酸水素カリウム、クロム酸、塩酸、硫酸、亜硫酸、チオ硫酸、硝酸、亜硝酸、ヨウ素酸等が挙げられ、また有機酸性物質として、酢酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、ニコチン酸、ベンゼンスルホン酸、安息香酸、酒石酸、リンゴ酸、ギ酸、酪酸、クエン酸、コハク酸、シュウ酸、ピクリン酸、ピコリン酸、フタル酸、スルファミン酸、スルファミル酸、アスパラギン酸、グリコール酸、グルタミン酸、フマル酸、マレイン酸、マロン酸、乳酸、オレイン酸等が挙げられ、これらは１種又は２種以上組み合わせて用いられる。
【００１５】
酸性物質の添加方法としては、ペースト樹脂の場合は、重合終了後のラテックスに添加した後、噴霧乾燥する方法が一般的である。またブレンド樹脂の場合は、重合後のスラリーに添加した後、脱水乾燥するが、若しくは、脱水後の含水樹脂に添加した後乾燥する方法が挙げられるが、後者の方が効率的である。
【００１６】
本発明において、ポリ塩化ビニル系ペースト樹脂又はペースト用ブレンド樹脂は、塩化ビニル単量体又はこれと共重合し得る単量体との混合物の重合物である。塩化ビニル単量体と共重合し得る他の単量体としては、例えばエチレン、プロピレンなどのオレフィン類、酢酸ビニル、ステアリン酸ビニルなどのビニルエステル類、アクリル酸メチル、メタクリル酸メチルなどのアクリル酸エステル類、マレイン酸またはフマル酸などの酸のエステル類及び無水物、アクリロニトリルなどのニトリル化合物、あるいは塩化ビニリデンの如きビニリデン化合物等が挙げられ、これらは単独または２種以上組み合わせて用いられる。重合方法は公知の方法でよく、ペースト樹脂は通常、微細懸濁重合又は乳化重合で、またブレンド樹脂は通常、懸濁重合法で製造される。
【００１７】
酸性物質添加によりケミカルエンボスが改良される原因については必ずしも明らかではないが、酸性物質が発泡抑制剤の活性を高めるか、若しくは、発泡剤の分解を遅延させるためと考えられる。
【００１８】
【実施例】
以下実施例を示し、本発明を更に具体的に説明するが、これらは何ら本発明を限定するものではない。尚、各種物性の測定及び評価用原反の作成は下記の方法で実施した。
【００１９】
〔樹脂分散液のｐＨ〕
樹脂と純水を１：２の割合で混合したリスラリーを、３０℃で１時間静置した後ｐＨメーター（株式会社堀場製作所製Ｍ−７）で測定した。
【００２０】
〔評価用原反作成〕
１．ペースト樹脂７０重量部、ブレンド樹脂３０重量部、ジオクチルフタレート５０重量部、炭酸カルシウム３０重量部、酸化チタン２．５重量部、発泡剤（アゾジカルボンアミド）２．５重量部、酸化亜鉛０．８重量部をプロペラ混合機で攪拌分散しプラスチゾルを調製した。
２．上記１．で調製したプラスチゾルを難燃紙上に約２５０μｍの厚さに塗工し、１６０℃で９０秒間加熱し成形した。
３．上記２．で得られた成形体にグラビア印刷機を用いて、発泡抑制剤（ベンゾトリアゾール）入りグラビアインキを塗布した。
【００２１】
〔発泡倍率測定〕
評価用原反を熱風循環式オーブンで２００℃で加熱し、発泡体を得た。得られた発泡体の発泡部の厚みを測定し、次式にて発泡倍率を算出した。
発泡倍率（倍）＝発泡厚み÷原反厚み
【００２２】
〔発泡抑制率測定〕
上記発泡倍率測定で用いたものと同じ発泡体を用いて、発泡体の発泡抑制部と発泡部の厚みを測定し、次式にて発泡抑制率を算出した。
実施例１
３００Ｌ重合機に、イオン交換水１３０重量部、塩化ビニル単量体１００重量部、重合開始剤として２，２′−アゾビスブチルバレロニトリル０．０１重量部及び乳化剤としてドデシルベンゼンスルホン酸ソーダ０．８重量部とステアリルアルコール０．３重量部を仕込み、この系を３０分間ホモジナイザーを用いて均質化処理した後、温度を５０℃に上昇させ重合し、重合圧５０℃における塩化ビニル飽和蒸気圧から１ｋｇ／ｃｍ２ 降下した時点で未反応単量体を回収して重合を終了しペースト樹脂ラテックスを得た。
このラテックスのｐＨは３．０５であった。このラテックス１００重量部に対してＨ３ ＰＯ４ を０．０００８６重量部（ポリマー１００重量部当たり０．００２０８重量部）添加してｐＨを３．００に調整した後噴霧乾燥し、ペースト樹脂を得た。得られたペースト樹脂と純水を１：２の割合で混合したリスラリーを３０℃で１時間静置した後、ｐＨメーターで測定した結果、ｐＨは４．９０であった。
得られたペースト樹脂を用いて、前記評価用原反作成で示した配合においてブレンド樹脂として鐘淵化学工業株式会社製ＰＢＭ−Ｂ５Ｆを用いてプラスチゾルを調製した後、発泡体評価を行った。その結果発泡抑制率は４０．２％で、発泡状態は良好なものであった。
【００２４】
実施例２〜４
３００Ｌ重合機に、懸濁安定剤として２０℃における４重量％水溶液粘度が９５ｃｐｓ で且つ鹸化度が８８モル％である水溶性部分鹸化ポリビニルアルコールを０．４５重量部溶解したイオン交換水１４０重量部を仕込み、重合開始剤としてジ−２−エチルヘキシルパーオキシジカーボネート０．０３７重量部と３，５，５−トリメチルヘキサノイルパーオキサイド０．０１９重量部及びシリコン消泡剤０．００１重量部を添加し、脱気後、塩化ビニル単量体１００重量部を仕込み、５４℃まで昇温して重合開始し、缶内圧が３ｋｇ／ｃｍ２ 低下した時未反応単量体を回収して重合終了しブレンド樹脂スラリーを得た。得られたスラリーのｐＨは４．２５であった。
次いで、このスラリーを用いて、添加する酸性物質と添加方法を下記の如く変えて実施例２〜４の各サンプルを作成した。
（サンプル作成方法）
実施例２：重合後スラリー１００重量部にＨ３ ＰＯ４ を０．０２８０重量部（ポリマー１００重量部当たり０．０７００重量部）添加し、脱水乾燥した。
実施例３：重合後スラリーから脱水した樹脂（脱水ケーキ）１００重量部にＨ３ ＰＯ４ を０．００５６重量部（ポリマー１００重量部当たり０．０７００重量部）添加し、均一に混合した後乾燥した。
実施例４：重合後スラリーから脱水した樹脂（脱水ケーキ）１００重量部にＮａＨＳＯ４ を０．００８９重量部（ポリマー１００重量部当たり０．０２２３重量部）添加し、均一に混合した後乾燥した。
各々乾燥して得た樹脂と純水を１：２の割合で混合したリスラリーを３０℃で１時間静置した後、ｐＨメーターで測定した結果、ｐＨは、実施例２では３．９０、実施例３では２．７０、実施例４では３．２１であった。
得られたブレンド樹脂を用いて、前記評価用原反作成で示した配合において、ペースト樹脂として鐘淵化学工業株式会社製ＰＳＭ−１７４を用いてプラスチゾルを調製した後、発泡体評価を行った。
その結果、実施例２〜４の発泡抑制率は、各々３５．３％、４１．６％、４５．８％で、その発泡状態は何れも良好なものであった。
【００２５】
比較例１、２
実施例１、２と同様の方法で重合し、各々ペースト樹脂及びブレンド樹脂を得て、酸性物質の添加をせずに乾燥処理した。
得られた樹脂と純水を１：２の割合で混合したリスラリーを３０℃で１時間静置した後、ｐＨメーターで測定した結果、ｐＨは各々５．８０（比較例１）、５．７２（比較例２）であり、実施例１、２に比較し高いものであった。これらを各々実施例１、２に準じて発泡体評価を行った結果、発泡抑制率は各々１５．８％（比較例１）、１６．４％（比較例２）と、実施例１、２と比較して悪いものであった。
【００２６】
比較例３
実施例３と同様の方法で重合し、Ｈ３ ＰＯ４ を脱水ケーキに過剰量添加し、リスラリーｐＨを２．０４とした他は、実施例３に準じて評価した。
その結果、発泡状態は非常に悪く、発泡抑制率は測定不能であった。
【００２７】
比較例４
実施例３の方法で重合し、Ｈ３ ＰＯ４ を脱水ケーキに過少量添加し、リスラリーｐＨを５．２５とした他は、実施例３に準じて評価した。
その結果、発泡抑制率は１７．８％と悪いものであった。
【００２８】
【表１】
表１の結果から明かなように、酸性物質の添加により樹脂のリスラリーｐＨを２．５〜５．０の範囲にコントロールすることにより、ケミカルエンボス性が改良されることが判る。
【００３０】
【発明の効果】
叙上のとおり、本発明によれば、ケミカルエンボス性に優れたポリ塩化ビニル系ペースト樹脂及びペースト用ブレンド樹脂を製造することができ、その有用性はすこぶる大である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polyvinyl chloride paste resin and a paste blend resin. More specifically, the present invention relates to a method for producing a polyvinyl chloride paste resin and a blend resin for paste, which are excellent in chemical embossing when kneaded with a plasticizer, a chemical foaming agent, a stabilizer, and the like to form a plastisol and then heat molded.
[0002]
[Prior art]
A polyvinyl chloride paste resin (hereinafter referred to as paste resin) is mixed with a compounding agent such as a plasticizer, a diluent, a stabilizer, and other fillers by stirring and kneading to form a sol, which is then dipped, slushed, rotated or coated. After molding by the above method, a processing method of heating and gelling this is adopted. The moldability in this processing method is largely governed by the fluidity of the sol, but paste coating resin (hereinafter referred to as blended resin) is used in combination to reduce the viscosity of the sol and improve the fluidity, especially for coating applications. You.
[0003]
In general, paste resins are produced by fine suspension polymerization or emulsion polymerization. The former method has a polydisperse particle size distribution of 0.1 to 3 μm, and the latter has a plurality of monodisperse particles of 0.1 to 3 μm. It usually has a particle size distribution. The polymer is in the form of an emulsified latex, which is usually spray-dried as it is to produce a paste resin.
[0004]
On the other hand, the particle diameter of the blend resin used as the fluidity improver of the sol is larger than that of the paste resin, and is an average particle diameter of 20 to 60 μm smaller than the usual polyvinyl chloride resin of 100 to 200 μm (hereinafter referred to as PVC resin). The particle form is a glassy low porosity particle, a single spherical particle with a smooth surface is good, and it has a good affinity with a plasticizer and the properties of the heat molded product are excellent. Desirably, in this production, a suspension polymerization method of a vinyl chloride monomer is generally used. The polymerized form is a slurry, which is usually dehydrated by centrifugal dehydration or the like and then dried by flash drying, fluidized drying or the like to produce a blend resin.
[0005]
Paste resins and blended resins are used for various purposes due to their convenience, but are used for wallpaper and flooring applications due to recent changes in lifestyles and increasing needs for comfort and convenience in living spaces. Are increasing.
[0006]
In the field of wallpaper and flooring, there is a tendency for emphasis on design, and as a means of achieving this, a method of providing irregularities along the pattern on the product surface has been commonly used. As a technical method, a chemical embossing method using a chemical foaming agent, a mechanical embossing method performed by mechanical means, or the like is used.
[0007]
Among them, as the chemical embossing method, paste resin (and blended resin), plasticizer, stabilizer, chemical foaming agent, etc. are kneaded to make a plastisol, which is pre-gelled to make a raw material, and a design is made on it Apply or transfer a printing ink that imparts properties. By incorporating a foaming inhibitor into the printing ink, a method is used in which, when subsequently heated and gelled, irregularities on the product surface are developed along the pattern. The greater the difference in the expansion ratio between the foamed portion and the foam suppression portion, the more significant the difference in the irregularities, and the higher the commercial value.
[0008]
Therefore, the technical point for increasing the difference in the expansion ratio, that is, for improving the chemical embossing property, is that the expansion portion expands sufficiently while the expansion inhibitor functions effectively in the expansion suppressing portion and the expansion ratio as much as possible. It is to suppress.
[0009]
However, in the field of wallpaper and flooring materials, which are the main applications in the paste resin market, various studies have been made on the chemical embossing property which is the key quality, but it has not been enough.
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and has as its object to provide a paste resin and a paste blend resin having excellent chemical embossability.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the desired object can be achieved by adjusting the pH of the aqueous dispersion of the paste resin and the blend resin within a specific range. The present invention has been completed.
[0012]
That is, the present invention provides an acidic substance to a polyvinyl chloride-based polymer such that the pH of an aqueous dispersion composed of 1 part by weight of a dried resin and 2 parts by weight of pure water is in the range of 2.5 to 5.0. Containing polyvinyl chloride paste resin and a method for producing a blend resin for paste (excluding a case where a water-soluble polymer having a carboxylic acid group in the side chain is contained), characterized by containing It is.
In the present invention, the pH of the aqueous dispersion composed of 1 part by weight of the dried resin and 2 parts by weight of pure water is defined as the reslurry obtained by mixing the dried resin and pure water at a ratio of 1: 2 at 30 ° C. It is a value measured with a pH meter after standing for 1 hour.
[0013]
In the present invention, the pH of the aqueous dispersion composed of 1 part by weight of the dried resin and 2 parts by weight of pure water needs to be in the range of 2.5 to 5.0. If the pH of the aqueous dispersion is lower than 2.5, the foamability and heat resistance of the molded article are significantly reduced, and if the pH is higher than 5.0, a sufficient effect cannot be obtained.
[0014]
The acidic substance is not particularly limited, and examples of the inorganic acidic substance include phosphoric acid, phosphorous acid, sodium hydrogen sulfate, potassium hydrogen sulfate, chromic acid, hydrochloric acid, sulfuric acid, sulfurous acid, thiosulfuric acid, nitric acid, nitrous acid, and iodic acid. Acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, nicotinic acid, benzenesulfonic acid, benzoic acid, tartaric acid, malic acid, formic acid, butyric acid, citric acid, succinic acid, oxalic acid, picric acid, Picolinic acid, phthalic acid, sulfamic acid, sulfamic acid, aspartic acid, glycolic acid, glutamic acid, fumaric acid, maleic acid, malonic acid, lactic acid, oleic acid, etc., and these are used alone or in combination of two or more. .
[0015]
As a method of adding the acidic substance, in the case of a paste resin, a method of adding to a latex after completion of polymerization and then spray-drying is generally used. In the case of a blended resin, a method of adding to a slurry after polymerization and drying by dehydration or a method of adding to a water-containing resin after dehydration and drying may be mentioned. The latter is more efficient.
[0016]
In the present invention, the polyvinyl chloride paste resin or the blend resin for paste is a polymer of a mixture of a vinyl chloride monomer or a monomer copolymerizable therewith. Other monomers copolymerizable with the vinyl chloride monomer include, for example, olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, and acrylic acids such as methyl acrylate and methyl methacrylate. Examples thereof include esters, esters and anhydrides of acids such as maleic acid and fumaric acid, nitrile compounds such as acrylonitrile, and vinylidene compounds such as vinylidene chloride. These may be used alone or in combination of two or more. The polymerization method may be a known method. The paste resin is usually produced by fine suspension polymerization or emulsion polymerization, and the blend resin is usually produced by suspension polymerization.
[0017]
Although the reason why the chemical emboss is improved by the addition of the acidic substance is not necessarily clear, it is considered that the acidic substance enhances the activity of the foaming inhibitor or delays the decomposition of the foaming agent.
[0018]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but these examples do not limit the present invention in any way. In addition, the measurement of various physical properties and preparation of a raw material for evaluation were performed by the following methods.
[0019]
(PH of resin dispersion)
The reslurry obtained by mixing the resin and pure water at a ratio of 1: 2 was left at 30 ° C. for 1 hour, and then measured with a pH meter (M-7, manufactured by Horiba, Ltd.).
[0020]
[Material for evaluation]
1. 70 parts by weight of paste resin, 30 parts by weight of blend resin, 50 parts by weight of dioctyl phthalate, 30 parts by weight of calcium carbonate, 2.5 parts by weight of titanium oxide, 2.5 parts by weight of blowing agent (azodicarbonamide), 0.8 part of zinc oxide The parts by weight were stirred and dispersed by a propeller mixer to prepare a plastisol.
2. The above 1. Was coated on flame-retardant paper to a thickness of about 250 μm, and heated at 160 ° C. for 90 seconds to mold.
3. The above 2. Using a gravure printing machine, a gravure ink containing a foaming inhibitor (benzotriazole) was applied to the molded body obtained in the above step.
[0021]
(Expansion ratio measurement)
The evaluation material was heated at 200 ° C. in a hot-air circulation oven to obtain a foam. The thickness of the foamed part of the obtained foam was measured, and the expansion ratio was calculated by the following equation.
Expansion ratio (times) = Thickness of foam / Thickness of raw fabric [0022]
(Expansion suppression rate measurement)
Using the same foam as that used in the measurement of the expansion ratio, the foam suppression portion of the foam and the thickness of the foam portion were measured, and the foam suppression ratio was calculated by the following equation.
Example 1
In a 300 L polymerization machine, 130 parts by weight of ion-exchanged water, 100 parts by weight of a vinyl chloride monomer, 0.01 part by weight of 2,2'-azobisbutylvaleronitrile as a polymerization initiator, and 0.1% of sodium dodecylbenzenesulfonate as an emulsifier. 8 parts by weight and 0.3 parts by weight of stearyl alcohol were charged, and the system was homogenized for 30 minutes using a homogenizer. Then, the temperature was raised to 50 ° C., and polymerization was carried out. At the time of dropping by 1 kg / cm 2 , unreacted monomer was recovered and polymerization was completed to obtain a paste resin latex.
The pH of this latex was 3.05. After adding 0.0086 parts by weight of H 3 PO 4 (0.00208 parts by weight per 100 parts by weight of the polymer) to 100 parts by weight of this latex to adjust the pH to 3.00, the mixture was spray-dried to obtain a paste resin. Was. The reslurry obtained by mixing the obtained paste resin and pure water at a ratio of 1: 2 was allowed to stand at 30 ° C. for 1 hour, and as a result of measurement with a pH meter, the pH was 4.90.
Using the obtained paste resin, a plastisol was prepared using PBM-B5F manufactured by Kanegafuchi Chemical Industry Co., Ltd. as a blend resin in the composition shown in the above-mentioned production of a raw material for evaluation, and then a foam was evaluated. As a result, the foaming suppression ratio was 40.2%, and the foaming state was good.
[0024]
Examples 2 to 4
140 parts by weight of ion-exchanged water obtained by dissolving 0.45 parts by weight of a water-soluble partially saponified polyvinyl alcohol having a viscosity of 4 cps at 20 ° C., a viscosity of 95 cps and a degree of saponification of 88 mol% as a suspension stabilizer in a 300 L polymerization machine. And 0.037 parts by weight of di-2-ethylhexylperoxydicarbonate, 0.019 parts by weight of 3,5,5-trimethylhexanoyl peroxide and 0.001 part by weight of a silicone antifoaming agent were added as polymerization initiators. After degassing, 100 parts by weight of a vinyl chloride monomer were charged, the temperature was raised to 54 ° C., and polymerization was started. When the internal pressure of the vessel was reduced by 3 kg / cm 2, unreacted monomer was recovered and polymerization was completed. A blend resin slurry was obtained. The pH of the obtained slurry was 4.25.
Next, using the slurry, samples of Examples 2 to 4 were prepared by changing the acidic substance to be added and the method of addition as described below.
(Sample preparation method)
Example 2: 0.0280 parts by weight of H 3 PO 4 (0.0700 parts by weight per 100 parts by weight of polymer) was added to 100 parts by weight of the slurry after polymerization, and the slurry was dehydrated and dried.
Example 3: 0.0056 parts by weight of H 3 PO 4 (0.0700 parts by weight per 100 parts by weight of polymer) was added to 100 parts by weight of a resin (dehydrated cake) dewatered from the slurry after polymerization, and the mixture was uniformly mixed and dried. did.
Example 4: 0.0089 parts by weight of NaHSO 4 (0.0223 parts by weight per 100 parts by weight of polymer) was added to 100 parts by weight of a resin (dehydrated cake) dewatered from the slurry after polymerization, and the mixture was uniformly mixed and dried.
The reslurry obtained by mixing the resin obtained by drying and pure water at a ratio of 1: 2 was allowed to stand at 30 ° C. for 1 hour and then measured with a pH meter. As a result, the pH was 3.90 in Example 2, and the pH was 3.90. In Example 3, it was 2.70, and in Example 4, it was 3.21.
Using the obtained blend resin, a plastisol was prepared using PSM-174 manufactured by Kanegabuchi Chemical Industry Co., Ltd. as a paste resin in the formulation shown in the above-mentioned production of a raw material for evaluation, and then the foam was evaluated.
As a result, the foaming suppression rates of Examples 2 to 4 were 35.3%, 41.6%, and 45.8%, respectively, and the foaming states were all good.
[0025]
Comparative Examples 1 and 2
Polymerization was performed in the same manner as in Examples 1 and 2 to obtain a paste resin and a blend resin, respectively, and dried without adding an acidic substance.
A reslurry obtained by mixing the obtained resin and pure water at a ratio of 1: 2 was allowed to stand at 30 ° C. for 1 hour, and then measured with a pH meter. As a result, the pH was 5.80 (Comparative Example 1) and 5.72, respectively. (Comparative Example 2), which was higher than Examples 1 and 2. These were evaluated for foams according to Examples 1 and 2, respectively. As a result, the foam suppression rates were 15.8% (Comparative Example 1) and 16.4% (Comparative Example 2), respectively. It was bad compared to.
[0026]
Comparative Example 3
Polymerization was carried out in the same manner as in Example 3, and an evaluation was made in the same manner as in Example 3 except that an excess amount of H 3 PO 4 was added to the dehydrated cake to adjust the reslurry pH to 2.04.
As a result, the foaming state was very poor, and the foaming inhibition rate could not be measured.
[0027]
Comparative Example 4
Polymerization was carried out by the method of Example 3, and evaluation was made in the same manner as in Example 3 except that a small amount of H 3 PO 4 was added to the dehydrated cake to adjust the reslurry pH to 5.25.
As a result, the foam suppression rate was as bad as 17.8%.
[0028]
[Table 1]
As is clear from the results shown in Table 1, the chemical embossing property is improved by controlling the reslurry pH of the resin in the range of 2.5 to 5.0 by adding an acidic substance.
[0030]
【The invention's effect】
As described above, according to the present invention, a polyvinyl chloride paste resin and a paste blend resin having excellent chemical embossing properties can be produced, and the usefulness thereof is extremely large.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12347897A JP3576351B2 (en) | 1997-04-24 | 1997-04-24 | Method for producing polyvinyl chloride paste resin and blend resin for paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12347897A JP3576351B2 (en) | 1997-04-24 | 1997-04-24 | Method for producing polyvinyl chloride paste resin and blend resin for paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10298297A JPH10298297A (en) | 1998-11-10 |
| JP3576351B2 true JP3576351B2 (en) | 2004-10-13 |
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| JP12347897A Expired - Fee Related JP3576351B2 (en) | 1997-04-24 | 1997-04-24 | Method for producing polyvinyl chloride paste resin and blend resin for paste |
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| BRPI0519009A2 (en) * | 2004-12-16 | 2008-12-23 | Asahi Kasei Chemicals Corp | industrial evaporation apparatus |
| JP7413767B2 (en) * | 2019-12-25 | 2024-01-16 | 東ソー株式会社 | Vinyl chloride resin for paste processing and vinyl chloride resin composition for paste processing using the same |
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