JPS63175057A - Vinyl chloride based polymer composition - Google Patents
Vinyl chloride based polymer compositionInfo
- Publication number
- JPS63175057A JPS63175057A JP557287A JP557287A JPS63175057A JP S63175057 A JPS63175057 A JP S63175057A JP 557287 A JP557287 A JP 557287A JP 557287 A JP557287 A JP 557287A JP S63175057 A JPS63175057 A JP S63175057A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- polymer composition
- chloride polymer
- based polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract 5
- -1 nonylphenyl Chemical group 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 125000005037 alkyl phenyl group Chemical group 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 20
- 229920001944 Plastisol Polymers 0.000 abstract description 15
- 239000004816 latex Substances 0.000 abstract description 15
- 229920000126 latex Polymers 0.000 abstract description 15
- 239000004999 plastisol Substances 0.000 abstract description 15
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 6
- 238000001694 spray drying Methods 0.000 abstract description 3
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000000178 monomer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YXFNFSBQEDFMHR-UHFFFAOYSA-N 2-(2-sulfoethoxy)ethanesulfonic acid Chemical class OS(=O)(=O)CCOCCS(O)(=O)=O YXFNFSBQEDFMHR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KPYCVQASEGGKEG-UHFFFAOYSA-N 3-hydroxyoxolane-2,5-dione Chemical compound OC1CC(=O)OC1=O KPYCVQASEGGKEG-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- BGPLHMAJJNBWGQ-UHFFFAOYSA-L [Na+].[Na+].O=C.OO.[O-]S[O-] Chemical compound [Na+].[Na+].O=C.OO.[O-]S[O-] BGPLHMAJJNBWGQ-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、低粘度のプラスチゾルを与えることの出来る
塩化ビニル系重合体組成物に係わる。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a vinyl chloride polymer composition capable of providing a plastisol with low viscosity.
「従来の技術」
ペースト用塩化ビニル系重合体は、通常水溶性の重合開
始剤を用いた乳化重合法または塩化ビニル単量体に溶解
するいわゆる油溶性重合開始剤を用い、塩化ビニル単量
体を機械的に水中に均一かつ微細に分散させた（均質化
処理した）ａ重合する微細懸濁重合法によって９１遺さ
れている。このとき、乳化剤として高級アルコール硫酸
エステル塩、アルキルスルホン酸塩、アル斗ルアリール
スルホン酸塩のような陰イオン界面活性剤が主に使用さ
れている。このようにして得られたペースト用塩化ビニ
ル系重合体は、例えば重合体に可塑剤、希釈胴、安定剤
等を配合して調製したプラスチゾル、オルガノゾル等の
ペースト分散液の粘度が高く、成形加工が困難になると
いう大きな欠点があった。``Prior art'' Vinyl chloride polymers for paste are usually produced by emulsion polymerization using a water-soluble polymerization initiator or by using a so-called oil-soluble polymerization initiator that dissolves in vinyl chloride monomer. 91 were carried out by a micro-suspension polymerization method in which a polymer is mechanically and uniformly and finely dispersed (homogenized) in water. At this time, anionic surfactants such as higher alcohol sulfate salts, alkyl sulfonate salts, and arylaryl sulfonate salts are mainly used as emulsifiers. The vinyl chloride polymer for paste obtained in this way has a high viscosity as a paste dispersion such as plastisol or organosol prepared by blending the polymer with a plasticizer, a diluent, a stabilizer, etc., and is difficult to mold. The major drawback was that it was difficult to
しかして、ゾル粘度を低下する等の目的で、重合後のラ
テックスに上述の陰イオン界面活性剤やポリオキシエチ
レンアルキルエーテル、ポリオキンエチレンポリオキシ
ブロビレンブロック共重合物、ソルビタンエステル、グ
リセリンアルキルエステルなどの非イオン界面活性剤の
１種または２種以上を適宜量加えて乾燥するペースト用
塩化ビニル系重合体のｇ１造方法や、またはゾル調製時
に一ヒ述した界面活性剤を加えることも行われている。Therefore, for the purpose of reducing sol viscosity, the above-mentioned anionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene polyoxybrobylene block copolymer, sorbitan ester, glycerin alkyl ester are added to the latex after polymerization. It is also possible to use the g1 manufacturing method of vinyl chloride polymer for paste, which involves adding an appropriate amount of one or more nonionic surfactants such as, and drying, or adding the surfactants mentioned above at the time of sol preparation. It is being said.
しかし、この様な一般的な方法では粘度低下の点で必ず
しも十分な結果は得られていない。However, such general methods do not always yield sufficient results in terms of viscosity reduction.
［発明が解決しようとする問題点」
本発明者らは、上述のような従来の欠点のない低粘度の
プラスチゾルを与える塩化ビニル系重合体組成物につい
て検討をおこなっており、既に、特定の陰イオン系界面
活性剤を重合の際の乳化剤として用いたり、或は、重合
後のｉｌＮｌＮ乳用乳化剤て用いる等により低粘度でか
つ粘度安定性、熱安定性の良好なプラスチゾルが得られ
ることを見出している（特願昭５９−１．６７３３１、
特願昭５９−１６７３３２）、この効果を更に高め、よ
り低粘度のプラスチゾルを与える塩化ビニル系重合体組
成物について検討を実施した結果、塩化ビニル系重合体
に特定の燐酸エステル系化合物を含有させることにより
、本発明の目的を達成しうろことを発見し本発明を完成
するに至った。[Problems to be Solved by the Invention] The present inventors have been studying a vinyl chloride polymer composition that provides a low-viscosity plastisol without the above-mentioned conventional drawbacks, and have already found certain problems. It was discovered that a plastisol with low viscosity and good viscosity stability and thermal stability can be obtained by using an ionic surfactant as an emulsifier during polymerization or as an emulsifier for ilNlN milk after polymerization. (Patent application 1986-1.67331,
(Japanese Patent Application No. 59-167332), as a result of research into a vinyl chloride polymer composition that further enhances this effect and provides plastisol with a lower viscosity, it was discovered that a specific phosphoric acid ester compound was incorporated into the vinyl chloride polymer. As a result, the inventors discovered that the object of the present invention could be achieved and completed the present invention.
すなわち、本発明の目的は、粘度が低いプラスチゾルを
与えることのできる塩化ビニル系重合体組成物を提供す
るにある。That is, an object of the present invention is to provide a vinyl chloride polymer composition that can provide plastisol with low viscosity.
「問題点を解決するための手段、１
しかして、本発明の要旨とするところは、塩化ビニル系
重合体１００重量部に、一般式［［］％式％（）
（式中、Ｒは炭素数８から３０のアルキル基またはアル
キルフェニル基
には１から３の整数、１および論は０から２の整数で、
ｋ＋１十−二３、
Ｍはアルカリ−＆属原子、
またはアンモニウム基、
ｎはＯから１５の整数
をそれぞれ示す。）
で−＆される燐酸エステルまたはその混合物を０．１〜
５重量部含有せしめた塩化ビニル系重合体組成物に存す
る。``Means for Solving the Problems, 1'' However, the gist of the present invention is to add 100 parts by weight of a vinyl chloride polymer with the general formula [[]% formula %() (wherein R is carbon The alkyl group or alkylphenyl group of numbers 8 to 30 is an integer of 1 to 3, 1 and 2 are integers of 0 to 2,
k+10-23, M is an alkali atom or an ammonium group, and n is an integer from O to 15, respectively. ) phosphoric acid ester or mixture thereof
5 parts by weight of the vinyl chloride polymer composition.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の組成物に用いる塩化ビニル系重合体とは、塩化
ビニル単量体または塩化ビニルとこれに共重合可能な他
の単量体、例えば、エチレン、プロピレン、ｎ−ブテン
のようなオレフィン類、酢酸ビニル、プロピオン酸ビニ
ル、ステアリン酸ビニルのようなビニルエステル、アク
リル酸、メタクリル酸、イタコン酸のような不飽和酸ま
たはそれらのアルキルエステル、メチルビニルエーテル
、エチルビニルエーテル、オクチルビニルエーテル、ラ
ウリルビニルエーテルのようなビニルエーテル、マレイ
ン酸、７マル酸あるいはこれらの無水物またはエステル
、芳香族ビニル化合物、不飽和ニトリル等の単量体の１
種又は２種以上との共重合体が挙げられる。塩化ビニル
と共重合可能な単量体は、上述のものに限定されるもの
ではなく、また共重合体の場合、共重合可能な単量体の
含有量は、共重合体の３０重量％以下、好ましくは２Ｏ
重量％以下の範囲であるのが望ましい。また本発明にお
いて用いる塩化ビニル系重合体の！！遣方法は、乳化重
合法または微ｍ懸濁重合法によるが、その時に使用する
乳化剤が特に下記、一般式［ｒｌｌ（式中、Ｒ５は炭素
数６〜１８のアルキル基、ｐはθ〜４の整数、
Ｘは−ＣＨ２−ＣＨ−ＣＨ，−または
Ｈ
−ｃＨ２−ＣＨｔ−で示される基
Ｍはアルカリ＊属原子またはアンモニウム基、
をそれぞれ示す、）
で表されるアルキルフェニルエーテルのスルホネ−Ｆ塩
であるのが好ましい。The vinyl chloride polymer used in the composition of the present invention refers to vinyl chloride monomer or vinyl chloride and other monomers copolymerizable therewith, such as olefins such as ethylene, propylene, and n-butene. , vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearate, unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid or their alkyl esters, such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, lauryl vinyl ether One of the monomers such as vinyl ether, maleic acid, 7-malic acid or anhydride or ester thereof, aromatic vinyl compound, unsaturated nitrile, etc.
Examples include species or copolymers with two or more species. Monomers copolymerizable with vinyl chloride are not limited to those mentioned above, and in the case of a copolymer, the content of monomers copolymerizable with vinyl chloride is 30% by weight or less of the copolymer. , preferably 2O
It is desirable that the amount is within the range of % by weight or less. Also, the vinyl chloride polymer used in the present invention! ! The method of polymerization is emulsion polymerization method or fine suspension polymerization method, and the emulsifier used at that time is particularly represented by the following general formula [rll (wherein R5 is an alkyl group having 6 to 18 carbon atoms, p is θ to 4 Sulfone-F of an alkylphenyl ether represented by Preferably it is salt.
なかでも上記一般式［ＩＴ］で表されるアルキル７エ二
ルエーテルのスルホネート塩がｐ−オクチルフェニルジ
オキシエチレン−３−スルホ−２−ヒドロキシプロピル
エーテルのアルカリ金属塩またはアンモニウム塩、もし
くは、ｐ−才クチルフェニルジオキシ−エチレン−２−
スルホエチルエーテルのアルカリ金属塩またはアンモニ
ウム塩であるのが最も好ましい。Among them, the sulfonate salt of alkyl 7 enyl ether represented by the above general formula [IT] is the alkali metal salt or ammonium salt of p-octylphenyldioxyethylene-3-sulfo-2-hydroxypropyl ether, or the p- Cutylphenyldioxy-ethylene-2-
Most preferred are the alkali metal or ammonium salts of sulfoethyl ether.
本発明の組成物の一成分である一般式［Ｉ］で表される
燐酸エステルは、式中のＲは炭素数８〜３０のアルキル
基またはアルキル７ヱニル基であり、待にアルキルフェ
ニル基が好ましい。In the phosphoric acid ester represented by the general formula [I] which is a component of the composition of the present invention, R in the formula is an alkyl group having 8 to 30 carbon atoms or an alkyl 7enyl group, and an alkylphenyl group is present. preferable.
ｋは１から３の整数であり、Ｉ、ｍはそれぞれθ〜２の
整数であって、ｋ＋ｌ＋ｍ＝３を満足する必要があるが
、ｋは１または２、−はＯであるのが好ましい。ｎはＯ
〜１５の整数であり、特に３〜１０の範囲にあるのが好
ましい。k is an integer from 1 to 3, I and m are each integers from θ to 2, and it is necessary to satisfy k+l+m=3, but preferably k is 1 or 2, and - is O. n is O
It is an integer of 15 to 15, preferably in the range of 3 to 10.
該燐酸エステルを混合物として用いる場合、陽＝０で、
ｋ＝、１のものとに＝２のものを混合するのが好ましい
が、その混合比は、ｋ＝１：に＝２で示す時１：９〜９
：１、特に、１：４〜４：１の範囲にあるのが好ましい
。When the phosphoric acid ester is used as a mixture, positive = 0,
It is preferable to mix k = 1 with k = 2, but the mixing ratio is 1:9 to 9 when k = 1: to = 2.
:1, particularly preferably in the range of 1:4 to 4:1.
該燐酸エステルまたはその混合物は、例えハ燐酸のモノ
、及びジ（アルキルフェニルポリオキシエチレン）エス
テル、もしくはそれらのアルカリ金属塩またはアンモニ
ウム塩が挙げられる６該燻酸エステル（混合物）は、塩
化ビニル系重合体１００重量部に対して、Ｏ−１〜５重
量部、好ましくは０．３〜３重量部の範囲で含有されて
いるのが望ましい。Examples of the phosphoric acid ester or mixture thereof include mono- and di(alkylphenylpolyoxyethylene) esters of phosphoric acid, or alkali metal salts or ammonium salts thereof.6 The smoking acid ester (mixture) is a vinyl chloride-based ester. It is desirable that the content is in the range of 1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the polymer.
塩化ビニル系重合体に一般式［Ｉ］で表される燐酸エス
テルまたはその混合物を含有せしめるには、例えば次の
各種方法が採用される。In order to incorporate the phosphoric acid ester represented by the general formula [I] or a mixture thereof into the vinyl chloride polymer, the following various methods are employed, for example.
■ 乳化重合または微細懸濁重合時に、該燐酸エステル
を、乳化剤または補助乳化剤として存在せしめ、得られ
た塩化ビニル系重合体ラテックスをそのまま噴霧乾燥す
る。(2) The phosphoric acid ester is made to exist as an emulsifier or an auxiliary emulsifier during emulsion polymerization or fine suspension polymerization, and the resulting vinyl chloride polymer latex is directly spray-dried.
■ 乳化重合または微細懸濁重合して得られた塩化ビニ
ル系重合体ラテックスに、該燐酸ニスチルを調整用乳化
剤として添加して、そのラテックスを噴霧乾燥する。(2) The nistyl phosphate is added as a controlling emulsifier to a vinyl chloride polymer latex obtained by emulsion polymerization or fine suspension polymerization, and the latex is spray-dried.
■ 乳化重合または微＃Ｉ患濁重合して得られた塩化ビ
ニル系重合体から可塑剤、安定剤等を添加してプラスチ
ゾルを調製する際に、該燐酸エステル（混合物）を、添
加する。(2) The phosphoric acid ester (mixture) is added when plastisol is prepared by adding a plasticizer, stabilizer, etc. from a vinyl chloride polymer obtained by emulsion polymerization or fine #I turbidity polymerization.
勿論、塩化ビニル系重合体に燐酸エステル（混合物）を
含有せしめる方法は、上述の方法だけに限定されるもの
ではなく、各種の方法が採用され得るが、本発明の組成
物では上述の■または■の方法によって調９１されたも
のが好ましく、待に■のように乳化重合または微＃Ｉ患
濁重合した塩化ビニル系重合体ラテックスに、燐酸エス
テル（混合物）を添加したものを噴霧乾燥したものが、
組成物の製造ヒまたゾルの調整上好ましい態様である。Of course, the method of incorporating the phosphoric acid ester (mixture) into the vinyl chloride polymer is not limited to the above-mentioned method, and various methods may be adopted. Preferably, it is prepared by the method (2), which is prepared by spray-drying a vinyl chloride polymer latex that has been subjected to emulsion polymerization or slight #I turbidity polymerization as in (2), to which a phosphoric acid ester (mixture) is added. but,
This is a preferred embodiment for the preparation of the composition and for the preparation of the sol.
「発明の効果」
本発明の組成物からｌｌＩ整されたプラスチゾルの粘度
は、低剪断速度領域のみならず、高剪断速度領域におい
ても低い値を示し、プラスチゾルの流動性に優れ、この
効果は塗布法によるプラスチゾルの加工分野において特
に有利である。例えば、低剪断速度範囲におけるゾル粘
度が低いため、ペーストゾルの取扱い、例えば供給、ろ
過、脱泡が容易となり、また高剪断速度範囲におけるゾ
ル粘度も低いため、高速度での塗布が可能になり床材、
壁材等の製造に好適である。"Effects of the Invention" The viscosity of the plastisol prepared from the composition of the present invention is low not only in the low shear rate region but also in the high shear rate region, and the fluidity of the plastisol is excellent. It is particularly advantageous in the field of processing plastisols by method. For example, the low sol viscosity in the low shear rate range facilitates handling of the paste sol, e.g. feeding, filtration, and defoaming, and the low sol viscosity in the high shear rate range allows application at high speeds. flooring,
Suitable for manufacturing wall materials, etc.
さらに本発明の塩化ビニル系重合体組成物は一般式［Ｉ
］で表される燐酸エステル＊たはその混合物を重合後の
ラテックスに添加して分散させた後に単に噴霧乾燥する
だけで得ることができ、経済的に、また捏業−ヒ極めて
有利である。Furthermore, the vinyl chloride polymer composition of the present invention has the general formula [I
] or a mixture thereof can be obtained by simply adding and dispersing the phosphoric acid ester * or a mixture thereof to the polymerized latex and then spray-drying it, which is extremely advantageous economically and in terms of fabrication.
「実施例１
次に本発明を実施例にて更に詳述するが、本発明はその
要旨を越えない限り、以下の実施例によって限定される
ものではない。Example 1 Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the following Examples unless the gist thereof is exceeded.
なお、実施例中に記載された「部」及び「％」は、重量
基準によった。Note that "parts" and "%" described in the examples are based on weight.
また、テストに用いたプラスチゾルの配合は、次の通り
である。The formulation of plastisol used in the test is as follows.
塩化ビニル系重合体組成物 １００部７タル酸ノ
２−エチルヘキシル ７０部炭酸カルシウム
１５０部Ｃａ−Ｚｎ系安定剤
３部アゾ系発泡剤（アゾノカルボンアミド）
５部希釈剤（ミネラルスピリット） １０部各テ
スト方法は以下の通りである。Vinyl chloride polymer composition 100 parts 2-ethylhexyl 7-talate 70 parts calcium carbonate
150 parts Ca-Zn stabilizer
3-part azo blowing agent (azonocarbonamide)
5 parts diluent (mineral spirits) 10 parts Each test method is as follows.
Ｂ型精度（センチポイズ）
ＢＨ型粘度計（東京計器製造所製）Ｎｏ、Ｇローターを
用い５０ｒｐ−の回転数、２３℃で測定した。B-type precision (centipoise) Measurement was carried out using a BH-type viscometer (manufactured by Tokyo Keiki Seisakusho) No. G rotor at a rotational speed of 50 rpm and 23°C.
但し、上記配合系から安定剤を除いた配合物を用いた。However, a formulation was used in which the stabilizer was removed from the above formulation system.
ＢＭ型粘度（センチボイズ）
ＢＭ型粘度計（東京計器！！！！遣所製）Ｎｏ、３０−
ターを用い６ ｒｐｍ、１２ｒｐ槍の回転数、２３℃で
測定した。BM type viscosity (centiboise) BM type viscometer (manufactured by Tokyo Keiki!!!! Kensho) No. 30-
Measurements were made using a rotor at 6 rpm, 12 rp spear rotation speed, and 23°C.
〈実施例１、比較例１．２〉
撹拌機を備えた容積２Ｏ０１の重合槽に脱イオン水８０
ｋｇ、平均粒径０．５μの塩化ビニル重合体種子ラテッ
クス（乳化剤ニラウリル硫酸ナトリウム、重合開始剤：
過硫酸カリウム−重亜硫酸ナトリウム系使用）を重合
体種子として４．ｆ３ｋＲ仕込んだ後脱気して塩化ビニ
ル７５．２ｋｇを加えた。<Example 1, Comparative Example 1.2> In a polymerization tank with a volume of 2001 equipped with a stirrer, 80 g of deionized water was added.
kg, vinyl chloride polymer seed latex with an average particle size of 0.5μ (emulsifier sodium nilauryl sulfate, polymerization initiator:
4. Using potassium persulfate-sodium bisulfite system) as a polymer seed. After charging f3kR, it was degassed and 75.2 kg of vinyl chloride was added.
温度を５７℃に昇温した後、全量で０．０５％（対塩化
ビニル）の過酸化水素−ホルムアルデヒドナトリウムス
ルホキシレートのレドックス開始剤を連続的に添加した
。更に、重合率が重合体種子と塩化ビニルの合計量の１
０％に達したときから不合の終わりまでの間乳化剤とし
てｐ−オクチルフェニルノオキシエチレン−３−スルホ
−２−ヒドロキシプロピルエーテルナトリウム塩を約８
％の水溶液として塩化ビニルに対して毎時０．０８％の
割合で連続的に添加した。After raising the temperature to 57°C, a redox initiator of hydrogen peroxide-sodium formaldehyde sulfoxylate in a total amount of 0.05% (based on vinyl chloride) was continuously added. Furthermore, the polymerization rate is 1 of the total amount of polymer seeds and vinyl chloride.
About 8% of p-octylphenylnooxyethylene-3-sulfo-2-hydroxypropyl ether sodium salt was added as an emulsifier from the time the concentration reached 0% until the end of the incorporation.
% aqueous solution at a rate of 0.08% per hour relative to vinyl chloride.
重合圧が５７℃における塩化ビニルの飽和圧から１ｋｇ
／ａｍ”降下したときに重合を停正し、未反応モノマー
を回収した。得られたラテックス粒子の平均粒径は、０
．９μであった。該ラテックスを３分し、その２つにそ
れぞれ第１表に示す燐酸エステル混合物及びラウリル硫
酸ナトリウムを重合体当＋）１．０％調整用乳化剤とし
て添加した後噴ｎ乾燥し、次いで粉砕して塩化ビニル重
合体組成物を得た。1kg from the saturation pressure of vinyl chloride at a polymerization pressure of 57℃
/am”, the polymerization was stopped and unreacted monomers were collected.The average particle size of the obtained latex particles was 0.
．． It was 9μ. The latex was divided into three parts, and a phosphoric acid ester mixture shown in Table 1 and sodium lauryl sulfate were added to each of the two parts as an emulsifier for adjusting 1.0% (per polymer), and then sprayed and dried, and then pulverized. A vinyl chloride polymer composition was obtained.
これらの塩化ビニル重合体組成物を用いで調製したプラ
スチゾルのゾル粘度を測定し、第１表に記載した。（第
１表は次頁）
〈実施例２、比較例３．４〉
実施例１において乳化剤としてラウリル硫酸ナトリウム
を、重合開始剤として過硫酸カリウム−メタ重亜硫酸ナ
トリウム系を用い、そして重合温度を５０℃とした以外
は、全〈実施例１と同様にして塩化ビニル系重合体を得
た。これに、ＰＩＳ２表に示す燐酸エステルもしくはド
デシルベンゼンスルホン酸ナトリウムを重合体当り０．
５％調整用乳化剤として添加した、塩化ビニル重合体組
成物を用いてプラスチゾルを調整した。得られたゾルの
粘度を第２表に示す。The sol viscosities of plastisols prepared using these vinyl chloride polymer compositions were measured and are listed in Table 1. (Table 1 is on the next page) <Example 2, Comparative Example 3.4> In Example 1, sodium lauryl sulfate was used as the emulsifier, potassium persulfate-sodium metabisulfite system was used as the polymerization initiator, and the polymerization temperature was changed. A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the temperature was 50°C. To this, phosphoric acid ester or sodium dodecylbenzenesulfonate shown in PIS 2 table was added at 0.0% per polymer.
Plastisols were prepared using a vinyl chloride polymer composition added as a 5% controlling emulsifier. The viscosity of the obtained sol is shown in Table 2.
〈実施例３〜６、比較例５〜９〉
撹拌機を備えた容積２Ｏ０１の予備混合槽にイオン交換
水１００に、、ラウロイルパーオキサイド６００ｇ、ラ
ウリル硫酸ナトリウム４００ｇ、ラウリルアルコール２
Ｏ０ｇを添加し次いで予備混合槽を脱気し塩化ビニル単
量体６０ｋｇを添加し攪拌しながら３５℃に保持した。<Examples 3 to 6, Comparative Examples 5 to 9> In a premixing tank with a volume of 2001 equipped with a stirrer, 100 g of ion-exchanged water, 600 g of lauroyl peroxide, 400 g of sodium lauryl sulfate, and 2 g of lauryl alcohol were added.
After adding Og, the premix tank was degassed, and 60 kg of vinyl chloride monomer was added, and the temperature was maintained at 35° C. with stirring.
均一に撹拌後孔化機を使用し所望の液滴径に分散しなが
ら予め脱気しておいた攪拌機を備えた容積２Ｏ０１の反
応槽に移送した。分散液の移送完了後、反応槽の温度を
昇温し公知の方法で重合を行った。得られたラテックス
中の種子重合体粒子の平均径は０．５μであった。After stirring uniformly, the mixture was dispersed into a desired droplet size using a porous machine and transferred to a reaction tank with a volume of 2001 equipped with a stirrer which had been previously degassed. After the transfer of the dispersion liquid was completed, the temperature of the reaction tank was raised and polymerization was carried out by a known method. The average diameter of the seed polymer particles in the obtained latex was 0.5μ.
上記のようにして調整した種子重合体を用いて重合を次
のように行った。Polymerization was carried out as follows using the seed polymer prepared as described above.
攪拌機を備えた容積２Ｏ０ １の重合槽に脱イオン水８
０に、、種子重合体ラテックス５ｋｇ、炭酸水素ナトリ
ウム２Ｏｇを仕込んだ後脱気して塩化ビニル単量体７５
ｋｇを仕込み、温度を５０℃に昇温した後、予め溶解し
ておいた亜硫酸水素ナトリウムの０．３％水溶液を少量
ずづ重合槽へ連続的に添加し重合を開始した。亜硫酸水
素ナトリウムの添加開始後一定の反応速度で反応するよ
うに調整した。更に重合率が１０％に達したときがら、
重合終了までの間、乳化剤として第３表に示す界面活性
剤を約８％の水溶液として塩化ビニル単量体に対して毎
時０．１％の割合で連続的に添加した。乳化剤全添加量
は塩化ビニルに対し０．６％であった。重合圧が５０℃
における塩化ビニルの飽和圧から１ ｋｇ／ ０ｍ２降
下したときに重合を停止し、未反応モノマーを回収した
。いずれの乳化剤によっても得られたラテックスの平均
粒径は１．０〜１．１μであり、ラテックスの安定性は
良好であった。得られたラテックスに表に示す調整用乳
化剤を加えて噴霧乾燥した後、粉砕して塩化ビニル系重
合体組成物を得た。この塩化ビニル系重合体組成物より
調整したプラスチゾルを上述のテスト方法により粘度を
測定した。結果を第３表に示す。Deionized water 8 in a 200 1 volume polymerization tank equipped with a stirrer
0, 5 kg of seed polymer latex and 20 g of sodium bicarbonate were added, and then degassed to obtain 75% of vinyl chloride monomer.
kg was charged and the temperature was raised to 50° C., and then a 0.3% aqueous solution of sodium hydrogen sulfite, which had been dissolved in advance, was continuously added little by little to the polymerization tank to start polymerization. After the addition of sodium bisulfite was started, the reaction rate was adjusted to be constant. Furthermore, when the polymerization rate reached 10%,
Until the polymerization was completed, a surfactant shown in Table 3 as an emulsifier was continuously added as an approximately 8% aqueous solution at a rate of 0.1% per hour to the vinyl chloride monomer. The total amount of emulsifier added was 0.6% based on vinyl chloride. Polymerization pressure is 50℃
Polymerization was stopped when the vinyl chloride saturation pressure had dropped by 1 kg/0 m2 from the saturation pressure of vinyl chloride at , and unreacted monomers were collected. The average particle diameter of the latex obtained with any emulsifier was 1.0 to 1.1 μm, and the stability of the latex was good. The emulsifier for adjustment shown in the table was added to the obtained latex, the mixture was spray-dried, and then pulverized to obtain a vinyl chloride polymer composition. The viscosity of plastisol prepared from this vinyl chloride polymer composition was measured by the above-mentioned test method. The results are shown in Table 3.
手続補正書
昭和６２年３月、２μ８
昭和６２年特許顆第５５７２号
２ 発明の名称
塩化ビニル系重合体組成物
３ 補正をする者
事件との関係 特許出願人
名称 三菱化成ビニル株式会社
４代理人〒１００
東京都千代田区丸の内二丁目５番２号
５ 補正命令の日付 自発
６ 補正により増加する発明のＷＬＯ
７補正の対象 明＃ＩＩ書の発明の詳細な説明の欄８
補正の内容
（２）明＃Ｉｌ書！ｌＳ９頁第１行目、第１５行目、及
ゾ第１７行目に「調整」とあるをそれぞれ「調製」に訂
正する。Procedural amendment March 1988, 2μ8 Patent No. 5572 of 1988 2 Name of the invention Vinyl chloride polymer composition 3 Relationship with the case of the person making the amendment Name of patent applicant Mitsubishi Kasei Vinyl Co., Ltd. 4 Agent 2-5-2-5 Marunouchi, Chiyoda-ku, Tokyo 100 Date of amendment order Spontaneous 6 WLO of inventions increased by amendment 7 Subject of amendment Column 8 for detailed explanation of the invention in Ming #II book
Contents of amendment (2) Ming #Il book! 1S page 9, lines 1, 15, and 17, the words ``adjustment'' are corrected to ``preparation.''
（３）明細書第１２頁第１７行目に「実施例１」とある
を「実施例１〜３」に訂正する。(3) "Example 1" on page 12, line 17 of the specification is corrected to "Examples 1 to 3."
（４）明細書第１２頁第１７行目に［３分し、その２つ
に」とあるを「５分し、その４つに１に訂正する。(4) In the 17th line of page 12 of the specification, the phrase ``divided into 3, then into 2'' is corrected to ``divided into 5, and then into 1 into 4.''
（５）明細書第１２頁第１９行目に［調整用乳化剤ｊと
あるをＦｒｆＲ製用乳製剤乳化剤１する。(5) On page 12, line 19 of the specification, "Adjusting emulsifier j" is used as FrfR emulsifier emulsifier 1.
（６）明細書第１３頁第５行目に［実施例２１とあるを
「実施例４〜６」に訂正する。(6) On page 13, line 5 of the specification, [Example 21 is corrected to read "Examples 4 to 6."
（７）明細書第１２頁第１７行目及び第９行目に「実施
例１」とあるをそれぞれ「実施例１〜３１に訂正する。(7) "Example 1" in the 17th line and 9th line of page 12 of the specification is corrected to "Examples 1 to 31," respectively.
（８）明細書第１２頁第１７行目及び第１４行目にｒｆ
ｌ１９Ｊとあるをそれぞれ「１１製」に訂正する。(8) rf on page 12, line 17 and line 14 of the specification
Correct the text ``l19J'' to ``Made in 11.''
（９）明細書第１４頁の第１表を以下の通りに補正する
。(9) Table 1 on page 14 of the specification is amended as follows.
第 １ 表
（１０）明細書ｔｊ４１４頁のｔＩ％２表を以下の通り
に補正する。Table 1 (10) The tI%2 table on page 414 of the specification is amended as follows.
第 ２ 表
（１１）明細書第１５頁第１行目に「実施例３〜６、比
較例５〜９」とあるを［実施例７〜１２、比較例５〜１
０」に訂正する。Table 2 (11) In the first line of page 15 of the specification, "Examples 3 to 6, Comparative Examples 5 to 9" is replaced with [Examples 7 to 12, Comparative Examples 5 to 1]
Correct it to 0.
（１２）明細書第１６頁第１４行目及び第１７行目に［
調９１とあるをそれぞれ「調製」に訂正する。(12) On page 16, line 14 and line 17 of the specification [
Correct the words ``key 91'' to ``preparation.''
（１３）明ｍ書ｔＰＪ１７頁全文を別紙の通りに補正す
る。(13) The entire text of page 17 of the Memorandum of Understanding shall be amended as per the attached sheet.
Claims (2)
I ］ （ＲＯ（ＣＨ＿２ＣＨ＿２Ｏ）ｎ）ｋＰＯ（ＯＨ）ｌ（
ＯＭ）ｍ・・・・・・［ I ］ （式中、Ｒは炭素数８から３０のアルキル基またはアル
キルフェニル基、 ｋは１から３の整数、 ｌ及びｍは０から２の整数で、ｋ＋ｌ＋ｍ＝３Ｍはアル
カリ金属原子、またはアンモニウム基、ｎは０から１５
の整数 をそれぞれ示す。） で表されるリン酸エステルまたはその混合物を０．１〜
５重量部含有せしめた塩化ビニル系重合体組成物。(1) 100 parts by weight of a vinyl chloride polymer was added with the general formula [
I] (RO(CH_2CH_2O)n)kPO(OH)l(
OM)m...[I] (wherein, R is an alkyl group or alkylphenyl group having 8 to 30 carbon atoms, k is an integer of 1 to 3, l and m are integers of 0 to 2, k+l+m=3M is an alkali metal atom or ammonium group, n is 0 to 15
Indicate each integer. ) Phosphate ester or mixture thereof represented by 0.1 to
A vinyl chloride polymer composition containing 5 parts by weight.
物が、Ｒがノニルフェニル基、ｍ＝０、ｎ＝９、であっ
て、ｋ＝１かつｌ＝２、もしくは、ｋ＝２かつｌ＝１で
あるものの混合物でその混合比（ｋ＝１：ｋ＝２）が１
：４〜４：１である特許請求の範囲第１項記載の塩化ビ
ニル系重合体組成物。(2) A mixture of phosphoric esters represented by the general formula [I], where R is a nonylphenyl group, m=0, n=9, and k=1 and l=2, or k=2 and l=1, and the mixing ratio (k=1:k=2) is 1
The vinyl chloride polymer composition according to claim 1, wherein the polyvinyl chloride polymer composition has a ratio of:4 to 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP557287A JPS63175057A (en) | 1987-01-13 | 1987-01-13 | Vinyl chloride based polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP557287A JPS63175057A (en) | 1987-01-13 | 1987-01-13 | Vinyl chloride based polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63175057A true JPS63175057A (en) | 1988-07-19 |
| JPH0547581B2 JPH0547581B2 (en) | 1993-07-19 |
Family
ID=11614932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP557287A Granted JPS63175057A (en) | 1987-01-13 | 1987-01-13 | Vinyl chloride based polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63175057A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04226321A (en) * | 1990-05-16 | 1992-08-17 | Nippon Zeon Co Ltd | Manufacture of window glass with gasket |
| JP2007297060A (en) * | 2006-04-27 | 2007-11-15 | Ajinomoto Co Inc | Blister package for syringe |
| US20210198449A1 (en) * | 2018-06-07 | 2021-07-01 | Eastman Chemical Company | Highly filled plastisols |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5391958A (en) * | 1977-08-17 | 1978-08-12 | Katsuta Kako Kk | Stabilized halogeneecontaining resin composition |
| JPS588407A (en) * | 1981-07-07 | 1983-01-18 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JPS5876441A (en) * | 1981-10-31 | 1983-05-09 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride pasty resin composition and vinyl chloride pasty resin sol composition |
| JPS5928227A (en) * | 1982-08-09 | 1984-02-14 | Victor Co Of Japan Ltd | Magnetic recording medium |
| JPS59219378A (en) * | 1983-05-27 | 1984-12-10 | Shiraishi Chuo Kenkyusho:Kk | Vinyl chloride resin paste sol composition |
| JPS60161451A (en) * | 1984-01-30 | 1985-08-23 | Sumitomo Chem Co Ltd | Vinyl chloride based resin composition for powder molding |
| JPS60226542A (en) * | 1984-04-25 | 1985-11-11 | Mitsubishi Kasei Vinyl Co | Flame-retardant vinyl chloride resin composition |
| JPS6116950A (en) * | 1984-07-02 | 1986-01-24 | Mitsubishi Kasei Vinyl Co | Vinyl chloride resin film for agriculture |
| JPS6144939A (en) * | 1984-08-10 | 1986-03-04 | Mitsubishi Kasei Vinyl Co | Vinyl chloride polymer composition |
| JPS61101544A (en) * | 1984-10-25 | 1986-05-20 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
-
1987
- 1987-01-13 JP JP557287A patent/JPS63175057A/en active Granted
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5391958A (en) * | 1977-08-17 | 1978-08-12 | Katsuta Kako Kk | Stabilized halogeneecontaining resin composition |
| JPS588407A (en) * | 1981-07-07 | 1983-01-18 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JPS5876441A (en) * | 1981-10-31 | 1983-05-09 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride pasty resin composition and vinyl chloride pasty resin sol composition |
| JPS5928227A (en) * | 1982-08-09 | 1984-02-14 | Victor Co Of Japan Ltd | Magnetic recording medium |
| JPS59219378A (en) * | 1983-05-27 | 1984-12-10 | Shiraishi Chuo Kenkyusho:Kk | Vinyl chloride resin paste sol composition |
| JPS60161451A (en) * | 1984-01-30 | 1985-08-23 | Sumitomo Chem Co Ltd | Vinyl chloride based resin composition for powder molding |
| JPS60226542A (en) * | 1984-04-25 | 1985-11-11 | Mitsubishi Kasei Vinyl Co | Flame-retardant vinyl chloride resin composition |
| JPS6116950A (en) * | 1984-07-02 | 1986-01-24 | Mitsubishi Kasei Vinyl Co | Vinyl chloride resin film for agriculture |
| JPS6144939A (en) * | 1984-08-10 | 1986-03-04 | Mitsubishi Kasei Vinyl Co | Vinyl chloride polymer composition |
| JPS61101544A (en) * | 1984-10-25 | 1986-05-20 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04226321A (en) * | 1990-05-16 | 1992-08-17 | Nippon Zeon Co Ltd | Manufacture of window glass with gasket |
| JP2007297060A (en) * | 2006-04-27 | 2007-11-15 | Ajinomoto Co Inc | Blister package for syringe |
| US20210198449A1 (en) * | 2018-06-07 | 2021-07-01 | Eastman Chemical Company | Highly filled plastisols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0547581B2 (en) | 1993-07-19 |
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| EXPY | Cancellation because of completion of term |