TW200837119A - Aggregate particle comprising vinyl chloride resin and process for production thereof - Google Patents
Aggregate particle comprising vinyl chloride resin and process for production thereof Download PDFInfo
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- TW200837119A TW200837119A TW96137109A TW96137109A TW200837119A TW 200837119 A TW200837119 A TW 200837119A TW 96137109 A TW96137109 A TW 96137109A TW 96137109 A TW96137109 A TW 96137109A TW 200837119 A TW200837119 A TW 200837119A
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- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
200837119 九、發明說明： 【發明所屬之技術領域】 本發明係關於包含氯乙稀樹脂之凝集體粒子及其製造方 法。進一步詳細而言，係關於含有對布料具有不滲透性之 漿料加工用氯乙烯樹脂的凝集體粒子及其製造方法。 【先前技術】200837119 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to aggregate particles comprising a vinyl chloride resin and a method for producing the same. More specifically, it relates to agglomerated particles containing a vinyl chloride resin for slurry processing which is impervious to cloth and a method for producing the same. [Prior Art]
以氯乙烯樹脂披覆之片、手套、袋等，因機械強度較強 且耐磨損性、耐藥品性、耐油性優良，故而廣泛地應用於 水產業、農業、礦業等多個領域中。 先前以來，將氯乙烯樹脂披覆於布料所成之產品係按照 下述方式而製造，將_光機、擠壓機、射出機等所成形 之，乙烯樹脂的溶融體流延於布料，或者將氯乙稀樹脂與 鄰苯二甲酸二辛酯等增塑劑航之塑料轉噴霧塗佈或浸 潰於布料。為了以高生產速度自動生產塗佈有較薄之氯乙 烯樹脂的產品，例如手套、袋物等時，較之流延熔融體之 方法，使用塑料溶膠之喷霧塗佈或浸潰方法於經濟上更加 喷霧塗佈、浸潰方法時， 塑枓，合膠係黏稠之液體，故而 存在將其向布料舍你、、'夺、主 透、且渗透至布^面况 』料轉會向布料中渗 布科月面，加熱處理塑料溶 體亦會向布料背面炎读> & 胗化熔融 卄月面滲透之情形。若塑料溶 布料背面滲透，心導σ /以広融體向 壞產品之性能。尤立是 不良攸而破 亦會給使用者”時，即使係局部之滲透， 使用者帶來不便，導致產品價值受損。 125418.doc 200837119 作為防止塑料溶膠滲透至布料之方法， 料之方法、改良塑料轉之黏度性/有預處理布 均不足以防止塑料溶膠之渗透。方法’然而任一者 雖然有添加水溶性高分子、且實施噴霧乾燥之 利文獻υ’然而’添加水溶性高分子之後，會導致乳膠之 黏度上升，出現堵塞噴霧乾燥之噴嘴等。Sheets, gloves, bags, etc. coated with vinyl chloride resin are widely used in many fields such as aquaculture, agriculture, and mining because of their high mechanical strength, excellent wear resistance, chemical resistance, and oil resistance. Conventionally, a product obtained by coating a vinyl chloride resin on a cloth is manufactured in the following manner, and a melt of a vinyl resin formed on a fabric, an extruder, an injection machine, or the like is cast on a cloth, or The plasticizer such as vinyl chloride resin and dioctyl phthalate is spray coated or impregnated into the fabric. In order to automatically produce products coated with a thinner vinyl chloride resin, such as gloves, bags, etc., at a high production speed, it is economical to use a spray coating or impregnation method of a plastisol as compared to a method of casting a melt. In the case of spray coating and dipping, the plastic is a viscous liquid, so there is a tendency to move it to the fabric, to "take, pass through, and penetrate into the cloth." The medium permeable fabric has a lunar surface, and the heat-treated plastic solution also illuminates the back of the fabric. && If the back of the plastic soluble cloth penetrates, the core guide σ / the performance of the melted product to the bad product. When Yuli is broken, it will also be given to the user. Even if it is partially infiltrated, the user is inconvenienced and the value of the product is impaired. 125418.doc 200837119 As a method for preventing the penetration of the plastisol into the fabric, the method of the material The modified plastics have a viscosity/pretreatment cloth which is not enough to prevent the penetration of the plastisol. However, although there is a method of adding a water-soluble polymer and performing spray drying, the literature has a high water solubility. After the molecule, the viscosity of the latex rises, and the nozzle that blocks the spray drying appears.
雖然有利用自身發熱型之高速旋轉混合機，於m代 之溫度對凝集漿料用氯乙烯樹脂進行熱處理、使其融合之 方法（專利文獻2) ’然而無法均_地進行熱處理，從而無法 改善對布料之非滲透性。 μ 又，提出有於低溫粉碎氯乙烯樹脂之懸浮聚合物，調整 樹脂粒徑分布，使粒子具有某種程度之強度的方法（專= 文獻3)’然而非滲透性並不充分。 [專利文獻1]日本專利特開昭48_丨MW號公耜 [專利文獻2]曰本專利特公昭46-7 177號公報 [專利文獻3]曰本專利特公平2-40692號公報 【發明内容】 本發明為解決上述先前之問題，而提供一種適用於對布 料無滲透性之漿料加工用氯乙烯樹脂粒子的、包含氯乙稀 樹脂之凝集體粒子及其製造方法。 [解決問題之技術手段] 本發明之包含氯乙烯樹脂之凝集體粒子之特徵在於：其 係向一次粒子之平均粒子徑在0.^2.0 μπι之範圍内的氣乙 烯樹脂乳膠中，含有選自水溶性高分子及無機鹽中之至少 125418.doc 200837119 種之5^劑、且矣举乾》夕隹7 f 、二之减集體粒子，上述凝集體粒子 係由上述一次粒子隼会而勒# k、+、n & 呆口而t/成，上述旋集體粒子之平均粒 子徑在5 μιη〜40 μιη之範圍内。 本發明之包含氯乙烯樹脂之凝集㈣子之製造方法之特 徵在於：向-次粒子之平均粒子徑在Gi〜2g㈣之範圍内 的氣乙烯樹脂乳膠中’添加選自水溶性高分子及無機鹽中 至v-種之凝聚劑’而製成包含上述氯乙烯樹脂之凝集體 孝子之此口 Jc /合液’藉由將上述混合水溶液喷霧乾燥，從 而獲得平均粒子徑為5 μπι〜4〇 μπΐ2凝集體粒子。 【實施方式】 本發明可提供—種包含對布料具有不渗透性之裝料加工 用氯乙烯樹脂之凝集體粒子’該包含裝料加工用氯乙烯樹 脂之凝集體粒子中包含一次粒子之平均粒子徑在〇1〜2〇 叫!圍内的氯乙物旨、及選自水溶性高分子… 鹽中至少—種之凝聚劑，上述凝集體粒子係由上述-次粒 子集合而形成’上述凝集體粒子之平均粒子徑在5叫〜4〇 叫之範圍内’藉此，對布料具有不渗透性。又，本發明 可藉由下述方式而有效製作對布料具有不滲透性之聚料加 工用氣乙烯樹絲子，卩卩，於讀直前混合氯乙烯樹脂之 礼膠、以及水溶性高分子及/或水溶性電解質，且立即實 施噴霧乾燥。該方法尤其適用於量產中。 進而，本發明可提供-種對布料具有不渗透性之包含聚 枓加工用氯乙稀樹脂之凝集體粒子，該包含㈣加工用氯 乙浠樹脂之凝集體粒子係，於—次粒子之平均粒子徑在 125418.doc 200837119 0.1〜2.0 μΐη之範圍内的氯乙烯㈣乳膠中包含選自非離子 性界面活性劑(Α)及氯乙烯聚合物以外之乳化聚合乳膠⑻ :之至少一種成分、及選自水溶性高分子及無機鹽中至少 -種之凝聚劑、且經乾燥之凝集體粒子，上述凝集體粒子 係^上述―次粒子集合而形成’上述凝集體粒子之平均粒 子徑在5 μηι〜40 μηι之範圍内。 本發明之包含氯乙稀樹脂之凝集體粒子係，對布料具有 不渗透性之聚料加工用氯乙稀樹脂。χ，該聚料加工用氯 乙浠樹脂係藉由下述方式而獲得，即，對於經微細懸浮或 礼化聚合所獲得之氯乙烯樹脂之基本粒子，使特定之非離 子性界面活性劑或氯乙稀聚合物以外之聚合物粒子存在於 乳膝中’其後以特定凝聚劑使其凝集，藉此而獲得且有流 =之凝錄子，且對該具有流㈣之凝錄子實施喷霧 乾，。再者，本說明書中之「布料」係指，織物… 品、不織布等使用有纖維之片狀物。 本發明中所使用之氯乙烯系樹脂係藉由下述方式而獲 得’即，將氯乙烯單體、或氯乙稀單體，及可與其共聚: 之單體的混合物放入水介質中’向其中加入乳化劑:、且： 據需要而加入高級醇、高級脂肪酸等助分散劑，進而添二 油溶性聚合起始劑而均質化後’進行微細懸浮聚合、或加 入水溶性起始劑而進行乳化聚合、播種乳化聚合等。 本發明之氯乙烯樹脂的一次粒子係平均粒子裡通常為 〇从1〜2.0 μΐη的微粒子’其係水性均質分散液（乳膠），然而 若為了實現本發明之目的則並不限於該範圍。考慮到聚合 125418.doc 200837119 之穩疋性，較好的是0.1 pm〜17 μηι，更好的是〇ι〜i4 μιη 〇 氯乙烯單體及與其共聚合所得之單體並無特別限制，可 使用：乙烯、丙烯、丁烯等烯烴類，乙酸乙烯酯、丙酸乙 烯酯、硬脂酸乙烯酯等乙烯酯類，甲基乙烯基醚、乙基乙 烯基醚、辛基乙烯基醚、月桂基乙烯基鱗等乙稀基鱗類， 偏氯乙烯等亞乙烯基類，丙烯酸、甲基丙烯酸、反丁烯二 酸、順丁稀二酸、衣康酸、順丁烯二酸酐、衣康酸酐等不 飽和緩酸及其酸軒，丙烯酸甲g旨、丙烯酸⑽、順丁婦二 酸單甲醋、順丁婦二酸二甲醋、順丁稀二酸丁基节醋等： 飽和叛酸醋類’苯乙稀、"基苯乙稀、^乙烯苯等芳香 族乙烯系化合物’丙稀腈等不飽和腈類，$而是鄰苯二甲 酸二烯丙轉交聯性單料可純乙料聚合之 周知之單體。該黧罝體曰 、人A ，.二之使用1較好的是，未滿與氯乙缚 之混合物的5 0重量％。 r 用於聚合之乳化劑並無特別限制，然而相對於每單體 100重量份，陰離子性只而 體 、 界面/舌性劑通常使用0·1〜3重量份尤 右。作為陰離子性界面活性劑可： 酸、烷基苯磺酸、烷美♦ 9 I、烷基硫 &基石貝基琥轴酸、心烯 磷酸酯等鉀、鈉、銨鹽等。 〃 ^烷基醚 作為用於聚合之油溶性 醯 合汪起始劑，可使用 、二_3,5,5-過氧化二ψ冀口 * 、乳化一月桂 化二碳酸二異丙輯、：:·=，：二酿基類’過氧 酸酯類，第三丁基過氧化―仏乙酯等過氧化二碳 —甲基乙酸醋、過氧化新癸酸第 125418.doc 200837119 一 、之氧酯類等有機過氧化物起始劑，及2 jg —p gi 、 5 ^ 鳳ι 八 月 ’2’·偶氮雙（2,4-二甲基戊腈）、22*钽 > 雜 T M/Xmj 2,2-偶氮雙（4_甲 人土 * f二甲基戊腈）等偶氮系起始劑。作為用於乳化聚 合之水溶性起始劑，可使用過硫酸銨、過硫酸钾、過硫酸 -氧化氫水等’根據需要亦可併用亞硫酸鈉、硫代硫 I鈉、甲醛次硫酸鈉2水鹽、抗壞血酸、抗壞血酸鈉等還 原劑。該等亦可單獨使用、亦可混合2種以上使用。 本發明中所使用之凝聚劑，係選自水溶性高分子及無機 鹽（電解質）中之至少-者。亦即’係水溶性高分子、無機 鹽（電解質）或水溶性高分子與無機鹽（電解質）之組合。 作為水溶性高分子係合成高分子，# :含有丙稀酿基之 單體聚合物（共聚物）[聚（甲基）丙烯醯胺、聚（甲基）丙烯酸 (鹽）及聚（甲基）丙烯酸酯等]、乙烯系聚合物（共聚物）[聚乙 烯醇、聚乙烯吡咯烷酮、聚乙烯甲醚、含有羧基夕乙 聚合物（共聚物）（聚乙酸乙烯酯等）及聚對苯乙烯磺酸（鹽） 專]、聚脉、t氧化乙稀及聚乙稀亞胺等。作為天然高分 子係多糖類（澱粉、糊精、葡甘露聚醣、半乳甘露聚糖、 ***膠、三仙膠、果膠、卡拉膠、刺槐豆膠、瓜爾膠、 黃耆膠、甲殼質、聚葡萄胺糖、普魯蘭及海藻酸鹽等）， 及蛋白質（白明膠、酪蛋白及膠原蛋白等）等。作為半合成 高分子，可列舉：纖維素醚（甲基纖維素、乙基纖維素、 苄基纖維素、三苯甲基纖維素、氰基乙基纖維素、胺基乙 基纖維素、羥基甲基纖維素、羥基乙基纖維素、乙基輕乙 基纖維素、甲基羥丙基纖維素、羧甲基纖維素及羧乙基纖 125418.doc -11- 200837119 維素等）及澱粉衍生物（可溶性澱粉、甲基澱粉及緩甲澱粉 等）等。該等水溶性高分子可單獨添加，亦可組合2種以上 進行添加。 作為水溶性高分子之添加量，相對於氯乙烯樹脂1〇〇重 量份’較好的是〇·〇1重量份〜10重量份，更加較好的是〇1 重量份〜2重量份。若在上述範圍内則可獲得不滲透性更 高、漿料黏度保持在較佳範圍、且具有流動性之漿料，從 而可使得送液線或喷嘴之通過性較佳，噴霧乾燥亦良好。 關於電解質，具體而言可列舉：解離成Na+、κ+、 Mg2+、、W、Η+ 等，或 C1-、Br·、S(V·、s〇32·、 NCV、Ν〇3·、Ρ〇43·、C〇32·、〇H-等離子之化合物等。作為 用以獲得上述電解質之無機鹽，可列舉：Nac卜〖Ο、In the case of a high-speed rotary mixer using a self-heating type, a method of heat-treating and blending a gelled slurry with a vinyl chloride resin at a temperature of m is used (Patent Document 2). However, heat treatment cannot be performed uniformly, and thus it is impossible to improve. Impervious to cloth. Further, there has been proposed a method of low-temperature pulverization of a suspension polymer of a vinyl chloride resin to adjust the particle size distribution of the resin to impart a certain degree of strength to the particles (Specific Document 3). However, the impermeability is not sufficient. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In order to solve the above-mentioned problems, the present invention provides an aggregate particle containing a vinyl chloride resin and a method for producing the same, which are suitable for a vinyl chloride resin particle for slurry processing which is impervious to a cloth. [Technical means for solving the problem] The aggregate particle containing the vinyl chloride resin of the present invention is characterized in that it is selected from the group consisting of a gas-vinyl resin latex having an average particle diameter of the primary particles in the range of 0.1 to 2.0 μm. At least 125418.doc 200837119 of the water-soluble polymer and the inorganic salt, and the collective particles of the 矣 干 》 隹 f f f f f 、 、 、 、 、 、 、 、 , , 上述 上述 上述 上述 上述 上述k, +, n & linger and t/cheng, the average particle diameter of the above-mentioned spheroidal particles is in the range of 5 μm to 40 μm. The method for producing agglomerated (tetra) of a vinyl chloride resin according to the present invention is characterized in that a solvent selected from the group consisting of a water-soluble polymer and an inorganic salt is added to a gas-ethylene resin latex having an average particle diameter in the range of Gi 2 g (4). The medium-to-v-type coagulant is prepared to form the Jc/liquid mixture of the condensate of the above-mentioned vinyl chloride resin by spray-drying the above mixed aqueous solution to obtain an average particle diameter of 5 μπι 4 〇 Ϊ́πΐ2 aggregate particles. [Embodiment] The present invention provides an aggregate particle comprising a vinyl chloride resin for charging processing which is impervious to a cloth. The aggregate particle containing the primary particle in the aggregate particle of the vinyl chloride resin for charging processing The 〇1~2 〇 ! ! ! ! ! ! ! ! ! ! ! ! ! ! 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯 氯The average particle diameter of the body particles is within the range of 5 to 4 〇 ' ', thereby being impervious to the cloth. Moreover, the present invention can effectively produce a gas-processed vinyl filament yarn for processing a material which is impervious to cloth by the following means, and a scent of a vinyl chloride resin and a water-soluble polymer before reading straight. / or water soluble electrolyte, and spray drying is carried out immediately. This method is especially suitable for mass production. Further, the present invention can provide an aggregate particle comprising a polyvinyl chloride resin for processing a polyamide which is impervious to a cloth, and comprises (4) an aggregate particle system of a chloroacetic resin for processing, which is an average of the secondary particles. The vinyl chloride (tetra) latex having a particle diameter in the range of 125418.doc 200837119 0.1 to 2.0 μΐη comprises at least one component selected from the group consisting of a nonionic surfactant (Α) and a vinyl chloride polymer (8): Agglomerating agent selected from at least one of a water-soluble polymer and an inorganic salt, and dried aggregated particles, wherein the aggregated particles are formed by the above-mentioned "secondary particles" to form an average particle diameter of the above aggregated particles of 5 μηι Within the range of ~40 μηι. The agglomerate particle system comprising a vinyl chloride resin of the present invention is a vinyl chloride resin for processing a polymer having impermeability to a cloth. χ, the chloroacetic acid resin for processing a polymer material is obtained by using a specific nonionic surfactant or a basic particle of a vinyl chloride resin obtained by fine suspension or ritual polymerization. The polymer particles other than the vinyl chloride polymer are present in the nipple', and then aggregated with a specific coagulant, thereby obtaining a condensate having a flow = and performing the condensate on the stream (4) Spray dry. In addition, the term "clothing" as used in the present specification means a sheet using fibers such as a fabric, a non-woven fabric, or the like. The vinyl chloride resin used in the present invention is obtained by "forming a mixture of a vinyl chloride monomer or a vinyl chloride monomer, and a monomer copolymerizable therewith in an aqueous medium". An emulsifier is added thereto: and: a co-dispersant such as a higher alcohol or a higher fatty acid is added as needed, and then a second oil-soluble polymerization initiator is added to be homogenized to perform a fine suspension polymerization or a water-soluble starter. Emulsification polymerization, seeding emulsion polymerization, and the like are carried out. The primary particle-based average particle of the vinyl chloride resin of the present invention is usually a fine particle of 〜 from 1 to 2.0 μΐ, which is an aqueous homogeneous dispersion (latex), but is not limited to this range for the purpose of the present invention. Considering the stability of the polymerization 125418.doc 200837119, it is preferably 0.1 pm to 17 μηι, more preferably 〇ι~i4 μιη 〇 vinyl chloride monomer and the monomer obtained by copolymerization thereof are not particularly limited, Use: olefins such as ethylene, propylene, butylene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearate, methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, laurel Ethylene-based scales such as vinyl scales, vinylidenes such as vinylidene chloride, acrylic acid, methacrylic acid, fumaric acid, cis-succinic acid, itaconic acid, maleic anhydride, and itacon Unsaturated acid such as acid anhydride and its acid sulphate, acrylic acid, acrylic acid (10), cis-butane dicarboxylic acid monomethyl vinegar, cis-butane dicarboxylic acid dimethyl vinegar, cis-butyl phthalate vinegar, etc. Acidic vinegars such as styrene, " phenyl benzene, ethylene benzene and other aromatic vinyl compounds such as acrylonitrile and other unsaturated nitriles, $ is a phthalic acid diene-trans crosslinkable material. A well-known monomer for the polymerization of pure ethylene. Preferably, the use of the carcass, human A, and the second is less than 50% by weight of the mixture bound to the chlorine. r The emulsifier used for the polymerization is not particularly limited. However, the anionic body, the interface/tongue agent is usually used in an amount of from 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer. The anionic surfactant may be a potassium, a sodium or an ammonium salt such as an acid, an alkylbenzenesulfonic acid, an alkylene IX 9 I, an alkylsulfide & sulphate succinic acid or a heart olefin phosphate. 〃 ^Alkyl ether is used as an oil-soluble hydrazine initiator for polymerization. It can be used, bis-3,5,5-diperoxide oxime*, emulsified monolaurin diisopropylate, :·=,: Di-branched bases 'peroxyacid esters, t-butyl peroxy- oxime ethyl esters, etc., such as peroxydicarbonate-methylacetate vinegar, peroxy neodecanoic acid 125418.doc 200837119 I. Organic peroxide initiators such as oxyesters, and 2 jg —p gi , 5 ^ feng ι August '2' azobis(2,4-dimethylvaleronitrile), 22*钽> An azo initiator such as TM/Xmj 2,2-azobis (4-methylate*f dimethylvaleronitrile). As a water-soluble initiator for emulsion polymerization, ammonium persulfate, potassium persulfate, persulfate-hydrogen peroxide water, etc. may be used. If necessary, sodium sulfite, sodium thiosulfate I, sodium sulfoxylate sulfate, and sodium sulfonate may be used in combination. , reducing agents such as ascorbic acid and sodium ascorbate. These may be used alone or in combination of two or more. The coagulant used in the present invention is selected from at least one of a water-soluble polymer and an inorganic salt (electrolyte). That is, it is a combination of a water-soluble polymer, an inorganic salt (electrolyte), or a water-soluble polymer and an inorganic salt (electrolyte). As a water-soluble polymer-based synthetic polymer, #: a monomeric polymer (copolymer) containing an acrylonitrile group [poly(meth)acrylamide, poly(meth)acrylic acid (salt), and poly(methyl) Acrylate, etc.], ethylene-based polymer (copolymer) [polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyl-containing vinyl polymer (copolymer) (polyvinyl acetate, etc.) and poly-p-styrene Sulfonic acid (salt) special], poly vein, t ethylene oxide and polyethyleneimine. As a natural polymer polysaccharide (starch, dextrin, glucomannan, galactomannan, gum arabic, sanxian gum, pectin, carrageenan, locust bean gum, guar gum, gum tragacanth, carapace Quality, polyglucamine, pullulan and alginate, and proteins (white gelatin, casein, collagen, etc.). Examples of the semisynthetic polymer include cellulose ether (methylcellulose, ethylcellulose, benzylcellulose, tritylcellulose, cyanoethylcellulose, aminoethylcellulose, and hydroxyl group). Methyl cellulose, hydroxyethyl cellulose, ethyl light ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose and carboxyethyl fiber 125418.doc -11- 200837119, etc.) and starch Derivatives (soluble starch, methyl starch, slow starch, etc.), etc. These water-soluble polymers may be added singly or in combination of two or more. The amount of the water-soluble polymer to be added is preferably 1 part by weight to 10 parts by weight, more preferably 1 part by weight to 2 parts by weight, based on 1 part by weight of the vinyl chloride resin. If it is within the above range, a slurry having higher impermeability, a slurry viscosity maintained in a preferable range, and fluidity can be obtained, whereby the liquid supply line or the nozzle can be passed, and spray drying is also good. Specific examples of the electrolyte include dissociation into Na+, κ+, Mg2+, W, Η+, or the like, or C1-, Br·, S (V·, s〇32·, NCV, Ν〇3·, Ρ 〇43·, C〇32·, 〇H-plasma compound, etc. As an inorganic salt for obtaining the above electrolyte, Nac Ο, Ο,
Na2S〇4、CaCl2、A1Cl3等。關於添加量，相對於氣乙稀樹 脂〗00重量份，較好的是〇1〜1〇重量份。更好的县η%'舌 量份。電解質之添加量若在上述範圍内，則易於獲得凝； 粒子，不滲透性更佳，喷霧乾燥亦良好。 根據獲得具有流動性之裝料的觀點，較好的是電解質中 具有Ν&+等1價金屬離子之硫酸鈉。亦可使用2價、3價之金 =鹽、然而存在降低乳膠之穩定性之情形，故而需要注 意。 :聚：之水溶性高分子與電解質添加於氯乙浠樹脂乳膠 :二可為固體、水溶液之任一者，然而根據分散觀 是水溶液形態’進而較好的是一输一邊向 礼膠中添加。水溶性高分子與電解質之向乳膠之添加，較 125418.doc -12- 200837119 好的是於氯乙烯樹脂之乳化聚合之後半階段、或聚合結束 後添加。添加凝聚劑時之乳膠溫度，亦可選定為混凝 聚劑後之混合物的黏度不會增高之範圍。 本發明中較好的是，於添加凝聚劑之前，進而添加非離 子性界面活性劑。非離子性界面活性劑有助於有效製作凝 集粒子。作為非離子性界面活性劑，可列舉：聚氧化稀化 合物、聚氧乙稀院基縫、聚氧乙烯烧基苯峻、去水山梨醇 脂肪酸醋、聚氧乙稀去水山梨醇脂肪酸醋、聚氧乙稀脂肪 酿醋、甘油單脂肪酸酯等。 添加非離子性界面活性劑時，其添加時間較好的是，在 添加凝聚劑之水溶性高分子及無機鹽（電解f)之前實施添 加°藉此’即《料濃度為35重量％以上之較高濃度，亦 可保持其流動性，從而可利用泵進行輸送。 :離子性界面活性劑之添加量，相對於氯乙烯樹脂⑽ 重里伤，為o.ow重量份之範圍。較好的是〇〇5〜〇5重量 ^更好的是(M5〜0.35重量份1在上述範圍内，則可提 冋;旋集粒子之生產性。 本發明中所使狀氯乙料合物料的乳化聚合乳膠， 能夠發揮不滲透性改善劑之功能。作為氯乙烯聚合物以外 之礼化聚合乳膠，可列舉：（甲基)丙埽酸I系均聚物、(甲 基）丙稀酸醋與（甲基）丙稀酸醋之共聚合物、及乙烯-乙酸 乙烯酯共聚合物等。 氯=浠聚合物以外之乳化聚合乳膠之添加量，相對於氯 乙~樹脂1 〇 0重量份，較好的I 、 1 乂好的疋所含有之聚合物為1〜10重 125418.doc -13- 200837119 量份之範圍。若在上述範圍内則可進一步提高對布料之不 渗透性效果。 較好的是，對上述所凝集之漿料進行熱處理。藉由熱處 理’使所凝集之粒子強固地融合，從而凝集粒子成為更加 易於展現不滲透性之構造。熱處理溫度係氯乙烯聚合物之 玻璃轉移溫度（約80。〇(參照P〇lymer Handb〇〇k. μ edition. V/63頁及VI/222頁）以上。較好的是95〜15〇它。更Na2S〇4, CaCl2, A1Cl3, and the like. The amount of addition is preferably from 1 to 1 part by weight based on 00 parts by weight of the ethylene glycol resin. Better county η%' tongue volume. When the amount of the electrolyte added is within the above range, coagulation is easily obtained; particles are more excellent in impermeability, and spray drying is also good. From the viewpoint of obtaining a fluid charge, sodium sulfate having a monovalent metal ion such as Ν &+ is preferred in the electrolyte. It is also possible to use a divalent or trivalent gold = salt, but there is a case where the stability of the latex is lowered, so care is required. : Poly: the water-soluble polymer and electrolyte are added to the chloroacetic acid resin latex: two can be either solid or aqueous solution, however, according to the dispersion view is the aqueous solution form, and it is better to add one side to the gum . The addition of the water-soluble polymer and the electrolyte to the latex is preferably carried out in the half stage after the emulsion polymerization of the vinyl chloride resin or after the end of the polymerization, as compared with 125418.doc -12-200837119. The temperature of the latex when the coagulant is added may also be selected as the range in which the viscosity of the mixture after the coagulating agent is not increased. In the present invention, it is preferred to further add a nonionic surfactant before the addition of the coagulant. Nonionic surfactants help to efficiently produce aggregated particles. Examples of the nonionic surfactant include a polyoxygen oxide compound, a polyoxyethylene base crack, a polyoxyethylene burnt base, a sorbitan fatty acid vinegar, and a polyoxyethylene sorbitan fatty acid vinegar. Polyoxyethylene fat vinegar, glycerin mono-fatty acid ester and the like. When a nonionic surfactant is added, the addition time is preferably carried out before the addition of the water-soluble polymer and the inorganic salt (electrolytic f) of the coagulant, whereby the concentration of the material is 35 wt% or more. At higher concentrations, it also maintains its fluidity so that it can be pumped. The amount of the ionic surfactant added is in the range of o. ow by weight relative to the vinyl chloride resin (10). More preferably, 〇〇5 to 〇5 by weight is more preferably (M5 to 0.35 parts by weight of 1 in the above range, the sputum can be extracted; the productivity of the spheroidal particles. Emulsified polymer latex of the material can function as an impermeability improver. As a lithiated polymer latex other than a vinyl chloride polymer, (meth)propionic acid I-based homopolymer, (meth) propylene a copolymer of acid vinegar and (meth) acrylate vinegar, and an ethylene-vinyl acetate copolymer, etc. The addition amount of the emulsified polymer latex other than chlorine = bismuth polymer, relative to the chloroethyl~resin 1 〇0 The parts by weight of the preferred I, 1 疋 疋 为 为 125 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 418 Preferably, the agglomerated slurry is heat-treated. The agglomerated particles are strongly fused by heat treatment to agglomerate the particles into a structure which is more likely to exhibit impermeability. The heat treatment temperature is a vinyl chloride polymer. Glass transition temperature (about 80. 〇 (see P〇lymer Handb〇〇k. Μ edition. V / 63 and pages VI / 222 pages) or more. 95~15〇 it is preferred. More
好的疋U〇〜145°C。熱處理時間較好的是在1〜120分鐘之範 圍内。更好的是在5〜30分鐘之範圍内。 將上述經熱處理之漿料直接利用噴霧乾燥機進行乾燥 從而可獲得漿料加工用氯乙烯樹脂。 作為本發財所制之噴霧乾燥機，可使用具有加壓噴 嘴（一流體噴嘴）、二流體噴嘴、旋轉圓盤式（圓盤式）等作 為霧化器（噴霧器）之噴霧乾燥機。 較好的是，乾燥係於常壓下熱風乾燥。所供給之熱風溫 度，係用於漿料用氣乙稀樹脂之乾燥中之—般溫度，在 100〜220t之範圍内，乾燥機出口溫度通常在5卜1〇代之 範圍内。乾燥時間（乾燥機滯留時間）較㈣是2〇〜18〇秒。 關於由喷霧乾燥所獲得之噴霧乾燥粒子之平均粒子徑， 當制噴嘴式乾燥機時，可㈣喷嘴徑、乳m料之供 給量、供給空氣量、固形分濃度等進行調整^當使用旋 轉圓盤式乾燥機時，可根攄 J很艨％轉囡盤之旋轉數、乳膠或滎 料之供給置、固形分:望 7 衫^ 刀，辰度專進行調整。喷霧乾燥所獲得之 氣乙細樹脂粒子之早於 之千均粒子徑一般調整在5〜120 μιη之範圍 125418.doc -14- 200837119 内。藉此而獲得之噴霧乾燥粒子之平均粒子徑 μη之範圍内，則可直接用作產品（凝集體粒子）。 〜4〇 經過噴霧乾燥所獲得之粒子，亦可利^所周知 加以粉碎後進行使用。作為粉碎機， 、 j 1文用辊子研磨機、、 南速旋轉粉碎機、球磨機、氣流式粉碎機。 若凝集體粒子（以下亦稱作「樹脂粒子」 過小，則塑料溶膠之黏度會增高。 =粒子徑 力 方面，若平均叙 控過大，則塑料溶膠中之粗粒增加，伴隨時間之复 等會沈澱，故須要混合。根據該觀點，樹脂粒子：平均粒 子徑在5 — _之範圍内’較好的是5 _ f 圍。當過度實施粉碎時，存在無法獲 ^ 傾向。 T平乂1土之不滲透性的 本發明之氯乙浠樹脂粒子，較好的是 & V、粒子内部具有適 度空間，且最少增塑劑量較好的是5〇重量份以上。 向經噴霧乾燥機乾燥之漿料加工用氣 χ細―— 用虱乙烯樹脂粒子中混 郇本一甲酸二辛酯、己二酸二辛 ,.^ ^ 曰塑劑，進而，根 據$要添加適量之碳_等填充劑、發泡劑、穩定％、減 黏劑、抗氧化劑、紫外線吸收劑、難燃劑、抗靜電：、潤 滑劑、顏料、表面處理劑、搖變劑、黏著性職予劑等，加 以混合、混練，從而獲得漿料加工用氣 月 氣乙烯樹脂組合物 (塑料溶膠)。 一般而言，為了改善對布料塗佈、| 〜 神文潰塑料溶膠而獲 传之片、手套、袋等產品的柔軟 1ΛΛ^ ^ 相對於氯乙烯樹脂 100重ΐ份，使用80〜160重量份之較多量 里的增塑劑。雖然 125418.doc -15· 200837119 可知，增塑劑量越多則越易於引起滲透入布料背面，然而 本發明之漿料加工用氯乙烯樹脂粒子即使調配有高份數之 增塑劑亦不會引起滲透入布料背面。 [實施例] 繼而，藉由實施例進一步詳細說明本發明，然而本發明 並不限於該4示例。下述實施例、比較例中，僅記载為 「％」、「份」者分別表示「重量％」、「重量份」。 響 (1) 一次粒子、凝集體粒子、喷霧粒子之平均粒子徑 使用 MicroTRAC HRA MODEL9320-X1〇〇(日機裝股份有 限公司），測定粒子徑分布，以體積基準之中值直徑作為 平均粒子徑。測定條件為：溫度25t：，物質資訊係透明、 折射率1.51者，未發現球形粒子，載體係使用水、折射率 為1·33者。又，SET ZER〇設為1〇秒，計量1〇秒，不進行 DRY CUT計算。 (2)無滲透性評估 _ 相對於水料加工用氯乙浠樹脂粒子100重量份，調配〗40 重量份之增塑劑（鄰苯二曱酸二辛醋）、及3重量份之穩定劑 (旭電化（股）製商品名”SC73")，於室溫以石川式擂潰機混 • 合消泡10分鐘，藉此而獲得塑料溶膠。對布料之滲透試驗 . 係進行下述膠化熔融滲透試驗，即，於使用木棉絲29.5支 (棉支數）之針織物（兩面2段光滑圓形針織）、24隔距、工英 忖37針眼、單位面積重量216 g/m2之布上，將上述塑料溶 膠於室溫流延塗層約3 mm之厚度後，立即放入18〇它之熱 風循環爐中，實施3分鐘加熱處理且使其凝膠熔融，之 125418.doc •16- 200837119 後，調查熔融體是否已向布料背面滲透。 評估·以目視觀察，若於布之背面並無凝膠滲透則評估 為A，若有少許滲透則為B，若凝膠已滲透至布之背面則 為C之二專級評估。 (3)剝離性評估 將上述⑺中評估為A之樣品之膠化物自布剝離，根據以 下基準實施判定。再者’測定面積為4 cm2(縱橫各2⑽之 正方形）。Good 疋U〇~145°C. The heat treatment time is preferably in the range of 1 to 120 minutes. More preferably, it is within the range of 5 to 30 minutes. The above heat-treated slurry is directly dried by a spray dryer to obtain a vinyl chloride resin for slurry processing. As the spray dryer manufactured by the present invention, a spray dryer having a pressure nozzle (a fluid nozzle), a two-fluid nozzle, a rotary disk type (disc type) or the like as a atomizer (a sprayer) can be used. Preferably, the drying is hot air drying under normal pressure. The hot air temperature to be supplied is the temperature in the drying of the ethylene resin for the slurry, and the outlet temperature of the dryer is usually in the range of 5 to 1 Torr in the range of 100 to 220 tons. The drying time (dryer residence time) is 2〇~18〇 seconds compared to (4). Regarding the average particle diameter of the spray-dried particles obtained by spray drying, when a nozzle type dryer is used, it is possible to adjust (4) the nozzle diameter, the supply amount of the milk material, the supply air amount, the solid concentration, and the like. When the disc dryer is used, it can be adjusted according to the number of rotations of the 囡 囡 囡 、 、 、 、 、 、 、 、 乳 乳 乳 乳 乳 乳 : : : : : : : : : : : : : : : : : : : : The particle diameter of the particles of the ethylene resin particles obtained by spray drying is generally adjusted to be in the range of 5 to 120 μηη, 125418.doc -14-200837119. The spray-dried particles obtained by this can be used as a product (aggregate particles) directly within the range of the average particle diameter μη. ～4〇 The particles obtained by spray drying can also be pulverized and used. As a pulverizer, a j 1 roller roll mill, a south speed rotary pulverizer, a ball mill, and an air flow pulverizer. If the aggregate particles (hereinafter also referred to as "resin particles" are too small, the viscosity of the plastisol will increase. = In terms of particle diameter, if the average control is too large, the coarse particles in the plastisol will increase, and the time will be repeated. Precipitated, it is necessary to mix. According to this point of view, the resin particles: the average particle diameter is in the range of 5 - _, preferably 5 _ f. When excessive pulverization is carried out, there is a tendency to be unable to obtain. The impervious chloroacetic resin particles of the present invention are preferably & V, having a moderate space inside the particles, and preferably having a minimum plasticizing amount of 5 parts by weight or more. Drying by a spray dryer For the processing of the slurry, the gas is fine--mixed with dioctyl phthalate, dioctyl adipate, dioctyl adipate, and ^^ 曰 plasticizer, and further, according to the amount of carbon to be added , foaming agent, stable %, viscosity reducer, antioxidant, UV absorber, flame retardant, antistatic: lubricant, pigment, surface treatment agent, rocking agent, adhesive agent, etc., mixed, Mixing, thus obtaining slurry plus In the case of a gas-in-the-air ethylene resin composition (plastic sol), in general, in order to improve the coating of the cloth, the product of the glove, the bag, etc. The vinyl resin is 100 parts by weight, and a plasticizer in a large amount of 80 to 160 parts by weight is used. Although 125418.doc -15·200837119, the more the plasticizing amount, the more likely it is to infiltrate into the back of the fabric, but the present invention The vinyl chloride resin particles for slurry processing do not cause penetration into the back surface of the fabric even if a high proportion of the plasticizer is formulated. [Examples] Next, the present invention will be described in further detail by way of examples, but the invention is not limited thereto 4. In the following examples and comparative examples, only "%" and "parts" are respectively indicated as "% by weight" and "parts by weight". (1) Primary particles, aggregate particles, spray particles The average particle diameter was measured using a MicroTRAC HRA MODEL9320-X1 (Nikkiso Co., Ltd.), and the particle diameter distribution was measured, and the volume-based median diameter was used as the average particle diameter. The measurement conditions were: temperature 25t: The material information is transparent, the refractive index is 1.51, no spherical particles are found, the carrier uses water, and the refractive index is 1.33. Further, SET ZER〇 is set to 1 〇 second, and the measurement is 1 〇 second, and the DRY CUT calculation is not performed. (2) Non-permeability evaluation _ 40 parts by weight of a plasticizer (phthalic acid dioctyl vinegar) and 3 parts by weight of a stabilizer with respect to 100 parts by weight of chloroacetic resin particles for water processing (The product name "SC73" of Asahi Kasei Co., Ltd.) was mixed with Ishikawa-type machine at room temperature for 10 minutes to obtain a plastisol. Penetration test on cloth. Melt penetration test, that is, on a fabric using 29.5 pieces of cotton yarn (cotton count) (two sides of 2 smooth circular knitting), 24 gauges, 37 inches of industrial inch, and a weight per unit area of 216 g/m2 After casting the above plastisol at a thickness of about 3 mm at room temperature, immediately put it into a hot air circulating furnace of 18 Torr, heat treatment for 3 minutes and melt the gel, 125418.doc • 16- After 200837119, it was investigated whether the melt had penetrated into the back of the fabric. Evaluation· Visually, if there is no gel penetration on the back of the cloth, it is evaluated as A, if there is a little penetration, it is B. If the gel has penetrated to the back of the cloth, it is the C-level evaluation. (3) Evaluation of peelability The gel of the sample evaluated as A in the above (7) was peeled off from the cloth, and the judgment was carried out based on the following criteria. Furthermore, the measurement area was 4 cm 2 (squares of 2 (10) in each of the vertical and horizontal directions).
AA:膠化物於布上之殘留量未滿〇 〇3 g。 A:膠化物於布上之殘留量係〇 〇3 §以上。 (4)塑料溶膠黏度測定 將塑料溶膠於之忮溫水槽中浸潰i小時後，使用 BR〇〇KFIELD型黏度計（T〇K1MEKt)，由N〇 3轉子川進 行測定1分鐘後，讀取值，作為塑料溶膠黏度。 (實施例1)AA: The residual amount of the gel on the cloth is less than 〇3 g. A: The residual amount of the gel on the cloth is 〇3 § or more. (4) Determination of viscosity of plastisol After immersing the plastisol in a warm water bath for 1 hour, it was measured by N〇3 rotor tube using a BR〇〇KFIELD type viscometer (T〇K1MEKt) for 1 minute, and then read. Value, as plastisol viscosity. (Example 1)
向附夾套之3 0 0公升耐壓容零中 投入110 Kg之氣乙烯單 體、110 Kg之離子交換水、 銅五水合物，且升溫至5〇。(3 40 g之過硫酸銨、〇·3 g之硫酸 ’一邊授拌，一邊連續添加1 重量％之亞硫酸鈉水溶液盘】Λ舌曰。/ 备 岭履與10重之肉豆蔻酸銨水溶 液’猎此進 <亍聚合。聚合愿六白4替威 1 σ Μ力自初期壓力（0·7 MPa)降低至 0·15 MPa實施聚合後，回你綠赵 α 口收殘留之早體而獲得氯乙烯樹脂 乳膠。最終所獲得之乳膠之璧+ i Λ > 吵 < 對初期投入之單體及追加單體 的總量（以下記作全單體量）之聚合轉化率為9〇%。又，所 獲得之乳膠的-次粒子之平均粒子徑為〇3 。 125418.doc -17- 200837119 以使氯乙婦樹脂之固形分濃度為3〇重量％之方式，向聚 口乳膠中添加離子交換水。此時之混合物溫度為6〇。〇。其 _人’對於氯乙烯樹脂，將1重量份之硫酸鈉以10重量％水 溶液添加，接著，將〇·5重量份之聚乙烯醇（日本合成化學 (股）製商品名”Gosenol ΚΗ·17” ：皂化價約為8〇 _1%)以3 重量％水溶液添加。藉此獲得平均粒子徑為20 μπι之凝集 粒子（添加凝聚劑後、且乾燥前之乳膠），使用圖3所示之二110 Kg of ethylene monomer, 110 Kg of ion-exchanged water, copper pentahydrate, and a temperature of 5 Torr were charged into a jacket of 300 liters of pressure resistance. (3 40 g of ammonium persulfate, 〇·3 g of sulfuric acid' while mixing, while continuously adding 1% by weight of sodium sulfite solution tray] Λ tongue 曰. / 备岭履 and 10 heavy ammonium myristate aqueous solution This is a <亍polymerization. The polymerization is willing to take six white 4 weiwei 1 σ Μ force from the initial pressure (0·7 MPa) to 0. 15 MPa to carry out the polymerization, return to your green Zhao α mouth to collect the residual body Vinyl chloride resin latex. The final latex obtained by the emulsion + i Λ > noisy < The initial conversion of the total amount of monomer and additional monomer (hereinafter referred to as the total monomer amount) polymerization conversion rate of 9〇% Further, the average particle diameter of the secondary particles of the obtained latex is 〇3. 125418.doc -17- 200837119 Adding the solid concentration of the vinyl urethane resin to the condensed latex Ion-exchanged water. The temperature of the mixture at this time is 6 Torr. 其. For the vinyl chloride resin, 1 part by weight of sodium sulfate is added as a 10% by weight aqueous solution, and then 5 parts by weight of polyvinyl alcohol is added. (Japan Synthetic Chemicals Co., Ltd. product name "Gosenol ΚΗ·17": The saponification price is about 8〇 _1%) is added in a 3% by weight aqueous solution, thereby obtaining aggregated particles having an average particle diameter of 20 μm (after adding a coagulant and before drying), using the two shown in FIG.
流體噴嘴式噴霧乾燥機，於所供給之溫風入口溫度為 0 C出口溫度為71 C之條件下，乾燥該添加凝聚劑後 之乳膠。乾餘機滞留時間為1 〇〇秒。所獲得之包含氯乙烯 樹脂粒子之凝集體粒子（相關於乾燥乳膠後之樹脂。再 者，疋義凝集體粒子時，與乾燥方法無關）之平均粒子徑 為 6 μιη 〇 所獲得之凝集體粒子的掃描型電子顯微鏡（随）1〇〇〇倍 之照片如圖【所示。凝集體粒子係不定形。圖2係随刪〇 倍之照片。可確認其為凝集體粒子。一次粒子(基本粒子) 之間彼此獨立，並未融合。 結果、黏度之經時變化 (實施例2) 作為具有流動性之乳膠的評估，係於室溫敎添加凝聚 劑後之乳膠黏度。表1表示凝聚劑之添加份數、以㈣ 添加後之混合物的黏度、乾燥粒子徑，表2表示渗透試驗 學工業（股）METOLOSESM-進行與實施例1相同之操 除了使用甲基纖維素（信越化 400)作為水溶性高分子以外， I25418.doc -18- 200837119 作，且實施評估。 (實施例3) 除了不添加硫酸鈉以外，進行與實施例1相同之操作 且實施評估。 (實施例4) 向附水套之300公升耐壓容器中投入11() Kg之氯乙稀單 體、110 Kg之離子交換水、20 g之十二烷基硫酸鈉、4〇 c 之過硫酸錢、0.3 g之硫酸銅五水合物，升溫至5〇， 攪拌，一邊連續添加1重量％亞硫酸鈉水溶液與1〇重量％肉 豆蔻酸銨水溶液，藉此進行聚合。聚合壓力自初期壓力 (0.7 MPa)降低至0.15 MPa實施聚合後，回收殘留之單體而 獲得氯乙烯樹脂乳膠。最終所獲得之乳膠之、對初期投入 之單體及添加之單體的總量（以下記作全單體量）之聚合轉 化率為90重量％。又，所獲得之乳膠的一次粒子之平均粒 子徑為0.15 μπι。 以使氯乙烯樹脂之固形分濃度為30重量％之方式，向聚 合乳膠中添加離子交換水。此時之混合物溫度為6〇它。其 -人’對於氯乙稀樹脂，將1重量份之硫酸鈉以〗〇重量％水 >谷液添加’接著，將〇·5重量份之聚乙烯醇（日本合成化學 (股）製商品名"Gosenol ΚΗ·17” ：皂化價約為80 mol%)以3 重量％水溶液添加。藉此獲得平均粒子徑20 μπι之凝集粒 子’使用圖3所示之二流體噴嘴式喷霧乾燥機，於所供給 之溫風入口溫度為180°C、出口溫度為71°C之條件下，乾 燥該添加凝聚劑後之乳膠。所獲得之包含氯乙烯樹脂粒子 125418.doc -19- 200837119 之凝集體粒子之平均粒子徑為20 μιη。 (實施例5) 除了更換二流體噴嘴、改變噴霧粒子徑以外，進行與實 施例1相同之操作，且實施評估。 、貝 (實施例6) 利用粉碎機粉碎實施例4中所獲得之樹脂粒子。所獲得 之氯乙烯樹脂粒子的平均粒子徑為1〇 pm。 于 (實施例7) 除了不添加水溶性高分子之聚乙烯醇以外，進行與實施 例1相同之操作，且實施評估。 (實施例8) 除了將喷霧裝置更換為旋轉圓盤以外，進行與實施 =同之操作’且實施評估。將所調製之塑料溶膠於机保 官一天後，粗粒分離、沈澱於容器底。然而，若加以混 合’則達到可再使用之位準。 (實施例9) 除了將喷霧裝置更換為旋轉圓盤以外，實施與實施例i 相同之操作，獲得平均粒子徑3〇 μιη之乾燥粒子。使用微 型粉碎機ΑΡ-Β將上述乾燥粒子粉碎，獲得平均粒子徑為15 Km之氯乙烯樹脂粒子，且對其實施評估。 (實施例10) 除了改變旋轉圓盤之旋轉數以外，實施與實施例9相同 之操作，獲得平均粒子徑100 μη1之乾燥粒子。使用微型粉 碎機ΑΡ-Β將其粉碎，獲得平均粒子徑為25 μπι之氯乙烯樹 125418.doc -20- 200837119 脂粒子，對其實施評估。 (比較例1) 除了不添加水溶性高分子之聚乙烯醇、電解質之芒硝以 外，進行與實施例1相同之操作，且實施評估。 (比較例2) 利用噴射粉碎機粉碎實施例6中所獲得之樹脂粒子。然 而，所獲得之粒子過於細小，不滲透性之評估結果不良。 (比較例3) 7實施例1中經聚合而獲得之氯乙烯樹脂之乳膠中添加} =量份之硫酸鋁，接著添加〇·5重量份之聚乙烯醇。乳膠 正體凝固，從而無法供給至向噴霧乾燥機，故無法獲得噴 務乾無之樣品。 (比較例4) 除了減J噴霧裝置之旋轉數以外，進行與實施例8相同 之操作，且實施評估。將所調製之塑料溶膠於25七保管一 天後，有大量粗粒分離、沈澱於容器底。又，於表中，不 渗透性表示為C等級。 125418.doc 21- 200837119 [表l] 凝聚劑 添加凝聚劑後之乳 膠黏度 (mPa.s) 噴霧方式 乾燥粒子 平均徑 (m) 粉碎之 有無 電解質 (重量份） 水溶性高分子 (重量份） 實施例1 硫酸鈉(1.0) PVA*(0.5) 100 二流體噴嘴 6 無 實施例2 硫酸鈉(1.0) 甲基纖維素(0.5) 100 二流體噴嘴 12 無 實施例3 無 PVA(0.5) 400 二流體喷嘴 10 無 實施例4 硫酸鈉α〇) PVA(0.5) 100 二流體喷嘴 20 無 實施例5 硫酸鈉(1.0) PVA(0.5) 100 二流體噴嘴 30 無 實施例6 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 10 有 實施例7 硫酸鈉(1.0) 無 20 二流體噴嘴 15 無 實施例8 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 40 無 實施例9 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 15 有 實施例10 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 25 有 比較例1 無 無 5 二流體噴嘴 20 有 比較例2 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 2 有 比較例3 硫酸鋁(1.0) PVA(0.5) 無法測定 - - - 比較例4 硫酸鈉(1.0) PVA(0.5) 100 旋轉圓盤 50 無The fluid nozzle type spray dryer dries the latex after the addition of the coagulant under the condition that the supplied warm air inlet temperature is 0 C and the outlet temperature is 71 C. The dry machine residence time is 1 sec. Agglomerated particles obtained by agglomerating particles containing vinyl chloride resin particles (corresponding to resins after drying latex. Further, when the agglomerated particles are not related to the drying method), the average particle diameter is 6 μηη The scanning electron microscope (with) 1 〇〇〇 photo is shown in the figure [. Aggregate particles are amorphous. Figure 2 is a photo taken with the deletion. It can be confirmed that it is agglomerated particles. The primary particles (basic particles) are independent of each other and are not fused. As a result, the change in viscosity with time (Example 2) As a latex having fluidity, the latex viscosity after adding a coagulant at room temperature was evaluated. Table 1 shows the number of additions of the coagulant, the viscosity of the mixture after (4) addition, the diameter of the dried particles, and Table 2 shows that the permeation test industry (stock) METOLOSESM- performed the same operation as in Example 1 except that methyl cellulose was used ( Shin-Etsu Chemicals 400) As a water-soluble polymer, I25418.doc -18-200837119 was used and evaluated. (Example 3) The same operation as in Example 1 was carried out except that sodium sulfate was not added, and evaluation was carried out. (Example 4) 11 () Kg of a vinyl chloride monomer, 110 Kg of ion-exchanged water, 20 g of sodium lauryl sulfate, 4 〇c was charged into a 300 liter pressure vessel having a water jacket. Sulfuric acid money and 0.3 g of copper sulfate pentahydrate were heated to 5 Torr, and the mixture was stirred while continuously adding a 1% by weight aqueous solution of sodium sulfite and an aqueous solution of 1% by weight of ammonium myristate to carry out polymerization. The polymerization pressure was lowered from the initial pressure (0.7 MPa) to 0.15 MPa, and after the polymerization was carried out, the residual monomer was recovered to obtain a vinyl chloride resin latex. The polymerization conversion ratio of the final obtained monomer to the total amount of the monomer and the added monomer (hereinafter referred to as the total monomer amount) was 90% by weight. Further, the average particle diameter of the primary particles of the obtained latex was 0.15 μm. Ion-exchanged water was added to the polymer latex so that the solid content concentration of the vinyl chloride resin was 30% by weight. The mixture temperature at this time is 6 〇. In the case of the vinyl chloride resin, 1 part by weight of sodium sulfate is added to the weight % water > gluten solution, and then, 5 parts by weight of polyvinyl alcohol (product of the Japanese synthetic chemistry) The name "Gosenol ΚΗ17": saponification price is about 80 mol%) is added in a 3% by weight aqueous solution, thereby obtaining agglomerated particles having an average particle diameter of 20 μm. Using the two-fluid nozzle type spray dryer shown in FIG. The latex obtained by adding the coagulant is dried under the condition that the supplied warm air inlet temperature is 180 ° C and the outlet temperature is 71 ° C. The obtained agglomeration containing the vinyl chloride resin particles 125418.doc -19- 200837119 The average particle diameter of the bulk particles was 20 μm. (Example 5) The same operation as in Example 1 was carried out except that the two-fluid nozzle was replaced and the spray particle diameter was changed, and evaluation was carried out. (Example 6) Using a pulverizer The resin particles obtained in Example 4 were pulverized. The obtained vinyl chloride resin particles had an average particle diameter of 1 μm. (Example 7) Except that polyvinyl alcohol having no water-soluble polymer was added, the examples were carried out. 1 same operation (Example 8) In addition to replacing the spray device with a rotating disk, perform the same operation as the operation = and perform the evaluation. After the modified plastisol is applied to the machine for one day, the coarse particles are Separated and precipitated on the bottom of the container. However, if it was mixed, it reached the level of reusability. (Example 9) The same operation as in Example i was carried out except that the spray device was replaced with a rotating disk to obtain an average value. The dried particles having a particle diameter of 3 μm were pulverized by using a micropulverizer ΑΡ-Β to obtain vinyl chloride resin particles having an average particle diameter of 15 Km, and were evaluated. (Example 10) In addition to changing the rotating circle The same operation as in Example 9 was carried out, except that the number of rotations of the disk was carried out, and dried particles having an average particle diameter of 100 μη 1 were obtained, which were pulverized using a micro-grinder ΑΡ-Β to obtain a vinyl chloride tree having an average particle diameter of 25 μm. -20- 200837119 The lipid particles were evaluated. (Comparative Example 1) The same procedure as in Example 1 was carried out except that the polyvinyl alcohol of the water-soluble polymer and the Glauber's salt of the electrolyte were not added. (Comparative Example 2) The resin particles obtained in Example 6 were pulverized by a jet mill. However, the obtained particles were too small, and the evaluation results of the impermeability were poor. (Comparative Example 3) 7 Implementation In the latex of the vinyl chloride resin obtained by the polymerization in Example 1, an amount of aluminum sulfate was added, followed by the addition of 5 parts by weight of polyvinyl alcohol. The latex was solidified and could not be supplied to the spray dryer, so that it could not be A sample which was not sprayed was obtained. (Comparative Example 4) The same operation as in Example 8 was carried out except that the number of rotations of the J spray device was reduced, and evaluation was carried out. After the prepared plastisol was stored for one day at 25, a large amount of coarse particles were separated and precipitated at the bottom of the container. Further, in the table, the impermeability is expressed as C grade. 125418.doc 21- 200837119 [Table l] Latex viscosity after coagulant addition of coagulant (mPa.s) Average dry diameter of particles by spray method (m) Electrolytic (parts by weight) of pulverized water-soluble polymer (parts by weight) Example 1 Sodium sulfate (1.0) PVA* (0.5) 100 Two-fluid nozzle 6 None Example 2 Sodium sulfate (1.0) Methylcellulose (0.5) 100 Two-fluid nozzle 12 No Example 3 No PVA (0.5) 400 Two fluid Nozzle 10 No Example 4 Sodium sulfate α〇) PVA (0.5) 100 Two-fluid nozzle 20 None Example 5 Sodium sulfate (1.0) PVA (0.5) 100 Two-fluid nozzle 30 None Example 6 Sodium sulfate (1.0) PVA (0.5 100 Rotating Disc 10 Example 7 Sodium Sulfate (1.0) No 20 Two-fluid Nozzle 15 No Example 8 Sodium Sulfate (1.0) PVA (0.5) 100 Rotating Disc 40 No Example 9 Sodium Sulfate (1.0) PVA ( 0.5) 100 rotating disc 15 Example 10 Sodium sulfate (1.0) PVA (0.5) 100 Rotating disc 25 Comparative Example 1 None 5 Two-fluid nozzle 20 Comparative Example 2 Sodium sulfate (1.0) PVA (0.5) 100 Rotating disc 2 has Comparative Example 3 Aluminum sulfate (1.0) PVA (0.5) Unable to measure - - - Comparative Example 4 Sodium sulfate (1.0) PVA(0.5) 100 rotating disc 50
備註1 : PVA係聚乙烯醇之簡稱。 [表2] 無滲透性評估 剝離性評估 塑性溶膠黏度 調製1小時後 mPa.s 調製1天後 mPa.s 黏度比 1天後之黏度/1小時後之黏度 實施例1 A A 1640 1590 0.97 實施例2 A A 1700 1670 0.98 實施例3 A A 2510 1460 0.58 實施例4 A A 1660 1680 0.99 實施例5 A A 1300 1450 1.12 實施例6 A A 1500 1480 0.99 實施例7 B - 850 890 1.05 實施例8 B - 1350 1460 1.08 實施例9 A A 1600 1550 0.97 實施例10 A A 1600 1500 0.94 比較例1 C - 700 750 1.07 比較例2 C - 900 850 0.94 比較例3 無法評估 - 無法測定 - - 比較例4 c - 1300 1400 1.08 如表1-2所示，本發明之實施例1〜10中，無滲透性評估 較高、塑料溶膠黏度特性亦較高。 (實施例11) 向附水套之300公升耐壓容器中投入110 Kg之氯乙烯單 體、110 Kg之離子交換水、40 g之過硫酸銨、0.3 g之硫酸 -22 - 125418.doc 200837119 銅五水合物’且升溫至5 0 °C ’於一邊授摔，一邊連續添加 1 wt%之亞硫酸鈉水溶液與10 wt%之肉豆蔻酸銨水溶液， 藉此進行聚合。聚合壓力自初期壓力（0.7 MPa)降低至0.15 MPa實施聚合後，回收殘留之單體而獲得氯乙烯樹脂乳 膠。最終所獲得之乳膠之、對初期投入之單體及添加之單 體的總量（以下記作全單體量）之聚合轉化率為90 wt%。所 獲得之乳膠的一次粒子之平均粒子徑為0·35 μηι。又，乳 膠之固形分濃度為46 wt%。 其次，相對於氯乙烯樹脂100重量份，向該乳膠添加1重 量份之硫酸鈉作為10 wt%水溶液。 其次，調製聚乙烯醇（曰本合成化學（股）製：Gosenol KH-17 :皂化價約為80 mol%)之3 wt%水溶液。 將上述兩種水溶液，以流體（乳膠與電解質水溶液）3 1為 54 kg/hr(47公升/hr)、水溶性高分子水溶液33為3.6 kg/hr之 供給速度，供給至圖4所示之安裝有二液混合型之二流體 式喷霧喷嘴（股份有限公司ATMAX製、CNW200)之噴霧乾 燥機（供給條件係，溫風入口溫度180°C、出口溫度為71°C) 中，於二流體噴嘴内之滯留時間為0.15 sec以下。利用喷 霧乾燥機乾燥自二流體式噴霧噴嘴所喷出之粒子。所獲得 之氣乙烯樹脂粒子的平均粒子徑為65 μπι。 如圖6所示，一次粒子為不定形。圖7係提高倍率者，然 而基本粒子彼此之間獨立，並未融合。圖6係本實施例中 所獲得之凝集體粒子之掃描型電子顯微鏡（SEM)l000倍的 照片，圖7係上述SEM之10000倍的照片。 125418.doc -23- 200837119Remark 1: PVA is an abbreviation for polyvinyl alcohol. [Table 2] Non-permeability evaluation Peeling evaluation Plasticity viscous viscosity modulation 1 hour after mPa.s Modulation of mPa.s viscosity after 1 day of viscosity after 1 day / viscosity after 1 hour Example 1 AA 1640 1590 0.97 Example 2 AA 1700 1670 0.98 Example 3 AA 2510 1460 0.58 Example 4 AA 1660 1680 0.99 Example 5 AA 1300 1450 1.12 Example 6 AA 1500 1480 0.99 Example 7 B - 850 890 1.05 Example 8 B - 1350 1460 1.08 Implementation Example 9 AA 1600 1550 0.97 Example 10 AA 1600 1500 0.94 Comparative Example 1 C - 700 750 1.07 Comparative Example 2 C - 900 850 0.94 Comparative Example 3 Unevaluable - Unmeasurable - - Comparative Example 4 c - 1300 1400 1.08 As shown in Table 1 As shown in Fig. 2, in Examples 1 to 10 of the present invention, the non-permeability evaluation was high and the plastisol viscosity characteristics were also high. (Example 11) 110 Kg of vinyl chloride monomer, 110 Kg of ion-exchanged water, 40 g of ammonium persulfate, and 0.3 g of sulfuric acid were added to a 300 liter pressure vessel having a water jacket. -22 - 125418.doc 200837119 The copper pentahydrate was heated to 50 ° C. While stirring, a 1 wt% aqueous solution of sodium sulfite and a 10 wt% aqueous solution of ammonium myristate were continuously added to carry out polymerization. The polymerization pressure was lowered from the initial pressure (0.7 MPa) to 0.15 MPa, and after the polymerization was carried out, the residual monomer was recovered to obtain a vinyl chloride resin emulsion. The polymerization conversion ratio of the final obtained monomer to the total amount of the monomer and the added monomer (hereinafter referred to as the total monomer amount) was 90 wt%. The average particle diameter of the primary particles of the obtained latex was 0·35 μηι. Further, the solid content of the latex was 46 wt%. Next, to the latex, 1 part by weight of sodium sulfate was added as a 10 wt% aqueous solution with respect to 100 parts by weight of the vinyl chloride resin. Next, a 3 wt% aqueous solution of polyvinyl alcohol (manufactured by Sigma Chemical Co., Ltd.: Gosenol KH-17: saponification price: about 80 mol%) was prepared. The above two aqueous solutions were supplied to the supply rate of 3.6 kg/hr in a fluid (latex and aqueous electrolyte solution) 31 at 54 kg/hr (47 liter/hr) and water-soluble polymer aqueous solution 33 at 3.6 kg/hr. A two-fluid type two-fluid spray nozzle (ATMAX, CNW200) spray dryer (supply condition, temperature inlet temperature 180 °C, outlet temperature 71 °C) is installed. The residence time in the fluid nozzle is 0.15 sec or less. The particles ejected from the two-fluid spray nozzle were dried by a spray dryer. The obtained ethylene resin particles had an average particle diameter of 65 μm. As shown in Fig. 6, the primary particles are indeterminate. Fig. 7 is a person who increases the magnification, but the elementary particles are independent of each other and are not fused. Fig. 6 is a photograph of a scanning electron microscope (SEM) of the aggregate particles obtained in the present embodiment at 1,000 times, and Fig. 7 is a photograph of 10,000 times the SEM. 125418.doc -23- 200837119
利用miCr〇n股份有限公司製微型粉碎機AP_B 型粉碎機，將賴得之樹㈣子粉碎。所獲得之樹脂粒子 之平均粒子徑為1 〇 μι^。 表3表不乾無粒子徑、粉該* 杨碎粒子杈、不滲透性之評估結 果0 (實施例12) 除了使用甲基纖維素（信越化學工業（股）met〇l〇sesm·The tree (4) of the tree was crushed by a micro-pulverizer AP_B type pulverizer manufactured by MiCr〇n Co., Ltd. The average particle diameter of the obtained resin particles was 1 〇 μι^. Table 3 shows the results of evaluation of no particle diameter, powder, granules, and impermeability (Example 12) except for the use of methyl cellulose (Shin-Etsu Chemical Industry Co., Ltd. met〇l〇sesm·
4〇〇)作為水溶性高分子以外’進行與實施例η相同之操 作、且實施評估。 (實施例13) 除了不添加硫義以外，進行與實施例11相同之操作， 且實施評估。 (實施例14) 除了將霧化器更換為圖4所示之旋轉圓盤式之外，以與 實施例U相同之方法獲得乾燥樹脂粒子。圓盤之直徑為^ 、疑轉數為15000 rpm、流體（乳膠與電解質水溶液如 之供給速度係54 kg/hr(47公升/hr)，而水溶性高分子水溶 液33之供給速度係3·6 kg/hr。兩種水溶液在旋轉圓盤上之 滞留時間為1 see以了。所獲得《氯乙烯樹脂粒子之平均粒 子彷為60 μιη。利用Hosokawa micron股份有限公司製微型 粉碎機AP-B型粉碎機將上述氯乙烯樹脂粒子粉碎。所獲得 之樹脂粒子的平均粒子徑為8 μ ιη。 (比較例5) 向乳膠中添加1重量份之硫酸鈉、0·5重量份之PVA，且 125418.doc -24- 200837119 以混合後之樹脂固形分濃度為40 wt%之方式添加、混合各 水溶液後，急速成為”***”狀（難以流動之狀態），從而 無法送至霧化器。故而，可確認，量產中須要於噴霧直前 混合上述各成分之水溶液。 (參考例1)4)) The same operation as in Example η was carried out as the water-soluble polymer, and evaluation was carried out. (Example 13) The same operation as in Example 11 was carried out except that sulphur was not added, and evaluation was carried out. (Example 14) Dry resin particles were obtained in the same manner as in Example U except that the atomizer was replaced with the rotary disk type shown in Fig. 4 . The diameter of the disc is ^, the number of suspected revolutions is 15000 rpm, the fluid (the latex and the aqueous electrolyte solution are supplied at a speed of 54 kg/hr (47 liters/hr), and the supply speed of the water-soluble polymer aqueous solution 33 is 3·6. Kg/hr. The residence time of the two aqueous solutions on the rotating disc was 1 see. The average particle size of the vinyl chloride resin particles was 60 μηη. Using the micro-pulverizer AP-B type manufactured by Hosokawa Micron Co., Ltd. The above-mentioned vinyl chloride resin particles were pulverized by a pulverizer, and the obtained resin particles had an average particle diameter of 8 μm. (Comparative Example 5) 1 part by weight of sodium sulfate and 0.5 parts by weight of PVA were added to the latex, and 125418 .doc -24- 200837119 After adding and mixing the respective aqueous solutions in such a manner that the solid content of the resin after mixing is 40 wt%, it rapidly becomes "tofu" (it is difficult to flow) and cannot be sent to the atomizer. It can be confirmed that in the mass production, it is necessary to mix the aqueous solution of each of the above components directly before spraying (Reference Example 1).
向乳膠中添加1重量份之硫酸鈉、0.5重量份之PVA * (Polyvinyl Alcohol，聚乙烯醇），且以混合後之樹脂固形 分濃度為20 wt%之方式而添加、混合各水溶液後，獲得具 • 有流動性之漿料。利用實施例14之乾燥機將其處理、粉碎 後’獲得平均粒子徑為7 μηι之樹脂粒子。該粒子顯示良好 之不滲透性。1 part by weight of sodium sulfate and 0.5 part by weight of PVA* (Polyvinyl Alcohol, polyvinyl alcohol) were added to the latex, and each of the aqueous solutions was added and mixed in such a manner that the solid content of the resin after mixing was 20% by weight. • With a fluid slurry. This was treated and pulverized by the dryer of Example 14 to obtain resin particles having an average particle diameter of 7 μm. The particles show good impermeability.
125418.doc •25· 200837119125418.doc •25· 200837119
剝離 性 C C < < 1 < 無滲 透性 < < < < 1 < 粉碎後 之平均 粒徑 (m) 〇 Os 〇〇 1 卜 乾燥粒子 之平均 粒徑 (μιη) 〇 〇〇 § 1 喷霧狀態 岽 良好 製寒碧 fe 礙 < W W ^ PQ ^ C X 鲦嗖 t2> 雜 罅瘐 必,fc2- 鲦嗖 々t t2_ η 輪唉 J,0 t2_ 喷霧前，於 槽内混合 喷霧前，於 槽内混合 流體Β 3 wt% 之 PVA水溶液 3 wt% 之 甲基纖維素 水溶液 3 wt% 之 PVA水溶液 3 wt% 之 PVA水溶液 J K W、穴笔 3 9 〇 流體A Φ $輕 讀'颤 乳膠 鲶颧 ^ Μ f <姨 鲶翻关 K ^ ^ f 4焱 驗讕< ^ 水溶性 高分子 PVA 甲基纖 維素 PVA PVA PVA PVA 無機鹽 (電解質） 硫酸鈉 硫酸鈉 硫酸鈉 硫酸鈉 硫酸鈉 霧化器 韜 *Sl Ψ Μ妒 ^ Ψ ,1如 韜 ^ ¥ 旋轉 圓盤 旋轉 圓盤 旋轉 圓盤 實施例 11」 實施例 12 實施例 13 實施例 14 比較例 5 參考例 1 -26- I25418.doc 200837119 如以上所示，可確認：藉由本發明之實施例，連續地混 合經乳化聚合等而獲得之氯乙烯樹脂之乳膠、或預先向該 乳膠中溶解無機鹽所得纟、以&水溶性高分子水溶液，且 於混合物之流動性喪失之前利用霧化器使其微粒化，且實 施喷霧乾燥、粉碎，藉此可獲得對布料具有不滲透性之塑 料溶膠。 (實施例15) 向附水套之300公升耐壓容器中投入11〇 Kg之氣乙烯單 體、no Kg之離子交換水、40 g之過硫酸銨、〇.3 g之硫酸 銅五水合物，且升溫至5(rc，於一邊攪拌，一邊連續添加 1重量％亞硫酸鈉水溶液與1〇重量％肉豆蔻酸銨水溶液，藉 此進行聚合。聚合壓力自初期壓力（〇·7 Mpa)降低至〇 15 MPa實施聚合後，回收殘留之單體而獲得氯乙烯樹脂乳 膠。最終所獲得之乳膠之、對初期投入之單體及添加之單 體的總量（以下記作全單體量）之聚合轉化率為9〇%。所獲 得之乳膠的一次粒子之平均粒子徑為〇.35 μιη。又，乳膠 之固形分濃度為46.4 wt%。 將上述所獲得之乳膠1077.6 g(固形分為500 g)放入至3 L 不鏽鋼容器中。一邊攪拌，一邊添加1 g之非離子性界面 活丨生(曰本油月曰股份有限公司製商品名"pmn⑽n 1〇2，，)(相 對於氯乙烯樹脂，為〇·2重量份）。進而添加46 6 g之離子 交換水。此時之混合物的溫度為30Ό。其次，對氣乙烯樹 脂添加50 g之1重量份之硫酸鈉作為10重量％水溶液，接 著，添加83·3 g之〇·5重量份之聚乙烯醇（日本合成化學（股） 125418.doc -27- 200837119Peelability CC < 1 < Non-permeability <<< 1 < Average particle diameter after pulverization (m) 〇Os 〇〇1 Average particle diameter of dry particles (μιη) 〇〇 〇§ 1 Spray state 岽Good system 寒fefe &< WW ^ PQ ^ CX 鲦嗖t2> Chowder must, fc2- 鲦嗖々t t2_ η rim J,0 t2_ before spraying, in the tank Mixing the fluid in the tank before mixing spray Β 3 wt% PVA aqueous solution 3 wt% methyl cellulose aqueous solution 3 wt% PVA aqueous solution 3 wt% PVA aqueous solution JKW, burr 3 9 〇 fluid A Φ $ light Read 'Vibrating Latex 鲶颧^ Μ f <姨鲶翻姨鲶K ^ ^ f 4焱焱< ^ Water-soluble polymer PVA Methylcellulose PVA PVA PVA PVA Inorganic salt (electrolyte) Sodium sulfate sodium sulfate Sodium sulphate sodium sulphide atomizer S *Sl Ψ Μ妒 ^ Ψ , 1 such as 韬 ^ ¥ Rotating disk rotating disk rotating disk embodiment 11" Example 12 Example 13 Example 14 Comparative Example 5 Reference Example 1 - 26- I25418.doc 200837119 As indicated above, it can be confirmed that the embodiment of the present invention Continuously mixing a latex of a vinyl chloride resin obtained by emulsion polymerization or the like, or a hydrazine obtained by dissolving an inorganic salt in the latex in advance, and a water-soluble polymer aqueous solution, and using a nebulizer before the fluidity of the mixture is lost It is microparticulated, and spray drying and pulverization are carried out, whereby a plastisol which is impervious to cloth can be obtained. (Example 15) 11 g of ethylene monomer, no Kg of ion-exchanged water, 40 g of ammonium persulfate, and 3 g of copper sulfate pentahydrate were placed in a 300 liter pressure vessel having a water jacket. The temperature was raised to 5 (rc), and while stirring, a 1% by weight aqueous solution of sodium sulfite and an aqueous solution of 1% by weight of ammonium myristate were continuously added to carry out polymerization. The polymerization pressure was lowered from the initial pressure (〇·7 Mpa) to 〇. After the polymerization is carried out at 15 MPa, the residual monomer is recovered to obtain a vinyl chloride resin latex. The polymerization of the finally obtained latex, the total amount of the initially charged monomer and the added monomer (hereinafter referred to as the total monomer amount) is polymerized. The conversion rate was 9 %. The average particle diameter of the primary particles of the obtained latex was 〇.35 μιη. Further, the solid content of the latex was 46.4 wt%. The latex obtained above was 1077.6 g (solid form was divided into 500 g). Put it in a 3 L stainless steel container. Add 1 g of non-ionic interface to the agitation while stirring (trade name "曰n Oil Yuet Co., Ltd." "pmn(10)n 1〇2,,) (relative to chlorine) Vinyl resin, 〇·2 parts by weight) 46 6 g of ion-exchanged water. The temperature of the mixture at this time was 30 Ό. Next, 50 g of 1 part by weight of sodium sulfate was added to the gas-containing vinyl resin as a 10% by weight aqueous solution, followed by the addition of 83·3 g of 〇·5 Parts by weight of polyvinyl alcohol (Japan Synthetic Chemicals Co., Ltd.) 125418.doc -27- 200837119
，商品名"G— KH_17":皂化價約為8G则1%)作為3重 量％水溶液。其後，繼續攪拌5分鐘而獲得漿料。藉此獲 得氯乙烯樹脂之固形分濃度為4〇重量％、平均粒子徑為2〇 μΠ1之凝集粒子（添加凝聚劑後，乾燥前之乳膠），使用二流 體喷嘴式噴霧乾燥機於供給之溫風人口溫度為18代、出 &為81 C之條件下使該添加凝聚劑後之乳谬乾燥。乾 燥機滞留時間為⑽秒。所獲得之包含氯乙烯樹脂粒子之 凝集體粒子(乳膠乾燥後之樹脂，再者，定義凝集體粒子 時’與乾燥方法無關）之平均粒子徑為6叫。 (實施例16) 除了添加1.5 限公司製商品名 重量份）以外， 估0 g之非離子性界面活性劑（日本油脂股份有 "ΡΓ〇η〇υη 1〇2”）（相對於氯乙烯樹脂，為0.3 進行與實施例15相同之操作，且實施評 (實施例17) 將實施例15中所獲得之聚氯乙婦乳膠i〇77 6 §(固形分為 500 g)放入至3 L之不鏽鋼容器中。—邊㈣，一邊添加 29.0 g㈣㈣乳膠⑽股份有时司製商品名"ae945h" 固形分濃度51.75%)(相對於氯乙烯樹脂，固形分為3重量 份）。進而，添加435.3 g之離子交換水。此時之混合物溫 度為3GC °其次，對於氯乙烯樹脂，將1重量份之硫酸鈉 ，10重量％水溶液添加50 g’接著，重量份之聚乙浠 醇（日本〇成化學（股）製商品名"G〇sen〇l 息化價 約為8〇 m°1%)以3重量％水溶液添加如g。其後，繼續授 125418.doc -28- 200837119 拌5分鐘，獲得漿料。藉此獲得氯乙烯樹脂之固形分濃声 為30重量％、平均粒子徑為25 μπι之凝集粒子（添加凝聚劑 後，乾燥前之乳膠）。與實施例1 5同樣地實施評估。 (實施例18) 添加14.5 g之丙烯酸系乳膠（JSr股份有限公司製商品名 "AE945H”固形分濃度51·75%)(相對於氯乙烯樹脂，固形分 為1.5重量份)。除了添加456 3 g之離子交換水以外，進行 與實施例17相同之操作，且實施評估。 (實施例19) 添加58 g之丙烯酸系乳膠卩8|1股份有限公司製商品名 ” AE945H”固形分濃度51·75%)(相對於氯乙烯樹脂，固形分 為6重i伤）。除了添加435·3 g之離子交換水以外，進行與 實施例1 7相同之操作，且實施評估。 (實施例20) 除了添加26.5 g之乙烯-乙酸乙烯酯共聚合物乳膠（昭和 南分子股份有限公司製商品名"AD-10"固形分濃度 5 6.52/〇)(相對於氯乙烯樹脂，固形分為3重量份）、451.7 g 之離子交換水以外，進行與實施例17相同之操作，且實施 評估。 (實施例21) 添加29.4 g之丙烯酸系乳膠（JSR股份有限公司製商品名 〇568固形分濃度51 _0%)(相對於氯乙烯樹脂，固形分為3 重里伤）除了添加448·8 g之離子交換水以外，進行與實 施例17相同之操作，且實施評估。 125418.doc -29· 200837119 (實施例22) (1)乳膠製造例1, the trade name "G-KH_17": saponification price is about 8G, 1%) as a 3% by weight aqueous solution. Thereafter, stirring was continued for 5 minutes to obtain a slurry. Thus, agglomerated particles having a solid content concentration of 4% by weight of a vinyl chloride resin and an average particle diameter of 2 〇μΠ1 (a latex after the addition of a coagulant and before drying) were obtained, and a two-fluid nozzle type spray dryer was used for the supply temperature. The temperature of the wind population was 18 generations, and the chyle after the addition of the coagulant was dried under the condition of 81 C. The dryer residence time is (10) seconds. The average particle diameter of the obtained aggregated particles containing vinyl chloride resin particles (resin after drying the latex, and when the aggregated particles are defined, irrespective of the drying method) is 6 Å. (Example 16) A non-ionic surfactant (Japanese fats and oils shares "ΡΓ〇η〇υη 1〇2") (compared to vinyl chloride) was evaluated in addition to the weight of the product name of the company limited to 1.5%. The same operation as in Example 15 was carried out for the resin, and the evaluation was carried out (Example 17). The polychloroethylene latex i〇77 6 § (solid type divided into 500 g) obtained in Example 15 was placed in 3 In the stainless steel container of L. - side (four), add 29.0 g (four) (four) latex (10) shares, sometimes the product name "ae945h" solid content concentration 51.75%) (solid content is divided into 3 parts by weight relative to vinyl chloride resin). 435.3 g of ion-exchanged water. The temperature of the mixture at this time is 3GC °. Next, for vinyl chloride resin, 1 part by weight of sodium sulfate, 10% by weight of aqueous solution is added to 50 g'. Next, parts by weight of polyethylenol (Japanese 〇 The chemical name (trade name) of the product name "G〇sen〇l interest rate is about 8〇m °1%) is added as a g in a 3 wt% aqueous solution. Thereafter, continue to grant 125418.doc -28- 200837119 mix 5 In minutes, the slurry is obtained, thereby obtaining a solid content of the vinyl chloride resin. Aggregated particles of 30% by weight and having an average particle diameter of 25 μm (after addition of a coagulant, the latex before drying) were evaluated in the same manner as in Example 15. (Example 18) 14.5 g of an acrylic latex (JSr) was added. Co., Ltd. product name "AE945H" solid content concentration 51.75%) (solid content is 1.5 parts by weight relative to vinyl chloride resin). The same operation as in Example 17 was carried out except that 456 3 g of ion-exchanged water was added, and evaluation was carried out. (Example 19) 58 g of an acrylic latex 卩8|1 product name "AE945H" solid content concentration of 51·75% was added (the solid content was 6 weight i damage with respect to the vinyl chloride resin). The same operation as in Example 17 was carried out except that 435 g of ion-exchanged water was added, and evaluation was carried out. (Example 20) In addition to the addition of 26.5 g of an ethylene-vinyl acetate copolymer latex (trade name "AD-10" of the Showa South Molecular Co., Ltd." (solid content concentration 5 6.52 / 〇) (relative to the vinyl chloride resin, The same operation as in Example 17 was carried out, except that the solid form was divided into 3 parts by weight) and 451.7 g of ion-exchanged water, and evaluation was carried out. (Example 21) 29.4 g of an acrylic latex (trade name: 568, manufactured by JSR Co., Ltd., solid content of 51 _0%) was added (solids were divided into three weights with respect to the vinyl chloride resin) except for the addition of 448·8 g. The same operation as in Example 17 was carried out, except for ion-exchanged water, and evaluation was carried out. 125418.doc -29· 200837119 (Example 22) (1) Latex production example 1
向8 L之可分離燒瓶中投入25〇〇 g之離子交換水。以氮取 代氣相分後開始攪拌，添加2〇 g之十二烷基苯磺酸鈉、 200 g之甲基丙烯酸甲酯，將内溫設為7〇(>c。添加羟之 2%過硫酸鉀水溶液，開始聚合。5分鐘後，添加18〇〇 §之 苯乙烯且進行3小時，進而進行聚合丨小時。所獲得之乳膠 的轉化率為99%。乳膠之固形分濃度為39·4 wt%。 ’ (2)凝集粒子之製造與評估 除了添加37·7 g之乳膠製造例}中所獲得之乳膠（相對於 氯乙烯樹脂，固形分為3重量份）、44〇 6 §之離子交換水以 外，進行與實施例17相同之操作，且實施評估。、 (實施例23) (1)乳膠製造例2 於實施例22之乳膠製造例，替代曱基丙埽酸甲酉旨而 使用丙烯酸丁醋，進行聚合。所獲得之乳膠之轉化^為 99.5%。乳膠之固形分濃度為39 8糾％。 .、、、 (2)凝集粒子之製造與評估 添加37.9 g之乳膠製造例2中所獲得之乳膠（相對於# 烯樹脂，固形分為3重量份除了添加44〇4 g之離子= 水以外，進行與實施例17㈣之操作，且實施評估。乂換 (實施例24) 將實施例15中戶斤獲得之濃度為40%之凝集乳 有攪拌機之3 L耐壓容器中，一邊 又入至附 視午 逯吹入蒸氣升 125418.doc -30- 200837119 溫至120t：，於120它保持15分鐘。冷卻後，取出乳膠，與 實施例15—樣進行乾燥、評估。以掃描型電子顯微鏡 (SEM、1000倍）可確認，所獲得之凝集粒子相融合。 (實施例25) • 除了於實施例24中將溫度設為14(TC以外，進行與實施 例24相同之操作、且實施評估。以8£]^(1〇〇〇倍）可確認， ' 所獲得之凝集粒子相融合。 (實施例26) 鲁 於實施例1 5中，將二流體噴嘴改變為旋轉圓盤，改變嘴 霧粒徑，從而獲得平均粒子徑6〇 μπι之乾燥粒子。利用 Hosokawa micron股份有限公司製微型粉碎機Αρ_Β型粉碎 機將其粉碎，從而獲得平均粒子徑為4〇 μιη之樹脂。除此 以外，進行與實施例15相同之操作、且實施評估。 (比較例6) 除了不添加非離子性界面活性劑、水溶性高分子之聚乙 φ 烯醇、以及電解質之芒硝以外，進行與實施例丨5相同之操 作、且實施評估。 (比較例7) ‘ 向實施例15中經聚合而獲得之氯乙烯樹脂之乳膠中添加 . 1重量份之硫酸銘，接著，添加〇·5重量份之聚乙烯醇。乳 膠全體凝固，而無法供給至喷霧乾燥機，從而無法獲得喷 霧乾燥之樣品。 、 (比較例8) 除了替代實施例17中之丙烯酸系乳膠而添加29.2 • §之t 125418.doc •31 - 200837119 乙^乙歸醋乳膠（昭和高分子股份有限公司製商品名"SH-5〇2固形分濃度51·45%)(相對於氯乙烯樹脂，固形分為3重 β伤）以及449· 1 g之離子交換水以外，進行與實施例17 相同之操作，且實施評估。 (比較例9) (1) 乳膠製造例3 貝施例22之乳膠製造例1中，替代曱基丙烯酸甲酯而使 用苯乙缚進行聚合。所獲得之乳膠之轉化率為99%。乳膠 之固形分濃度為39,6 wt%。 (2) 凝集粒子之製造與評估 除了替代實施例17中之丙烯酸系乳膠而添加381 g之乳 膠製造例3中所獲得之聚苯乙烯乳膠(相對於氣乙烯樹脂， 口开y刀為3重里份）、以及440.2 g之離子交換水以外，進行 與實施例17相同之操作，且實施評估。 以上條件與結果匯總於表4。 125418.doc -32- 20083711925 μg of ion-exchanged water was placed in an 8 L separable flask. After the gas phase was replaced by nitrogen, stirring was started, 2 g of sodium dodecylbenzenesulfonate and 200 g of methyl methacrylate were added, and the internal temperature was set to 7 〇 (> c. 2% of added hydroxy group) The aqueous solution of potassium persulfate was started, and polymerization was started. After 5 minutes, styrene of 18 Å was added and carried out for 3 hours, and further polymerization was carried out for several hours. The conversion of the obtained latex was 99%. The solid content of the latex was 39. 4 wt%. ' (2) Preparation and evaluation of aggregated particles except for the addition of 37·7 g of latex production example} (Compared to vinyl chloride resin, solid content is 3 parts by weight), 44〇6 § The same operation as in Example 17 was carried out except for ion-exchanged water, and evaluation was carried out. (Example 23) (1) Latex Production Example 2 In the latex production example of Example 22, instead of the mercaptopropionate The polymerization was carried out using butyl acrylate, and the obtained latex was converted to 99.5%. The solid content of the latex was 39 8 %. . . . , (2) Manufacture and evaluation of aggregated particles 37.9 g of latex was added. The latex obtained in 2 (relative to #ene resin, the solid form is divided into 3 parts by weight except for The operation of Example 17 (4) was carried out with the addition of 44 〇 4 g of ions = water. The evaluation was carried out. (Example 24) The concentration of 40% of the agglutinated milk obtained in Example 15 was agitator 3 In the pressure-resistant container, one side enters the attached afternoon and the steam is raised to 125,418.doc -30-200837119 to 120t: and it is kept for 15 minutes at 120. After cooling, the latex is taken out, and the sample is carried out as in the case of Example 15. Drying and evaluation. It was confirmed by scanning electron microscopy (SEM, 1000 times) that the obtained aggregated particles were fused. (Example 25) • Except that in Example 24, the temperature was set to 14 (TC was carried out and implemented). The same operation as in Example 24 was carried out, and the evaluation was carried out. It was confirmed by 8 £] (1〇〇〇 times) that the obtained aggregated particles were fused. (Example 26) In Example 15, the two fluids were used. The nozzle was changed to a rotating disk, and the particle size of the nozzle was changed to obtain dried particles having an average particle diameter of 6 μm, which was pulverized by a pulverizer of a micro-grinder Hρ_Β type manufactured by Hosokawa Micron Co., Ltd. to obtain an average particle diameter of 4 〇μιη resin. In addition to this The same operation as in Example 15 was carried out and evaluation was carried out. (Comparative Example 6) Execution and implementation were carried out except that a nonionic surfactant, a water-soluble polymer polyethylene enol, and an electrolyte of Glauber's salt were not added. Example 5 The same operation was carried out and evaluation was carried out. (Comparative Example 7) '1 part by weight of sulfuric acid was added to the latex of the vinyl chloride resin obtained by polymerization in Example 15, and then, 5 parts by weight was added. The polyvinyl alcohol. The latex was solidified and could not be supplied to the spray dryer, so that the spray-dried sample could not be obtained. (Comparative Example 8) In addition to the acrylic latex in the alternative of Example 17, the addition of 29.2 • § t 125418.doc • 31 - 200837119 Ethyl acetate to vinegar (trade name of Showa Polymer Co., Ltd. "SH- The same operation as in Example 17 was carried out, and the evaluation was carried out, except that the solid concentration of 5〇2 was 5·45%) (solidified into three-fold β-injury to the vinyl chloride resin) and 449·1 g of ion-exchanged water. (Comparative Example 9) (1) Latex Production Example 3 In Latex Production Example 1 of Example 22, polymerization was carried out by using phenylethyl amide instead of methyl methacrylate. The conversion of the obtained latex was 99%. The solids concentration of the latex was 39,6 wt%. (2) Production and Evaluation of Aggregated Particles In addition to the acrylic latex in Example 17, 381 g of latex was added to the polystyrene latex obtained in Production Example 3 (relative to the gas-vinyl resin, the mouth-opening y knife was 3 cc. The same operation as in Example 17 was carried out except for the use of 440.2 g of ion-exchanged water, and evaluation was carried out. The above conditions and results are summarized in Table 4. 125418.doc -32- 200837119
【寸略〕 塑料溶膠黏度V12 mPas 2920 2700 2300 1920 2000 2280 2340 2990 1250 1460 1320 1500 〇 卜 1 18500 9000 剝離性 < < AA AA < 1 1 馨 1 無滲透 性評價 < C < < < < < < < < < < U m PQ 乾燥粒子平 均徑(μπι) v〇 2 〇 ο 12 o ON rj o 1 12 00 喷霧方式 二流體喷嘴 二流體喷嘴 二流體喷嘴 二流體喷嘴 1二流體喷嘴1 二流體喷嘴 1二流體喷嘴ι 1二流體喷嘴 二流體喷嘴 二流體喷嘴 二流體喷嘴 旋轉圓盤 二流體喷嘴 1 二流體喷嘴 二流體喷嘴 熱處理(°C) 礫 #: m 碳 碟 ο 1 碟 凝集後之漿料 濃度(wt%) 〇 〇 m ΓΟ ir> ro ο m »n m Ό m ο m 凝固 水溶性高分子 (重量份） 〇 ίτΓ 〇 CL, ir? 〇< PVA(0.5) 〇 CU ίτΓ Ο ? o eu, PVA(0.5) d Oh PVA(0.5) ίτΓ d Oh PVA(0.5) m ίτΓ e ί〇" 〇 PL, irT 〇 Ρη 電解質 (重量份） ¥ gv —· ¥ t-H « 硫酸納(1.0) 硫酸鈉（1·0) gs v—H € w 硫酸鈉(1.0) ¥ 硫酸鈉(1.0) 键 w 硫酸鈉(1.0) 二 键 一· ¥ 硫酸鈉(1.0) 鉍.· ΦΊ ON irT ν〇^ δ *〇 § 0568*5(3) δ s ί 碟 磲 磲 rn 箐 g ffi 00 Η C/l CL, * _ vg ^ 寒麵 % W UIL十 TTTV *s rn S pL P-102 (0.2) ο 二 ο ώ o o 2 P-102 (0,2) s cL g f-h ώ o 二 o 〇< 〇 〇 4ί 碟 實施例15 實施例16 實施例17 實施例18 1 實施例19 實施例20 實施例21 實施例22 實施例23 實施例24 實施例25 實施例26 比較例6 比較例7 比較例8 比較例9 -33- 。镲龊 WIS韶s^^h鉍举 VS : £雄« 。赛浞>遛1键费肊硪&-龄傘|1^:9捃寧 〇 fHise.w§o9sH^05。框鉍阳<4嗟你拿^tf:sa>89s :»0拔準 。镲龊w=ol-ov=3rD5。框鉍e<<^你傘¾屮Φ砸备淫举2OV : 17捃孽 。#ΗΐΜ=Ης 寸 63¥=蟀05。框鉍阳<<醛枇傘^ffisr#Hln1763v :cns1te> 。sswisso龄傘 VAd : Z 捃擊 。练铤 w:sl §0u2dl:3r65。框鉍砣<<>& 你^^槳淚-40 ,#sl-d :一雄擊 125418.doc 200837119 如表4所示，如本發明之實 界面活性制可提高處理濃度讀加非離子性 料溶膠黏度亦優良。亦即，添加不二透性之評估良好’塑 士加選自由氯乙烯聚合 之（甲基）丙烯酸酯系均聚物、（ 酸醋之共聚合物、及乙…丙㈣醋與(甲基)丙烯 烯乙酸乙烯醋共聚合物所組成之 群中之至少一種乳化聚合乳膠 攻之 離性亦良好，塑料溶膠黏度亦優良。 到 【圖式簡單說明】 圖^係本發明實施m中所獲得之凝集體粒子之掃描 子顯微鏡（SEM)IOOO倍之照片。 圖2係上述SEM之10000倍的照片。 圖3係本發明中之-例的製造製程的概略說明圖。 圖4係本發明中之-例的噴霧器（二流體喷嘴）之[Insufficient] Plastic sol viscosity V12 mPas 2920 2700 2300 1920 2000 2280 2340 2990 1250 1460 1320 1500 〇 1 1 18500 9000 Peelability << AA AA < 1 1 Xin 1 No permeability evaluation < C <<<<<<<<<<<<<<<<<<<<<<<> U m PQ Dry Particle Average Diameter (μπι) v〇2 〇ο 12 o ON rj o 1 12 00 Spray Two-fluid Nozzle Two-Fluid Nozzle Fluid nozzle two fluid nozzle 1 two fluid nozzle 1 two fluid nozzle 1 two fluid nozzle ι 1 two fluid nozzle two fluid nozzle two fluid nozzle two fluid nozzle rotating disc two fluid nozzle 1 two fluid nozzle two fluid nozzle heat treatment (°C) gravel #: m Carbon disc ο 1 slurry concentration after agglomeration (wt%) 〇〇m ΓΟ ir> ro ο m »nm Ό m ο m solidified water-soluble polymer (parts by weight) 〇ίτΓ 〇CL, ir? 〇 < PVA(0.5) 〇CU ίτΓ Ο ? o eu, PVA(0.5) d Oh PVA(0.5) ίτΓ d Oh PVA(0.5) m ίτΓ e 〇 quotPL, irT 〇Ρη electrolyte (parts by weight) ¥ Gv —· ¥ tH « sodium sulfate (1.0) sodium sulfate (1·0) gs v— H € w Sodium sulfate (1.0) ¥ Sodium sulfate (1.0) Key w Sodium sulfate (1.0) Two-bond one · ¥ Sodium sulfate (1.0) 铋.· ΦΊ ON irT ν〇^ δ *〇§ 0568*5(3) δ s ί 磲磲 磲磲 箐 fg ffi 00 Η C/l CL, * _ vg ^ cold noodle% W UIL ten TTTV *s rn S pL P-102 (0.2) ο 二ο ώ oo 2 P-102 (0 2) s cL g fh ώ o 2 o 〇 < 〇〇 4ί Disc Example 15 Example 16 Example 17 Example 18 1 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Implementation Example 25 Example 26 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 -33-.镲龊 WIS韶s^^h铋 VS : £雄«. Celluloid > 遛 1 key fee 肊硪 & - age umbrella | 1 ^: 9 捃 〇 〇 fHise.w § o9sH ^ 05. Box 铋阳<4嗟You take ^tf:sa>89s :»0 to pull the standard.镲龊w=ol-ov=3rD5. Box 铋e<<^You umbrella 3⁄4屮Φ砸Preparation 2OV: 17捃孽. #ΗΐΜ=Ης Inch 63¥=蟀05. Box 铋阳<<aldose umbrella ^ffisr#Hln1763v: cns1te> Sswisso age umbrella VAd : Z sniper. Practice w:sl §0u2dl: 3r65. Box 铋砣<<>& You ^^ Paddles-40, #sl-d: A male strike 125418.doc 200837119 As shown in Table 4, the actual interface activity system according to the present invention can increase the processing concentration read plus The nonionic sol has excellent viscosity. That is, the evaluation of the addition of the non-permeability is good. The plastics are selected from the group consisting of (meth)acrylate homopolymers polymerized with vinyl chloride, (co-polymers of acid and vinegar, and ethyl acetate (tetra) and (methyl) The at least one emulsion polymerized latex of the group consisting of propylene vinyl acetate vinegar copolymer is also excellent in dissociation, and the viscosity of the plastisol is also excellent. [Simplified description of the drawing] Figure 2 is obtained in the practice m of the present invention. Fig. 2 is a photograph of 10,000 times the SEM of the above-mentioned SEM. Fig. 3 is a schematic explanatory view of a manufacturing process of the example of the present invention. Fig. 4 is a view of the present invention. Example of a sprayer (two fluid nozzle)
明圖。 W 圖5係本發明中之一例的噴霧器（旋轉圓盤式霧化器）之 概略說明圖。 ％ 圖6係本發明實施例丨丨中所獲得之凝集體粒子的掃描型 電子顯微鏡(SEM)IOOO倍之照片。 圖7係上述SEM之10000倍的照片。 【主要元件符號說明】 2 3 4 噴霧乾燥機本體 噴霧器 乳膠供給線 小滴 125418.doc -34- 200837119 5 加熱空氣 6 壓縮空氣 7 隨伴流 8 粉體取出線 9 > 16 閥 10 喷霧乾燥機 11 袋遽、1§本體 12 過濾器 13 減壓區域 14 排氣線 20 袋濾器 30、40 噴霧器 31、41 流體（乳膠與電解質水溶液之混合流 體） 32 、 34 、 36 、 42 、 44 導管 33、43 水溶性高分子水溶液 35 喷霧用空氣 37 二流體喷嘴 38、47 噴霧液滴 45 旋轉圓盤 46 旋轉軸 48 混合區域 125418.doc -35-Ming map. Fig. 5 is a schematic explanatory view of a sprayer (rotary disk atomizer) which is an example of the present invention. Fig. 6 is a photograph of a scanning electron microscope (SEM) 1000 times of aggregated particles obtained in Examples of the present invention. Fig. 7 is a photograph of 10000 times the above SEM. [Main component symbol description] 2 3 4 Spray dryer body sprayer latex supply line droplet 125418.doc -34- 200837119 5 Heated air 6 compressed air 7 with accompanying flow 8 powder take-up line 9 > 16 valve 10 spray drying Machine 11 bag 遽, 1 § body 12 filter 13 decompression zone 14 vent line 20 bag filter 30, 40 sprayer 31, 41 fluid (mixed fluid of latex and electrolyte solution) 32, 34, 36, 42 , 44 conduit 33 , 43 water-soluble polymer aqueous solution 35 spray air 37 two-fluid nozzles 38, 47 spray droplets 45 rotating disk 46 rotating shaft 48 mixing area 125418.doc -35-
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| TWI415867B (en) * | 2010-09-17 | 2013-11-21 | Kaneka Corp | Vinyl chloride resin aggregated particles, a method for producing the same, and a glove using the same |
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| MY171736A (en) * | 2011-05-31 | 2019-10-25 | Kaneka Corp | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| JP6515476B2 (en) * | 2013-10-25 | 2019-05-22 | 東ソー株式会社 | Vinyl chloride polymer latex, polyol composition and method for producing the same |
| JP6582422B2 (en) * | 2014-07-18 | 2019-10-02 | 東ソー株式会社 | Vinyl chloride polymer latex, polyol composition and production method thereof |
| CN111741984B (en) * | 2018-02-16 | 2022-12-27 | 株式会社钟化 | Vinyl chloride resin aggregate particles, method for producing same, composition for metal can coating, composition for marking film, and coating film |
| WO2023189509A1 (en) * | 2022-03-31 | 2023-10-05 | 日本ゼオン株式会社 | Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate |
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| 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 |
| JP4022642B2 (en) * | 2002-07-08 | 2007-12-19 | 東ソー株式会社 | Particle size control agent for vinyl chloride resin latex, vinyl chloride resin latex using the same, and method for producing vinyl chloride resin for paste processing |
| CN101128518A (en) * | 2005-02-28 | 2008-02-20 | 株式会社钟化 | Process for producing aggregated latex particle |
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| TWI415867B (en) * | 2010-09-17 | 2013-11-21 | Kaneka Corp | Vinyl chloride resin aggregated particles, a method for producing the same, and a glove using the same |
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