JPH011731A - Spray-dried emulsion polymer, process for producing the same, PCT-processing aid comprising the same, and molding material containing the same - Google Patents
Spray-dried emulsion polymer, process for producing the same, PCT-processing aid comprising the same, and molding material containing the sameInfo
- Publication number
- JPH011731A JPH011731A JP63-137622A JP13762288A JPH011731A JP H011731 A JPH011731 A JP H011731A JP 13762288 A JP13762288 A JP 13762288A JP H011731 A JPH011731 A JP H011731A
- Authority
- JP
- Japan
- Prior art keywords
- spray
- emulsion polymer
- weight
- dried
- dried emulsion
- 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
- 239000004908 Emulsion polymer Substances 0.000 title claims description 60
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 6
- 239000012778 molding material Substances 0.000 title claims description 4
- 239000002245 particle Substances 0.000 claims description 68
- 239000000843 powder Substances 0.000 claims description 61
- 239000004816 latex Substances 0.000 claims description 29
- 229920000126 latex Polymers 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 25
- 238000001694 spray drying Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 6
- -1 alkyl methacrylate Chemical compound 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000004902 Softening Agent Substances 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000428 dust Substances 0.000 description 21
- 238000009826 distribution Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000008016 pharmaceutical coating Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229920001944 Plastisol Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004999 plastisol Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229940114077 acrylic acid Drugs 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 210000004072 lung Anatomy 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
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 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
- 230000000007 visual effect Effects 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、実質的に、純粋な状態でガラス転移温度６０
℃以上を有する乳化重合体の凝集ラテックス粒子のみか
らｐ？成っている粉末粒子よりなる粉末状の噴霧乾燥乳
化重合体並びにその製法、これよシ々るＰｖＣ−加工助
剤及びこれを含有する成形材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has a glass transition temperature of 60% in a substantially pure state.
p from only the agglomerated latex particles of the emulsion polymer having a temperature of ℃ or higher. This invention relates to a powdery spray-dried emulsion polymer consisting of powder particles consisting of powder particles, a method for producing the same, a PvC processing aid, and a molding material containing the same.
噴霧乾燥乳化重合体粉末は公知である：これは屡々極め
て低い軟化温度全有しかつ抗粘結剤（Ａｎｔｉｂａｃｋ
ｍｉｔｔｅｌ ）と混合され、従って粉末粒子は貯蔵の
際に粘着しない（西ドイツ国特許公開（ＤＥ−Ａ）第３
３４４２４２号明細書参照）西ドイツ国特許公開（ＤＥ
−Ａ）第２６１４２６１号明細書忙、薄膜形成最低温度
ＣＭＦＴ）０℃以上を有する乳化重合体の水性分散液か
ら贋造されるような粉末が記載される。重合体に適用技
術上要求される柔軟性を与えるために、ＭＦＴが０℃と
なるまでの量の軟化剤を添加し、かつその後に噴霧乾燥
によシ粉末を生成させる。この場合も、６０℃以上にあ
るガラス転移温度を有する水溶性試剤の添加によシ粉粒
の粘着を阻止する。Spray-dried emulsion polymer powders are known: they often have very low overall softening temperatures and contain anti-caking agents (Antiback).
mittel) so that the powder particles do not stick together during storage (West German Patent Application (DE-A) No. 3).
344242) West German Patent Publication (DE
-A) No. 2,614,261 describes such powders as are produced from aqueous dispersions of emulsion polymers having a minimum film-forming temperature CMFT) of 0° C. or higher. In order to give the polymer the flexibility required by the application technology, a softener is added in an amount up to an MFT of 0° C. and then spray-dried to form a powder. In this case as well, the addition of a water-soluble agent with a glass transition temperature above 60° C. prevents the powder particles from sticking.
この軟質粉末に対して、本発明は、６０℃よシ高いピカ
ー軟化温度（ＶＥＴ）を有する硬質乳化重合体に関する
。In contrast to this soft powder, the present invention relates to hard emulsion polymers with a Picker softening temperature (VET) higher than 60°C.
このような乳化重合体の噴霧乾燥も公知である。すなわ
ち西ドイツ国特許公開（ＤＥ−Ａ）第２６２９９２４号
明細書に依れば、２０〜８０℃の範囲にあるＭＦＴを有
する乳化重合体の水性分散液を蝋の添加下に噴霧乾燥し
て再分散可能な粉末にする。再分散の際には軟化剤を一
緒に使用することができる。一定の軟化性添加剤、例え
ばカプロラクタムが噴霧乾燥粉末に含有されていてよい
。噴霧乾燥粉末の特性は、蝋の存在で決定的に影響され
る：これは、粉粒中に含有されるラテックス粒子へ結合
作用を及ぼす。Spray drying of such emulsion polymers is also known. That is, according to DE-A 2 629 924, an aqueous dispersion of an emulsion polymer having an MFT in the range of 20 to 80° C. is redispersed by spray drying with the addition of wax. Make it into a powder if possible. A softener can be used together with the redispersion. Certain softening additives, such as caprolactam, may be included in the spray-dried powder. The properties of the spray-dried powder are decisively influenced by the presence of wax: it exerts a binding effect on the latex particles contained in the powder granules.
それに対して本発明による粉末は実際に、６０℃以上の
ＶＥＴを有する乳化重合体の凝集されたラテックス粒子
より成る。要するにこれは、ラテックス粒子のほかには
、物理的な粒子特性。In contrast, the powder according to the invention actually consists of agglomerated latex particles of emulsion polymers with a VET of above 60°C. In short, this is the physical particle property of latex particles.
例えばその剛性又はその間隙性への影響を及ぼすような
量で存在する成分を含有しない。ラテックス粒子のほか
に少量で存在するが、しかし粉末粒子の特性に認めうる
影響を及ぼさない副成分には、基礎となっているラテッ
クスの助剤例えば乳化剤又は塩が属する。It does not contain components present in such amounts as to affect, for example, its stiffness or its porosity. Subcomponents which are present in small amounts in addition to the latex particles, but which do not have an appreciable influence on the properties of the powder particles, include auxiliaries of the basic latex, such as emulsifiers or salts.
この種の典型的な噴霧乾燥乳化重合体は西ドイツ国特許
（ＤＥ）第２１０１８０８号明、ｍ書から公知のＰＶＣ
−加工助剤である。これは、その粒子が、粗く凝集した
微粒子から成っている粉末からなる。この粒子構造は次
のことによって達成される、すなわち、基礎となってい
る乳化重合体の水性分散液の噴霧乾燥を比較的低い空気
排出温度で実施して個々の小滴もしくは粉粒のラテック
ス粒子をそれが共半融又は溶融する程高くには加熱しな
い。弛るい微細構造は、ＰＶＣ−加工助剤の加工特性に
有利に作用する。A typical spray-dried emulsion polymer of this type is the PVC known from German Patent No. 2101808, M.
- It is a processing aid. It consists of a powder whose particles consist of coarsely agglomerated fine particles. This particle structure is achieved by spray drying an aqueous dispersion of the underlying emulsion polymer at relatively low air discharge temperatures to form latex particles in the form of individual droplets or granules. is not heated so high that it becomes co-melting or melting. The loose microstructure has an advantageous effect on the processing properties of the PVC processing aid.
しかしこれは、噴霧乾燥の際にかなシな割合の極めて微
細な粉粒が生じるという欠点を有する。However, this has the disadvantage that during spray drying a small proportion of very fine particles are produced.
この微細成分は噴霧乾燥装置のサイクロン分離器中に完
全には保持され得ないので、収量損失及び放出された重
合体塵による環境負荷が生じる。粉末状の製品での取シ
扱いの際にも障害となる粉塵が発生しうる。This fine component cannot be completely retained in the cyclone separator of the spray dryer, resulting in yield losses and environmental burdens due to released polymer dust. Dust can also be generated when handling powdered products.
確かにこの欠点は、噴霧乾燥装置における温度を、粉粒
のラテックス粒子が相互に溶融する程度に高める場合に
、簡単に回避することができる。しかしそれによって、
ＰＶＣ−成形材料に導入する際には溶解性（Ａｕｆｓｃ
ｈｌｉｅｚｂａｒｋｅｉｔ ）が悪化する。分離が困難
な微細塵が生成せずかつ取扱いの際に皿状の摩擦ぐずが
生成せず、しかし他方では粒子がＰｖＣ−成形材料へ導
入する際には急速にかつ完全に溶解される程度に粉粒の
ラテックス粒子が相互に半融するように正確に噴霧乾燥
装置中の温度を調整することは極めて困難である。Indeed, this disadvantage can be easily avoided if the temperature in the spray drying device is increased to such an extent that the latex particles of the powder melt into one another. But by doing so,
When incorporated into PVC molding materials, the solubility (Aufsc
hliezbarkeit) worsens. No fine dust is formed that is difficult to separate and no dish-like friction debris is formed during handling, but on the other hand the particles are dissolved quickly and completely when introduced into the PvC molding compound. It is extremely difficult to precisely adjust the temperature in the spray dryer so that the latex particles of the powder are fused together.
西ドイツ国特許公開（ＤＥ−Ａ）第３４０５６５１号明
細書に依れば、減少された微細塵含量を有する噴霧乾燥
乳化重合体が２つのモードのある（ ｂｉｍｏｄａｌｅ
ｎ ）プラスチック分散液から得られる。この粉末にお
いても微細塵含量の更なる減少が望ましい。According to DE-A 34 05 651, spray-dried emulsion polymers with reduced fine dust content are prepared in two modes (bimodale).
n) Obtained from plastic dispersions. A further reduction in the fine dust content is also desirable in this powder.
従って、純粋な状態でビカー軟化温度６０℃以上を有す
る乳化重合体の凝集されたラテックス粒子からのみ実際
に組成されている粉粒よりなる粉末状の噴霧乾燥乳化重
合体を皿状ではないが容易に可溶な形で開発すること及
びより高い収率で製造することが課題であった。本発明
は、粉粒中にラテックス粒子のほかに、ラテックス粒子
へ結合作用を及ぼしかつそれによるだけで不所望の塵生
成を阻止する他の成分、例えば蝋又は油の言うに値する
量を含有するような噴霧乾燥乳化重合体には関係しない
。Therefore, it is easy to form a spray-dried emulsion polymer in the form of a powder, which is actually composed only of agglomerated latex particles of an emulsion polymer having a Vicat softening temperature of 60° C. or more in its pure state, but not in a dish-like form. The challenge was to develop it in a soluble form and to produce it in higher yields. The invention provides that, in addition to the latex particles, the powder granules contain significant amounts of other components, such as waxes or oils, which have a binding effect on the latex particles and thereby only prevent the undesired dust formation. It does not concern spray-dried emulsion polymers such as
粉粒中に含有されるラテックス粒子が、乳化重合体と相
容性の高沸点軟化剤の有効量を含有する場合に、噴霧乾
燥乳化重合体は要求される特性を有することが判明した
。軟化剤はラテックス粒子のほかに分離された相として
存在するした本発明による粉末の示差（ｄｉｆｆｅｒｅ
ｎｔｉｅｌ−布
ｌｅ ）もしくは積分（ｉｎｔｅｇｒａｌｅ ）粒度分
配曲線を示す。It has been found that spray-dried emulsion polymers have the required properties when the latex particles contained in the powder contain an effective amount of a high boiling point softener that is compatible with the emulsion polymer. The softener is present as a separate phase in addition to the latex particles in the powder according to the invention.
Figure 2 shows the integral particle size distribution curve.
噴霧乾燥乳化重合体の溶解性を得るために、乳化重合体
のラテックス粒子は粉粒中で凝集された形で得られるこ
とが重要である。しかしながら、ラテックス粒子が表面
力（０ｂｅｒｆｌａｃｈｅ−ｎｋｒ’ｍｆｔｅ ）によ
ってのみ弛るく相接して付着しかつ最小の機械力によっ
てすでに分離され得る場合には、本発明の目的は完全に
は達成されない。他方で、ラテックス粒子は、完全に相
互に溶融して顕微鏡像で半透明にみえるガラス様塊状物
になっていてもいけない。むしろラテックス粒子は同様
の粉粒で隣接の粒子とできるだけ点状でのみ半融し又は
溶接していなければならない。との粉粒は顕微鏡像では
白色又はやや半透明の塊状物にみえる。小粒は圧潰の際
にその粉砕にほとんど感じられない抵抗を示しかつ固体
支持体上に塗布して平層にすることができる。In order to obtain solubility of the spray-dried emulsion polymer, it is important that the latex particles of the emulsion polymer are obtained in agglomerated form in powder granules. However, the object of the invention is not completely achieved if the latex particles adhere loosely to each other only by surface forces and can already be separated by minimal mechanical forces. On the other hand, the latex particles must not completely melt together into glass-like agglomerates that appear translucent in the microscopic image. Rather, the latex particles should be semi-fused or welded to similar particles and adjacent particles as far as possible only in points. The powder particles appear as white or slightly translucent lumps in a microscopic image. The pellets exhibit almost imperceptible resistance to their crushing during crushing and can be coated into a flat layer on a solid support.
軟化剤不在で個々のラテックス粒子の初期溶融に同様の
状態は、噴霧乾燥の際の極めて狭い温度範囲でのみ達成
可能であるが、軟化剤含有の分散液の噴霧乾燥では、所
望の半融状態が達成される範囲を容易に調整することが
できる。Whereas a state similar to the initial melting of individual latex particles in the absence of a softener is achievable only in a very narrow temperature range during spray drying, the desired semi-molten state can be achieved in the spray drying of dispersions containing softeners. The range in which this is achieved can be easily adjusted.
軟化剤の１％又は数％の添加はすでに噴霧乾燥の際に収
率を約１０％又はそれ以上高めることは驚異的である。It is surprising that the addition of 1% or even a few % of softeners increases the yield by about 10% or more during spray drying.
更に、以前はより強い溶融の性の粉末に比較して本粉末
の溶解性が更に改善されるという事実はより驚異的であ
る。すなわち軟化剤を含有しない粉末を透明なＰＶＣ−
成形材料と共に加工する際に、多くの場合に、不十分な
可塑化により末だ溶解されない粒子又は帯状物又は線状
物が認められる。本発明による粉末は同じ加工条件下で
この種の障害をよシ少な示すか
ぐ−又は全く示さない。典型的なＰｖＣ−混合物はポリ
塩化ビニル（ＰＶＣ）７０〜９９．９重量％及び本発明
による噴霧乾燥乳化重合体０．１〜２０重量％を含有す
る。有利な量比は（９０〜９９）＝（１〜１０）重量％
である。Furthermore, the fact that the solubility of the present powder is further improved compared to previously more strongly melting powders is even more surprising. In other words, the powder containing no softener is mixed with transparent PVC-
During processing with molding compositions, particles or bands or wires are often found which are not yet dissolved due to insufficient plasticization. The powders according to the invention exhibit less or no disturbances of this type under the same processing conditions. A typical PvC mixture contains 70-99.9% by weight of polyvinyl chloride (PVC) and 0.1-20% by weight of the spray-dried emulsion polymer according to the invention. Advantageous quantitative ratios are (90-99) = (1-10)% by weight
It is.
本発明は、それが考察の前面にあるとはいえＰＶＣ−加
工助剤に限定されるものではない。収率損失、環境汚染
及び粉塵負荷による同じような障害は、その粉粒が弛ろ
く凝集された、すなわち非硬化性溶融のラテックス粒子
よりなる全ての噴霧乾燥乳化重合体で生じうる。これは
、溶融粒子よりも速く有機溶剤に溶ける又は軟化剤と均
質のプラスチゾル又は例えば医薬被覆としての熱ゲル化
被覆を生じるという利点を有する。The invention is not limited to PVC-processing aids, although this is in the foreground. Similar problems due to yield loss, environmental contamination, and dust loading can occur with all spray-dried emulsion polymers whose powder particles consist of loosely agglomerated, ie, non-curing, molten latex particles. This has the advantage of producing plastisols or thermogelling coatings, for example as pharmaceutical coatings, which dissolve faster in organic solvents or are homogeneous with softeners than do molten particles.
従って、ＶＥＴ６０℃以上、殊に８０℃以上を有しかつ
前記の粉末の形で有利に使用可能である全ての乳化重合
体を使用することができる；ヒカー軟化温度（ＶＥＴ）
はＤＩＮ５３４６０ により測定する。捩シ振動試験
における減衰最大値の温度ＣＤｌＮ５３４５５によるＴ
ｇｄｙｎ ） ｆ乳化Ｘ合体の特徴付けに引用すること
もできる；これは８０℃以上である。It is therefore possible to use all emulsion polymers which have a VET of above 60° C., in particular above 80° C., and which can advantageously be used in the form of the powders mentioned; Hiker softening temperature (VET)
is measured according to DIN 53460. Temperature of maximum damping value in torsional vibration test T by CDlN53455
gdyn) f can also be cited in the characterization of the emulsion X coalescence; it is above 80 °C.
６０℃以上にあるＶＥＴを有する典型的乳化重合体は、
硬質ホモポリマーを生じるモノマーから５０重量％以上
、殊に７０〜１００重量％までかつ軟質ホモポリマーを
生じるコモノマーから５０重量％以下、殊に０〜３０重
量％まで構成されている。硬質ホモポリマーとはこの場
合ＶＥＴ＞６０℃を有するもの、軟質ホモポリマーとば
ＶＥＴ（５０℃を有するものが解される。A typical emulsion polymer with a VET of 60°C or higher is
It is composed of 50% by weight or more, especially 70 to 100% by weight of monomers forming hard homopolymers, and up to 50% by weight, especially 0 to 30% by weight of comonomers forming soft homopolymers. In this case, hard homopolymers are understood to mean those having a VET>60° C., and soft homopolymers are understood to mean those having a VET (50° C.).
最初の種類のモノマーの例は、メチル−、エチル−、イ
ンプロピル−５〆−ブチル−及びシクロヘキシル−メタ
クリレート、スチロール、ビニルドルオール、α−メチ
ルスチロール、アクリル−及びメタクリルニトリル、ア
クリル−及びメタクリル酸、マレイン−及びイタコン酸
及び塩化ビニルである。第２の種類の七ツマ−の例はア
クリル酸のアルキルエステル及びメタクリル酸のＣ〉２
−アルキルエステル、酢酸ビニル、オレフィン及びビニ
ルアルキルエーテルである。Examples of monomers of the first type are methyl-, ethyl-, impropyl-5〆-butyl- and cyclohexyl-methacrylate, styrene, vinyldolol, alpha-methylstyrene, acrylic- and methacrylnitrile, acrylic- and methacrylic acid. , maleic and itaconic acid and vinyl chloride. Examples of the second type of 7mers are alkyl esters of acrylic acid and C〉2 of methacrylic acid.
- alkyl esters, vinyl acetate, olefins and vinyl alkyl ethers.
噴霧乾燥粉末の形で製造されかつ使用されるこの種の公
知の乳化重合体には、例えば次のものが属する、すなわ
ち、
１）西ドイツ国特許（ＤＥ−Ｃ） 第２１０１８０８号
明細書に依る、メチルメタクリレート７０〜９５％及び
軟質ホモポリマーを生じるコモン有す、、ポ、−一を含
有す、Ｂｐｖｃ−加工。剤ｉ２）西ドイツ国特許（ＤＥ
−Ｃ）第２５１１２３８号明細書及び西ドイツ国特許公
開（ＤＥ−Ａ）第３０４９１７９号明細書による、水溶
性モノマー、例えば不飽和モノ−及びジカルボン酸、こ
のような酸のアミノアルキルエステル及びアミノアルキ
ルアミド、そのヒドロキシアルキルエステル及びアミド
、ビニルピロリドン又はビニルイミダゾール及び水に不
溶性のモノマー、例えばスチロール、酢酸ビニル、オレ
フィン、アクリル−又はメタクリル酸のＣ−アルキル１
〜１０
エステルのコポリマーよりなる、医薬被覆の製造のため
の粉末状結合剤；
３）西ドイツ国特許（ＤＥ ）第３２０８７９１号明細
書又は第３４３８２９１号明細書に依る、酸性又はアル
カリ性範囲で塩を生成するモノマー、例えば不飽和カル
ボン酸又はこのような酸のアミノアルキルエステル又は
アミノアルキルアミド１５〜８０％もしくは４級アンモ
ニウム塩基を有するモノマー５〜２０％及び残りの部分
は水に不溶性のコモノマー、例えばアクリル−又はメタ
クリル酸のアルキルエステルよりなるコポリマーを含有
する医薬被覆分散液の製造のための再分散可能な粉末；
４）西ドイツ国特許（ＤＥ−Ｃ）第２５４３０７３号明
細書及び欧州特許機構（ＥＰ−８）第３０５９０号明細
書に依る、メチルメタクリレート及び塩基性コモノマー
、例えばビニルイミダゾール〉５０％カラ、又上コア／
シェル（Ｋｅｒｎ ／５ｃｈａｌｅ ）−乳化重合体（
この際コアは少なくとも一部はアクリルエステル又は高
級メタクリルエステルよりなりかつシェルはメチルメタ
クリレートから〉５０％まで成る）から構成される装
軟化剤含有のプラスチゾルの製造のための重合体粉末。Known emulsion polymers of this type which are prepared and used in the form of spray-dried powders include, for example: 1) according to DE-C 2101808; Bpvc-processing containing 70-95% methyl methacrylate and a common to yield a soft homopolymer. Agent i2) West German patent (DE
-C) Water-soluble monomers, such as unsaturated mono- and dicarboxylic acids, aminoalkyl esters and aminoalkylamides of such acids, according to DE 2511238 and DE-A 30 49 179; , their hydroxyalkyl esters and amides, vinylpyrrolidone or vinylimidazole and water-insoluble monomers such as styrene, vinyl acetate, olefins, C-alkyl 1 of acrylic or methacrylic acid
Powder binders for the production of pharmaceutical coatings consisting of copolymers of ~10 esters; 3) producing salts in the acidic or alkaline range according to DE 3208791 or DE 3438291; 15 to 80% of monomers containing unsaturated carboxylic acids or aminoalkyl esters or aminoalkylamides of such acids or 5 to 20% of monomers having quaternary ammonium bases and the remainder being water-insoluble comonomers, such as acrylics. redispersible powders for the production of pharmaceutical coating dispersions containing copolymers consisting of - or alkyl esters of methacrylic acid; 4) DE-C 2543073 and EP-C; 8) Methyl methacrylate and basic comonomers, e.g. vinylimidazole>50% empty, also upper core/
Shell (Kern/5chale) - emulsion polymer (
Polymer powder for the production of plastisols containing softeners, the core consisting at least in part of acrylic esters or higher methacrylic esters and the shell consisting of up to >50% of methyl methacrylate.
前記の特許明細書にＶＥＴ＜６０℃を有する重合体が同
様に記載されている限り、本発明の使用はＶＥＴ＞６０
℃、特に〉８０℃を有するそれについてのみ重要であり
、それというのもとのあ
温合のみ前記の塵問題が生じるからである。これはビカ
ー軟化温度が増加すると共に増える。Insofar as the above-mentioned patent specification likewise describes polymers with a VET<60°C, the use of the present invention also applies to polymers with a VET<60°C.
℃, especially >80.degree. C., is of interest only, since only at higher temperatures does the above-mentioned dust problem occur. This increases with increasing Vicat softening temperature.
本発明の典型的乳化重合体は７０〜１５０℃、特に８０
〜１３０℃の範囲のビカー軟化温度を有する。Typical emulsion polymers of the invention are 70-150°C, especially 80°C.
It has a Vicat softening temperature in the range of ~130°C.
乳化重合体の分子量は自体公知の方法で使用例の必要性
に応じて適合する。例えばｐｖｃ−加工助剤として使用
すべき乳化重合体の分子量（重量平均値）は５００００
０〜数百万、特に０．７〜生百万の範囲にあってよい。The molecular weight of the emulsion polymer is adapted in a manner known per se to the needs of the application. For example, the molecular weight (weight average value) of the emulsion polymer to be used as a PVC processing aid is 50,000.
It may range from 0 to several million, in particular from 0.7 to several million.
ラテックス粒子の粒度は、噴霧可能性が保証されている
限シは、絶対的でない。非常に微細な分配の分散液は高
い固体含量で濃厚液状でありかつ難噴霧性である。粗粉
分配の分散液、殊に狭い粒度分布を有するものは高すぎ
る剪断感受性のために、屡々噴露の際に困難を惹起する
。The particle size of the latex particles is not critical, as long as sprayability is guaranteed. The very finely divided dispersions are thick liquids with a high solids content and are difficult to spray. Coarse-grained dispersions, especially those with a narrow particle size distribution, often cause difficulties during spraying because of their excessive shear sensitivity.
本発明により使用すべき乳化重合体のための最も有利な
粒度ば０．０８〜１、特に０．１〜０．５μｍである。The most preferred particle size for the emulsion polymers to be used according to the invention is from 0.08 to 1, in particular from 0.1 to 0.5 μm.
噴霧乾燥のために使用する分散液の粘度は、有利に５０
００ ｍＰａ、ｓ以下、殊に１０００ｍＰａ、ｓ以下で
あシ、これは固体含量６０重量％以下及び粒度０．３μ
ｍ以上に大抵あてはまる。より微細分配の分散液はより
低い固体含量、例えば３０〜５０％を必要とする。２つ
のモードのある分散液は比較的に高い固体含量でも良好
に噴霧することができかつ特に良好な収率及び低い微細
粉塵含量を生じる。The viscosity of the dispersion used for spray drying is preferably 50
00 mPa, s or less, in particular 1000 mPa, s or less, with a solids content of 60% by weight or less and a particle size of 0.3μ
Mostly applicable to m or more. More finely divided dispersions require lower solids contents, for example 30-50%. The bimodal dispersions can be sprayed well even at relatively high solids contents and give particularly good yields and low fines contents.
本発明による噴霧乾燥乳化重合体中に含有される高沸点
軟化剤は、噴霧乾燥中にラテックス小滴もしくは粉粒中
に存在するラテックス粒子を僅かに軟化させるという課
題を有し、従ってこれらは相互の接触位置で互いに融接
又は共生溶融する。この課題を満たすために、軟化剤は
噴霧乾燥機中で支配する条件で蒸発してはいけない。こ
の理由から本発明によシ、噴霧乾燥乳化重合体が空気流
から分離される温度以上で標準圧下で沸騰する高沸点軟
化剤を使用する。殊に沸点は２００℃以下ではない。標
準圧下で分解せずに沸騰する非揮発性の軟化剤を使用す
ることもできる。The high-boiling softeners contained in the spray-dried emulsion polymers according to the invention have the task of slightly softening the latex particles present in the latex droplets or granules during spray-drying, so that they are mutually exclusive. fused or symbiotically melted to each other at the contact point. To meet this task, the softener must not evaporate under the conditions prevailing in the spray dryer. For this reason, according to the invention, a high boiling softener is used which boils under standard pressure above the temperature at which the spray-dried emulsion polymer is separated from the air stream. In particular, the boiling point is not below 200°C. It is also possible to use non-volatile softeners that boil under standard pressure without decomposing.
軟化剤と乳化重合体との相容性は少なくとも乾燥機中で
支配する温度で重要である。乾燥乳か
化重合体が過剰量の軟化剤中に溶は石−もしくは混合物
が可視的に広汎に均質及び澄明に見える程に強くその中
に膨潤する場合に、相容性が生じる。これは、そのよう
な均質性が長時間、例えば２４時間後及び排出温度（Ａ
ｕｓｔｒｉｔｔｓｔｅｍ−ｐｅｒａｔａｒ ）への加熱
後にはじめて出現する場合で十分である。The compatibility of the softener with the emulsion polymer is important, at least at the temperatures prevailing in the dryer. Compatibility occurs when the dry emulsified polymer swells into an excess of softener so strongly that the solution or mixture appears visibly broadly homogeneous and clear. This is because such homogeneity is maintained for a long time, e.g. after 24 hours and at the discharge temperature (A
It is sufficient if it appears for the first time after heating to the struttstem-peratar).
軟化剤として適当な物質は、化学的に単一の物質群を形
成しない。すでに前記の相容性並びに排出温度より低い
融点は特性的である。殊に融点は２０℃以下にある。軟
化剤の極性特徴は当然乳化重合体のそれにほぼ等しくさ
れるべきである。ＰＶＣ−加工助剤として適当な、主に
メチルメタクリレートから構成される非極性乳化重合体
には、似たような非極性軟化剤、例えばジブチルフタレ
ート、ジオクチルフタレート又はフタール酸の他のアル
キルエステル、アジピン酸又はセバシン酸のアルキルエ
ステル、塩素化パラフィン、トリアルキルホスフェート
、脂肪族又は芳香脂肪族ポリエステル等がこれに該当す
る。原則的に同様にＰＶＣのために適当な全軟化剤を使
用することができ、この際フタレート軟化剤の群はその
卓越した工業的重要性のために特に強調すべきである；
適当な軟化剤の詳細な記載は、′クンストストツフーノ
・イドプツホ（Ｋｕｎｓｔｓｔｏｆｆ −Ｈａｎｄｂｕ
ｃｈ ） 〃、２／１巻７ ｘ ／ｌ／ ｉ −（Ｈ，
に、 Ｆｅｌｇｅｎ ）著、（）・ンサー（Ｈａｎｓｅ
ｒ ）出版、第２版、１９８５年、６０９〜６５９頁）
にある。Substances suitable as softeners do not chemically form a single group of substances. The abovementioned compatibility as well as the melting point below the discharge temperature are characteristic. In particular, the melting point is below 20°C. The polar character of the softener should of course be approximately equal to that of the emulsion polymer. Non-polar emulsion polymers mainly composed of methyl methacrylate, which are suitable as PVC processing aids, may also contain similar non-polar softeners, such as dibutyl phthalate, dioctyl phthalate or other alkyl esters of phthalic acid, adipine. Examples include alkyl esters of acids or sebacic acid, chlorinated paraffins, trialkyl phosphates, aliphatic or araliphatic polyesters, and the like. In principle, it is likewise possible to use all suitable softeners for PVC, the group of phthalate softeners being particularly emphasized due to their outstanding industrial importance;
A detailed description of suitable softeners can be found in Kunststoff-Handbu.
ch ) 〃, Volume 2/1 7 x /l/ i −(H,
Felgen), Hanse ()
r) Publishing, 2nd edition, 1985, pp. 609-659)
It is in.
同じ軟化剤は、ＰＡＭＡ−プラスチゾルで使用可能な噴
霧乾燥乳化重合体にも適当である。The same softeners are also suitable for spray-dried emulsion polymers that can be used in PAMA-plastisols.
この目的に適当な若干の軟化剤は西ドイツ国特許（ＤＥ
−Ｃ）第２５４３５４２号明細書に挙げられている。Some softeners suitable for this purpose are described in the West German patent (DE
-C) Listed in specification No. 2543542.
明らかによシ極性の強い軟化剤は、親水性のモノマーか
ら部分的に構成され、例えば医薬被覆の製造に用いられ
る乳化重合体に必要とされる。これには、例えばクエン
酸のエチルエステル及び他の低級アルキルエステル及び
分子量２００〜ａｏｏｏを有するポリエチレングリコー
ル、糖アルコールの脂肪酸エステル又はそのオキシエチ
ル化生成物、例えばソルビタンモノオレエート（場合に
よジオキシエチル化された）が属する。Clearly highly polar emollients are partly composed of hydrophilic monomers and are required, for example, in emulsion polymers used in the production of pharmaceutical coatings. These include, for example, ethyl esters of citric acid and other lower alkyl esters and polyethylene glycols with molecular weights from 200 to aooo, fatty acid esters of sugar alcohols or their oxyethylated products, such as sorbitan monooleate (optionally dioxyethylated). ) belongs.
軟化剤の量は、所望の効果が生じるように測られねばな
らない。少なすぎる軟化剤を使用する場合には、粉塵生
成が十分に抑制されない。The amount of softener must be measured to produce the desired effect. If too little softener is used, dust formation will not be sufficiently suppressed.
高すぎて測られた軟化剤含量では、噴霧乾燥機中でポリ
マーからの被覆物が生じうる。有効量は当然乳化重合体
の硬度もしくはＶＥＴに依る。If the softener content is measured too high, coatings from the polymer can occur in the spray dryer. The effective amount will of course depend on the hardness or VET of the emulsion polymer.
これが６０℃に近い場合には、それが１２０℃又はそれ
以上である場合よりも少ない軟化剤で通例間に合う。他
方有効範囲内の軟化剤量が危険が少ないと実証された。If it is close to 60°C, less softening agent is usually needed than if it is 120°C or higher. On the other hand, softener amounts within the effective range were demonstrated to be less hazardous.
すなわち多くの場合に１〜５重量％の添加量の間で言う
に値する程の作用相異は認められなかった。一般如有効
な量範囲は、そのつどポリマー重量に対して、０゜５〜
２０重量％及び有利な範囲は１〜８重量％である。That is, in many cases, no appreciable difference in effect was observed between the addition amounts of 1 to 5% by weight. A generally useful amount range is from 0°5 to 0.5°, in each case based on the weight of the polymer.
20% by weight and an advantageous range from 1 to 8% by weight.
軟化剤は種々の方法で乳化重合体中て入れることができ
る。それを完成分散液に添加しかつ乳化重合体中に装入
する寸で攪拌するもしくは放置することができる。軟化
剤をすでに製造の際に分散液中に加えることはよシ簡単
である。例えばあらかじめ装入した水相中にそれを乳化
させることができ、従ってそれは添加されたモノマー相
と混合しかつすでにラテックス粒子の生成の際にその中
に入る。流入法洸よる乳化重合の際には、軟化剤を漸次
に流入するモノマー相と混合することが有利である。Softeners can be incorporated into emulsion polymers in a variety of ways. It can be added to the finished dispersion and stirred or allowed to stand for charging into the emulsion polymer. It is much easier to add the softener to the dispersion already during production. For example, it can be emulsified in the aqueous phase initially introduced, so that it mixes with the added monomer phase and enters it already during the formation of the latex particles. During emulsion polymerization by the inflow method, it is advantageous to mix the softener gradually with the inflowing monomer phase.
噴霧乾燥は公知方法で行なう。大工業的には、順
通例噴入された分散液と一流で上から下へ熱空気を流し
通すいわゆる噴霧塔を使用する。分散液を１本又は数本
のノズルを通して噴霧し又は有利に急速回転する穿孔円
盤を用いて噴霧する。Spray drying is performed by a known method. In large industry, so-called spray towers are used, in which the injected dispersion and hot air are passed in one flow from top to bottom. The dispersion is sprayed through one or several nozzles or preferably using a rapidly rotating perforated disk.
進入熱空気は、温度１００〜２５０℃、有利に１５０〜
２５０℃を有する。噴霧乾燥乳化重合体の特性のために
空気の排出温度は、決定的で６Ｄ、すなわち、乾燥粉粒
が、噴霧塔底部で又はサイクロン分離器中で空気流から
分離される温度である。この温度はできるだけ、軟化剤
を含有しない乳化重合体が半融又は溶融するはずの温度
以下でなければならない。多くの場合に排出温度５０〜
９０℃が好適である。排出温度は一定の空気流で単位時
間毎に連続的に噴入される分散液量の変化によシ調整す
ることができる。軟化剤量及び乾燥機中の温度操作の最
適合で、個々の粉粒において弱い半融状態が達成され、
その際一方ではラテックス粒子は、それが粉塵生成下で
すり減らない程にしつかシ十分に結合していで、他方で
は結合は疎性十分であシ、従って粉末はＰＶＣ−溶融物
中に急速にかつ容易に溶ける又は均質に分配される。The incoming hot air has a temperature of 100-250°C, preferably 150-250°C.
It has a temperature of 250°C. Due to the nature of the spray-dried emulsion polymer, the air discharge temperature is critical and is 6D, ie the temperature at which the dry powder is separated from the air stream at the bottom of the spray tower or in a cyclone separator. This temperature should, as far as possible, be below the temperature at which the emulsion polymer, which does not contain a softener, would be semi-melted or molten. In many cases, the discharge temperature is 50~
90°C is preferred. The discharge temperature can be adjusted by changing the amount of dispersion continuously injected per unit time with a constant air flow. By optimally adjusting the amount of softener and controlling the temperature in the dryer, a weak semi-molten state is achieved in the individual grains,
On the one hand, the latex particles are bonded together sufficiently so that they are not worn away under dust formation, and on the other hand, the bonding is sufficiently loose that the powder quickly enters the PVC melt. and easily soluble or homogeneously distributed.
粉粒の内部でのラテックス粒子の容易な半融は種々の方
法で認められる。噴霧乾燥の際の収率の上昇は、噴霧乾
燥装置の空気流から完全には分離されず、かつそれによ
って一部失なわれ減少される微細粒成分に依る。同じ理
由から粉末の取扱いの際、例えば詰める場合に明らかＫ
より少ない粉塵生成となる。この作用は殆んどすでに各
々の測量なしで明白である；粉末３０７を詰めた粉末ビ
ンを、内容物を振った後に直ちに開ける場合忙、軟化剤
を含有しない粉末内容物では目に見える雲様の粉塵が漏
出し、一方本発明による粉末は雲様の粉塵がまったく発
生しないか又は高々弱少に発生する。粉末ビンの内部で
も最初の場合では強い粉塵生成が生じ、これは１０〜２
０秒間ではじめて沈積しかつガラス壁への明らかな被覆
（Ｂｅｌａｇ ）を残す。それに反して本発明による軟
化剤含有粉末は数秒間内に沈積しかつガラス壁への基膜
を残さない。Facile melting of latex particles inside the powder grain is observed in a variety of ways. The increase in yield during spray drying is due to the fine particulate component not being completely separated from the air stream of the spray drying device and thereby being partially lost and reduced. For the same reason, when handling powders, for example when packing, K
Less dust is produced. This effect is almost already obvious even without individual measurements; when a powder bottle filled with powder 307 is opened immediately after shaking the contents, a visible cloud-like appearance occurs with powder contents that do not contain softeners. of dust escapes, whereas the powder according to the invention generates no cloud-like dust or at most only a small amount of cloud-like dust. Strong dust formation also occurs inside the powder bottle in the first case, which is 10-2
It deposits only after 0 seconds and leaves a clear coating (Belag) on the glass wall. In contrast, the softener-containing powder according to the invention deposits within a few seconds and leaves no base film on the glass wall.
減少された粉塵生成は持続性であると判る。The reduced dust production is found to be persistent.
軟化剤を含有しない粉末は機械的振動時に摩耗形
により一層微細粒を替成するが、この結果は本発明によ
る粉末では僅少である。機械的荷重時における粉粒の安
定性は超音波処理によシ可視′することができる。この
目的のために、水中の粉末の極めて希釈された水性懸濁
液各６０Ｑ ｍｌを、８００ｍ１入シフラスコ中、１−
ＩＦ−周波数４０ｋＨｚ及びＨＦ−出力５０／１００ワ
ツトで超音波浴（ソルツクス（ＳＯｎｏｒｅｘ）Ｔに５
２、製造者バンプリア （Ｂａｎｄｅｌｉｎ ） ）中
で１０秒間超音波処理した。その前後に粒度分布を測定
セルを流通する水中粉粒懸濁液の吸光の測定により測定
した：測定装置“クラチル・パルトスコープ（Ｋｒａｔ
ｅｌＰａｒｔｏｓｋｏｐ ） Ｆ“、クラチル社（Ｋｒ
ａｔｅｌ ＧｍｂＨ）製、ゲッチンゲン。第１図は超
音波処理の前後の差異のある粒度分布を示している。例
１に依る軟化剤を含有しない粉末及び軟化剤を含有する
粉末の分嬰曲線の最大値は超音波処理前には同じ値であ
るが、後者はより僅少の微細粒分を認めることができる
。超音波処理後の微細粒成分（１０ミクロメーター以下
の小粒）は軟化剤を含有しない粉末では１５容量％であ
シ、これに反して軟化剤含有の粉末は１容量％以下であ
る。最大値の変位は両方の場合で粒崩壊を認めさせるが
、これは本発明による軟化剤含有粉末の場合には著るし
く僅少である。While powders without softeners undergo mechanical vibrations to form finer grains due to abrasion, this result is minimal for the powders according to the invention. The stability of the powder particles under mechanical loading can be visualized by ultrasonication. For this purpose, 60Q ml each of a very dilute aqueous suspension of the powder in water was added to 1-
5 in an ultrasonic bath (SOnorex) T at IF-frequency 40 kHz and HF-power 50/100 Watts.
2. Sonicated for 10 seconds in a Bandelin (manufacturer). Before and after that, the particle size distribution was measured by measuring the light absorption of the powder suspension in water flowing through the measuring cell.
elPartoskop) F”, Kracil Co., Ltd. (Kr
Atel GmbH), Göttingen. Figure 1 shows the different particle size distributions before and after ultrasonication. The maximum values of the division curves of the powder without softener and the powder containing softener according to Example 1 are the same before sonication, but in the latter case a smaller fraction of fine particles can be recognized. . After ultrasonic treatment, the fine particle component (small particles of 10 micrometers or less) is 15% by volume for the powder without softener, whereas it is less than 1% by volume for the powder containing softener. The displacement of the maximum value makes grain collapse visible in both cases, which is significantly smaller in the case of the softener-containing powder according to the invention.
粉塵状態の評価のため、１９８３年のゝゝマキシマーＬ
／−アルバイツプラツツコンシエントラチオーネン・ラ
ント・ピオロギッシエ・アルバイツストソフトレランツ
ヴエルテ（ＭａｘｉｍａｌｅＡｒｂｅｉｔｓｐｌａｔｚ
ｋｏｎｚｅｎｔｒａｔｉｏｎｅｎ ｕｎｄ ｂｉｏ
ｌｏｇ−ｉｓｃｈｅ Ａｒｂｅｉｔｓｓｔｏｆｆｔｏ
ｌｅｒａｎｚｗｅｒｔｅ ）“ に関−ｊるＤＦＧ−報
告（Ｍｉｔｔｅｉ ｌｕｎｇ ） ＸＩＸによシ、１０
μｍ以下の大きさの粉粒の割合が重要である。この大き
さの粒子は呼吸の際に肺胞内へ侵入可能でありかつ障害
を起しうる。従って微細粉塵生成の減少は労働衛生上極
めて重要である。For evaluation of dust condition, 1983 Maximer L
/-MaximaleArbeitsplatz
konzentrationen und bio
log-ische Arbeitsstoffto
DFG-Report on (Mittei Lung) XIX, 10
The proportion of powder particles with a size of μm or less is important. Particles of this size can enter the alveoli during breathing and can cause damage. Reducing fine dust production is therefore extremely important for occupational health.
軟化剤を含有しない粉末中の微細粉塵粒の数割合が屡々
５０％以上である場合には、これは軟化剤５％の添加に
より３０％以下、場合により２０％以下の値まで減少す
ることができる。If the fraction of fine dust particles in powders without softeners is often more than 50%, this can be reduced by the addition of 5% softener to a value of less than 30%, sometimes even less than 20%. can.
第２〜５図が示すように、微細粉塵の量割合は、屡々そ
の高い数割合を良好には認めさせない。As Figures 2 to 5 show, the proportion of fine dust often does not allow its high proportion to be appreciated.
次に軟化剤添加の作用を若干のポリマー例で説明する。Next, the effect of adding a softener will be explained using some polymer examples.
使用される乳化重合体は軟化剤の不在で次の特性を有し
た：
八 組成、メチルメタクリレート９５％、エチルアクリ
レート５％
ピカー軟化温度（ＶＥＴ） ｌ Ｏ８℃２０℃における
剪断弾性率： Ｇ＝１６０ＯＮ／簡Ｂ 組成、メチルメ
タクリレート８８％、ブチルアクリレート１２％
ピカー軟化温度（７５丁）１０５℃
２０℃における剪断弾性率： Ｇ＝１４０ＯＮ／嘔Ｃ組
成、メチルメタクリレート７５％、ブチルメタクリレー
ト２５％
ピカー軟化温度（ＶＥＴ）９０℃
２０℃における剪断弾性率： Ｇ＝１３０ＯＮ／ＷＩｎ
次の表は実験噴霧乾燥装置中での噴霧乾燥の際の粉末収
率によりかつＰＶＣ９７％及びポリマーＡ、Ｂ及び０３
％よりなる押出混合物の特性により、一部は乳化重合成
分の容器に（Ｖ）、一部は流入するモノマー乳化液にＣ
Ｍ）かつ一部は重合終了した分散液に（Ｄ）加えられた
軟化剤としてのジオクチルフタレートの本発明による添
加の有利な作用結果を示す。更にピカー軟化温度（ＶＥ
Ｔ）及び２０℃における剪断弾性率（Ｇ２０）の値は熱
的ポリマー特性への軟化剤添加の作用結果を示している
。The emulsion polymer used had the following properties in the absence of softeners: 8 Composition, 95% methyl methacrylate, 5% ethyl acrylate Picar softening temperature (VET) l Shear modulus at 20 °C at 8 °C: G = 160 ON /Simple B Composition, 88% methyl methacrylate, 12% butyl acrylate Picar softening temperature (75 pieces) 105°C Shear modulus at 20°C: G = 140ON/C composition, 75% methyl methacrylate, 25% butyl methacrylate Picar softening temperature (VET) Shear modulus at 90°C and 20°C: G=130ON/WIn
The following table shows the powder yield during spray drying in an experimental spray dryer and PVC 97% and polymers A, B and 03.
Due to the characteristics of the extrusion mixture consisting of
FIG. 3 shows the advantageous effects of the addition according to the invention of dioctyl phthalate as softener (M) and (D) added to a partially polymerized dispersion. Furthermore, Pikar softening temperature (VE
The values of T) and shear modulus (G20) at 20° C. show the effect of the softener addition on the thermal polymer properties.
例１
還流冷却器、攪拌機及び流入容器を備えた１００６入り
の下請鋼製反応容器中でベルオキシ二硫酸アンモニウム
２２及びＣ１，−パラフィンスルホネート（商標：バイ
エル社（ＢａｙｅｒＡＧ）ノｘムルｉ トール（Ｅｍｕ
ｌｇａｔｏｒ ） Ｋ２Ｏ） １２５’を蒸留水１６
Ｋ９中に８０℃で溶かす。この溶液に、メタクリル酸メ
チルエステル３８に９．アクリル酸エチルエステル２
Ｋ９、前記の乳化剤９０２、ベルオキシ二硫酸アンモニ
ウム１８ｊ及び蒸留水２３ Ｋ９から前もって製造した
乳化液を攪拌下８０℃で４時間以内で滴加する。その後
に調製物を８０℃で２時間保ち、室温に冷却し、希苛性
ソーダ溶液でｐｉ−ＩＩｏ、０に調整しかつ細かいメツ
シュの織物篩を通して濾過する。固体含量５１％及び粘
度４９０ｍＰａ、ｓを有する凝固物無しの分散液を得る
。平均粒径は２５０ ｎｍである。換算粘度（クロロホ
ルム中２０℃で測定）は２５７ ｍｌ／ ９である。引
続き分散液の半分に、水性乳化液として加入攪拌される
ジオクチルフタレートｌ Ｋｇを加える。Example 1 Ammonium peroxydisulfate 22 and C1,-paraffin sulfonate (Trademark: Bayer AG) No.
lgator) K2O) 125' with distilled water 16
Dissolve in K9 at 80°C. To this solution, add 38% of methacrylic acid methyl ester and 9%. Acrylic acid ethyl ester 2
K9, the emulsifier 902 described above, ammonium peroxydisulfate 18j and distilled water 23 The emulsion previously prepared from K9 is added dropwise under stirring at 80 DEG C. within 4 hours. The preparation is then kept at 80 DEG C. for 2 hours, cooled to room temperature, adjusted to pi-IIo, 0 with dilute caustic soda solution and filtered through a fine mesh fabric sieve. A coagulum-free dispersion is obtained with a solids content of 51% and a viscosity of 490 mPa,s. The average particle size is 250 nm. The reduced viscosity (measured in chloroform at 20 °C) is 257 ml/9. 1 kg of dioctyl phthalate, which is stirred in as an aqueous emulsion, is then added to half of the dispersion.
分散液の両成分をそのつどそれ自体噴霧乾燥装置中で回
転円板噴霧器によシ噴霧しかつ１６０℃の空気と同流で
乾燥する。この際分散液対空気の量比は、噴霧物が７５
℃の空気排出温度：これは第２図及び第３図にグラフで
示されて１こいる。The two components of the dispersion are in each case themselves sprayed in a spray-drying apparatus using a rotating disk atomizer and dried in a stream of air at 160.degree. At this time, the ratio of the dispersion liquid to air was 75.
Air discharge temperature in °C: This is shown graphically in Figures 2 and 3.
特性値： 軟化剤不含 軟化剤５％含
有約ｌ○ミクロメーター
以下の粒子の容量割合 １％ 約０％約
１０ミクロメーター
以下の粒子の数割合 ５３％ １３％
例２
還流冷却器、攪拌器及び流入容器を備えた１００を入り
下請鋼製反応容器中で硫酸ナトリウム２０２、ベルオキ
シュ硫酸カリウム２２、ドライアイス０．２ ＫＬｉ及
びパラフィンスルホネート（商標：バイエル社のエムル
ガトールに３０）６０ｒを水１６に９中に８０℃で溶か
す。この溶液に、メタクリル酸メチルエステル３０に９
、メタクリル酸ブチルエステルｌＯＫ？、ジオクチルフ
タレート２に９、前記の乳化剤８８２及び水２５ Ｋ９
から前もって製造した乳化液を攪拌下で８０℃で３時間
以内に滴加する。引続き調製物を更に２時間８０℃で保
ち、室温に冷却し、硫酸ナトリウム２Ｏｆを添加しかつ
細かいメツシュの織物篩を介して濾過する。Characteristic values: Contains no softener Contains 5% softener Approximately 1○ Capacity ratio of particles of less than 10 micrometers 1% Approximately 0% Number of particles of approximately 10 micrometers or less 53% 13%
Example 2 Sodium sulfate 202, potassium beroxysulfate 22, dry ice 0.2 KLi and paraffin sulfonate (trademark: Emulgatol from Bayer) in a 100 ml subcontracted steel reaction vessel equipped with a reflux condenser, a stirrer and an inflow vessel. 30) Dissolve 60r in 16 to 9 parts of water at 80°C. Add 9 parts to 30 parts of methyl methacrylate to this solution.
Is methacrylic acid butyl ester OK? , dioctyl phthalate 2 to 9, the above emulsifier 882 and water 25 K9
The emulsion prepared beforehand is added dropwise under stirring at 80° C. within 3 hours. The preparation is then kept at 80.degree. C. for a further 2 hours, cooled to room temperature, added with 2Of sodium sulfate and filtered through a fine mesh woven sieve.
固体含量５１．２％及び粘度５９５ ｍＰａ、ｓを有す
る凝結物無しの分散液が得られる。平均粒径は１６６
ｎｍである。ポリマーの換算粘度は５００ｍ１／？であ
る。A coagulum-free dispersion is obtained with a solids content of 51.2% and a viscosity of 595 mPa,s. Average particle size is 166
It is nm. The equivalent viscosity of the polymer is 500 m1/? It is.
比較のために、モノマー乳化液中のジオクチルフタレー
ト成分不含のもう１種の調製物を製造する。固体含量は
この場合５０．２％、粘度５１０ ｍＰａ、ｓである。For comparison, another preparation is prepared without the dioctyl phthalate component in the monomer emulsion. The solids content in this case is 50.2%, the viscosity 510 mPa,s.
粒度（１７０ｎｍ）及び換算粘度（５１４ｍｌ／ｒ）は
実際に無変化である。The particle size (170 nm) and reduced viscosity (514 ml/r) remain virtually unchanged.
両分散液を例１におけるように噴霧乾燥する。Both dispersions are spray dried as in Example 1.
得られる粉末について粒度分布を測定しかつ第４及び５
図にグラフで示す。The particle size distribution of the obtained powder was measured and the fourth and fifth
This is shown graphically in the figure.
特性値： 軟化剤不含 軟化剤５％含
有ｌ○ミクロメーター
以下の粒子の容量割合 約１％ 約０％
１０ミクロメーター
以下の粒子の数割合 ５４％ ２４
％例３
例２をジオクチルフタレート量０．４ Ｋｇ（２Ｋ９の
代りに）を用いて繰り返し、従って軟化剤割合は１％で
ある。軟化剤不含の調製物に比べて噴霧乾燥粉末の視覚
的評価によシ塵生成の明らかな減少を認める。Characteristic values: Contains no softener Contains 5% softener Volume percentage of particles smaller than l○ micrometer Approx. 1% Approx. 0%
Percentage of particles smaller than 10 micrometers 54% 24
Example 3 Example 2 is repeated using an amount of dioctyl phthalate of 0.4 Kg (instead of 2K9), so the softener proportion is 1%. Visual evaluation of the spray-dried powders shows a clear reduction in dust production compared to preparations without softeners.
第１図〜第５図は公知技術水準によるものに比較した本
発明による粉末の示差もしくは積分粒度分布曲線を示し
、第１図は例１の超音波処理の前及び後の示差容量分布
曲線を示し、第２図は例１の軟化剤不含の粒度分布曲線
を示し、第３図は例１の軟化剤含有の粒度分布曲線を示
し、第牛図は例２の軟化剤不含の粒度分布曲線を示しか
つ第５図は例２の軟化剤含有の粒度分布曲線を示してい
る。1 to 5 show the differential or integral particle size distribution curves of the powder according to the invention compared to those according to the state of the art; FIG. 1 shows the differential volume distribution curves of Example 1 before and after ultrasonic treatment; Figure 2 shows the particle size distribution curve of Example 1 without a softener, Figure 3 shows the particle size distribution curve of Example 1 with a softener, and Figure 2 shows the particle size distribution curve of Example 2 without a softener. Figure 5 shows the particle size distribution curve of Example 2 containing softener.
Claims (1)
温度を有する乳化重合体の凝集ラテックス粒子のみから
成つている粉粒よりなる粉末状の噴霧乾燥乳化重合体に
おいて、ラテックス粒子は乳化重合体と相容性の高沸点 軟化剤を含有することを特徴とする、噴霧乾燥した乳化
重合体。 ２、軟化剤０．５〜２０重量％を含有する、請求項１記
載の噴霧乾燥乳化重合体。 ３、ラテックス粒子は粉粒で部分的に相互に半融もしく
は溶融している、請求項１又は２記載の噴霧乾燥乳化重
合体。 ４、微粒子成分を総粒子数の３０％以下で含有する請求
項１から３までのいずれか１項記載の噴霧乾燥乳化重合
体。 ５、メチルメタクリレート７０〜１００重量％、アルキ
ルアクリレート又はメチルメタクリレートとは異なるア
ルキルメタクリレート０〜２０重量％、それと共重合可
能な他のビニルモノマー０〜１０重量％までから構成さ
れている、請求項１から４までのいずれか１項記載の噴
霧乾燥乳化重合体。 ６、少なくとも５０００００の分子量（重量平均値）を
有する、請求項５記載の噴霧乾燥乳化重合体。 ７、少なくとも７０００００の分子量を有する、請求項
６記載の噴霧乾燥乳化重合体。 ８、請求項１から７までのいずれか１項記載による噴霧
乾燥乳化重合体を製造するために、それと相容性の高沸
点軟化剤を含有する乳化重合体の水性分散液を噴霧乾燥
させること を特徴とする、噴霧乾燥乳化重合体の製法。 ９、噴霧乾燥温度以上で沸騰する軟化剤を含有する分散
液を使用する、請求項８記載の方法。 １０、噴霧乾燥乳化重合体を、軟化剤を含有しない乳化
重合体が半融する又は溶融する温度以下で、噴霧乾燥の
ために使用される空気流から分離させる、請求項８又は
９記載の方法。 １１、乳化重合体を４０〜９０℃で空気流から分離させ
る、請求項１０記載の方法。 １２、請求項１から７までのいずれか１項記載の噴霧乾
燥乳化重合体よりなる、ＰＶＣ−加工助剤。 １３、ポリ塩化ビニル（ＰＶＣ）８０〜９９．９重量％
及び請求項１もしくは請求項１から７までのいずれか１
項記載の噴霧乾燥重合体０．１〜２０重量％よりなる混
合物。 １４、ＰＶＣ又は主として塩化ビニルから構成されたコ
ポリマー８０〜９９．９重量％及び請求項１から７まで
のいずれか１項記載の噴霧乾燥乳化重合体０．１〜２０
重量％を含有する成形材料。[Scope of Claims] 1. A spray-dried emulsion polymer in the form of a powder consisting of granules consisting essentially only of agglomerated latex particles of an emulsion polymer having a Vicat softening temperature higher than 60° C. in its pure state. , a spray-dried emulsion polymer, characterized in that the latex particles contain a high-boiling softener that is compatible with the emulsion polymer. 2. The spray-dried emulsion polymer according to claim 1, which contains 0.5 to 20% by weight of a softener. 3. The spray-dried emulsion polymer according to claim 1 or 2, wherein the latex particles are partially fused or fused together. 4. The spray-dried emulsion polymer according to any one of claims 1 to 3, which contains a fine particle component in an amount of 30% or less of the total number of particles. 5. It is composed of 70 to 100% by weight of methyl methacrylate, 0 to 20% by weight of an alkyl acrylate or an alkyl methacrylate different from methyl methacrylate, and 0 to 10% by weight of another vinyl monomer copolymerizable therewith.Claim 1 The spray-dried emulsion polymer according to any one of 4 to 4. 6. The spray-dried emulsion polymer according to claim 5, having a molecular weight (weight average value) of at least 500,000. 7. The spray-dried emulsion polymer of claim 6 having a molecular weight of at least 700,000. 8. Spray-drying an aqueous dispersion of an emulsion polymer containing a high-boiling softener compatible therewith in order to produce a spray-dried emulsion polymer according to any one of claims 1 to 7. A method for producing a spray-dried emulsion polymer, characterized by: 9. Process according to claim 8, characterized in that a dispersion containing a softening agent boiling above the spray drying temperature is used. 10. The process according to claim 8 or 9, wherein the spray-dried emulsion polymer is separated from the air stream used for spray-drying at a temperature below which the emulsion polymer without softener is semi-melted or melts. . 11. The method of claim 10, wherein the emulsion polymer is separated from the air stream at 40-90<0>C. 12. A PVC processing aid consisting of a spray-dried emulsion polymer according to any one of claims 1 to 7. 13. Polyvinyl chloride (PVC) 80-99.9% by weight
and claim 1 or any one of claims 1 to 7
A mixture consisting of 0.1 to 20% by weight of the spray-dried polymer described in Section 3. 14. 80-99.9% by weight of PVC or a copolymer mainly composed of vinyl chloride and 0.1-20% of the spray-dried emulsion polymer according to any one of claims 1 to 7.
Molding material containing % by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873719241 DE3719241A1 (en) | 1987-06-06 | 1987-06-06 | SPRAY-DRYED EMULSION POLYMER, METHOD FOR THE PRODUCTION AND USE THEREOF AND MOLDING DIMENSIONED THEREOF |
| DE3719241.8 | 1987-06-06 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH011731A true JPH011731A (en) | 1989-01-06 |
| JPS641731A JPS641731A (en) | 1989-01-06 |
| JP2614898B2 JP2614898B2 (en) | 1997-05-28 |
Family
ID=6329346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63137622A Expired - Lifetime JP2614898B2 (en) | 1987-06-06 | 1988-06-06 | Spray-dried emulsion polymer, process for preparing the same, PCT-processing aid comprising the same, and molding material containing the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5017631A (en) |
| EP (1) | EP0294663B1 (en) |
| JP (1) | JP2614898B2 (en) |
| AT (1) | ATE55399T1 (en) |
| CA (1) | CA1324453C (en) |
| DE (2) | DE3719241A1 (en) |
| ES (1) | ES2017003B3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4220782A1 (en) * | 1992-06-25 | 1994-01-05 | Basf Ag | Process for the preparation of solid pharmaceutical sustained release forms |
| DE4426873A1 (en) | 1994-07-29 | 1996-02-01 | Basf Ag | Mineral building materials modified with polymers that contain at least one compound added |
| KR100354557B1 (en) * | 1997-05-15 | 2002-09-30 | 간사이 페인트 가부시키가이샤 | Granulated powdery paint and process for producing the same |
| FR2792546B1 (en) * | 1999-04-26 | 2003-01-03 | Rhodia Chimie Sa | SOLID COMPOSITION INCLUDING AT LEAST ONE LOW MELTING-POINT SURFACTANT |
| JP3913691B2 (en) * | 2003-02-28 | 2007-05-09 | 三洋電機株式会社 | Hydrogen storage alloy, hydrogen storage alloy electrode, and nickel metal hydride storage battery using the same |
| JP5069857B2 (en) | 2004-02-16 | 2012-11-07 | 三菱レイヨン株式会社 | Resin modifier and resin composition and molded article using the same |
| US20080139713A1 (en) * | 2004-12-08 | 2008-06-12 | Lg Chem, Ltd. | Processing Aid For Pvc and Method For Manufacturing the Same |
| JP4878129B2 (en) * | 2005-06-29 | 2012-02-15 | 三菱レイヨン株式会社 | Resin modifier and resin composition and molded product using the same |
| CN103980413A (en) * | 2014-06-04 | 2014-08-13 | 随州市晶辉高分子材料有限公司 | Preparation method of foaming modifier for foaming PVC (poly vinyl chloride) wood-plastic composite |
| CN113683792A (en) * | 2021-07-27 | 2021-11-23 | 上海莱布星科技有限公司 | Wax powder and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2543542C2 (en) * | 1975-09-30 | 1986-10-02 | Röhm GmbH, 6100 Darmstadt | Process for making a plastisol |
| DE2614261C3 (en) * | 1976-04-02 | 1984-08-23 | Hoechst Ag, 6230 Frankfurt | Process for the production of dispersible dispersion powders |
| DE3344242A1 (en) * | 1983-12-07 | 1985-06-20 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING A REDISPERGABLE DISPERSION POWDER AND ITS APPLICATION |
| DE3405651A1 (en) * | 1984-02-17 | 1985-08-22 | Röhm GmbH, 6100 Darmstadt | POWDERED EMULSION POLYMERISATES AND METHOD FOR THE PRODUCTION THEREOF |
-
1987
- 1987-06-06 DE DE19873719241 patent/DE3719241A1/en not_active Withdrawn
-
1988
- 1988-05-27 DE DE8888108464T patent/DE3860426D1/en not_active Expired - Lifetime
- 1988-05-27 EP EP88108464A patent/EP0294663B1/en not_active Expired - Lifetime
- 1988-05-27 ES ES88108464T patent/ES2017003B3/en not_active Expired - Lifetime
- 1988-05-27 AT AT88108464T patent/ATE55399T1/en not_active IP Right Cessation
- 1988-06-06 CA CA000568747A patent/CA1324453C/en not_active Expired - Lifetime
- 1988-06-06 JP JP63137622A patent/JP2614898B2/en not_active Expired - Lifetime
-
1989
- 1989-12-26 US US07/462,274 patent/US5017631A/en not_active Expired - Lifetime
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