JPH0219146B2 - - Google Patents
Info
- Publication number
- JPH0219146B2 JPH0219146B2 JP55133017A JP13301780A JPH0219146B2 JP H0219146 B2 JPH0219146 B2 JP H0219146B2 JP 55133017 A JP55133017 A JP 55133017A JP 13301780 A JP13301780 A JP 13301780A JP H0219146 B2 JPH0219146 B2 JP H0219146B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersion
- vinylidene chloride
- weight
- parts
- film
- 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.)
- Expired - Lifetime
Links
- 239000006185 dispersion Substances 0.000 claims description 90
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 239000004815 dispersion polymer Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 159000000001 potassium salts Chemical class 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- -1 alcohol sulfate salts Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 230000002087 whitening effect Effects 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- LFJIAQOELDZMAR-UHFFFAOYSA-N n-methylprop-2-enamide;propane-1-sulfonic acid Chemical compound CNC(=O)C=C.CCCS(O)(=O)=O LFJIAQOELDZMAR-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、バリヤー性に優れ、熱水処理により
白化変質せず、かつ優れた耐ブロツキング性及び
ホツトスリツプ性等を有する塗膜を与える塩化ビ
ニリデン系重合体水性分散体に関する。
塩化ビニリデン系重合体水性分散体は、その乾
燥塗膜がバリヤー性、耐溶剤性及び低透湿性等の
特性に優れていて、食品包装分野等において用い
られるプラスチツクフイルムや紙等の表面加工に
広く使用されている。
しかし、この種の公知の分散体は、通常、塩化
ビニリデン含有率が94重量％未満の単量体混合物
の乳化重合によつて得られるものであり、かかる
分散体の塗膜は、たとえば食品殺菌のためコーテ
イング直後の塗膜を熱水処理した場合に白化変質
する欠点があつた。また、この種分散体の塗布乾
燥フイルムは、ロール状に巻き取つた場合の塗布
面どうしがブロツキングを起しやすく、また塗布
面どうしのスリツプ性（すべり性）、特に製袋時
のヒートシールの際に必要なヒートスリツプ性が
劣る等の欠点があつた。
他方、塩化ビニリデンの共重合体比率の高い重
合体は、成膜直後の結晶化速度が速く結晶性に優
れ、熱水処理時に白化変質せず、耐ブロツキング
性、ヒートスリツプ性等にも優れていることが判
明したが、塩化ビニリデン含有率の高い重合体の
分散体は、貯蔵安定性（保存安定性）が悪く、保
存中に分散体の凝集、すなわち樹脂分の凝固によ
り水相と樹脂相に分離しやすく、分散体の可使用
期間が著しく短かく、さらに分散体を保存すると
成膜性が低下してくる等の欠点があつた。
本発明者等は、塩化ビニリデン系重合体水性分
散体の上記の欠点を改良するために種々研究を重
ねた結果、塩化ビニリデン含有率の比較的に低い
単量体混合物の乳化重合によつて得られた通常の
塩化ビニリデン系重合体水性分散体に、塩化ビニ
リデン含有率が94.0重量％以上の単量体混合物の
乳化重合によつて得られた結晶性の高い塩化ビニ
リデン系重合体水性分散体を特定の割合で配合す
ることによつて、その目的を達成できることを知
り、本発明に到達したのである。
すなわち、本発明の塩化ビニリデン系重合体水
性分散体は、
(a) 塩化ビニリデン 90.0〜93.5重量％、
(b) 不飽和カルボン酸、アクリルアミド及びメタ
クリルアミドからなる群より選ばれた単量体
0.1〜2.5重量％、
(c) 前記(b)以外の、塩化ビニリデンと共重合可能
なビニル単量体 4.0〜10.0重量％、
よりなる単量体混合物の乳化重合によつて得られ
た比較的に結晶性の低い塩化ビニリデン系重合体
水性分散体（）と、
(i) 塩化ビニリデン 94.0〜98.0重量％、
(ii) 不飽和カルボン酸及びそのナトリウム塩、
カリウム塩、アンモニウム塩、アクリルアミ
ド並びにメタクリルアミドからなる群より選
ばれた単量体 0.1〜2.5重量％、
(iii) モノオレフイン性不飽和スルホン酸及びそ
のナトリウム塩、カリウム塩、アンモニウム
塩からなる群より選ばれた単量体
0.1〜2.0重量％、
(iv) 前記(ii)及び(iii)の単量体以外の、塩化ビニ
リ
デンと共重合可能なビニル単量体
5.8重量％以下
よりなる単量体混合物の乳化重合によつて得られ
た比較的に結晶性の高い塩化ビニリデン系重合体
水性分散体（）とを、前記の塩化ビニリデン系
重合体水性分散体（）の樹脂分100重量部に対
して、前記の塩化ビニリデン系重合体水性分散体
（）の樹脂分が0.5〜50重量部になる割合におい
て混合してなる分散体である。
本発明における前記の比較的に結晶性の低い塩
化ビニリデン系重合体水性分散体（）は、一般
によく知られているので、その詳しい説明を省略
する。
また、本発明における前記の比較的に結晶性の
高い塩化ビニリデン系重合体水性分散体（）を
製造するための単量体混合物において、塩化ビニ
リデン(i)の割合が94.0重量％未満になると、重合
体の塩化ビニリデン含有率が比較的に低くなるた
め、成膜直後における結晶化速度が遅く、即ち結
晶性が低いため、本発明の最終分散体〔分散体
（）と分散体（）の混合物をいう。以下同
じ。〕の塗膜の熱水処理時の白化変質を防止でき
ず、またその塗膜の耐ブロツキング性やスリツプ
性を充分に改善できなくなる。またその割合が
98.0重量％を超えると、分散体（）自体及び本
発明の最終分散体の安定性、特に貯蔵（保存）安
定性が悪くなる。
単量体(ii)は重合体粒子に親水性を付与せしめる
作用をするものであり、それにより分散体（）
自体及び本発明の最終分散体の安定性を高め、か
つそれらの分散体の重合体粒子の基材等に対する
接着性を高める作用をする。その不飽和カルボン
酸としては、たとえばアクリル酸、メタクリル
酸、クロトン酸、イタコン酸、マレイン酸、フマ
ル酸及びそれらのナトリウム塩、カリウム塩、ア
ンモニウム塩等があげられる。単量体(ii)の割合が
0.1重量％未満になると乳化重合時の安定性が悪
くなるし、本発明の最終分散体の安定性やその重
合体粒子の基材等に対する接着性が悪くなる。ま
た、その割合が2.5重量％を超えると、親水性が
大きくなりすぎ、たとえば本発明の最終分散体塗
膜の水蒸気透過性が低下してくる。
単量体(iii)は、親水性の単量体であり、これを共
重合させることにより自巳乳化性が向上し、粒子
を安定化させる。そのモノオレフイン性不飽和ス
ルホン酸としては、たとえばビニルスルホン酸、
メチルアクリルアミドプロパンスルホン酸等があ
げられる。単量体(iii)の割合が0.1重量％未満では
分散体（）及び本発明の最終分散体の安定化に
充分な効果を発揮できなくなるし、その割合が
2.0重量％を超えると、重合体の親水性が過剰に
なりすぎて、本発明の最終分散体より得られる塗
膜の水蒸気透過性が大きくなり、実用的でなくな
る。
単量体(iv)としては、たとえば塩化ビニル、アク
リル酸エステル、メタクリル酸エステル、アクリ
ロニトリル、メタクリロニトリル、ビニルエステ
ル（たとえば酢酸ビニル、プロピオン酸ビニル
等）、及びビニルエーテル（たとえばビニルメチ
ルエーテル、ビニルエチルエーテル等）があげら
れる。これらの単量体は単量体混合物に対して
5.8重量％以下の割合で使用される。
上記単量体(ii)〜(iv)は、それぞれの群の単量体の
１種類を用いてもよいし、２種以上併用すること
もできる。
本発明において用いる分散体（）及び分散体
（）を得るための乳化重合は、いずれも通常の
方法により行なわせることができ、その重合温度
は通常、35〜70℃の範囲である。
それらの乳化重合における乳化剤としては、た
とえば高級アルコール硫酸エステル塩、アルキル
ベンゼンスルホン酸塩、ポリオキシエチレンアル
キルサルフエート塩、ポリオキシエチレンアルキ
ルフエノールエーテルサルフエート塩等の陰イオ
ン性界面活性剤、ポリオキシエチレンアルキルエ
ーテル、ポリオキシエチレンアルキルフエノー
ル、エチレンオキサイドプロピレンオキサイドブ
ロツク共重合体、ソルビタン誘導体等の非イオン
性界面活性剤を好適に使用できる。
また、それらの重合開始剤としては、たとえば
過硫酸カリウム、過硫酸アンモニウム等の過硫酸
塩、過硫酸水素、ベンゾイルパーオキサイド、ク
メンハイドロパーオキサイド、ｔ−ブチルハイド
ロパーオキサイド等の過酸化物、アゾビスイソブ
チロニトリル等が一般に用いられ、特に水溶性開
始剤及び水溶性のレドツクス型開始剤が好適に使
用できる。
本発明で用いる前記の比較的に結晶性の低い塩
化ビニリデン系重合体水性分散体（）のみで
は、塩化ビニリデンの共重合比率が比較的に低い
ので、造膜直後における結晶化速度が遅く、その
ために塗膜が熱水処理時に白化変質しやすい。ま
た、得られる塗膜の耐ブロツキング性、スリツプ
性、ホツトスリツプ性等の性能も悪い。他方、本
発明で用いる前記の比較的に結晶性の高い塩化ビ
ニリデン系水性分散体（）は、造膜直後におけ
る結晶化速度が速いので、そのために造膜直後か
ら結晶化度が高く、耐ブロツキング性、スリツプ
性、ホツトスリツプ性に優れ、その塗膜を熱水白
化処理しても白化変質しないが、その反面におい
てこれ単独では重合体粒子の安定性、特にその貯
蔵安定性に乏しく、かつ貯蔵中に速やかに結晶化
するために成膜性、特に30℃以下の低温での成膜
性が悪い。
しかるに、本発明にしたがつて前記分散体
（）と前記分散体（）とを、分散体（）の
樹脂分100重量部に対して分散体（）の樹脂分
が0.5〜50重量部、好ましくは５〜30重量部にな
るような割合で混合すると、分散体（）の結晶
性の高い重合性が結晶核として作用し、分散体
（）の重合体の結晶化速度を促進させるので、
最終分散体の造膜直後における結晶化速度は速く
なり、そのために耐ブロツキング性、スリツプ
性、ホツトスリツプ性などの性能も分散体（）
単独より形成される塗膜と比較して優れたものと
なり、同時にその塗膜を熱水処理しても白化変質
しなくなる。また、ガスバリアー性についても、
比較的に結晶化度の高い分散体（）を単独で用
いた場合には、結晶化度が高いため、分散体粒子
が硬く、通常の成膜条件での造膜過程において十
分な粒子の融着がおこらず、そのために塩化ビニ
リデン系重合体本来の性能であるガス遮断性を十
分に発揮できないが、これに比較的結晶化度の低
い分散体（）に混合した場合には、（）の粒
子は（）の分散体内であたかも結晶化度を高め
るフイラーの様に作用し、最終分散体より得られ
る塗膜のガス遮断性を向上させる。すなわち、分
散体（）の粒子は分散体（）の粒子によつて
造膜を助けられて成膜が容易となる。これは成膜
後のフイルムを考えれば、比較的に結晶化度の低
い分散体塗膜中に結晶化度の高いフイラーが存在
したと同様となり、その結晶核フイラーは周囲の
比較的結晶化度の低い部分の結晶化を促進させる
ので、最終分散体は、造膜直後においても結晶化
速度が速く、その時点における結晶化度も十分に
高いので、最終分散体より得られる塗膜のガス遮
断性は、分散体（）単独のそれよりも十分に優
れたものとなる。しかも、その分散体は、貯蔵安
定性及び長期保存後の成膜性も著しく良好であ
る。
最終分散体において、より結晶化度の高い分散
体（）の割合が増加してくると、その増加と共
に塗膜の耐ブロツキング性、ホツトスリツプ性な
どが改善されてくるが、逆に、ガスバリアー性能
は、分散体（）のそれに近づいてくる。これ
は、最終分散体中に硬い（結晶化度が高い）分散
体粒子がより多く含まれるので、通常の成膜条件
では十分な粒子の融着がおこらないためである。
しかし、この塗膜に十分な熱をかけて粒子を完全
に融着させれば、塗膜は耐ブロツキング性、ホツ
トスリツプ性などの性能と共に塩化ビニリデン系
重合体本来のガスバリアー性をも発揮できるよう
になる。
以下に分散体例及び実施例をあげて詳述する。
これらの例における部及び％は、特に付記しない
限り重量基準によるものである。
分散体例 ′
温度調節器、撹拌機、供給容器、温度計及び窒
素ガス導入管を備えた反応容器内に、
水 200部
ドデシルベンゼンスルホン酸ソーダ １部
過硫酸カリウム 1.6部
を仕込み、内部を窒素ガス置換してから減圧に
し、再び窒素ガス導入してから減圧にした。次い
で、この反応容器を50℃に保つて撹拌しながら、
これに窒素ガス置換をした別容器内より、
塩化ビニリデン 500部
アクリル酸メチル 41部
アクリル酸 ９部
水 250部
ドデシルベンゼンスルホン酸ソーダ 10部
よりなる混合物を定量ポンプを用いて10時間かけ
て連続的に送入した。
所定量の送入を終了後、反応器の内圧が０Kg／
cm2Ｇになるまで50℃の温度を保つて撹拌を続け、
固形分含有量が約55％の塩化ビニリデン系重合体
水性分散体を得た。以下、この分散体を「分散体
′」という。
なお、分散体′の製造に用いた単量体組成は
下記のとおりであつた。
塩化ビニリデン 90.9％
アクリル酸メチル 7.5％
アクリル酸 1.6％
分散体例 ′
分散体例′において用いたと同一の反応容器
内に、
水 250部
ドデシルベンゼンスルホン酸ソーダ １部
過硫酸カリウム 1.5部
を仕込み、分散体例′におけると同様にして窒
素ガス置換をした後減圧してから、反応器内を50
℃に保つて撹拌しながら、これに窒素ガス置換を
した別容器内より、
塩化ビニリデン 475部
アクリル酸メチル 15部
アクリル酸 7.5部
ビニルスルホン酸 2.5部
水 250部
ドデシルベンゼンスルホン酸ソーダ ８部
よりなる混合物を定量ポンプで10時間かけて連続
的に送入した。
所定量の送入を終了後、反応器内圧が０Kg／cm2
Ｇになるまで50℃の温度を保つて撹拌を続け、固
形分含有量が約50％の塩化ビニリデン系重合体水
性分散体を得た。この水性分散体を固形分含有量
が25％になるように水で希釈した。以下、この分
散体を「分散体′」という。
なお、分散体′の製造に用いた単量体組成は
下記のとおりであつた。
塩化ビニリデン 95％
アクリル酸メチル ３％
アクリル酸 1.5％
ビニルスルホン酸 0.5％
分散体例 ″
ビニル単量体の組成を表１に示すように変更し
たほかは、分散体′の製造法と同様にして分散
体″を製造した。
分散体′、分散体′、及び分散体″におけ
る重合体の単量体組成、並びにこれらの分散体及
びその塗膜の物性を試験した結果は表１に示すと
おりであつた。
The present invention relates to an aqueous vinylidene chloride polymer dispersion that provides a coating film that has excellent barrier properties, does not undergo whitening when treated with hot water, and has excellent blocking resistance and hot slip properties. Vinylidene chloride polymer aqueous dispersions have excellent dry coating properties such as barrier properties, solvent resistance, and low moisture permeability, and are widely used in the surface treatment of plastic films and paper used in the food packaging field. It is used. However, known dispersions of this type are usually obtained by emulsion polymerization of monomer mixtures containing less than 94% by weight of vinylidene chloride, and coatings of such dispersions can be used, for example, for food sterilization. Therefore, when the coating film was treated with hot water immediately after coating, it had the disadvantage of whitening and deterioration. In addition, when coated and dried film of this type of dispersion is wound up into a roll, the coated surfaces tend to block each other, and the coated surfaces have slipping properties, especially when heat sealing during bag making. However, there were drawbacks such as poor heat slip properties, which are necessary in some cases. On the other hand, polymers with a high copolymer ratio of vinylidene chloride have a fast crystallization rate immediately after film formation, have excellent crystallinity, do not turn white during hot water treatment, and have excellent blocking resistance, heat slip properties, etc. However, dispersions of polymers with a high vinylidene chloride content have poor storage stability, and during storage, aggregation of the dispersion, that is, coagulation of the resin component, causes the aqueous phase and resin phase to separate. The dispersion has disadvantages such as easy separation, extremely short shelf life of the dispersion, and poor film-forming properties when the dispersion is stored. The present inventors have conducted various studies to improve the above-mentioned drawbacks of vinylidene chloride-based polymer aqueous dispersions, and as a result, they have found that they can be obtained by emulsion polymerization of a monomer mixture with a relatively low content of vinylidene chloride. A highly crystalline vinylidene chloride polymer aqueous dispersion obtained by emulsion polymerization of a monomer mixture with a vinylidene chloride content of 94.0% by weight or more is added to the conventional vinylidene chloride polymer aqueous dispersion obtained by It was discovered that the objective could be achieved by blending in a specific ratio, and the present invention was achieved. That is, the aqueous vinylidene chloride polymer dispersion of the present invention comprises (a) 90.0 to 93.5% by weight of vinylidene chloride, (b) a monomer selected from the group consisting of unsaturated carboxylic acids, acrylamide, and methacrylamide.
0.1 to 2.5% by weight, (c) 4.0 to 10.0% by weight of a vinyl monomer copolymerizable with vinylidene chloride other than the above (b). (i) vinylidene chloride 94.0 to 98.0% by weight, (ii) unsaturated carboxylic acid and its sodium salt,
0.1 to 2.5% by weight of a monomer selected from the group consisting of potassium salts, ammonium salts, acrylamide, and methacrylamide; (iii) monoolefinic unsaturated sulfonic acids and their sodium salts, potassium salts, and ammonium salts; selected monomers
0.1 to 2.0% by weight, (iv) A vinyl monomer copolymerizable with vinylidene chloride other than the monomers (ii) and (iii) above.
A relatively highly crystalline vinylidene chloride polymer aqueous dispersion () obtained by emulsion polymerization of a monomer mixture containing 5.8% by weight or less is mixed with the vinylidene chloride polymer aqueous dispersion ( This is a dispersion prepared by mixing 100 parts by weight of the resin content of the vinylidene chloride polymer aqueous dispersion (2) with the resin content of 0.5 to 50 parts by weight. The relatively low crystallinity vinylidene chloride polymer aqueous dispersion (2) used in the present invention is generally well known, so a detailed explanation thereof will be omitted. Furthermore, in the monomer mixture for producing the relatively highly crystalline vinylidene chloride polymer aqueous dispersion () according to the present invention, when the proportion of vinylidene chloride (i) is less than 94.0% by weight, Since the vinylidene chloride content of the polymer is relatively low, the crystallization rate immediately after film formation is slow, that is, the crystallinity is low. means. same as below. It is not possible to prevent the paint film from whitening and deterioration during hot water treatment, and it is also impossible to sufficiently improve the blocking resistance and slip property of the paint film. Also, the percentage
If it exceeds 98.0% by weight, the stability of the dispersion itself and the final dispersion of the present invention, especially the storage stability, will deteriorate. Monomer (ii) acts to impart hydrophilicity to the polymer particles, thereby forming a dispersion ().
It functions to enhance the stability of itself and the final dispersion of the present invention, and to enhance the adhesion of the polymer particles of these dispersions to substrates and the like. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and their sodium, potassium, and ammonium salts. The proportion of monomer (ii) is
If the amount is less than 0.1% by weight, the stability during emulsion polymerization will deteriorate, and the stability of the final dispersion of the present invention and the adhesion of its polymer particles to substrates will deteriorate. Moreover, if the proportion exceeds 2.5% by weight, the hydrophilicity becomes too large, and, for example, the water vapor permeability of the final dispersion coating of the present invention decreases. Monomer (iii) is a hydrophilic monomer, and by copolymerizing it, self-emulsifying property is improved and particles are stabilized. Examples of the monoolefinic unsaturated sulfonic acid include vinyl sulfonic acid,
Examples include methyl acrylamide propane sulfonic acid. If the proportion of monomer (iii) is less than 0.1% by weight, it will not be possible to exhibit a sufficient effect in stabilizing the dispersion () and the final dispersion of the present invention;
If it exceeds 2.0% by weight, the hydrophilicity of the polymer becomes too excessive, and the water vapor permeability of the coating film obtained from the final dispersion of the present invention increases, making it impractical. Examples of the monomer (iv) include vinyl chloride, acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, vinyl esters (such as vinyl acetate and vinyl propionate), and vinyl ethers (such as vinyl methyl ether and vinyl ethyl ether). ether, etc.). These monomers are
Used at a proportion of 5.8% by weight or less. The above monomers (ii) to (iv) may be used alone or in combination of two or more of the monomers in each group. The dispersion () used in the present invention and the emulsion polymerization for obtaining the dispersion () can be carried out by conventional methods, and the polymerization temperature is usually in the range of 35 to 70°C. Examples of emulsifiers used in these emulsion polymerizations include anionic surfactants such as higher alcohol sulfate salts, alkylbenzene sulfonate salts, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenol ether sulfate salts, polyoxyethylene Nonionic surfactants such as alkyl ethers, polyoxyethylene alkylphenols, ethylene oxide propylene oxide block copolymers, and sorbitan derivatives can be suitably used. Examples of polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate, peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, and azobisulfate. Isobutyronitrile and the like are generally used, and water-soluble initiators and water-soluble redox-type initiators are particularly suitable. If only the aqueous vinylidene chloride polymer dispersion () with relatively low crystallinity used in the present invention has a relatively low copolymerization ratio of vinylidene chloride, the crystallization rate immediately after film formation is slow; The paint film is susceptible to whitening and deterioration during hot water treatment. Furthermore, the properties of the resulting coating film, such as blocking resistance, slip resistance, and hot slip resistance, are also poor. On the other hand, the relatively highly crystalline vinylidene chloride aqueous dispersion () used in the present invention has a high crystallization rate immediately after film formation. It has excellent slip resistance, slip resistance, and hot slip resistance, and does not whiten or deteriorate even when the coating film is treated with hot water whitening. Because it crystallizes rapidly, film forming properties are poor, especially at low temperatures below 30°C. However, according to the present invention, the dispersion () and the dispersion () are mixed so that the resin content of the dispersion () is 0.5 to 50 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the resin content of the dispersion (). When mixed at a ratio of 5 to 30 parts by weight, the highly crystalline polymerizability of the dispersion () acts as a crystal nucleus and accelerates the crystallization rate of the polymer in the dispersion ().
The crystallization rate of the final dispersion immediately after film formation becomes faster, and as a result, the performance of the dispersion (), such as blocking resistance, slip property, and hot slip property, also improves.
It is superior to a coating film formed by itself, and at the same time, the coating film does not whiten or change in quality even if it is treated with hot water. Also, regarding gas barrier properties,
When a dispersion with a relatively high degree of crystallinity () is used alone, the dispersion particles are hard due to the high degree of crystallinity, and sufficient particle fusion cannot be achieved during the film forming process under normal film forming conditions. As a result, vinylidene chloride-based polymers cannot fully exhibit their original performance of gas barrier properties, but when mixed with dispersion (), which has a relatively low degree of crystallinity, The particles act like a filler that increases the degree of crystallinity within the dispersion () and improve the gas barrier properties of the coating film obtained from the final dispersion. That is, the particles of the dispersion () are assisted in film formation by the particles of the dispersion (), making it easy to form a film. Considering the film after film formation, this is similar to the presence of a filler with a high degree of crystallinity in a dispersion coating film with a relatively low degree of crystallinity, and the crystal nucleus filler has a relatively low degree of crystallinity in the surrounding area. The final dispersion has a high crystallization rate even immediately after film formation, and the degree of crystallinity at that point is sufficiently high, so the gas barrier of the coating film obtained from the final dispersion is high. The properties are sufficiently superior to those of the dispersion alone. Furthermore, the dispersion has extremely good storage stability and film-forming properties after long-term storage. In the final dispersion, as the proportion of the dispersion with higher crystallinity () increases, the blocking resistance and hot slip properties of the coating film improve, but on the contrary, the gas barrier performance approaches that of dispersion(). This is because the final dispersion contains more hard (highly crystallized) dispersion particles, so that sufficient fusion of the particles does not occur under normal film forming conditions.
However, if sufficient heat is applied to this coating film to completely fuse the particles, the coating film will be able to exhibit properties such as blocking resistance and hot slip properties, as well as the gas barrier properties inherent to vinylidene chloride polymers. become. Dispersion examples and examples will be given and explained in detail below.
Parts and percentages in these examples are by weight unless otherwise noted. Example of dispersion 200 parts of water, 1 part of sodium dodecylbenzenesulfonate, and 1.6 parts of potassium persulfate were placed in a reaction vessel equipped with a temperature controller, stirrer, supply container, thermometer, and nitrogen gas inlet tube, and the inside was filled with nitrogen gas. After replacing the air, the pressure was reduced, nitrogen gas was introduced again, and the pressure was reduced. Next, while keeping the reaction vessel at 50°C and stirring,
To this, a mixture consisting of 500 parts of vinylidene chloride, 41 parts of methyl acrylate, 9 parts of acrylic acid, 250 parts of water, and 10 parts of sodium dodecylbenzenesulfonate was added continuously over a period of 10 hours using a metering pump from a separate container purged with nitrogen gas. Sent to. After finishing feeding the specified amount, the internal pressure of the reactor becomes 0 kg/
Continue stirring while maintaining the temperature at 50℃ until cm 2 G.
An aqueous vinylidene chloride polymer dispersion having a solids content of approximately 55% was obtained. Hereinafter, this dispersion will be referred to as "dispersion'". The monomer composition used to produce the dispersion' was as follows. Vinylidene chloride 90.9% Methyl acrylate 7.5% Acrylic acid 1.6% Dispersion example 250 parts of water, 1 part of sodium dodecylbenzenesulfonate, and 1.5 parts of potassium persulfate were charged in the same reaction vessel used in 'Dispersion example'. After replacing with nitrogen gas and reducing the pressure in the same manner as in , the inside of the reactor was heated to 50℃.
While maintaining the temperature at °C and purging with nitrogen gas, a separate container was prepared containing 475 parts of vinylidene chloride, 15 parts of methyl acrylate, 7.5 parts of acrylic acid, 2.5 parts of vinylsulfonic acid, 250 parts of water, and 8 parts of sodium dodecylbenzenesulfonate. The mixture was pumped continuously with a metering pump over a period of 10 hours. After finishing feeding the specified amount, the reactor internal pressure is 0Kg/cm 2
Stirring was continued while maintaining the temperature at 50° C. until the temperature reached G, to obtain an aqueous vinylidene chloride polymer dispersion with a solid content of about 50%. This aqueous dispersion was diluted with water to a solids content of 25%. Hereinafter, this dispersion will be referred to as "dispersion'". The monomer composition used to produce the dispersion' was as follows. Vinylidene chloride 95% Methyl acrylate 3% Acrylic acid 1.5% Vinyl sulfonic acid 0.5% Example of dispersion ``Dispersion was carried out in the same manner as in the manufacturing method of dispersion'' except that the composition of the vinyl monomer was changed as shown in Table 1. The body was manufactured. Table 1 shows the results of testing the monomer compositions of the polymers in dispersion ', dispersion ', and dispersion ', as well as the physical properties of these dispersions and their coatings.
【表】
表１の注
各試験方法及び評価は下記によつた。
(1) 耐ブロツキング性
肉厚12μのポリエステル系フイルム（三菱樹脂
株式会社商品名 ダイアホイル）に、乾燥塗布量
が５ｇ／m2になるように分散体を塗布し、100℃
で３分間乾燥させた。
得られたフイルムの塗布面どうしを重ね合わ
せ、250ｇ／cm2の荷重を加えて40℃の温度で24時
間処理したのち、塗布面の粘着性を調べて下記の
とおり評価した。
Ａ……全く抵抗もなく塗面同志が剥離する。
Ｂ……指先で２、３度軽くこすつた後、サラリ
と剥離する。
Ｃ……若干、抵抗あるが塗面に傷がつくことな
く剥離する。
Ｄ……剥がすときに抵抗があり塗面に傷がつ
く。
(2) ホツトスリツプ性
(1)において得られた塗布乾燥フイルムの塗布面
どうしを重ね合わせ、そのすべり性を下記のとお
りに評価した。
Ａ……何の抵抗もなくよく滑る。
Ｂ……殆んど抵抗なく滑る。
Ｃ……滑るが若干抵抗有り。
Ｄ……可成り抵抗有り滑り悪い。
(3) 耐熱水白化性
肉厚15μのポリアミドフイルム（ユニチカ社商
品名 エムブレン）に、乾燥塗布量が５ｇ／m2に
なるように分散体を塗布し、100℃で３分間乾燥
後、95℃の熱水に30分間浸漬し、取り出したフイ
ルムの白化の程度を調べて下記のとおり評価し
た。
Ａ……透明
Ｂ……うす青く呈色
Ｃ……青白く呈色
Ｄ……白化する
(4) 酸化バリアー性
(1)で得られた塗布フイルムの乾燥後、60℃で１
時間エージング処理したのち、酸素透過率測定装
置（MoCoN社製OX−Tran100型）を用いて、
20℃、相対湿度（RH）100％の条件下で酸素バ
リアー性を測定した。
評価数値の単位は下記のとおりである。
c.c.／m2・24hr・20℃・100％RH
(5) 貯蔵安定性
分散体を常温で放置し、凝固を起すまでの期間
で評価した。
(6) 保存後の成膜性
分散体を常温放置して保存したものの下記の成
膜時の成膜性を調べて評価した。
肉厚12μのポリエステル系フイルム（三菱樹脂
株式会社商品名 ダイアホイル）に、乾燥塗布量
が５ｇ／m2になるように分散体を塗布し100℃で
３分間乾燥させた。
実施例 １〜３
分散体′（固形分55％）の100部に対して、分
散体′（固形分25％）を約４部（樹脂比100／
1.82）（実施例１）、又は約22部（樹脂比100／10）
（実施例２）、又は約66部（樹脂比100／30）（実施
例３）の割合でそれぞれ混合して撹拌し分散体を
得た。
実施例 ４〜５
実施例２及び実施例３において、分散体′の
代りに分散体″を用い、そのほかは同様にして
それぞれ分散体を得た。
上記各実施例で得られた分散体の組成割合、並
びに分散体及びその塗膜の物性試験結果は表２に
示すとおりであつた。[Table] Notes on Table 1 Each test method and evaluation were as follows. (1) Blocking resistance The dispersion was applied to a polyester film with a wall thickness of 12 μm (trade name: Diafoil, manufactured by Mitsubishi Plastics Co., Ltd.) so that the dry coating amount was 5 g/m 2 , and the film was heated at 100°C.
and dried for 3 minutes. The coated surfaces of the obtained films were placed one on top of the other and treated at a temperature of 40° C. for 24 hours under a load of 250 g/cm 2 .The tackiness of the coated surfaces was examined and evaluated as follows. A...The coated surfaces peel off with no resistance at all. B: After rubbing lightly with your fingertips two or three times, it peels off smoothly. C: There is some resistance, but it peels off without damaging the painted surface. D: There is resistance when peeling off, causing scratches on the painted surface. (2) Hot slip property The coated surfaces of the coated and dried films obtained in (1) were overlapped and their slip properties were evaluated as follows. A...It slides well without any resistance. B...Slides with almost no resistance. C...It slips, but there is some resistance. D...Significant resistance and poor slippage. (3) Resistance to hot water whitening The dispersion was applied to a polyamide film with a wall thickness of 15 μm (Unitika's product name Emblen) so that the dry coating amount was 5 g/m 2 , and after drying at 100°C for 3 minutes, it was heated at 95°C. The film was immersed in hot water for 30 minutes, and the degree of whitening of the removed film was examined and evaluated as follows. A...Transparent B...Pale blue color C...Bluish white color D...Whitening (4) Oxidation barrier property After drying the coated film obtained in (1), 1 at 60℃
After time aging treatment, using an oxygen permeability measuring device (MoCoN OX-Tran100 model),
Oxygen barrier properties were measured at 20°C and 100% relative humidity (RH). The units of evaluation values are as follows. cc/ m2・24hr・20℃・100%RH (5) Storage stability The dispersion was left at room temperature and evaluated based on the period until solidification occurred. (6) Film-forming property after storage The dispersion was stored at room temperature and its film-forming property was examined and evaluated as described below. The dispersion was applied to a polyester film (trade name: Diafoil, manufactured by Mitsubishi Plastics Co., Ltd.) with a wall thickness of 12 μm at a dry coating amount of 5 g/m 2 and dried at 100° C. for 3 minutes. Examples 1 to 3 About 4 parts of dispersion' (solid content 25%) to 100 parts of dispersion' (solid content 55%) (resin ratio 100/
1.82) (Example 1), or about 22 parts (resin ratio 100/10)
(Example 2) or approximately 66 parts (resin ratio 100/30) (Example 3) were mixed and stirred to obtain a dispersion. Examples 4 to 5 Dispersions were obtained in the same manner as in Examples 2 and 3, except that ``dispersion'' was used instead of ``dispersion''. Composition of the dispersion obtained in each of the above examples The ratio and the physical property test results of the dispersion and its coating film were as shown in Table 2.
【表】
表２に示された結果から明らかなように、分散
体（）に分散体（）を混合することによつ
て、混合分散体の貯蔵安定性及び保存後の成膜性
が著しく良好となるとともに、その塗膜物性も著
しく向上する。[Table] As is clear from the results shown in Table 2, by mixing dispersion () with dispersion (), the storage stability and film forming properties after storage of the mixed dispersion are significantly improved. At the same time, the physical properties of the coating film are also significantly improved.
Claims (1)
クリルアミドからなる群より選ばれた単量体
0.1〜2.5重量％、 (c) 前記(b)以外の、塩化ビニリデンと共重合可能
なビニル単量体 4.0〜10.0重量％、 よりなる単量体混合物の乳化重合によつて得られ
た比較的に結晶性の低い塩化ビニリデン系重合体
水性分散体（）と、 (i) 塩化ビニリデン 94.0〜98.0重量％、 (ii) 不飽和カルボン酸及びそのナトリウム塩、
カリウム塩、アンモニウム塩、アクリルアミ
ド並びにメタクリルアミドからなる群より選
ばれた単量体 0.1〜2.5重量％、 (iii) モノオレフイン性不飽和スルホン酸及びそ
のナトリウム塩、カリウム塩、アンモニウム
塩からなる群より選ばれた単量体
0.1〜2.0重量％、 (iv) 前記(ii)及び(iii)の単量体以外の、塩化ビニ
リ
デンと共重合可能なビニル単量体
5.8重量％以下 よりなる単量体混合物の乳化重合によつて得られ
た比較的に結晶性の高い塩化ビニリデン系重合体
水性分散体（）とを、前記の塩化ビニリデン系
重合体水性分散体（）の樹脂分100重量部に対
して、前記の塩化ビニリデン系重合体水性分散体
（）の樹脂分が0.5〜50重量部になる割合におい
て混合してなる塩化ビニリデン系重合体水性分散
体。[Scope of Claims] 1 (a) 90.0 to 93.5% by weight of vinylidene chloride, (b) a monomer selected from the group consisting of unsaturated carboxylic acid, acrylamide, and methacrylamide
0.1 to 2.5% by weight, (c) 4.0 to 10.0% by weight of a vinyl monomer copolymerizable with vinylidene chloride other than the above (b). (i) vinylidene chloride 94.0 to 98.0% by weight, (ii) unsaturated carboxylic acid and its sodium salt,
0.1 to 2.5% by weight of a monomer selected from the group consisting of potassium salts, ammonium salts, acrylamide, and methacrylamide; (iii) monoolefinic unsaturated sulfonic acids and their sodium salts, potassium salts, and ammonium salts; selected monomers
0.1 to 2.0% by weight, (iv) A vinyl monomer copolymerizable with vinylidene chloride other than the monomers (ii) and (iii) above.
A relatively highly crystalline vinylidene chloride polymer aqueous dispersion () obtained by emulsion polymerization of a monomer mixture containing 5.8% by weight or less is mixed with the vinylidene chloride polymer aqueous dispersion ( An aqueous vinylidene chloride polymer dispersion prepared by mixing 100 parts by weight of the resin content of the vinylidene chloride polymer aqueous dispersion () with a resin content of 0.5 to 50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13301780A JPS5757741A (en) | 1980-09-26 | 1980-09-26 | Aqueous dispersion of vinylidene chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13301780A JPS5757741A (en) | 1980-09-26 | 1980-09-26 | Aqueous dispersion of vinylidene chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5757741A JPS5757741A (en) | 1982-04-07 |
| JPH0219146B2 true JPH0219146B2 (en) | 1990-04-27 |
Family
ID=15094844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13301780A Granted JPS5757741A (en) | 1980-09-26 | 1980-09-26 | Aqueous dispersion of vinylidene chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5757741A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2194186T5 (en) * | 1997-04-25 | 2009-05-11 | Asahi Kasei Kabushiki Kaisha | LATEX CHLORIDE POLYVINYLIDENE AND PROCEDURE FOR MANUFACTURING |
| BRPI0819881B1 (en) * | 2007-11-30 | 2019-10-22 | Unitika Ltd | methods for producing a polyamide film with a vinylidene chloride copolymer layer and a laminate |
| JP2009274223A (en) * | 2008-05-12 | 2009-11-26 | Unitika Ltd | Vinylidene chloride copolymer coating film |
| MX336849B (en) * | 2011-05-04 | 2016-02-03 | Uniseal Solutions Inc | Improved polymeric composition for cement based substructures. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598240A (en) * | 1978-12-07 | 1980-07-26 | Dow Chemical Co | Polyacrylic ester rubberrdenatured vinylidene chloride copolymer composition |
-
1980
- 1980-09-26 JP JP13301780A patent/JPS5757741A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598240A (en) * | 1978-12-07 | 1980-07-26 | Dow Chemical Co | Polyacrylic ester rubberrdenatured vinylidene chloride copolymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5757741A (en) | 1982-04-07 |
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