JPS6139334B2 - - Google Patents
Info
- Publication number
- JPS6139334B2 JPS6139334B2 JP52125255A JP12525577A JPS6139334B2 JP S6139334 B2 JPS6139334 B2 JP S6139334B2 JP 52125255 A JP52125255 A JP 52125255A JP 12525577 A JP12525577 A JP 12525577A JP S6139334 B2 JPS6139334 B2 JP S6139334B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- ethylenically unsaturated
- latex
- copolymer
- 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
Links
- 229920000126 latex Polymers 0.000 claims description 42
- 239000004816 latex Substances 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 150000005673 monoalkenes Chemical class 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 claims 1
- 230000003000 nontoxic effect Effects 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- -1 methylaminoethyl Chemical group 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 229940048053 acrylate Drugs 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006681 (C2-C10) alkylene group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- HDEFKPTUGHCBCD-UHFFFAOYSA-N 2-ethenoxy-n-methylethanamine Chemical compound CNCCOC=C HDEFKPTUGHCBCD-UHFFFAOYSA-N 0.000 description 1
- CEYHHQSTMVVZQP-UHFFFAOYSA-N 2-ethenoxyethanamine Chemical compound NCCOC=C CEYHHQSTMVVZQP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- HGPIBSKXWXWYJB-UHFFFAOYSA-N C(C=C)(=O)O.S(=O)(=O)(O)CC[Na] Chemical compound C(C=C)(=O)O.S(=O)(=O)(O)CC[Na] HGPIBSKXWXWYJB-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-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
- GSQPGDXDLNLVHS-UHFFFAOYSA-N S(=O)(=O)(O)CCC[Na].C(C(=C)C)(=O)O Chemical compound S(=O)(=O)(O)CCC[Na].C(C(=C)C)(=O)O GSQPGDXDLNLVHS-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical group CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical class CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000008199 coating composition Substances 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
- 230000002950 deficient Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-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
- 238000002156 mixing Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 238000012856 packing Methods 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
- 238000007639 printing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
本発明は新規な共役ジオレフイン系共重合体ラ
テツクスに関し、さらに詳しくは、脂肪族共役ジ
オレフイン、エチレン系不飽和酸単量体、エチレ
ン系不飽和アミン単量体並びにモノオレフイン系
単量体よりなる単量体を乳化重合して得られ、か
つそのゲル化点がPH3.5〜8.5の範囲にある新規な
共役ジオレフイン系共重合体ラテツクスに関す
る。
従来より、塗工紙用のバインダー、不織布や人
工皮革などの繊維結合用バインダー或いはカーペ
ツトのパツキング用バインダーとして、天然ゴム
ラテツクスを始め種々の合成ラテツクスが使用さ
れている。
塗被紙用としては、カルボキシル変性スチレン
−ブタジエン共重合体ラテツクスが特に一般的に
用いられている。しかし、このカルボキシル変性
スチレン−ブタジエン共重合体ラテツクスを用い
て処理したオフセツト印刷用塗被紙は、表面強
度、光沢などの数々の点で優れた性質を有してい
るが、紙への塗布工程に於いて、低濃度、低粘度
塗被液で塗被した場合、或いは高温短時間で乾燥
した場合には、塗被紙としての吸水性が不足しイ
ンク転移不良のトラブルを起すことが多く、さら
には塗被速度を上げるうえでも大きな障害となつ
ている。この様な現象は原紙表面に塗被されたコ
ート層中のバインダーが原紙の方へ移行したりあ
るいはコート層表面へ移行することによりコート
層中でのバインダーの分布に不均一を来たすいわ
ゆるマイグレーシヨンに可成り帰因するものと考
えられている。
紙処理におけると同様繊維処理においても、例
えば不織布の製造においてもバインダーの布表面
へのマイグレーシヨンによりバインダーの付着量
が布の表面と内部で不均一になり、強度の低下、
不織布層間のはく離、風合を硬くする等の問題が
生じて来る。このように処理工程におけるマイグ
レーシヨンの発生は印刷用紙、不織布、カーペツ
ト等の製造において不良品発生の原因になり、マ
イグレーシヨンの改善されたラテツクスが要望さ
れている。
本発明者らは、オフセツト印刷用塗被紙用に適
したバインダーとしての重合体ラテツクスについ
て検討を重ねた結果、脂肪族共役ジオレフイン20
〜50重量％、エチレン系不飽和酸単量体0.5〜20
重量％、エチレン系不飽和アミン単量体0.5〜20
重量％並びにモノオレフイン系単量体10〜79重量
％よりなる単量体を、水性媒体中乳化剤の存在下
に重合して得られ、かつそのゲル化点がPH3.5〜
8.5の範囲にある共役ジオレフイン系共重合体ラ
テツクスを顔料のバインダーとして用いれば、前
記の如き諸欠点を解消でき、しかも極めて優れた
諸性能を有する塗被紙が得られることを見い出し
た。さらには、この共役ジオレフイン系共重合体
ラテツクスは優れた接着性、強度特性を示すと共
に、マイグレーシヨンが少ないので、塗被紙用の
バインダーとしての他、不織布などの繊維処理の
バインダーとしてカーペツトのバツキング用バイ
ンダーとして、或いは含浸紙用のラテツクスとし
て有用であることを見い出し、本発明を完成させ
るに至つた。
すなわち本発明の目的は紙や繊維などの処理に
おけるバインダーとして有用な新規な共役ジオレ
フイン系共重合体ラテツクスを提供することにあ
る。本発明のこの目的は脂肪族共役ジオレフイン
20〜50重量％、エチレン系不飽和酸単量体0.5〜
20重量％、エチレン系不飽和アミン単量体0.5〜
20重量％、モノオレフイン系単量体10〜79重量％
から成り、乳化剤含有量がポリマーに対して１重
量％以下であり、ゲル化点がPH3.5〜8.5の間にあ
る共重合体ラテツクスにより達成される。
本発明の共重合体ラテツクスは公知の乳化重合
技術によつて製造されるが、重合中の凝固物発生
を防止するためには、エチレン系不飽和酸単量体
とエチレン系不飽和アミン単量体とが、同時には
重合系内に存在しないような条件で製造すること
が好ましい。すなわち、第１段階では脂肪族共役
ジオレフイン、エチレン系不飽和酸単量体、モノ
オレフイン系単量体よりなるラテツクスを公知の
乳化重合技術によつて製造し、反応終了後に第２
段階としてエチレン系不飽和アミンを単独で、又
は脂肪族共役ジオレフイン、モノオレフイン系単
量体と共に添加し、反応を続行、完結させる。第
１段階終了後に系のPHを７以上に、好ましくは９
以上にすべくアンモニア水、アミン等の揮発性の
アルカリ性物質を添加することにより望ましい結
果が得られる。本発明においてラテツクス重合時
に使用する乳化剤は、アニオン系界面活性剤、非
イオン系界面活性剤、両性界面活性剤の単独又は
混合系が用いられるが、乳化剤を多量に用いた場
合は紙等への適用工程で泡立ちのトラブルが生ず
るばかりでなく、ラテツクス適用製品の耐水性を
維持することが困難になるため、乳化剤使用量は
ポリマーに対して１重量％以下、好ましくは0.5
重量％以下で製造することが必要である。
本発明の共重合体を構成する単量体のうち、脂
肪族共役ジオレフインは重合体に必要な可とう性
を与えるものである。共重合体中20重量％以下の
場合には、共重合体が硬くなりすぎる。また、50
重量％を越える場合には、耐水性が低下し、好ま
しいラテツクス適用製品が得られない。本発明で
用いられる脂肪族共役ジオレフインとしては、
１・３−ブタジエン、２−メチル−１・３−ブタ
ジエン、２−クロロ−１・３−ブタジエンなどが
含まれる。エチレン系不飽和酸単量体は、接着力
を高めるため、及び、共重合体ラテツクスのコロ
イドとしての安定性を向上させるために、更には
エチレン系不飽和アミンと併用することによりラ
テツクスのゲル化点の調整を行うために、必須の
成分である。共重合体中の量は0.5〜20重量％で
好ましくは１〜10重量％である。共重合体中の量
が0.5重量％以下の場合には、その目的を達成す
ることが困難であり、20重量％を越えると本発明
の範囲内のゲル化点を付与することが困難にな
る。エチレン系不飽和酸単量体としては、アクリ
ル酸、メタクリル酸、クロトン酸、ケイ皮酸、イ
タコン酸、フマル酸、マレイン酸、ブテントリカ
ルボン酸などの不飽和カルボン酸；イタコン酸モ
ノエチルエステル、フマル酸モノブチルエステ
ル、及びマレイン酸モノブチルエステルなどの不
飽和ジカルボン酸のモノアルキルエステル；アク
リル酸スルフオエチルNa塩、メタクリル酸スル
フオプロピルNa塩、アクリルアミドプロパンス
ルフオン酸などの不飽和スルフオン酸又はそのア
ルカリ塩などが含まれる。エチレン系不飽和アミ
ンは、ラテツクスにゲル化点を与え、本発明の目
的を達成するための必須の成分である。共重合体
中の量は0.5〜20重量％で好ましくは１〜10重量
％である。共重合体中の量が0.5重量％以下の場
合には、その目的を達成するのが困難であり、20
重量％を越える場合には、本発明の範囲内のゲル
化点を付与するのが困難になるばかりでなく、共
重合体ラテツクス製造時に凝固物発生などのトラ
ブルを生ずる。本発明で用いられるエチレン系不
飽和アミンとしては、○イ一般式
（式中R1はＨ又はメチル基、R2はC2〜10のアルキ
レン基、R3及びR4はＨ又はC1〜12のアルキル
基、Ａは
The present invention relates to a novel conjugated diolefin copolymer latex, and more specifically, a monomer comprising an aliphatic conjugated diolefin, an ethylenically unsaturated acid monomer, an ethylenically unsaturated amine monomer, and a monoolefin monomer. The present invention relates to a novel conjugated diolefin copolymer latex which is obtained by emulsion polymerization of a conjugated diolefin copolymer and has a gel point in the range of PH3.5 to 8.5. Conventionally, various synthetic latexes including natural rubber latex have been used as binders for coated paper, binders for binding fibers such as nonwoven fabrics and artificial leather, and binders for carpet packing. For coated papers, carboxyl-modified styrene-butadiene copolymer latexes are particularly commonly used. However, coated paper for offset printing treated using this carboxyl-modified styrene-butadiene copolymer latex has excellent properties in many respects such as surface strength and gloss, but the paper coating process When coating with a low concentration, low viscosity coating liquid, or when drying at high temperatures for a short time, the water absorption of the coated paper is insufficient, often causing problems with poor ink transfer. Furthermore, it is also a major obstacle in increasing the coating speed. This phenomenon is caused by so-called migration, where the binder in the coating layer coated on the surface of the base paper migrates toward the base paper or onto the surface of the coating layer, causing uneven distribution of the binder in the coating layer. It is believed that this is largely attributable to Similar to paper processing, in fiber processing, for example in the production of non-woven fabrics, migration of the binder to the fabric surface causes the amount of binder adhering to be uneven on the fabric surface and inside, resulting in a decrease in strength and
Problems such as peeling between the nonwoven fabric layers and hardening of the texture arise. As described above, the occurrence of migration during processing steps causes the occurrence of defective products in the production of printing paper, nonwoven fabrics, carpets, etc., and there is a demand for latex with improved migration. As a result of repeated studies on polymer latex as a binder suitable for coated paper for offset printing, the present inventors found that aliphatic conjugated diolefin 20
~50% by weight, ethylenically unsaturated acid monomer 0.5~20
Weight%, ethylenically unsaturated amine monomer 0.5-20
% by weight and a monoolefin monomer of 10 to 79% by weight, obtained by polymerizing a monoolefin monomer in the presence of an emulsifier in an aqueous medium, and whose gel point is PH3.5 to 79% by weight.
It has been found that by using a conjugated diolefin copolymer latex having a molecular weight in the range of 8.5 as a binder for pigments, the above-mentioned drawbacks can be overcome and coated paper with extremely excellent performance can be obtained. Furthermore, this conjugated diolefin copolymer latex exhibits excellent adhesion and strength properties, and has little migration, so it can be used as a binder for coated paper, and as a binder for fiber treatment such as nonwoven fabrics for carpet backing. The present inventors have discovered that it is useful as a binder for paper or as a latex for impregnated paper, and have completed the present invention. That is, an object of the present invention is to provide a novel conjugated diolefin copolymer latex useful as a binder in the treatment of paper, fibers, etc. This object of the invention is directed to aliphatic conjugated diolefins.
20~50% by weight, ethylenically unsaturated acid monomer 0.5~
20% by weight, ethylenically unsaturated amine monomer 0.5~
20% by weight, monoolefin monomer 10-79% by weight
This is achieved by a copolymer latex with an emulsifier content of 1% by weight or less based on the polymer and a gel point between PH3.5 and 8.5. The copolymer latex of the present invention is produced by a known emulsion polymerization technique, but in order to prevent the formation of coagulates during polymerization, it is necessary to add an ethylenically unsaturated acid monomer and an ethylenically unsaturated amine monomer to the copolymer latex. It is preferable to produce the polymer under conditions such that the polymer and the polymer are not simultaneously present in the polymerization system. That is, in the first step, a latex consisting of an aliphatic conjugated diolefin, an ethylenically unsaturated acid monomer, and a monoolefin monomer is produced by a known emulsion polymerization technique, and after the reaction is completed, a latex is produced in the second step.
As a step, an ethylenically unsaturated amine is added alone or together with an aliphatic conjugated diolefin or monoolefin monomer, and the reaction is continued and completed. After the first stage, the pH of the system should be 7 or higher, preferably 9.
Desired results can be obtained by adding volatile alkaline substances such as aqueous ammonia and amines. In the present invention, the emulsifier used during latex polymerization may be an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant, singly or in combination. Not only does foaming trouble occur during the application process, but it also becomes difficult to maintain the water resistance of latex-applied products, so the amount of emulsifier used should be 1% by weight or less, preferably 0.5% by weight based on the polymer.
It is necessary to manufacture at a weight percent or less. Among the monomers constituting the copolymer of the present invention, aliphatic conjugated diolefin provides the necessary flexibility to the polymer. If it is less than 20% by weight in the copolymer, the copolymer becomes too hard. Also, 50
If the amount exceeds % by weight, the water resistance decreases and a desirable latex application product cannot be obtained. The aliphatic conjugated diolefin used in the present invention includes:
These include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like. Ethylenically unsaturated acid monomers are used to increase adhesive strength and to improve the colloidal stability of copolymer latexes, and when used in combination with ethylenically unsaturated amines, gelling of latexes. This is an essential component for adjusting points. The amount in the copolymer is 0.5-20% by weight, preferably 1-10% by weight. If the amount in the copolymer is less than 0.5% by weight, it will be difficult to achieve the purpose, and if it exceeds 20% by weight, it will be difficult to provide a gel point within the range of the present invention. . Ethylenically unsaturated acid monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, butenetricarboxylic acid; itaconic acid monoethyl ester, fumaric acid, etc. Monoalkyl esters of unsaturated dicarboxylic acids such as acid monobutyl esters and maleic acid monobutyl esters; unsaturated sulfonic acids or their alkalis such as sulfoethyl sodium acrylate, sulfopropyl sodium methacrylate, and acrylamide propane sulfonic acid. Contains salt. The ethylenically unsaturated amine provides a gel point to the latex and is an essential component to achieve the objectives of the present invention. The amount in the copolymer is 0.5-20% by weight, preferably 1-10% by weight. If the amount in the copolymer is less than 0.5% by weight, it is difficult to achieve the purpose;
If it exceeds % by weight, it will not only be difficult to provide a gel point within the range of the present invention, but also problems such as the formation of coagulates will occur during the production of the copolymer latex. The ethylenically unsaturated amine used in the present invention has the general formula (In the formula, R 1 is H or a methyl group, R 2 is a C 2-10 alkylene group, R 3 and R 4 are H or a C 1-12 alkyl group, A is
【式】又は−Ｏ−を表
わす）
で表わされる単量体、例えば
メチルアミノエチル（メタ）アクリレート、ｔ
−ブチルアミノエチル（メタ）アクリレート、ジ
メチル−アミノエチル（メタ）アクリレート、ジ
メチルアミノプロピル（メタ）アクリレート、ジ
エチルアミノエチル（メタ）アクリレート、ジブ
チルアミノエチル（メタ）アクリレートなどのエ
チレン系不飽和カルボン酸のアミノアルキルエス
テル；メチルアミノエチル（メタ）アクリルアミ
ド、ジメチルアミノエチル（メタ）アクリルアミ
ド、ジメチルアミノプロピル（メタ）アクリルア
ミドなどのエチレン系不飽和カルボン酸のアミノ
アルキルアミド；アミノエチルビニルエーテル、
メチルアミノエチルビニルエーテル、ジメチルア
ミノエチルビニルエーテルなどのアミノアルキル
ビニルエーテル、など及び○ロ２−ビニルピリジ
ン、４−ビニルピリジン、２−メチル−５−ビニ
ルピリジン、２・４−ジエチル−５−ビニルピリ
ジンなどのビニルピリジン類などが含まれる。本
発明で用いられるモノオレフイン系単量体は共重
合体に適度な硬さを与えると共に耐水性を与える
上にも有効である。共重合体中の量は10〜79重量
％である。10重量％未満では上記の性質を共重合
体に与えることができず、79重量％を越えるとフ
イルム形成性が低下し、接着力の低下をもたら
す。モノオレフイン系単量体としては、スチレ
ン、α−メチルスチレン、モノクロルスチレン、
ビニルトルエンなどの芳香族ビニル化合物；アク
リル酸メチル、メタクリル酸メチル、アクリル酸
エチル、アクリル酸ブチル、などのアクリル酸又
はメタクリル酸のアルキルエステル；アクリロニ
トリル、メタクリロニトリルなどのエチレン系ニ
トリル化合物などが含まれ、更に要すれば前記モ
ノオレフイン系単量体と共にアクリル酸β−ヒド
ロキシエチル、アクリル酸β−ヒドロキシプロピ
ル、メタクリル酸β−ヒドロキシエチル、アクリ
ルアミド、メタクリルアミド、Ｎ−メチロールア
クリルアミド、ジアセトンアクリルアミド、アク
リル酸グリシジル、メタクリル酸グリシジル、ア
クロレイン、アリルアルコールなどの親水性単量
体を共重合成分として用いることが出来る。本発
明の共重合体ラテツクスは、PH3.5〜8.5の範囲に
ゲル化点を有していなければならない。ゲル化点
がPH3.5以下の場合にはマイグレーシヨンの改善
は見られずPH8.5以上の場合には、耐水性、表面
強度などが不十分なものとなる。
ゲル化点の測定は次のようにして行う。
Michaelisの緩衝液（日本化学会編、「化学便
覧基礎編（改訂２版）」 昭和50年６月20日発
行1495頁参照）を作成する。
緩衝液のPH域を「化学便覧」に示されたもの
よりも細くとる必要のある場合は、Ａ液、Ｂ液
の混合比率を「化学便覧」に示されたものより
も、こまかくとる。
内容積60mlの透明容器に上記緩衝液を約10ml
とる。
固形分濃度40％に調整した検体ラテツクスを
１滴（約0.1gr）加え、良く混合する。
約30分間25℃恒温室中で静置したのち、再度
良く混合し、凝固物発生の有無を観察する。
PHの高い緩衝液から低いものへ順次上記テスト
を行い、凝固物がはじめて発生した緩衝液のPHを
もつて、ラテツクスのゲル化点とする。
ゲル化点の調整は主としてエチレン系不飽和酸
単量体の種類、量、エチレン系不飽和アミン単量
体の種類、量、により行いうる。この他にゲル化
点に影響を与えるものに、乳化剤の種類、量、開
始剤の種類、量、親水性単量体の種類、量などが
あるが、本発明は、ゲル化点の調整方法について
何ら限定するものではない。
本発明の共重合体ラテツクスは、アンモニア水
等の揮発性アルカリ性物質を添加してPHを常に該
ラテツクスのゲル化点以上のPHに調整することに
より安定に保たれる。また該ラテツクスを紙、繊
維などの処理用バインダーとして使用する場合
も、揮発性アルカリ性物質の添加により処理用組
成物のPHを該ラテツクスのゲル化点以上のPHに調
整し安定化させる。
本発明の共重合体ラテツクスは、耐水性、接着
性、マイグレーシヨン等が改善されているので、
バインダーとして紙、繊維などの処理に非常に有
用である。
以下実施例により本発明を具体的に説明するが
本発明はこれら実施例に限定されるものではな
い。なお、実施例中の部数及び％は、すべて重量
部及び重量％を表す。
実施例 １
撹拌機付きタンクに次の組成を仕込み、モノマ
ーエマルジヨンを作成した。
水 48.0部
ラウリル硫酸ソーダ 0.2〃
重炭酸ソーダ 0.5〃
スチレン 59.1〃
ブタジエン 36.5〃
メタクリル酸 2.4〃
四塩化炭素 3.0〃
撹拌機付きオートクレーブに、水32部、エチレ
ンジアミン・テトラ醋酸の４ナトリウム塩0.1
部、ラウリル硫酸ソーダ0.1部、過硫酸カリウム
0.2部を仕込み前記モノマーエマルジヨンのうち
の10％をオートクレーブに移し、80℃に加温、１
時間反応させた。１時間後に、過硫酸カリウム
0.8部を水20部と共に仕込んだ後、残りのモノマ
ーエマルジヨンを４時間にわたつて、連続的にオ
ートクレーブに送り込んだ。この間、オートクレ
ーブは80℃に保つた。更に１時間80℃を維持した
のち、水蒸気蒸留により残留単量体を除去し、ア
ンモニア水を加え、ラテツクスのPHを9.0に調整
した。次に水4.0部を、ジメチルアミノエチルメ
タクリレート2.0部、過硫酸アンモニウム0.1部を
仕込み80℃で２時間反応させた。得られた共重合
体ラテツクスを、ラテツクスＡとする。
ゲル化点の測定結果を市販されている紙塗被用
スチレン−ブタジエン共重合体ラテツクス（、
）、メチルメタクリレート−ブタジエン共重合
体ラテツクス（）、と比較し第１表に示す。市
販のラテツクスはいずれもゲル化点を有しないか
あるいはゲル化のPHが１・４以下（Michaelisの
緩衝液の下限）であることが分る。[Formula] or -O-), for example, methylaminoethyl (meth)acrylate, t
- amino acids of ethylenically unsaturated carboxylic acids such as butylaminoethyl (meth)acrylate, dimethyl-aminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, etc. Alkyl esters; aminoalkylamides of ethylenically unsaturated carboxylic acids such as methylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide; aminoethyl vinyl ether,
Aminoalkyl vinyl ethers such as methylaminoethyl vinyl ether and dimethylaminoethyl vinyl ether, etc.; Contains vinylpyridines, etc. The monoolefin monomer used in the present invention is effective in imparting appropriate hardness and water resistance to the copolymer. The amount in the copolymer is 10-79% by weight. If it is less than 10% by weight, the above-mentioned properties cannot be imparted to the copolymer, and if it exceeds 79% by weight, film-forming properties will be reduced, leading to a decrease in adhesive strength. Examples of monoolefin monomers include styrene, α-methylstyrene, monochlorostyrene,
Includes aromatic vinyl compounds such as vinyltoluene; alkyl esters of acrylic acid or methacrylic acid such as methyl acrylate, methyl methacrylate, ethyl acrylate, and butyl acrylate; ethylene-based nitrile compounds such as acrylonitrile and methacrylonitrile. and, if necessary, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, β-hydroxyethyl methacrylate, acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, acrylic, together with the monoolefin monomer. Hydrophilic monomers such as glycidyl acid, glycidyl methacrylate, acrolein, and allyl alcohol can be used as copolymerization components. The copolymer latex of the present invention must have a gel point in the pH range of 3.5 to 8.5. If the gel point is below PH3.5, no improvement in migration will be seen, and if the gel point is above PH8.5, water resistance, surface strength, etc. will be insufficient. The gel point is measured as follows. Create Michaelis' buffer solution (see "Chemical Handbook Basic Edition (Revised 2nd Edition)" edited by the Chemical Society of Japan, page 1495, published June 20, 1975). If the PH range of the buffer solution needs to be narrower than that indicated in the "Chemistry Handbook," the mixing ratio of solutions A and B should be set narrower than that indicated in the "Chemistry Handbook." Add approximately 10 ml of the above buffer solution to a transparent container with an internal volume of 60 ml.
Take. Add 1 drop (approximately 0.1gr) of sample latex adjusted to a solid concentration of 40% and mix well. After standing in a constant temperature room at 25°C for about 30 minutes, mix well again and observe whether or not a coagulum has formed. The above test is performed in order from buffer solutions with high pH to buffer solutions with low pH, and the pH of the buffer solution where coagulation occurs for the first time is taken as the gelation point of the latex. The gelation point can be adjusted mainly by the type and amount of the ethylenically unsaturated acid monomer and the type and amount of the ethylenically unsaturated amine monomer. Other factors that affect the gel point include the type and amount of emulsifier, the type and amount of initiator, and the type and amount of hydrophilic monomer, but the present invention provides a method for adjusting the gel point. There is no limitation in any way. The copolymer latex of the present invention can be kept stable by adding a volatile alkaline substance such as aqueous ammonia to constantly adjust the pH to a pH higher than the gelling point of the latex. When the latex is used as a binder for treating paper, fibers, etc., the pH of the treating composition is adjusted to a pH higher than the gelling point of the latex and stabilized by adding a volatile alkaline substance. The copolymer latex of the present invention has improved water resistance, adhesion, migration, etc.
Very useful as a binder in processing paper, fibers, etc. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Note that all parts and percentages in the examples represent parts by weight and percentages by weight. Example 1 A monomer emulsion was prepared by charging the following composition into a tank equipped with a stirrer. Water 48.0 parts Sodium lauryl sulfate 0.2〃 Sodium bicarbonate 0.5〃 Styrene 59.1〃 Butadiene 36.5〃 Methacrylic acid 2.4〃 Carbon tetrachloride 3.0〃 In an autoclave equipped with a stirrer, 32 parts of water, 0.1 tetrasodium salt of ethylenediamine tetraacetic acid
part, sodium lauryl sulfate 0.1 part, potassium persulfate
Transfer 10% of the monomer emulsion into an autoclave, heat to 80°C, and add 0.2 parts.
Allowed time to react. After 1 hour, potassium persulfate
After charging 0.8 parts with 20 parts of water, the remaining monomer emulsion was continuously pumped into the autoclave over a period of 4 hours. During this time, the autoclave was kept at 80°C. After maintaining the temperature at 80°C for an additional hour, residual monomers were removed by steam distillation, and aqueous ammonia was added to adjust the pH of the latex to 9.0. Next, 4.0 parts of water, 2.0 parts of dimethylaminoethyl methacrylate, and 0.1 part of ammonium persulfate were added and reacted at 80°C for 2 hours. The obtained copolymer latex is referred to as latex A. The measurement results of the gelation point of commercially available styrene-butadiene copolymer latex for paper coating (
) and methyl methacrylate-butadiene copolymer latex () are shown in Table 1. It has been found that all commercially available latexes either have no gelation point or have a gelation pH of 1.4 or less (the lower limit of Michaelis' buffer).
【表】
実施例 ２
実施例１と同様の条件で第２表に示す組成の共
重合体ラテツクスを調製した。但し、不飽和単量
体を用いない比較例のラテツクス○ハについては重
合中の凝固物の発生を防止するためにジメチルア
ミノエチルメタクリレート添加前にラウリル硫酸
ソーダ0.6重量部添加した。ゲル化点の測定結果
を第２表に示す。[Table] Example 2 A copolymer latex having the composition shown in Table 2 was prepared under the same conditions as in Example 1. However, for Comparative Example latex (C) in which no unsaturated monomer was used, 0.6 parts by weight of sodium lauryl sulfate was added before adding dimethylaminoethyl methacrylate in order to prevent the formation of coagulum during polymerization. The measurement results of gel point are shown in Table 2.
【表】
実施例 ３
第３表に示す単量体組成を用いた以外は、実施
例１と同一の条件で共重合体ラテツクスを調製し
た。ゲル化点の測定結果を第３表に示す。[Table] Example 3 A copolymer latex was prepared under the same conditions as in Example 1 except that the monomer composition shown in Table 3 was used. Table 3 shows the measurement results of gel point.
【表】
実施例 ４
第４表に示す単量体組成を用いた以外は実施例
１と同一の条件でラテツクスを調整した。ゲル化
点の測定結果を第４表に示す。[Table] Example 4 A latex was prepared under the same conditions as in Example 1 except that the monomer composition shown in Table 4 was used. Table 4 shows the measurement results of gel point.
【表】
参考例
実施例１〜４の各共重合体ラテツクスを用い下
記の処方により紙塗被用組成物を作成した。。
処 方
カオリナイトクレー(1) 100
分散剤(2) 0.15
粘度調整剤(3) 0.3
アンモニア水（28％） 0.11
ラテツクス（固形分で） 18
(1) J.M.Huber社製品 ハイドロフアイン
(2) 東亜合成社製品 アロンＴ−40
(3) Kelco社製品 ケルギンMV
固形分濃度43％とし、各組成物のPHが8.7とな
るように、必要な場合は、アンモニア水を追加し
て調整した。
この組成物を、塗被原紙上に、塗被量が片面16
±１gr/m2となるようにアプリケーターバーを用
いて塗工し、塗工直後に、130℃の熱分で30秒間
乾燥した。得られた塗被紙を、20℃、65％R.H.
の恒温恒湿室中で一夜調湿したのち60℃、線圧
100Kg/cmの条件で２回スーパーウレンダー処理を
行い、下記の試験を行つた。結果を第５表に示
す。[Table] Reference Example A paper coating composition was prepared using each of the copolymer latexes of Examples 1 to 4 according to the following formulation. . Formula Kaolinite clay (1) 100 Dispersant (2) 0.15 Viscosity modifier (3) 0.3 Ammonia water (28%) 0.11 Latex (solid content) 18 (1) JMHuber product Hydrofain (2) Toagosei Aron T-40 (3) Kelco Product Kelgin MV The solid content concentration was 43%, and the pH of each composition was adjusted to 8.7 by adding aqueous ammonia, if necessary. This composition was applied onto the base paper to be coated in a coating amount of 16 mm on one side.
It was coated using an applicator bar to give a coating density of ±1 gr/m 2 , and immediately after coating, it was dried at 130° C. for 30 seconds. The obtained coated paper was heated at 20℃ and 65%RH.
After adjusting the humidity overnight in a constant temperature and humidity room, the temperature was reduced to 60℃ and linear pressure.
Super urethane treatment was performed twice under the condition of 100 kg/cm, and the following tests were conducted. The results are shown in Table 5.
【表】
本ラテツクスを紙処理用に使用することによつ
て第５表に示した如く、市販ラテツクス、、
（いずれもゲル化点を有していない）、比較ラ
テツクス○イ、○ロ（共にゲル化点を有しない）では
得られないマイグレーシヨン改善によるインク転
移性の向上が得られる。比較ラテツクス○ハ、○ニ、
○ホのようにゲル化点は本発明の範囲内にあるが、
該ラテツクスの組成が本発明外であるラテツクス
では顔料結合力が大巾に劣りDry−Pick及びWet
−Pickが劣る結果となる。本発明になるラテツ
クスはいずれもマイグレーシヨンが改善された、
さらに顔料結合力の強いラテツクスであることが
分る。[Table] By using this latex for paper processing, as shown in Table 5, commercially available latex,
(none of them has a gel point), comparative latexes A and B (none of which have a gel point) can improve ink transfer properties due to migration improvement that cannot be obtained. Comparison latex ○ha, ○d,
As shown in ○e, the gel point is within the scope of the present invention, but
Latexes whose compositions are outside the scope of the present invention have significantly poorer pigment binding strength than Dry-Pick and Wet-Pick.
−Pick will be inferior. All the latexes of the present invention have improved migration.
Furthermore, it can be seen that the latex has a strong pigment binding force.
Claims (1)
レン系不飽和酸単量体0.5〜20重量％、エチレン
系不飽和アミン単量体0.5〜20重量％、モノオレ
フイン系単量体10〜79重量％より成る単量体を水
性媒体中乳化剤の存在下に重合するに際し、エチ
レン系不飽和酸単量体とエチレン系不飽和アミン
単量体とが同時には重合系内に存在しない条件下
で重合して得られるゲル化点がPH3.5〜8.5の範囲
にあり、かつ揮発性アルカリ性物質により安定化
された新規な共役ジオレフイン系共重合体ラテツ
クス。 ２ 乳化剤がアニオン系界面活性剤、非イオン系
界面活性剤、両性界面活性剤の単独又は混合系で
あり、重合体に対して１重量％以下の量で使用さ
れる特許請求の範囲第１項記載の共重合体ラテツ
クス。[Claims] 1. 20 to 50% by weight of aliphatic conjugated diolefin, 0.5 to 20% by weight of ethylenically unsaturated acid monomer, 0.5 to 20% by weight of ethylenically unsaturated amine monomer, monoolefin monomer When polymerizing monomers consisting of 10 to 79% by weight in an aqueous medium in the presence of an emulsifier, an ethylenically unsaturated acid monomer and an ethylenically unsaturated amine monomer are simultaneously present in the polymerization system. A novel conjugated diolefin copolymer latex which is obtained by polymerization under non-toxic conditions and has a gel point in the range of PH3.5 to 8.5, and is stabilized with a volatile alkaline substance. 2. Claim 1, in which the emulsifier is an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant alone or in combination, and is used in an amount of 1% by weight or less based on the polymer. The copolymer latex described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12525577A JPS5458789A (en) | 1977-10-19 | 1977-10-19 | Novel conjugated diolefin copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12525577A JPS5458789A (en) | 1977-10-19 | 1977-10-19 | Novel conjugated diolefin copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5458789A JPS5458789A (en) | 1979-05-11 |
| JPS6139334B2 true JPS6139334B2 (en) | 1986-09-03 |
Family
ID=14905569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12525577A Granted JPS5458789A (en) | 1977-10-19 | 1977-10-19 | Novel conjugated diolefin copolymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5458789A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643310A (en) * | 1979-09-19 | 1981-04-22 | Sumitomo Naugatuck Co Ltd | Production of copolymer latex |
| JPS5643361A (en) * | 1979-09-19 | 1981-04-22 | Sumitomo Naugatuck Co Ltd | Paper coating composition |
| JPS57161194A (en) * | 1981-03-24 | 1982-10-04 | Sumitomo Naugatuck | Paper coating composition |
| JPS6163794A (en) * | 1984-08-31 | 1986-04-01 | 日本ゼオン株式会社 | Paper coating composition |
| JPS62253602A (en) * | 1985-12-27 | 1987-11-05 | Lion Corp | Production of crosslinked polymer latex |
| JP3736577B2 (en) * | 1995-12-29 | 2006-01-18 | 日本ゼオン株式会社 | Rubber composition and method for producing the same |
| JP4529438B2 (en) * | 2003-12-25 | 2010-08-25 | Ｄｉｃ株式会社 | Synthetic rubber latex |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832188A (en) * | 1971-08-20 | 1973-04-27 | ||
| JPS4938924A (en) * | 1972-08-17 | 1974-04-11 | ||
| JPS5266706A (en) * | 1975-11-19 | 1977-06-02 | Rohm & Haas | Mineral composition for coating pape containing latex and amphoteric polymer |
| JPS5286427A (en) * | 1976-01-13 | 1977-07-18 | Nippon Synthetic Chem Ind Co Ltd:The | Composition of coating for paper |
| JPS5949360A (en) * | 1982-09-14 | 1984-03-21 | Honda Motor Co Ltd | Air-intake device for motorcycle and the like |
-
1977
- 1977-10-19 JP JP12525577A patent/JPS5458789A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4832188A (en) * | 1971-08-20 | 1973-04-27 | ||
| JPS4938924A (en) * | 1972-08-17 | 1974-04-11 | ||
| JPS5266706A (en) * | 1975-11-19 | 1977-06-02 | Rohm & Haas | Mineral composition for coating pape containing latex and amphoteric polymer |
| JPS5286427A (en) * | 1976-01-13 | 1977-07-18 | Nippon Synthetic Chem Ind Co Ltd:The | Composition of coating for paper |
| JPS5949360A (en) * | 1982-09-14 | 1984-03-21 | Honda Motor Co Ltd | Air-intake device for motorcycle and the like |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5458789A (en) | 1979-05-11 |
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