JPS627925B2 - - Google Patents
Info
- Publication number
- JPS627925B2 JPS627925B2 JP55136658A JP13665880A JPS627925B2 JP S627925 B2 JPS627925 B2 JP S627925B2 JP 55136658 A JP55136658 A JP 55136658A JP 13665880 A JP13665880 A JP 13665880A JP S627925 B2 JPS627925 B2 JP S627925B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer
- copolymer latex
- monomers
- 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
- 239000000178 monomer Substances 0.000 claims description 45
- 229920001577 copolymer Polymers 0.000 claims description 28
- 239000004816 latex Substances 0.000 claims description 25
- 229920000126 latex Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000000576 coating method Methods 0.000 description 11
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 6
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- -1 alcohol sulfate esters Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 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
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000000034 method Methods 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZRBSVVRDXNHVFE-UHFFFAOYSA-N (3-chloro-2-hydroxybutyl) 2-methylprop-2-enoate Chemical compound CC(Cl)C(O)COC(=O)C(C)=C ZRBSVVRDXNHVFE-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- MAIIXYUYRNFKPL-UPHRSURJSA-N (z)-4-(2-hydroxyethoxy)-4-oxobut-2-enoic acid Chemical compound OCCOC(=O)\C=C/C(O)=O MAIIXYUYRNFKPL-UPHRSURJSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- GCTWZXLKCMVCKS-NSCUHMNNSA-N 4-o-(2-hydroxyethyl) 1-o-methyl (e)-but-2-enedioate Chemical compound COC(=O)\C=C\C(=O)OCCO GCTWZXLKCMVCKS-NSCUHMNNSA-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 239000002736 nonionic surfactant 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
Description
本発明は安定性の良好な共重合体ラテツクスの
製造方法に関する。
詳しくは、
(a) ヒドロキシアルキル基を含有する不飽和単量
体10〜45重量％およびエチレン系不飽和カルボ
ン酸単量体55〜90重量％から成る単量体混合物
１〜10重量部を乳化重合し、
(b) 得られた共重合体ラテツクスの存在下脂肪族
共役ジエン単量体20〜70重量％、アルケニル芳
香族単量体20〜70重量％および不飽和カルボン
酸アルキルエステル単量体３〜40重量％から構
成される単量体90〜99重量部を添加重合する
ことを特徴とする安定性の良好な共重合体ラテツ
クスの製造方法に関する。
一般に共重合体ラテツクスは単独で、あるいは
各種顔料、接着剤などと混合して紙被覆用あるい
はカーペツトのバツクサイジング用などに用いら
れている。
これらの用途に使用される共重合体ラテツクス
は重合中あるいは塗布工程中における機械的剪断
に対する安定性および各種顔料などとの混合時に
おける化学的安定性が充分であること、また接着
剤としての接着強度あるいは耐水性が充分である
ことなどが要求される。
更には進歩しつつある紙塗被加工技術および印
刷技術に適応するためには、すぐれたラテツク
ス、すなわち化学的、機械的安定性に優れるのみ
ならず、塗工紙の接着性、耐水性、耐ブリスター
性、耐ヒートセツトラフニング性に優れるなどの
高度の性能が要求される。
本発明者らは前記要求される性能を満足する共
重合体ラテツクスが得られる製造方法を研究した
結果本発明に到達した。
すなわち、本発明は、
(a) ヒドロキシアルキル基を含有する不飽和単量
体10〜45重量％およびエチレン系不飽和カルボ
ン酸単量体55〜90重量％から成る単量体混合物
１〜10重量部を乳化重合し、
(b) 得られた共重合体ラテツクスの存在下脂肪族
共役ジエン単量体20〜70重量％、アルケニル芳
香族単量体20〜70重量％および不飽和カルボン
酸アルキルエステル単量体３〜40重量％から構
成される単量体90〜99重量部を添加重合する
ことを特徴とする共重合体ラテツクスの製造方法
である。
本発明に使用される単量体で、第１段階で重合
されるヒドロキシアルキル基を含有する不飽和単
量体としては、β−ヒドロキシエチルアクリレー
ト、β−ヒドロキシエチルメタクリレート、ヒド
ロキシプロピルアクリレート、ヒドロキシプロピ
ルメタクリレート、ヒドロキシブチルアクリレー
ト、ヒドロキシブチルメタクリレート、３−クロ
ロ−２−ヒドロキシブチルメタクリレート、ジ−
（エチレングリコール）マレエート、ジ−（エチレ
ングリコール）イタコネート、２−ヒドロキシエ
チルマレエート、ビス（２−ヒドロキシエチル）
マレエートおよび２−ヒドロキシエチルメチルフ
マレート等が挙げられる。
これらの単量体は10〜45重量％で用いられる10
重量％未満では最終共重合体ラテツクスの安定性
が悪くなり、45重量％を越えると共重合体ラテツ
クスをバインダーとして用いた塗工紙の耐水性が
悪くなる。
同じく第１段階で重合されるエチレン系不飽和
カルボン酸単量体としては、アクリル酸、メタク
リル酸、フマル酸、マレイン酸およびイタコン酸
等が挙げられる。
これらの単量体は55〜90重量％で用いられる
が、55重量％未満では共重合体ラテツクスを用い
た塗工紙の耐水性が悪くなり、90重量％を越える
と共重合体ラテツクスの安定性が悪くなる。
以上の単量体は第１段階で重合され、その量は
全単量体を100部として１〜10重量部使される。
１重量部未満では安定な共重合体ラテツクスは
得られず、10重量部を越えると共重合体ラテツク
スの粘度が上昇し、塗工紙の耐水性も低下する。
次いで第２段階で重合される脂肪族共役ジエン
単量体としては、１・３−ブタジエン、２−メチ
ル−１・３−ブタジエンおよび２−クロロ−１・
３−ブタジエン等が挙げられる。
これらの単量体は20〜70重量％で用いられる。
20重量％未満では塗工紙の接着力が低下し、70重
量％を越えると塗工紙の耐水性が低下する。
同じく第２段階で重合されるアルケニル芳香族
単量体としてはスチレン、アルフアメチルスチレ
ン、メチルアルフアメチルスチレンおよびビニル
トルエン等があげられる。
これらの単量体は20〜70重量％で用いられるが
20重量％未満では塗工紙の耐水性が低下し、70重
量％を越えると塗工紙の接着力が低下する。
第２段階に重合される不飽和カルボン酸アルキ
ルエステル単量体としては、メチルアクリレー
ト、メチルメタクリレート、エチルアクリレー
ト、エチルメタクリレート、ブチルアクリレー
ト、２−エチルヘキシルアクリレート、グリシジ
ルメタクリレート、ジメチルフマレート、ジエチ
ルフマレート、ジメチルマレエート、ジエチルマ
レエート、ジメチルイタコネート、モノメチルフ
マレートおよびモノエチルフマレート等が挙げら
れる。
これらの単量体は３〜40重量％で用いられる
が、３重量％未満では塗工紙の耐光性が悪くな
り、40重量％を越えると塗工紙の耐水性が悪くな
る。
以上の第２段階に用いられる単量体は90〜99重
量部で用いられるが、90重量部未満では共重合体
ラテツクスの粘度が上昇し、塗工紙の耐水性も低
下する。
99重量％を越えると安定な共重合体は得られな
い。
また第２段階で重合される単量体は第１段階の
重合転化率（コンバージヨン）が80％以上進んだ
以後に加えられるのが塗工紙の耐水性や接着性の
面から好ましい。
本発明の共重合体ラテツクスは、第１段階、第
２段階いずれも公知の一括、分割、連続添加重合
法等で重合される。又、重合に際しては、公知の
乳化剤、重合開始剤、連鎖移動剤等が用いられ
る。
乳化剤としては高級アルコールの硫酸エステ
ル、アルキルベンゼンスルホン酸塩、脂肪族スル
ホン酸塩等のアニオン性界面活性剤あるいはポリ
エチレングリコールのアルキルエステル型、アル
キルフエニルエーテル型、アルキルエーテル型等
のノニオン性界面活性剤が一種又は二種以上で用
いられる。得られた共重合体ラテツクスの耐水性
を考慮した場合、全単量体量に対し２重量部以下
で使用することが好ましい。
開始剤としては、過硫酸カリウム、過硫酸アン
モニウム、過硫酸ナトリウム等の水溶性開始剤、
あるいはレドツクス系開始剤あるいは、過酸化ベ
ンゾイル等の油溶性開始剤が使用できる。
連鎖移動剤としては、メルカプタン類、ハロゲ
ン化炭化水素類等が使用できる。
以下に実施例を示すが、本発明は実施例によつ
て何ら限定はされない。
実施例 １
耐圧容器に表−１の第１段階の乳化重合に使用
する単量体100部に対して、ドデシルベンゼンス
ルフオン酸ナトリウム５部、過硫酸カリウム３
部、四塩化炭素20部、第３級ドデシルメルカプタ
ン１部、重炭酸ナトリウム３部、水400部の割合
で混合して、第１段階の乳化重合する単量体と混
合撹拌し、65℃に昇温して重合を行つた。
次いで表−１の第２段階の乳化重合に使用する
単量体100部に対してドデシルベンゼンスルフオ
ン酸ナトリウム0.5部、過硫酸カリウム0.5部、四
塩化炭素２部、第３級ドデシルメルカプタン0.1
部、水60部の割合で混合し、第２段階の乳化重合
する単量体と混合撹拌し、連続的に耐圧容器に添
加して重合を行つた。
重合転化率はいずれも99％以上であつた。
未反応単量体をストリツピングで除去した後
200メツシユの金網を通過させて共重合体ラテツ
クスＡ〜Ｆを得た。
共重合体ラテツクスの粘度および機械的安定性
は次の方法で測定した。
粘 度（cps）：
BL型粘度計（60rpm・25℃）によつて測定し
た。
機械的安定性（ｇ）：
200ｇの合成共重合体ラテツクスを取り、30分
間ハミルトンビーチミキサーにかけた後100メツ
シユに残る残渣量を測定して得られる。
The present invention relates to a method for producing a copolymer latex with good stability. Specifically, (a) emulsifying 1 to 10 parts by weight of a monomer mixture consisting of 10 to 45% by weight of an unsaturated monomer containing a hydroxyalkyl group and 55 to 90% by weight of an ethylenically unsaturated carboxylic acid monomer; (b) 20-70% by weight of aliphatic conjugated diene monomer, 20-70% by weight of alkenyl aromatic monomer and unsaturated carboxylic acid alkyl ester monomer in the presence of the resulting copolymer latex; The present invention relates to a method for producing a copolymer latex with good stability, which comprises adding and polymerizing 90 to 99 parts by weight of a monomer consisting of 3 to 40% by weight. Generally, copolymer latexes are used alone or mixed with various pigments, adhesives, etc. for paper coatings, carpet backsizing, etc. The copolymer latex used for these applications must have sufficient stability against mechanical shearing during polymerization or coating processes, sufficient chemical stability when mixed with various pigments, etc., and must have sufficient adhesion as an adhesive. It is required to have sufficient strength or water resistance. Furthermore, in order to adapt to the advancing paper coating and printing technologies, it is necessary to use a latex with excellent chemical and mechanical stability, as well as coated paper's adhesion, water resistance, and resistance. High performance is required, such as excellent blister resistance and heat-set roughening resistance. The present inventors have arrived at the present invention as a result of research into a manufacturing method that can produce a copolymer latex that satisfies the above-mentioned required performance. That is, the present invention provides (a) 1 to 10% by weight of a monomer mixture consisting of 10 to 45% by weight of an unsaturated monomer containing a hydroxyalkyl group and 55 to 90% by weight of an ethylenically unsaturated carboxylic acid monomer; (b) 20 to 70% by weight of aliphatic conjugated diene monomer, 20 to 70% by weight of alkenyl aromatic monomer and unsaturated carboxylic acid alkyl ester in the presence of the obtained copolymer latex; This is a method for producing a copolymer latex, characterized by adding and polymerizing 90 to 99 parts by weight of a monomer consisting of 3 to 40% by weight. Among the monomers used in the present invention, unsaturated monomers containing a hydroxyalkyl group that are polymerized in the first step include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl Methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxybutyl methacrylate, di-
(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl)
Examples include maleate and 2-hydroxyethylmethyl fumarate. These monomers are used at 10-45% by weight10
If it is less than 45% by weight, the stability of the final copolymer latex will be poor, and if it exceeds 45% by weight, the water resistance of coated paper using the copolymer latex as a binder will be poor. Similarly, examples of the ethylenically unsaturated carboxylic acid monomer polymerized in the first step include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid. These monomers are used in an amount of 55 to 90% by weight, but if it is less than 55% by weight, the water resistance of the coated paper using the copolymer latex will deteriorate, and if it exceeds 90% by weight, the stability of the copolymer latex will deteriorate. Sexuality becomes worse. The above monomers are polymerized in the first step, and the amount used is 1 to 10 parts by weight, based on 100 parts of the total monomers. If it is less than 1 part by weight, a stable copolymer latex cannot be obtained, and if it exceeds 10 parts by weight, the viscosity of the copolymer latex increases and the water resistance of the coated paper also decreases. The aliphatic conjugated diene monomers that are then polymerized in the second step include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2-chloro-1,
Examples include 3-butadiene. These monomers are used in amounts of 20-70% by weight.
If it is less than 20% by weight, the adhesive strength of the coated paper will decrease, and if it exceeds 70% by weight, the water resistance of the coated paper will decrease. Examples of alkenyl aromatic monomers that are similarly polymerized in the second step include styrene, alphamethylstyrene, methylalphamethylstyrene, and vinyltoluene. These monomers are used at 20-70% by weight.
If it is less than 20% by weight, the water resistance of the coated paper will decrease, and if it exceeds 70% by weight, the adhesive strength of the coated paper will decrease. Examples of the unsaturated carboxylic acid alkyl ester monomers to be polymerized in the second stage include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, Dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, and the like. These monomers are used in an amount of 3 to 40% by weight, but if it is less than 3% by weight, the light resistance of the coated paper will be poor, and if it exceeds 40% by weight, the water resistance of the coated paper will be poor. The monomer used in the second stage is used in an amount of 90 to 99 parts by weight, but if it is less than 90 parts by weight, the viscosity of the copolymer latex increases and the water resistance of the coated paper also decreases. If it exceeds 99% by weight, a stable copolymer cannot be obtained. Further, from the viewpoint of water resistance and adhesive properties of the coated paper, it is preferable that the monomer to be polymerized in the second stage is added after the polymerization conversion rate (conversion) in the first stage has progressed to 80% or more. The copolymer latex of the present invention is polymerized in both the first and second stages by known batch, division, continuous addition polymerization methods, etc. Further, during polymerization, known emulsifiers, polymerization initiators, chain transfer agents, etc. are used. Examples of emulsifiers include anionic surfactants such as higher alcohol sulfate esters, alkylbenzene sulfonates, and aliphatic sulfonates, and nonionic surfactants such as polyethylene glycol alkyl ester, alkyl phenyl ether, and alkyl ether types. are used singly or in combination of two or more. When considering the water resistance of the obtained copolymer latex, it is preferable to use 2 parts by weight or less based on the total amount of monomers. Examples of initiators include water-soluble initiators such as potassium persulfate, ammonium persulfate, and sodium persulfate;
Alternatively, a redox initiator or an oil-soluble initiator such as benzoyl peroxide can be used. As the chain transfer agent, mercaptans, halogenated hydrocarbons, etc. can be used. Examples are shown below, but the present invention is not limited in any way by the examples. Example 1 In a pressure-resistant container, 5 parts of sodium dodecylbenzenesulfonate and 3 parts of potassium persulfate were added to 100 parts of the monomer used in the first stage emulsion polymerization shown in Table 1.
1 part, 20 parts of carbon tetrachloride, 1 part of tertiary dodecyl mercaptan, 3 parts of sodium bicarbonate, and 400 parts of water. Polymerization was carried out by raising the temperature. Next, 0.5 parts of sodium dodecylbenzenesulfonate, 0.5 parts of potassium persulfate, 2 parts of carbon tetrachloride, and 0.1 parts of tertiary dodecyl mercaptan were added to 100 parts of the monomers used in the second stage emulsion polymerization shown in Table 1.
and 60 parts of water, mixed and stirred with the monomer to be subjected to emulsion polymerization in the second stage, and continuously added to a pressure vessel for polymerization. The polymerization conversion rate was 99% or more in all cases. After removing unreacted monomers by stripping
Copolymer latexes A to F were obtained by passing through a 200-mesh wire mesh. The viscosity and mechanical stability of the copolymer latex were measured by the following method. Viscosity (cps): Measured using a BL type viscometer (60 rpm, 25°C). Mechanical stability (g): Obtained by taking 200 g of synthetic copolymer latex and measuring the amount of residue remaining on 100 meshes after applying it to a Hamilton Beach mixer for 30 minutes.
【表】【table】
【表】
実施例 ２
耐圧容器に表−２〜表−４の第１段階の乳化重
合に使用する単量体100部に対してドデシルベン
ゼンスルフオン酸ナトリウム５部、過硫酸カルシ
ウム0.5部、四塩化炭素４部、第３級ドデシルメ
ルカプタン0.2部、重炭酸ナトリウム0.5部、水
400部の割合で混合して、第１段階の乳化重合す
る単量体と混合撹拌し、60℃に昇温して重合を行
つた。
次いで表−２〜表−４の第２段階の乳化重合に
使用する単量体100部に対してドデシルベンゼン
スルフオン酸ナトリウム0.5部、過硫酸カリウム
0.6部、四塩化炭素４部、第３級ドデシルメルカ
プタン0.2部、重炭酸ナトリウム0.5部、水60部の
割合で混合し、第２段階の乳化重合する単量体と
混合撹拌し、65℃に昇温された耐圧容器に連続的
に添加して重合を行つた。
なお表−３の比較例Ｑは単量体100部に対して
ドデシルベンゼンスルフオン酸ナトリウム0.5
部、過硫酸カリウム0.6部、四塩化炭素５部、第
３級ドデシルメルカプタン0.3部、重炭酸ナトリ
ウム0.5部、水110部の割合で耐圧容器内で混合
し、65℃に昇温後単量体を連続添加して重合を行
つた。
重合転化率はいずれも99％以上であつた。
未反応単量体をストリツピングで除去した後
200メツシユの金網を通過させて共重合体ラテツ
クスＧ〜Ｕを得た。[Table] Example 2 In a pressure-resistant container, 5 parts of sodium dodecylbenzenesulfonate, 0.5 parts of calcium persulfate, and 4 parts carbon chloride, 0.2 parts tertiary dodecyl mercaptan, 0.5 parts sodium bicarbonate, water
The mixture was mixed in a proportion of 400 parts, mixed with the monomer to be subjected to emulsion polymerization in the first stage, and stirred, and the temperature was raised to 60°C to carry out polymerization. Next, 0.5 parts of sodium dodecylbenzenesulfonate and potassium persulfate were added to 100 parts of the monomers used in the second stage of emulsion polymerization in Tables 2 to 4.
0.6 parts of carbon tetrachloride, 4 parts of carbon tetrachloride, 0.2 parts of tertiary dodecyl mercaptan, 0.5 parts of sodium bicarbonate, and 60 parts of water. Polymerization was carried out by continuously adding the mixture to a pressure-resistant container heated to an elevated temperature. In addition, Comparative Example Q in Table 3 contains 0.5 sodium dodecylbenzenesulfonate per 100 parts of monomer.
0.6 parts of potassium persulfate, 5 parts of carbon tetrachloride, 0.3 parts of tertiary dodecyl mercaptan, 0.5 parts of sodium bicarbonate, and 110 parts of water were mixed in a pressure vessel, and after heating to 65°C, the monomers were mixed. Polymerization was carried out by continuously adding . The polymerization conversion rate was 99% or more in all cases. After removing unreacted monomers by stripping
Copolymer latexes G to U were obtained by passing through a 200-mesh wire mesh.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ３
実施例１、２で得られた共重合体ラテツクスを
用いて次に示す配合によつて塗工液を作成した。
塗工紙の組成
カオリンクレー 70部（固形分）
炭酸カルシウム 30部（ 〃 ）
変性デンプン ８部（ 〃 ）
乳化共重合体ラテツクス 12部（ 〃 ）
（総固形分62％）
得られた塗工液を用いてコート紙用上質原紙を
ブレードコーターを用い、片面及び両面に塗工を
行い、乾燥を行つた。（塗工量は片面10ｇ／m2）
１昼夜相対湿度65％、温度20℃の条件で調湿を行
い、ついで線圧80Kg／cm、温度60℃、速度５ｍ／
min、2nipの条件でスーパーキヤレンダー処理を
行い試料とした。
得られた塗工紙の性能を表−５〜表−８に記
す。塗工液の性能は次の試験方法で行つた。
Γロール安定性：
塗工液をパタスタビリテスターを用いてゴムロ
ール間で練り、機械的剪断をかけ、ゴムロール上
に凝固物が発生するまでの時間（分）を測定す
る。時間の長い方が良好である。
塗工紙の性能は次の試験方法で行つた。
ΓRIドライピツク：
RI印刷機で印刷した時のピツキングの程度を
肉眼で判定し、１級（一番良好なもの）から５級
（一番悪いもの）の五段階法で評価した。６回の
平均値を示す。
ΓRIウエツトピツク：
RI印刷機で湿し水を用いて印刷した時のピツ
キングの程度を肉眼で判定し、１級（一番良好な
もの）から５級（一番悪いもの）の五段階法で評
価した。６回の平均値を示す。
Γ耐ブリスター性
両面印刷塗工紙を調湿（約６％）し、加熱した
オイルバスに投げ込み、ブリスターが発生する時
の最低温度を示す。[Table] Example 3 Using the copolymer latex obtained in Examples 1 and 2, a coating liquid was prepared according to the following formulation. Composition of coated paper Kaolin clay 70 parts (solid content) Calcium carbonate 30 parts (〃) Modified starch 8 parts (〃) Emulsion copolymer latex 12 parts (〃) (Total solid content 62%) Obtained coating liquid A high-quality base paper for coated paper was coated on one and both sides using a blade coater and dried. (Coating amount is 10g/m 2 on one side)
Humidity was controlled day and night at a relative humidity of 65% and a temperature of 20°C, then a linear pressure of 80 kg/cm, a temperature of 60°C, and a speed of 5 m/cm.
The sample was subjected to supercalender treatment under the conditions of min and 2 nip. The performance of the obtained coated paper is shown in Tables 5 to 8. The performance of the coating liquid was tested using the following test method. Γ roll stability: Knead the coating solution between rubber rolls using a patter stability tester, apply mechanical shear, and measure the time (minutes) until coagulation occurs on the rubber roll. The longer the time, the better. The performance of the coated paper was tested using the following test method. ΓRI Dry Picking: The degree of picking when printed with an RI printing machine was visually judged and evaluated on a five-point scale from grade 1 (best) to grade 5 (worst). The average value of 6 times is shown. ΓRI wet pick: The degree of picking when printing with dampening water on an RI printing machine is judged visually and evaluated on a five-point scale from grade 1 (best) to grade 5 (worst). did. The average value of 6 times is shown. Γ Blister resistance Double-sided printed coated paper is humidity-controlled (approximately 6%) and thrown into a heated oil bath, and the lowest temperature at which blisters occur is shown.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ４
実施例２の表−２に示す共重合体ラテツクスを
使用し、次に示す配合によつて塗工液を作成し
た。
塗工液の組成
カオリンクレー 70部（固形分）
重質炭酸カルシウム 30部（ 〃 ）
分散剤 0.2部（ 〃 ）
変性デンプン ７部（ 〃 ）
共重合体ラテツクス 12部（ 〃 ）
固形分が60％になるように塗工液を調整し塗工
液を中質原紙（メカニカルパルプ混入率15％）に
＃７ワイヤーロツドを用いて片面および両面に14
ｇ／m2の量を塗工した。乾燥後、スーパーカレン
ダー掛け処理を行つた。得られた塗工紙の各種性
結果を表−９に示す。
なお耐ヒートセツトラフニング性は次のように
して測定した。
両面塗工されたテスト片をRI印刷試験機にて
両面印刷を行い、そのテスト片を200〜250℃シリ
コン中に５秒間いれ、その後のヒートセツトラフ
ニングの出かたを肉眼で測定し１級（１番良好な
もの）から５級（１番悪いもの）の五段階法で評
価した。６回の平均値を示す。[Table] Example 4 Using the copolymer latex shown in Table 2 of Example 2, a coating liquid was prepared according to the following formulation. Composition of coating liquid Kaolin clay 70 parts (solid content) Heavy calcium carbonate 30 parts (〃) Dispersant 0.2 parts (〃) Modified starch 7 parts (〃) Copolymer latex 12 parts (〃) Solid content is 60% Adjust the coating solution so that
An amount of g/m 2 was applied. After drying, super calendering treatment was performed. Table 9 shows the results of various properties of the coated paper obtained. The heat-set roughening resistance was measured as follows. The double-sided coated test piece was printed on both sides using an RI printing tester, and the test piece was placed in silicone at 200 to 250°C for 5 seconds, and the subsequent heat set roughening was measured with the naked eye. Evaluation was made on a five-point scale from grade (best) to grade 5 (worst). The average value of 6 times is shown.
Claims (1)
単量体10〜45重量％およびエチレン系不飽和カ
ルボン酸単量体55〜90重量％から成る単量体混
合物１〜10重量部を乳化重合し、 (b) 得られた共重合体ラテツクスの存在下脂肪族
共役ジエン単量体20〜70重量％、アルケニル芳
香族単量体20〜70重量％および不飽和カルボン
酸アルキルエステル単量体３〜40重量％から構
成される単量体90〜99重量部を添加重合する ことを特徴とする共重合体ラテツクスの製造方
法。[Scope of Claims] 1 (a) Monomer mixture 1 to 10 consisting of 10 to 45% by weight of an unsaturated monomer containing a hydroxyalkyl group and 55 to 90% by weight of an ethylenically unsaturated carboxylic acid monomer (b) 20-70% by weight of aliphatic conjugated diene monomer, 20-70% by weight of alkenyl aromatic monomer and unsaturated alkyl carboxylate in the presence of the resulting copolymer latex; A method for producing a copolymer latex, which comprises adding and polymerizing 90 to 99 parts by weight of a monomer consisting of 3 to 40% by weight of an ester monomer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55136658A JPS5759923A (en) | 1980-09-29 | 1980-09-29 | Production of copolymer latex |
| KR1019810000594A KR840001691B1 (en) | 1980-09-29 | 1981-02-24 | Process for producing copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55136658A JPS5759923A (en) | 1980-09-29 | 1980-09-29 | Production of copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5759923A JPS5759923A (en) | 1982-04-10 |
| JPS627925B2 true JPS627925B2 (en) | 1987-02-19 |
Family
ID=15180467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55136658A Granted JPS5759923A (en) | 1980-09-29 | 1980-09-29 | Production of copolymer latex |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5759923A (en) |
| KR (1) | KR840001691B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1242831A (en) * | 1981-09-23 | 1988-10-04 | Ramesh N. Gujarathi | Multi-zoned continuous aqueous emulsion polymerization |
| JPS5966472A (en) * | 1982-10-07 | 1984-04-14 | Sony Corp | Adhesive composition |
| JP2003277455A (en) * | 2002-03-25 | 2003-10-02 | Jsr Corp | Method for producing polymer particle, polymer particle and carrier for physiologically active substance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5224058A (en) * | 1975-08-19 | 1977-02-23 | Nippon Hoso Kyokai <Nhk> | Circular polarized wave antenna |
-
1980
- 1980-09-29 JP JP55136658A patent/JPS5759923A/en active Granted
-
1981
- 1981-02-24 KR KR1019810000594A patent/KR840001691B1/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5224058A (en) * | 1975-08-19 | 1977-02-23 | Nippon Hoso Kyokai <Nhk> | Circular polarized wave antenna |
Also Published As
| Publication number | Publication date |
|---|---|
| KR830005279A (en) | 1983-08-13 |
| JPS5759923A (en) | 1982-04-10 |
| KR840001691B1 (en) | 1984-10-15 |
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