JPH0323089B2 - - Google Patents
Info
- Publication number
- JPH0323089B2 JPH0323089B2 JP58228344A JP22834483A JPH0323089B2 JP H0323089 B2 JPH0323089 B2 JP H0323089B2 JP 58228344 A JP58228344 A JP 58228344A JP 22834483 A JP22834483 A JP 22834483A JP H0323089 B2 JPH0323089 B2 JP H0323089B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- polymerization
- copolymer
- ethylenically unsaturated
- 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 - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 11
- 239000011790 ferrous sulphate Substances 0.000 description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 azo compound Chemical class 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 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
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 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
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
(産業上の利用分野)
本発明は、粘着力と凝集力とが適度にバランス
した共重合体の製造方法に関する。さらに詳しく
いえば、本発明は特定の成分および割合の単量体
成分を、重合開始剤としての過酸化水素およびレ
ドツクス用還元剤を特殊な方法で用いて乳化重合
させることによつて、上記性質を備えた共重合体
を製造する方法に関する。
(従来技術)
共重合性単量体を主原料として水分散型の共重
合体を製造する場合、これらをラジカル重合で得
るには、重合開始剤として過酸化物単独系、過酸
化物と還元剤とを組合わせたレドツクス開始系、
又はアゾ化合物単独系を用いるのが一般的であ
る。一方、感圧接着剤として重要な性能である、
粘着力と凝集力のバランスのとれた重合体を得る
には一般に分子量分布を低分子量から高分子量ま
で巾広くとることが必要とされている(特開昭56
−152802号公報)。このため、通常は共重合性単
量体の重合に当つて分子量調節剤を併用して低分
子量化を図り、所定の性能を得んとする場合が多
い。しかし、分子量調節剤を用いると低分子量化
する反面、目的としたような広い分子量分布は得
られず、せまい分布を有する重合体となる。更
に、改良法として分子量の異なる重合体のブレン
ドが挙げられるが効果は小さい。
また、不均質な分子量を有する重合体の製法な
どが提案されている(特開昭56−152802号公報な
ど)が異なつた平均分子量を有する高分子量体を
複数の段階を経て製造していくため煩雑である。
また、過酸化水素とレドツクス還元剤との組合
せを用いて単量体を乳化重合することも知られて
はいる(特開昭50−96688号公報、特開昭56−
152802号公報)。
しかしながら、工業生産性にすぐれ、かつ粘着
力と凝集力のバランスのすぐれた共重合体は得ら
れていなかつた。
(発明の目的)
このような現状に鑑み、本発明者らは、鋭意検
討を重ねた結果、複雑な重合法を用いることな
く、水分散型重合体にバランスのとれた粘着性を
付与する方法を発明するに至つた。
本発明は、粘着剤に適した共重合体を提供する
ことを目的としている。
本発明によつて得られた共重合体は、エマルジ
ヨンとして機械的、化学的に安定であり、乾燥後
の皮膜は良好な粘着力と凝集力を示し、耐水性も
良い。従つて、感圧性接着ラベル、テープ、シー
ト等の各種用途に有用である。
〈発明の構成〉
本発明は
(a) エチレン性不飽和モノカルボン酸、エチレン
性不飽和ジカルボン酸およびエチレン性不飽和
ジカルボン酸のモノエステルの群から選ばれた
少なくとも1種の単量体0.5〜7.0重量%、およ
び
(b) 前記(a)項の単量体以外の共重合可能なモノエ
チレン性単量体または/および共役ジオレフイ
ン
を、得られる共重合体のガラス転移温度が−20℃
以下となるように(b)の割合を選択して、重合開始
剤として過酸化水素の全量または一部をあらかじ
め仕込んでおき、レドツクス還元剤の全量もしく
は一部を重合反応系に回分的、逐次または連続的
に添加し、乳化剤を用いてエマルジヨン重合し、
共重合体を製造する方法である。
〈エチレン性不飽和モノカルボン酸、エチレン性
不飽和ジカルボン酸、そのモノエステル〉
本発明の共重合エマルジヨンに使用するエチレ
ン性不飽和カルボン酸等の単量体としては、アク
リル酸、メタクリル酸、クロトン酸等の不飽和モ
ノカルボン酸、イタコン酸、マレイン酸、フマー
ル酸等の不飽和ジカルボン酸のほかにイタコン酸
モノメチルエステル、マレイン酸モノエチルエス
テル等の不飽和ジカルボン酸のモノエステル等が
あり、これらを1種又は2種以上併用しても良
い。
本発明で用いるエチレン性不飽和カルボン酸ま
たはそのモノエステルは、エマルジヨンの重合安
定性、機械的安定性及び粘着性などに寄与するた
め、その使用量は、0.5〜7重量%、好ましくは
1〜5重量%である。0.5重量%未満では、重合
安定性、機械的安定性及び粘着性が悪くなり、一
方7重量%を越えると粘着用として使用した際の
耐水性が低下し、かつ共重合体エマルジヨンのPH
アツプ時の粘度が上昇し、取扱い上問題となる。
〈共役ジオレフイン〉
本発明で使用する共役ジオレフインとしては、
ブタジエン、イソプレン等があり、また、それら
の組み合わせでもよい。
〈共重合可能なモノエチレン性単量体〉
本発明で使用する共重合可能な単量体のうち、
エチレン性不飽和カルボン酸アルキルエステルと
しては、メチル(メタ)アクリレート、エチル
(メタ)アクリレート、ブチル(メタ)アクリレ
ート、2−エチルヘキシル(メタ)アクリレー
ト、ラウリル(メタ)アクリレート等があるが、
二種類以上の併用も差支えない。この明細書にお
いて「(メタ)アクリレート」とは、アクリレー
トとメタクリレートの両者を意味するものであ
る。下記の「(メタ)アクリルアミド」も同様で
ある。
共重合可能なビニル単量体としては、スチレ
ン、α−メチルスチレン、p−メチルスチレン、
ハロゲン化スチレン等の芳香族ビニル単量体、酢
酸ビニル、プロピオン酸ビニル等のビニルエステ
ル類その他としてアクリロニトリルなどがある。
更に感圧接着剤として使用する場合の粘着力、
タツク、凝集力を増すために官能基単量体として
(メタ)アクリルアミド、グリシジル(メタ)ア
クリレート、N−メチロール(メタ)アクリルア
ミド、2−ヒドロキシエチル(メタ)アクリレー
トなど、多ビニル基含有単量体として、ジビニル
ベンゼン、ジアリルフタレート、アリル(メタ)
アクリレート、などを用いることも可能である。
エチレン性不飽和カルボン酸単量体以外の上記
に挙げた単量体は1種又は2種以上を使用され
る。
好ましい単量体の組合せとしては、
エチレン性不飽和カルボン酸および共役ジオ
レフインを必須成分とする単量体の組合せ
エチレン性不飽和カルボン酸およびエチレン
性不飽和カルボン酸アルキルエステルを必須成
分とする単量体の組合せ
エチレン性不飽和カルボン酸、共役ジオレフ
インおよびエチレン性不飽和カルボン酸アルキ
ルエステルを必須成分とする
単量体の組合せがある。
の単量体の組合せにより得られる粘着剤は、
低温下での接着力にすぐれている。
の単量体の組合せにより得られる粘着剤は耐
候性にすぐれており、接着力も大きく、本発明の
特に好ましい例である。
本発明の共重合体エマルジヨンは粘着用として
用いるため、粘着力、初期タツク及び凝集力をバ
ランスさせる必要がある。そのため、共重合体の
ガラス転移温度Tgは−20℃以下、好ましくは−
60℃〜−40℃とすることが望ましく、具体的には
共重合可能な単量体の割合を適宜選択すれば良
い。Tgが−20℃を超えるとタツクが大巾に低下
する。また−60℃未満では凝集力が不充分であ
る。
〈還元剤〉
過酸化水素の使用量(全単量体に対して)は
0.01重量%以上であり、好ましくは0.1重量%以
上である。これに併用する還元剤としては、硫酸
第一鉄、グルコース、亜硫酸水素ナトリウム、ホ
ルムアルデヒド、ナトリウムスルホキシラート、
L−アスコルビン酸などがあり、硫酸第1鉄が特
に好ましい。
使用量は0.01〜1.0重量%、好ましくは0.03〜
0.5重量%であり、二種以上の併用も差支えない。
〈乳化剤〉
本発明に用いる重合用乳化剤としてはドデシル
ベンゼンスルホン酸ナトリウム、ラウリル硫酸ナ
トリウム、ナトリウムジオクチルスルホサクシネ
ート、ジナトリウムドデシルジフエニルエーテル
ジスルホネート等のアニオン性乳化剤、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
ンアルキルフエニルエーテル等のノニオン性乳化
剤等通常の乳化剤が挙げられる。乳化剤の使用量
は通常単量体100重量部あたり3重量部以下、好
ましくは2重量部以下である。
〈分子量調節剤〉
本発明においては、分子量の調節を過酸化水素
量、還元剤量で行なうことができるがこれに通常
の分子量調節剤を併用することも可能である。分
子量調節剤としては例えば、n−ドデシルメルカ
プタン、t−ドデシルメルカプタン、四塩化炭素
などがある。
〈重合方法〉
本発明は重合開始剤として過酸化水素とレドツ
クス用還元剤を使用し、かつ過酸化水素とレドツ
クス用還元剤を特定の方法で使用する所に特徴が
あり、その結果、乳化重合時の安定性が良好で、
かつ粘着力と凝集力が適度にバランスしたすぐれ
た共重合体が得られる。
過酸化水素の使用方法としては、過酸化水素の
全部又は1部をあらかじめ反応器に仕込んでおき
1部を仕込んだ場合は残りの過酸化水素は重合反
応系に回分または逐次あるいは連続的に使用され
る。過酸化水素は、重合開始時に好ましくは50重
量%以上、更に好ましくは70重量%以上を仕込ん
でおく。これらの過酸化水素の使い方は目標とす
る物性にあわせて、また、反応性の向上のため適
宜に決められる。
一方レドツクス還元剤の使用方法は重要であ
る。すなわちレドツクス用還元剤は全量又は1部
分を重合反応中に反応系に添加する。ここでの還
元剤の1部分とは、好ましくは全還元剤の少なく
とも70重量%更に好ましくは80重量%である。添
加方法としては回分的に添加するときは、好まし
くは添加する還元剤を3回以上にわけて添加す
る。その他逐次的または連続的に添加する。好ま
しい添加方法は逐次的又は連続的添加方法であ
る。
還元剤の添加方法は水に溶解して上記の方法で
添加しても良く、また、乳化した単量体と共に上
記に示した方法でも良い。重合温度は通常は60℃
以上、好ましくは70℃以上である。
還元剤の使用方法をこのようにすることによ
り、重合時の安定性がよく、粘着力の大きい共重
合体を製造することができる。
重合時の単量体/水の比は、乾燥時の熱量負荷
と高固形分化による粘度の上昇のバランスを考え
て、単量体100重量部に対し水は150重量部以下、
好ましくは100重量部以下である。
本発明の共重合体を粘着剤として使用する場
合、共重合体ラテツクスはPH7〜8に調整し、必
要に応じて、着色剤、充填剤、老化防止剤、消泡
剤などを添加することもできる。
(実施例)
以下に実施例及び比較例を挙げ本発明のより詳
細な説明に供する。当然のことながら、本発明は
以下の実施例にのみ限定されるものではない部及
び%は重量部及び重量%である。
〔実施例1〕
水40部、ドデシルベンゼンスルホン酸ソーダ
0.1部、過酸化水素0.7部を100反応器に仕込み、
80℃に内温を上げたのち、水60部、ブチルアクリ
レート90部、スチレン8部、アクリル酸2部、硫
酸第一鉄0.05部、ドデシルベンゼンスルホン酸ソ
ーダ0.9部、ポリオキシエチレンアルキルフエニ
ルエーテル(HLB17.2)0.5部、を5時間かけて
連続的に添加し、反応を進め、添加終了後85℃と
し、更に7時間反応させた。これにより仕込み単
量体の重合率が99%以上の安定性の良いエマルジ
ヨンを得た。これを25%アンモニア水でPH8に調
整したところ粘度は400cpsとなつた。このエマル
ジヨンポリマーのTgは−45℃であつた(示差走
査熱量計による以下同様)。このエマルジヨンを
厚さ25μmのポリエステルフイルムに、乾燥後膜
厚が20〜25μmとなるよう均一に塗布し、120℃
の熱風乾燥機で2分間乾燥したのち裁断して粘着
テープを得た。
〔実施例2〕
実施例1において、単量体をブチルアクリレー
ト90部、スチレン5部、メタクリル酸5部とした
以外はすべて同様の操作を行なつた。ここで得ら
れたエマルジヨンの単量体重合率は99%以上、ア
ンモニア水でPH8に調整後の粘度は800cpsであつ
た。Tgは−43℃であつた。
〔実施例3〕
実施例1において過酸化水素を1.2部とし、硫
酸第一鉄をL−アスコルビン酸0.15部に置換えた
以外はすべて同様の操作を行なつた。ここで得ら
れたエマルジヨンの単量体重合率は99%以上、ア
ンモニア水でPH8に調整後の粘度は500cpsであつ
た。Tgは−46℃であつた。
〔実施例4〕
実施例1においてブチルアクリレートを2−エ
チルヘキシルアクリレート80部、スチレン4.5部、
酢酸ビニル13部、アクリル酸2部、N−メチロー
ルアクリルアミド0.5部、n−ドデシルメルカプ
タン0.03部として、それ以外はすべて同様の操作
を行なつた。ここで得られたエマルジヨンの単量
体重合率は99%以上であつた。
Tgは−55℃であつた。PH8に調節後の粘度は
620cpsであつた。
〔実施例5〕
水80部、ジナトリウムドデシルジフエニルエー
テルジスルホネート0.5部、過酸化水素0.8部を
100反応器に仕込み内温を70℃としたのちブタ
ジエン70部、スチレン27部、アクリル酸3部、n
−ドデシルメルカプタン1.8部、硫酸第一鉄0.2
部、ジナトリウムドデシルジフエニルエーテルジ
スルホネート1.0部、水70部を15時間かけて連続
的に添加した。これを更に5時間75℃として反応
を進め、仕込み単量体の重合率が98%以上の安定
性の良いエマルジヨンを得た。これを減圧下水蒸
気で残留単量体を除き、濃縮後25%アンモニア水
でPH8に調整し、粘度300cpsのエマルジヨンを得
た。Tgは−49℃であつた。
以下の操作は実施例1と同様である。
〔実施例6〕
実施例1において過酸化水素1.0部、硫酸第一
鉄を0.1部とした以外は同様の操作を行なつた。
得られた共重合体のTgは−47℃であつた。
〔実施例7〕
実施例1における硫酸第一鉄の添加を、その
0.01部をあらかじめ反応器に仕込み、さらに内温
を上げて、水、単量体、乳化剤と同様に硫酸第一
鉄0.04部を連続的に添加したほかは、実施例1と
同様な操作を行なつた。Tgは−45.5℃であつた。
PH8での粘度は470cpsであつた。
〔比較例1〕
実施例1において開始剤を0.7部の過硫酸ナト
リウムに置換えた以外はすべて同様の操作を行な
つた。ここで得られたエマルジヨンの単量体重合
率は99%以上、アンモニア水でPH8に調整後の粘
度は120cps、Tgは−44℃であつた。
〔比較例2〕
実施例1においてアクリル酸を0.3部とした以
外はすべて同様の操作を行なつたが、重合安定性
及び得られたエマルジヨンの機械的安定性が極め
て悪かつた。Tgは−46℃で、粘度は160cpsであ
つた。
〔比較例3〕
実施例1において過酸化水素を2.0部とし、硫
酸単一鉄を用いないで、重合を行なつた。しかし
単量体の重合率が95%以下となり、重合終了前過
酸化水素0.1部、硫酸第一鉄0.01部添加して99%
以上の単量体重合率を得た。Tgは−46℃、PH8
での粘度は460cpsであつた。
〔比較例4〕
実施例1において、過酸化水素全量及び硫酸第
一鉄全量をあらかじめ100反応器に仕込んだ以
外はすべて同様の操作を行なつた。その結果得ら
れたエマルジヨンは安定性が悪く、重合中に凝集
物(ゲル)が発生した。このエマルジヨンポリマ
ーのTgは−44℃であつた。PH8での粘度は
240cpsであつた。
〔比較例5〕
実施例1において、ブチルアクリレートを65
部、スチレンを33部とした以外は同様の操作を行
なつた。得られたエマルジヨンポリマーのTgは
−15℃であつた。PH8での粘度は360cpsであつ
た。
以上の例で製造された共重合体を用いて造られ
た粘着テープの性能は第1表の通りであり、各試
験項目は下記の通りである。
粘着力; 厚さ2.0mm、幅50mm、長さ125mmの
SUS304鋼板をJIS Z0237に規定する方
法で研磨し、これに幅2.5cm、長さ5cm
の粘着テープを2Kgハンドロールで5回
圧着したのち、180゜の角度に300mm/分
の速度で剥離したときの強度を示す。温
度は20℃、湿度は80%の恒温恒湿下で測
定した。
タツク; JIS Z0237に準拠、傾斜板角度は30゜。
凝集力(ずれ距離); 粘着力測定で用いたのも
のと同様のSUS鋼板に重ね合わせ部が
2.5cm×2.5cmとなるよう粘着テープを置
き、2Kgハンドロールで5回圧着、テー
プ下端に1Kgのおもりを吊し40℃、湿度
80%の恒温恒湿下で測定した。
なお、要求性能は用途により異なる
が、ラベル用粘着剤の場合、粘着力600
g/cm巾以上、タツク8以上、ずれ距離
0が求められる。
(Industrial Application Field) The present invention relates to a method for producing a copolymer having an appropriate balance of adhesive force and cohesive force. More specifically, the present invention achieves the above properties by emulsion polymerizing specific components and proportions of monomer components using hydrogen peroxide as a polymerization initiator and a redox reducing agent in a special method. The present invention relates to a method for producing a copolymer comprising: (Prior art) When producing water-dispersed copolymers using copolymerizable monomers as main raw materials, in order to obtain these by radical polymerization, peroxide alone as a polymerization initiator, peroxide and reduction redox initiation system in combination with
Alternatively, it is common to use an azo compound alone. On the other hand, this is an important performance as a pressure-sensitive adhesive.
In order to obtain a polymer with a well-balanced adhesive force and cohesive force, it is generally necessary to have a wide molecular weight distribution from low molecular weight to high molecular weight (Japanese Patent Laid-Open No. 56
−152802). For this reason, when copolymerizable monomers are polymerized, a molecular weight regulator is often used in combination to lower the molecular weight in order to obtain desired performance. However, when a molecular weight regulator is used, although the molecular weight is lowered, the desired wide molecular weight distribution cannot be obtained, resulting in a polymer having a narrow distribution. Furthermore, as an improvement method, blending of polymers with different molecular weights may be mentioned, but the effect is small. In addition, methods for producing polymers with non-uniform molecular weights have been proposed (e.g., Japanese Patent Application Laid-Open No. 152802/1982), but in order to produce polymers with different average molecular weights through multiple steps, It's complicated. It is also known to emulsion polymerize monomers using a combination of hydrogen peroxide and a redox reducing agent (JP-A-50-96688, JP-A-56-96688;
152802). However, a copolymer with excellent industrial productivity and a good balance between adhesive strength and cohesive strength has not been obtained. (Purpose of the Invention) In view of the current situation, the present inventors have made extensive studies and have developed a method for imparting well-balanced tackiness to water-dispersed polymers without using complicated polymerization methods. He came to invent this. An object of the present invention is to provide a copolymer suitable for adhesives. The copolymer obtained by the present invention is mechanically and chemically stable as an emulsion, and the film after drying exhibits good adhesive strength and cohesive force, and has good water resistance. Therefore, it is useful for various uses such as pressure-sensitive adhesive labels, tapes, and sheets. <Structure of the Invention> The present invention provides (a) at least one monomer selected from the group of ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids, and monoesters of ethylenically unsaturated dicarboxylic acids. 7.0% by weight, and (b) copolymerizable monoethylenic monomer and/or conjugated diolefin other than the monomers in item (a) above, the resulting copolymer has a glass transition temperature of -20°C.
By selecting the ratio of (b) as shown below, the whole or a part of hydrogen peroxide is charged in advance as a polymerization initiator, and the whole or a part of the redox reducing agent is added to the polymerization reaction system batchwise or sequentially. or continuously added and emulsion polymerized using an emulsifier,
This is a method for producing copolymers. <Ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, monoester thereof> Monomers such as ethylenically unsaturated carboxylic acid used in the copolymer emulsion of the present invention include acrylic acid, methacrylic acid, and croton. In addition to unsaturated monocarboxylic acids such as acids, unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, there are also monoesters of unsaturated dicarboxylic acids such as itaconic acid monomethyl ester and maleic acid monoethyl ester. You may use 1 type or 2 or more types together. Since the ethylenically unsaturated carboxylic acid or its monoester used in the present invention contributes to the polymerization stability, mechanical stability, and tackiness of the emulsion, the amount used is 0.5 to 7% by weight, preferably 1 to 7% by weight. It is 5% by weight. If it is less than 0.5% by weight, polymerization stability, mechanical stability, and adhesiveness will deteriorate, while if it exceeds 7% by weight, water resistance will decrease when used as an adhesive, and the PH of the copolymer emulsion will decrease.
The viscosity increases when it is heated up, which poses a problem in handling. <Conjugated diolefin> The conjugated diolefin used in the present invention includes:
Examples include butadiene, isoprene, etc., and combinations thereof may also be used. <Copolymerizable monoethylenic monomer> Among the copolymerizable monomers used in the present invention,
Ethylenically unsaturated carboxylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.
There is no problem with the combination of two or more types. In this specification, "(meth)acrylate" means both acrylate and methacrylate. The same applies to "(meth)acrylamide" below. Examples of copolymerizable vinyl monomers include styrene, α-methylstyrene, p-methylstyrene,
Examples include aromatic vinyl monomers such as halogenated styrene, vinyl esters such as vinyl acetate and vinyl propionate, and acrylonitrile. Furthermore, the adhesive strength when used as a pressure sensitive adhesive,
Multi-vinyl group-containing monomers such as (meth)acrylamide, glycidyl (meth)acrylate, N-methylol (meth)acrylamide, and 2-hydroxyethyl (meth)acrylate are used as functional group monomers to increase the cohesive force. as, divinylbenzene, diallyl phthalate, allyl(meth)
It is also possible to use acrylate, etc. One or more of the above-mentioned monomers other than the ethylenically unsaturated carboxylic acid monomer may be used. Preferred monomer combinations include: A combination of monomers containing an ethylenically unsaturated carboxylic acid and a conjugated diolefin as essential components A monomer containing an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated carboxylic acid alkyl ester as essential components Combination of monomers There is a combination of monomers whose essential components are ethylenically unsaturated carboxylic acid, conjugated diolefin, and ethylenically unsaturated carboxylic acid alkyl ester. The adhesive obtained by the combination of monomers is
Excellent adhesive strength at low temperatures. The adhesive obtained by combining the above monomers has excellent weather resistance and high adhesive strength, and is a particularly preferred example of the present invention. Since the copolymer emulsion of the present invention is used for adhesive purposes, it is necessary to balance adhesive strength, initial tack, and cohesive strength. Therefore, the glass transition temperature Tg of the copolymer is −20°C or lower, preferably −
The temperature is preferably 60°C to -40°C, and specifically, the proportion of copolymerizable monomers may be appropriately selected. When Tg exceeds -20℃, tack drops significantly. Further, below -60°C, the cohesive force is insufficient. <Reducing agent> The amount of hydrogen peroxide used (relative to all monomers) is
It is 0.01% by weight or more, preferably 0.1% by weight or more. Reducing agents used in conjunction with this include ferrous sulfate, glucose, sodium bisulfite, formaldehyde, sodium sulfoxylate,
Examples include L-ascorbic acid, with ferrous sulfate being particularly preferred. The amount used is 0.01~1.0% by weight, preferably 0.03~
The content is 0.5% by weight, and two or more types may be used together. <Emulsifier> Examples of the emulsifier for polymerization used in the present invention include anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate, disodium dodecyl diphenyl ether disulfonate, polyoxyethylene alkyl ether, polyoxy Common emulsifiers include nonionic emulsifiers such as ethylene alkyl phenyl ether. The amount of emulsifier used is usually 3 parts by weight or less, preferably 2 parts by weight or less per 100 parts by weight of monomer. <Molecular weight regulator> In the present invention, the molecular weight can be controlled by the amount of hydrogen peroxide and the amount of reducing agent, but it is also possible to use a common molecular weight regulator in combination. Examples of molecular weight regulators include n-dodecylmercaptan, t-dodecylmercaptan, and carbon tetrachloride. <Polymerization method> The present invention is characterized in that hydrogen peroxide and a redox reducing agent are used as a polymerization initiator, and hydrogen peroxide and a redox reducing agent are used in a specific method. Good stability over time,
Moreover, an excellent copolymer having an appropriate balance of adhesive strength and cohesive strength can be obtained. The method for using hydrogen peroxide is to charge all or part of the hydrogen peroxide into the reactor in advance, and if one part is charged, the remaining hydrogen peroxide is used in the polymerization reaction system batchwise, sequentially, or continuously. be done. Hydrogen peroxide is preferably charged in an amount of 50% by weight or more, more preferably 70% by weight or more at the start of polymerization. The use of hydrogen peroxide is appropriately determined depending on the target physical properties and for improving reactivity. On the other hand, the method of using the redox reducing agent is important. That is, the redox reducing agent is added in its entirety or in part to the reaction system during the polymerization reaction. A portion of reducing agent here preferably represents at least 70%, more preferably 80% by weight of the total reducing agent. When adding the reducing agent in batches, the reducing agent is preferably added in three or more portions. Others are added sequentially or continuously. A preferred method of addition is a sequential or continuous addition method. The reducing agent may be added by the above-mentioned method after being dissolved in water, or may be added together with the emulsified monomer by the above-mentioned method. Polymerization temperature is usually 60℃
The temperature is preferably 70°C or higher. By using the reducing agent in this manner, it is possible to produce a copolymer with good stability during polymerization and high adhesive strength. The monomer/water ratio during polymerization is 150 parts by weight or less for 100 parts by weight of monomer, taking into consideration the balance between the heat load during drying and the increase in viscosity due to high solidification.
Preferably it is 100 parts by weight or less. When using the copolymer of the present invention as an adhesive, the copolymer latex may be adjusted to pH 7 to 8, and colorants, fillers, anti-aging agents, antifoaming agents, etc. may be added as necessary. can. (Example) Examples and comparative examples are given below to provide a more detailed explanation of the present invention. It should be understood that the invention is not limited only to the following examples. Parts and percentages are by weight. [Example 1] 40 parts of water, sodium dodecylbenzenesulfonate
Charge 0.1 part and 0.7 part of hydrogen peroxide into a 100 reactor.
After raising the internal temperature to 80℃, add 60 parts of water, 90 parts of butyl acrylate, 8 parts of styrene, 2 parts of acrylic acid, 0.05 parts of ferrous sulfate, 0.9 parts of sodium dodecylbenzenesulfonate, and polyoxyethylene alkyl phenyl ether. (HLB17.2) was continuously added over 5 hours to advance the reaction, and after the addition was completed, the temperature was raised to 85°C and the reaction was further continued for 7 hours. As a result, a highly stable emulsion with a polymerization rate of 99% or more of the charged monomers was obtained. When this was adjusted to pH 8 with 25% ammonia water, the viscosity was 400 cps. The Tg of this emulsion polymer was -45°C (as measured by differential scanning calorimetry). This emulsion was evenly applied to a polyester film with a thickness of 25 μm so that the film thickness after drying was 20 to 25 μm.
After drying in a hot air dryer for 2 minutes, the tape was cut to obtain an adhesive tape. [Example 2] The same operations as in Example 1 were carried out except that the monomers were 90 parts of butyl acrylate, 5 parts of styrene, and 5 parts of methacrylic acid. The monomer polymerization rate of the emulsion obtained here was 99% or more, and the viscosity after adjusting the pH to 8 with aqueous ammonia was 800 cps. Tg was -43°C. [Example 3] The same operations as in Example 1 were carried out except that hydrogen peroxide was changed to 1.2 parts and ferrous sulfate was replaced with 0.15 parts of L-ascorbic acid. The monomer polymerization rate of the emulsion obtained here was 99% or more, and the viscosity after adjusting the pH to 8 with aqueous ammonia was 500 cps. Tg was -46°C. [Example 4] In Example 1, butyl acrylate was replaced with 80 parts of 2-ethylhexyl acrylate, 4.5 parts of styrene,
The same operation was carried out except for using 13 parts of vinyl acetate, 2 parts of acrylic acid, 0.5 part of N-methylolacrylamide, and 0.03 part of n-dodecylmercaptan. The monomer polymerization rate of the emulsion obtained here was 99% or more. Tg was -55°C. The viscosity after adjusting to PH8 is
It was 620cps. [Example 5] 80 parts of water, 0.5 part of disodium dodecyl diphenyl ether disulfonate, and 0.8 part of hydrogen peroxide.
After charging 100 parts into a reactor and bringing the internal temperature to 70°C, add 70 parts of butadiene, 27 parts of styrene, 3 parts of acrylic acid, n
−1.8 parts of dodecyl mercaptan, 0.2 parts of ferrous sulfate
1 part of disodium dodecyl diphenyl ether disulfonate and 70 parts of water were continuously added over 15 hours. The reaction was further continued at 75° C. for 5 hours to obtain a highly stable emulsion with a polymerization rate of 98% or more of the charged monomers. Residual monomers were removed from this with steam under reduced pressure, and after concentration, the pH was adjusted to 8 with 25% aqueous ammonia to obtain an emulsion with a viscosity of 300 cps. Tg was -49°C. The following operations are the same as in Example 1. [Example 6] The same operation as in Example 1 was performed except that 1.0 part of hydrogen peroxide and 0.1 part of ferrous sulfate were used.
The Tg of the obtained copolymer was -47°C. [Example 7] The addition of ferrous sulfate in Example 1 was
The same operation as in Example 1 was carried out, except that 0.01 part of ferrous sulfate was charged into the reactor in advance, the internal temperature was further raised, and 0.04 part of ferrous sulfate was added continuously in the same way as water, monomer, and emulsifier. Summer. Tg was -45.5°C.
The viscosity at pH 8 was 470 cps. [Comparative Example 1] The same operations as in Example 1 were performed except that the initiator was replaced with 0.7 parts of sodium persulfate. The monomer polymerization rate of the emulsion obtained here was 99% or more, the viscosity after adjusting the pH to 8 with aqueous ammonia was 120 cps, and the Tg was -44°C. [Comparative Example 2] The same operations as in Example 1 were carried out except that 0.3 parts of acrylic acid was used, but the polymerization stability and the mechanical stability of the obtained emulsion were extremely poor. The Tg was -46°C and the viscosity was 160 cps. [Comparative Example 3] Polymerization was carried out in Example 1 except that hydrogen peroxide was changed to 2.0 parts and single iron sulfate was not used. However, the polymerization rate of the monomer was less than 95%, and when 0.1 part of hydrogen peroxide and 0.01 part of ferrous sulfate were added before the polymerization was completed, the polymerization rate reached 99%.
The above monomer polymerization rate was obtained. Tg is -46℃, PH8
The viscosity was 460 cps. [Comparative Example 4] The same operations as in Example 1 were carried out except that the entire amount of hydrogen peroxide and the entire amount of ferrous sulfate were charged into the 100 reactor in advance. The resulting emulsion had poor stability and agglomerates (gels) were generated during polymerization. The Tg of this emulsion polymer was -44°C. The viscosity at PH8 is
It was 240cps. [Comparative Example 5] In Example 1, butyl acrylate was
The same operation was carried out except that the amount of styrene was changed to 33 parts. The Tg of the obtained emulsion polymer was -15°C. The viscosity at PH8 was 360 cps. The performance of the adhesive tape made using the copolymer prepared in the above example is shown in Table 1, and each test item is as follows. Adhesive strength; thickness 2.0mm, width 50mm, length 125mm
SUS304 steel plate is polished by the method specified in JIS Z0237, and the width is 2.5cm and the length is 5cm.
This shows the strength when the adhesive tape is crimped 5 times with a 2 kg hand roll and then peeled off at an angle of 180° at a speed of 300 mm/min. The temperature was measured at a constant temperature of 20°C and the humidity was 80%. Tack: Compliant with JIS Z0237, inclined plate angle is 30°. Cohesive force (slip distance): The overlapping part is made of SUS steel plates similar to those used in the adhesive force measurement.
Place the adhesive tape so that it is 2.5cm x 2.5cm, press it 5 times with a 2Kg hand roll, hang a 1Kg weight on the bottom edge of the tape, and store at 40℃ and humidity.
Measured under constant temperature and humidity of 80%. The required performance varies depending on the application, but in the case of label adhesives, the adhesive strength is 600.
g/cm width or more, tack of 8 or more, and deviation distance of 0 are required.
【表】
(発明の効果)
本発明の方法により、第1表に示したとおり、
粘着力、タツク、凝集力のバランスのすぐれた粘
着剤に好適な共重合体が得られる。
還元剤と本発明の方法によらないで、過酸化水
素と併用して重合を開始させたときは特開昭50−
96688号公報に示されているように、重合時の安
定性の低下およびゲルの発生という問題が生じる
が、本発明の方法によればそのようなトラブルを
生じない。[Table] (Effects of the invention) By the method of the present invention, as shown in Table 1,
A copolymer suitable for a pressure-sensitive adhesive with an excellent balance of adhesive strength, tackiness, and cohesion can be obtained. When polymerization is initiated by using hydrogen peroxide in combination with a reducing agent and the method of the present invention, Japanese Patent Application Laid-Open No. 1989-1999
As shown in Japanese Patent No. 96688, problems such as decreased stability and generation of gel during polymerization occur, but the method of the present invention does not cause such problems.
Claims (1)
レン性不飽和ジカルボン酸およびエチレン性不
飽和ジカルボン酸のモノエステルの群から選ば
れた少なくとも1種の単量体0.5〜7.0重量%、 および、 (b) 前記(a)項の単量体以外の共重合可能なモノエ
チレン性単量体または/および共役ジオレフイ
ン を、得られる共重合体のガラス転移温度が−20℃
以下となるように(b)の割合を選択して、重合開始
剤として過酸化水素の全量または一部をあらかじ
め仕込んでおき、レドツクス還元剤の全量もしく
は一部を重合反応系に回分的、遂次または連続的
に添加し、乳化剤を用いてエマルジヨン重合する
ことを特徴とする共重合体の製造方法。[Scope of Claims] 1 (a) At least one monomer selected from the group of ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids, and monoesters of ethylenically unsaturated dicarboxylic acids 0.5 to 7.0 (b) a copolymerizable monoethylenic monomer or/and conjugated diolefin other than the monomers in item (a) above, and the resulting copolymer has a glass transition temperature of -20°C.
By selecting the ratio of (b) as shown below, all or part of hydrogen peroxide is charged in advance as a polymerization initiator, and all or part of the redox reducing agent is added to the polymerization reaction system batchwise or finally. A method for producing a copolymer, which comprises adding the copolymer subsequently or continuously and carrying out emulsion polymerization using an emulsifier.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22834483A JPS60120709A (en) | 1983-12-05 | 1983-12-05 | Production of copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22834483A JPS60120709A (en) | 1983-12-05 | 1983-12-05 | Production of copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60120709A JPS60120709A (en) | 1985-06-28 |
JPH0323089B2 true JPH0323089B2 (en) | 1991-03-28 |
Family
ID=16874986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22834483A Granted JPS60120709A (en) | 1983-12-05 | 1983-12-05 | Production of copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60120709A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8656984B2 (en) | 2007-11-20 | 2014-02-25 | Railtech International | Mold for direct-cast aluminothermic welding |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1333072A3 (en) * | 2002-01-30 | 2003-11-12 | Rohm And Haas Company | Ink composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5096688A (en) * | 1973-12-26 | 1975-07-31 | ||
JPS50140531A (en) * | 1974-03-08 | 1975-11-11 | ||
JPS56152802A (en) * | 1980-02-08 | 1981-11-26 | Rohm & Haas | Emulsion polymer containing heterogeneous molecular weight and its manufacture |
-
1983
- 1983-12-05 JP JP22834483A patent/JPS60120709A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5096688A (en) * | 1973-12-26 | 1975-07-31 | ||
JPS50140531A (en) * | 1974-03-08 | 1975-11-11 | ||
JPS56152802A (en) * | 1980-02-08 | 1981-11-26 | Rohm & Haas | Emulsion polymer containing heterogeneous molecular weight and its manufacture |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8656984B2 (en) | 2007-11-20 | 2014-02-25 | Railtech International | Mold for direct-cast aluminothermic welding |
Also Published As
Publication number | Publication date |
---|---|
JPS60120709A (en) | 1985-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2522344B2 (en) | Water-based pressure sensitive adhesive | |
US4564664A (en) | Emulsion-acrylic pressure-sensitive adhesives formed in two step polymerization | |
EP0252717B1 (en) | Curable pressure-sensitive adhesives, constructions embodying such adhesives and process for production of pressure-sensitive adhesive stock | |
US5889105A (en) | Aqueous dispersion-type acrylic polymer | |
JP4302371B2 (en) | Tape-shaped insulating material, insulating article, and water-dispersed acrylic adhesive for insulating material | |
JPH05105856A (en) | Water-dispersible self-adhesive composition and self-adhesive tape, label, or sheet | |
JPH0323089B2 (en) | ||
JPH023481A (en) | Acrylic pressure-sensitive adhesive composition | |
JPS5933602B2 (en) | Method of manufacturing pressure sensitive adhesive | |
JP2000192006A (en) | Emulsion-type pressure-sensitive adhesive | |
JPH08165464A (en) | Water-base pressure-sensitive adhesive | |
CA1337187C (en) | Eb-curable acrylic hot melt pressure-sensitive adhesives | |
JPS6312501B2 (en) | ||
JP2913528B2 (en) | Release agent for back surface treatment | |
JPH06100849A (en) | Pressure-sensitive adhesive | |
JP3670362B2 (en) | Emulsion composition for adhesive and method for producing the same | |
JP4362148B2 (en) | Method for producing water-dispersible acrylic pressure-sensitive adhesive | |
EP0656909B1 (en) | Novel polytelomerization process and polytelomeric products | |
JP3424271B2 (en) | Method for producing aqueous emulsion and pressure-sensitive adhesive | |
JPH0388813A (en) | Production of emulsion for adhesive | |
JPS61266480A (en) | Aqueous dispersion of copolymer for adhesive | |
JP3332303B2 (en) | Method for producing water-dispersible pressure-sensitive adhesive for re-peeling | |
CN115491153B (en) | Cross-linked aqueous acrylic ester segmented copolymer pressure-sensitive adhesive and preparation method thereof | |
JP4366708B2 (en) | Water-dispersed pressure sensitive adhesive for re-peeling | |
JPS58189274A (en) | Pressure-sensitive adhesive composition |