JPS6128686B2 - - Google Patents
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- Publication number
- JPS6128686B2 JPS6128686B2 JP16012176A JP16012176A JPS6128686B2 JP S6128686 B2 JPS6128686 B2 JP S6128686B2 JP 16012176 A JP16012176 A JP 16012176A JP 16012176 A JP16012176 A JP 16012176A JP S6128686 B2 JPS6128686 B2 JP S6128686B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymerizable unsaturated
- emulsion
- polymer
- polymerization
- 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
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- 239000000178 monomer Substances 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000004908 Emulsion polymer Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- -1 acrylic ester Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 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
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 150000003440 styrenes Chemical class 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl 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])* 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 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
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
Description
本発明は新規な乳化重合体の製造法に関し、更
に詳しくは高固型分であり、かつ低粘度である分
散安定性に優れた乳化重合体の製造法に関する。
従来、感圧接着剤として有用な乳化重合体は、
その要求される物性上カルボン酸基の存在が不可
欠とされ、この目的のためにアクリル酸が必須モ
ノマーとして汎用されていた。しかしながら、こ
のものの乳化共重合体で高固型分のものを製造す
ると極めて高粘度となるか、あるいは分散安定性
に欠けるものしか得られない。このため、従来の
低固型分の乳化重合体を用いると乾燥が遅く、ま
た、高固型分の乳化重合体を用いると塗工適性、
作業性に欠けるという問題があつた。
本発明者は上記問題点を解決するため、高固型
分であり、かつ低粘度の分散安定性に優れた乳化
重合体を得るため鋭意研究の結果、アクリル酸エ
ステル50〜80重量％、カルボン酸ビニル15〜45重
量％並びに重合性不飽和カルボン酸２〜７重量％
を乳化重合せしめた非架橋水性樹脂分散体を種ポ
リマーとして、0.3〜1.5重量％のジビニルベンゼ
ンを含む重合性不飽和モノマーを多段階重合せし
めることにより、例えば、55重量％以上もの高固
型分でありながら、1300CPS以下の低粘度の分散
安定性の優れた乳化重合体が得られるとの知見を
得、本発明に至つたものである。
本発明において、種ポリマーのモノマー成分と
して重合性不飽和カルボン酸が２重量％未満のと
きは、得られた乳化重合体の粘度が高くなり、７
重量％を越えると分散安定性に欠け、凝集破壊を
来たす事もあり好ましくない。また、カルボン酸
基含有のモノマー成分として不飽和二塩基酸を用
いて高固型分とすると、さらに低粘度で分散安定
性の優れた乳化重合体が得られる。
本発明において、重合性不飽和カルボン酸とし
ては、例えばアクリル酸、メタクリル酸、マレイ
ン酸、フマル酸、イタコン酸等が用いられる。
本発明において、種ポリマーの他のモノマー成
分として用いられるアクリル酸エステルとして
は、例えば、アクリル酸のメチル、エチル、プロ
ピル、ブチル、ヘキシル、２−エチルヘキシル、
デシル、ラウリル等のエステル類が、また、カル
ボン酸ビニルとしては、例えば、酢酸ビニル、プ
ロピオン酸ビニル、酪酸ビニル、カプロン酸ビニ
ル、バーサチツク酸ビニル、ステアリン酸ビニル
等の１種もしくは２種以上を挙げることができ
る。種ポリマーとしては分散安定性および感圧接
着剤に適用したときの物性等を考慮し、ガラス転
移点（Tg）が−20℃〜−60℃になるように各モ
ノマーの種類、配合比を決定するのが好ましく、
アクリル酸エステルが50〜80重量％、カルボン酸
ビニルが15〜45重量％の範囲から適宜選択するの
が好ましい。
種ポリマーとしての水性樹脂分散体を得るため
の乳化重合法は常法によればよく、適当量のポリ
オキシエチレンフエニルエーテル、ポリオキシエ
チレンアルキルエーテル等の非イオン系界面活性
剤、アルキルベンゼンスルホン酸ナトリウム、ア
ルキル硫酸ナトリウム、ポリオキシエチレンアル
キルフエノールエーテルスルホン酸ナトリウム等
の陰イオン系界面活性剤等から選ばれる一種もし
くは二種以上の乳化剤、並びに過硫酸アンモニウ
ム、必要ならば亜硫酸水素ナトリウムを併用した
レドツクス系等の水溶性重合開始剤が用いられ
る。
本発明において重合性不飽和モノマーとして
は、その60重量％以上が炭素数９以上のアクリル
酸エステル、すなわち、アクリル酸ヘキシル、ア
クリル酸２−エチルヘキシル、アクリル酸オクチ
ル、アクリル酸ラウリル等であればカルボン酸の
凝集力を効果的に発揮せしめるとともにカルボン
酸ビニルの非粘着性が補われ感圧接着剤として好
ましい乳化重合体が得られる。
この時、ジビニルベンゼンを該重合性不飽和モ
ノマーの0.3〜1.5重量％を併用することにより、
上記感圧接着剤物性、主として凝集力を効果的に
向上せしめることができ、さらに乳化重合体の粘
度を低下せしめるのに極めて有効である。ジビニ
ルベンゼンを種ポリマー製造時に用いると、安定
な水性樹脂分散体を得ることはできず、２段階目
以降に添加することが必須である。一般にジビニ
ルベンゼンを用いてポリマーを部分的に架橋する
ことは、良く知られた技法であるが、乳化重合に
おいて、２段階目以降に用いることが、本発明の
大きな特徴である。
ジビニルベンゼンの使用量は２段階目以降に使
用される重合性不飽和モノマーの0.3ないし1.5重
量％の範囲が好ましく、0.3重量％未満の場合は
粘度低下に有効ではなく、1.5重量％を越えると
製造時に凝集物が多く発生し、又安定な水性樹脂
分散体が得られないために好ましくない。
他の重合性不飽和モノマーとしては、アクリル
酸、マレイン酸、イタコン酸、フマル酸等の重合
性不飽和酸類、アクリル酸メチル、アクリル酸エ
チル、アクリル酸プロピル、アクリル酸ブチル、
アクリル酸２エチルヘキシル、アクリル酸ラウリ
ル等のアクリル酸エステル類、（メタ）アクリル
アミド、Ｎ−メチロール（メタ）アクリルアミ
ド、Ｎ−ブトキシ（メタ）アクリルアミド等のア
ミド類、スチレン、スチレン誘導体等のスチレン
類がある。
本発明において、種ポリマーと上記重合性不飽
和モノマーとの固型分重量比は100／20〜200、好
ましくは100／40〜85である。
本発明において、多段階重合は前記のように種
ポリマーの存在下に重合性不飽和モノマーを重合
することであり、重合性不飽和モノマーの重合は
種ポリマーのそれに連結して１段階又２段階以上
で行なう。工業的には種ポリマーの存在下で重合
性不飽和モノマーを１段階で重合する、すなわ
ち、全体では２段階重合が好ましい。本発明の実
施により、前記のような効果が得られると同時に
種ポリマー生成の際に残存するモノマーの減少に
も効果がある。
以下実施例および比較例によつて本発明を具体
的に説明する。例中部とは重量部を表わす。
The present invention relates to a novel method for producing an emulsion polymer, and more particularly to a method for producing an emulsion polymer having a high solid content, low viscosity, and excellent dispersion stability. Traditionally, emulsion polymers useful as pressure-sensitive adhesives are
The presence of a carboxylic acid group is considered essential due to the required physical properties, and acrylic acid has been widely used as an essential monomer for this purpose. However, if an emulsion copolymer of this kind is produced with a high solid content, the resulting product will only have extremely high viscosity or lack dispersion stability. For this reason, when conventional emulsion polymers with low solids content are used, drying is slow, and when emulsion polymers with high solids content are used, coating suitability and
There was a problem with the lack of workability. In order to solve the above problems, the present inventor conducted extensive research to obtain an emulsion polymer with high solid content, low viscosity, and excellent dispersion stability. 15-45% by weight of vinyl acid and 2-7% by weight of polymerizable unsaturated carboxylic acid
By using a non-crosslinked aqueous resin dispersion obtained by emulsion polymerization as a seed polymer, a polymerizable unsaturated monomer containing 0.3 to 1.5% by weight of divinylbenzene is polymerized in multiple stages, for example, a high solids content of 55% by weight or more can be obtained. However, it was found that an emulsion polymer with a low viscosity of 1300 CPS or less and excellent dispersion stability can be obtained, and this led to the present invention. In the present invention, when the amount of polymerizable unsaturated carboxylic acid as a monomer component of the seed polymer is less than 2% by weight, the viscosity of the obtained emulsion polymer increases, and
Exceeding this percentage by weight is undesirable because it lacks dispersion stability and may cause cohesive failure. Moreover, when an unsaturated dibasic acid is used as a monomer component containing a carboxylic acid group to increase the solid content, an emulsion polymer with even lower viscosity and excellent dispersion stability can be obtained. In the present invention, as the polymerizable unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. are used. In the present invention, examples of acrylic esters used as other monomer components of the seed polymer include methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl acrylate,
Esters such as decyl and lauryl, and examples of vinyl carboxylates include one or more of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl versatate, and vinyl stearate. be able to. For the seed polymer, the type and blending ratio of each monomer are determined in consideration of dispersion stability and physical properties when applied to pressure-sensitive adhesives, so that the glass transition point (Tg) is between -20℃ and -60℃. It is preferable to
It is preferable to select the acrylic acid ester in an amount of 50 to 80% by weight and the vinyl carboxylate in an amount of 15 to 45% by weight. The emulsion polymerization method for obtaining an aqueous resin dispersion as a seed polymer may be a conventional method, and an appropriate amount of a nonionic surfactant such as polyoxyethylene phenyl ether or polyoxyethylene alkyl ether, or an alkylbenzene sulfonic acid is used. A redox system containing one or more emulsifiers selected from anionic surfactants such as sodium, sodium alkyl sulfate, and sodium polyoxyethylene alkyl phenol ether sulfonate, as well as ammonium persulfate and, if necessary, sodium bisulfite. A water-soluble polymerization initiator such as the following is used. In the present invention, the polymerizable unsaturated monomer is carboxyl if 60% by weight or more of it is an acrylic ester having 9 or more carbon atoms, such as hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, etc. An emulsion polymer that effectively exhibits the cohesive force of the acid and compensates for the non-adhesiveness of the vinyl carboxylate is obtained, which is preferable as a pressure-sensitive adhesive. At this time, by using divinylbenzene in an amount of 0.3 to 1.5% by weight of the polymerizable unsaturated monomer,
It can effectively improve the physical properties of the pressure-sensitive adhesive, mainly the cohesive force, and is also extremely effective in reducing the viscosity of the emulsion polymer. If divinylbenzene is used during the production of the seed polymer, a stable aqueous resin dispersion cannot be obtained, and it is essential to add it at the second stage or later. Generally, partially crosslinking a polymer using divinylbenzene is a well-known technique, but a major feature of the present invention is that it is used in the second and subsequent stages of emulsion polymerization. The amount of divinylbenzene to be used is preferably in the range of 0.3 to 1.5% by weight of the polymerizable unsaturated monomer used in the second and subsequent stages; if it is less than 0.3% by weight, it is not effective in reducing the viscosity, and if it exceeds 1.5% by weight, This is not preferred because a large amount of aggregates are generated during production and a stable aqueous resin dispersion cannot be obtained. Other polymerizable unsaturated monomers include polymerizable unsaturated acids such as acrylic acid, maleic acid, itaconic acid, fumaric acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
There are acrylic acid esters such as 2-ethylhexyl acrylate and lauryl acrylate, amides such as (meth)acrylamide, N-methylol (meth)acrylamide, and N-butoxy (meth)acrylamide, and styrenes such as styrene and styrene derivatives. . In the present invention, the solid weight ratio of the seed polymer to the polymerizable unsaturated monomer is 100/20 to 200, preferably 100/40 to 85. In the present invention, multi-step polymerization is the polymerization of a polymerizable unsaturated monomer in the presence of a seed polymer as described above, and the polymerization of the polymerizable unsaturated monomer is carried out in one or two steps by linking to that of the seed polymer. That's all for now. Industrially, it is preferred to polymerize the polymerizable unsaturated monomer in one step in the presence of a seed polymer, ie, a two-step polymerization overall. By carrying out the present invention, the above-mentioned effects can be obtained, and at the same time, it is also effective in reducing the amount of monomer remaining during the production of the seed polymer. The present invention will be specifically explained below using Examples and Comparative Examples. Example: Chubu means parts by weight.
【表】
上記処方であらかじめ窒素ガスで置換された反
応罐および滴下槽に仕込む。重合反応は55℃で開
始し、反応罐が70℃となつた時滴下を開始する。
滴下時間は１時間とする。重合温度は70ないし73
℃の範囲で行い、約２時間で反応は終結し固型分
46重量％、粘度250CPS、PH1.3の水性樹脂分散体
を得る。次に、これを種ポリマーとし、下記のよ
うにして２段階重合を行う。[Table] Charge the above recipe into a reaction vessel and a dropping tank that have been purged with nitrogen gas. The polymerization reaction starts at 55°C, and dropping starts when the temperature of the reaction vessel reaches 70°C.
The dropping time is 1 hour. Polymerization temperature is 70 to 73
The reaction was completed in about 2 hours and the solid content was
An aqueous resin dispersion of 46% by weight, a viscosity of 250 CPS, and a pH of 1.3 is obtained. Next, using this as a seed polymer, two-stage polymerization is carried out as follows.
【表】
種ポリマーを反応罐に仕込み、窒素ガスで置換
し、反応温度を70℃に保つて重合開始剤を添加
後、上記処方のモノマー混合物を１時間で滴下す
る。反応は約２時間で終結した。
比較例 １
種ポリマーとしての水性樹脂分散体の製造にお
いて、実施例１−(1)中にジビニルベンゼンを全モ
ノマー組成の1.5部添加した組成混合物の乳化重
合を試みたが、凝集破壊を来たした。
以下実施例並びに比較例を表にまとめる。
実施例２、３、および比較例２
実施例１において、種ポリマーとしての水性樹
脂分散体製造におけるモノマー並びに２段階重合
に用いるモノマーを表１のようにして乳化重合体
を製造した。[Table] Charge the seed polymer into a reaction vessel, purge the vessel with nitrogen gas, maintain the reaction temperature at 70°C, add a polymerization initiator, and then dropwise add the monomer mixture of the above formulation over 1 hour. The reaction was completed in about 2 hours. Comparative Example 1 In the production of an aqueous resin dispersion as a seed polymer, an attempt was made to emulsion polymerize a composition mixture in Example 1-(1) in which 1.5 parts of divinylbenzene was added to the total monomer composition, but cohesive failure occurred. did. Examples and comparative examples are summarized in a table below. Examples 2, 3, and Comparative Example 2 In Example 1, an emulsion polymer was manufactured using the monomers used in the production of the aqueous resin dispersion as the seed polymer and the monomers used in the two-step polymerization as shown in Table 1.
【表】
各例により得られた乳化重合体の粘度および固
型分を表２に示す。[Table] Table 2 shows the viscosity and solid content of the emulsion polymers obtained in each example.
【表】
実施例および比較例で得られた乳化重合体を、
接着剤化した場合の接着剤物性、主として凝集力
は、ジビニルベンゼンの使用により未使用のもの
と比較しておよそ３〜10倍増加しており、このも
のの添加は接着剤物性の向上ならびに粘度低下に
極めて有利である。[Table] The emulsion polymers obtained in Examples and Comparative Examples are
When made into an adhesive, the physical properties of the adhesive, mainly the cohesive force, are increased approximately 3 to 10 times by the use of divinylbenzene compared to the unused adhesive, and the addition of divinylbenzene improves the physical properties of the adhesive and reduces the viscosity. This is extremely advantageous.
Claims (1)
酸ビニル15〜45重量％および重合性不飽和カルボ
ン酸２〜７重量％を乳化重合せしめた非架橋水性
極脂分散体を種ポリマーとして、0.3〜1.5重量％
のジビニルベンゼンを含む重合性不飽和モノマー
を多段階重合せしめることを特徴とする乳化重合
体の製造法。 ２ 重合性不飽和モノマーとして、60重量％以上
の炭素数９以上のアクリル酸エステルおよびジビ
ニルベンゼンを該重合性不飽和モノマーの0.3〜
1.5重量％を用いることを特徴とする、特許請求
の範囲第１項記載の乳化重合体の製造法。[Claims] 1. A non-crosslinked aqueous polar fat dispersion prepared by emulsion polymerization of 50 to 80% by weight of acrylic ester, 15 to 45% by weight of vinyl carboxylate, and 2 to 7% by weight of polymerizable unsaturated carboxylic acid. As polymer, 0.3-1.5% by weight
A method for producing an emulsion polymer, which comprises carrying out multi-step polymerization of a polymerizable unsaturated monomer containing divinylbenzene. 2. As a polymerizable unsaturated monomer, 60% by weight or more of an acrylic ester having 9 or more carbon atoms and divinylbenzene are added in an amount of 0.3 to 60% by weight of the polymerizable unsaturated monomer.
A method for producing an emulsion polymer according to claim 1, characterized in that 1.5% by weight is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16012176A JPS5384092A (en) | 1976-12-29 | 1976-12-29 | Preparation of emulsion polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16012176A JPS5384092A (en) | 1976-12-29 | 1976-12-29 | Preparation of emulsion polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5384092A JPS5384092A (en) | 1978-07-25 |
| JPS6128686B2 true JPS6128686B2 (en) | 1986-07-02 |
Family
ID=15708308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16012176A Granted JPS5384092A (en) | 1976-12-29 | 1976-12-29 | Preparation of emulsion polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5384092A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61252203A (en) * | 1985-05-02 | 1986-11-10 | Asahi Chem Ind Co Ltd | Production of high-concentration latex by emulsion polymerization |
| US5264530A (en) * | 1992-05-01 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Process of polymerization in an aqueous system |
| JP4808332B2 (en) * | 2000-08-03 | 2011-11-02 | ハイモ株式会社 | Method for producing polymer dispersion |
-
1976
- 1976-12-29 JP JP16012176A patent/JPS5384092A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5384092A (en) | 1978-07-25 |
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