JPS62270608A - Water-soluble acrylic copolymer - Google Patents
Water-soluble acrylic copolymerInfo
- Publication number
- JPS62270608A JPS62270608A JP11408986A JP11408986A JPS62270608A JP S62270608 A JPS62270608 A JP S62270608A JP 11408986 A JP11408986 A JP 11408986A JP 11408986 A JP11408986 A JP 11408986A JP S62270608 A JPS62270608 A JP S62270608A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- water
- copolymer
- formula
- acrylic copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006243 acrylic copolymer Polymers 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000001033 ether group Chemical group 0.000 claims abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- -1 polyoxyethylene Polymers 0.000 abstract description 26
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 229920000126 latex Polymers 0.000 abstract description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- RFIMISVNSAUMBU-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC=C RFIMISVNSAUMBU-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 3
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229940086737 allyl sucrose Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229920006037 cross link polymer 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
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 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
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野〕
この発明は水溶性アクリル系共重合体、詳しくは糊料、
ラテックス、陶磁器成形用の原料、化粧品、医薬品等に
使用する各種水溶液の増粘剤として、また生理用品や農
園芸用保水材或いは壁材としての水呼吸用として、さら
には消防の際の火災の拡散防止用等に有用な吸水剤若し
くは保水剤として使用する水溶性アクリル系共重合体に
関するものである。[Detailed Description of the Invention] 3. Detailed Description of the Invention [Field of Industrial Application] This invention relates to a water-soluble acrylic copolymer, specifically a paste,
As a thickener for various aqueous solutions used in latex, raw materials for ceramic molding, cosmetics, pharmaceuticals, etc., as a water-breathing material for sanitary products, as a water-retaining material for agricultural and horticultural purposes, and as wall materials, and as a fire protection agent during firefighting. This invention relates to a water-soluble acrylic copolymer used as a water-absorbing agent or water-retaining agent useful for diffusion prevention and the like.
アクリル酸やメタクリル酸のホモポリマー及びその塩類
のうち、特に高重合度品又は若干架橋せしめた高分子化
物は水中で高密度のアニオン同志による反発で分子が極
端に拡がって水中で高粘性を示すため、これら高分子化
物はか＼る性質を利用して増粘剤又は吸水性ポリマーと
して多方面に利用されている。Among homopolymers of acrylic acid and methacrylic acid and their salts, particularly those with a high degree of polymerization or slightly crosslinked polymers exhibit high viscosity in water due to the repulsion of their molecules by high-density anions. Therefore, these polymerized products are utilized in many ways as thickeners or water-absorbing polymers by taking advantage of their warm properties.
しかしながら、このポリマーは対立イオンに会うと電気
的な反発が失われて極端に粘度低下が起る欠点を有して
いる。However, this polymer has the disadvantage that when it encounters opposing ions, electrical repulsion is lost and the viscosity is extremely reduced.
すなわち１例えばポリアクリル酸ソーダのごときポリア
クリル酸の塩や、ポリメタクリル酸ソーダの如きボエメ
タクリル酸の塩等は水に溶解することにより優れた増粘
剤となりうるが、特定の電解質に対する感受性を持ち１
例えば水性系において塩化ナトリウムの如き電解質に会
うと、その粘度を急激に低下する傾向がある。Namely, 1. For example, salts of polyacrylic acid such as sodium polyacrylate and salts of boe methacrylic acid such as sodium polymethacrylate can be excellent thickeners when dissolved in water, but they may be sensitive to certain electrolytes. Hold 1
For example, encountering an electrolyte such as sodium chloride in an aqueous system tends to reduce its viscosity rapidly.
この塩化ナトリウムの如き電解質におけるナトリウムイ
オン（陽イオン）は、ポリアクリル酸ソーダの持つカル
ボキシルアニオン（陰イオン）に対立するもので、この
対立イオンの存在によりイオンが電気的に中和されて反
撥が失われもって前記した粘度低下が生ずるものと推定
される。The sodium ions (cations) in this electrolyte such as sodium chloride are opposed to the carboxyl anions (anions) of sodium polyacrylate, and the presence of this opposed ion electrically neutralizes the ions and causes repulsion. It is presumed that this loss causes the aforementioned viscosity reduction.
この問題を解決する方法として米国特許第３，９１５、
９２１号、同第４，５０９，９４９号等では、炭素数１
０〜３０のアルキル基を有するアクリル酸又はメタクリ
ル酸のエステルを共重合させることを提案している。As a method to solve this problem, U.S. Patent No. 3,915,
No. 921, No. 4,509,949, etc., the carbon number is 1.
It is proposed to copolymerize esters of acrylic or methacrylic acid with 0 to 30 alkyl groups.
しかしながら、前記した各米国特許における高級脂肪酸
エステル共重合体は、その粉末製品を水に溶解させる場
合に長い時間を要することが欠点であって、共重合体の
含量が多くなると透明な液とならずに乳白色の液となる
などの性質を有するために、その用途が自ずから限定さ
れるという不都合があった。However, the higher fatty acid ester copolymers in the above-mentioned U.S. patents have the disadvantage that it takes a long time to dissolve the powder product in water, and when the copolymer content increases, a clear liquid cannot be obtained. Since it has properties such as turning into a milky white liquid without water, it has the disadvantage that its uses are naturally limited.
この発明はか＼る現状に鑑み、少な（とも２種類の共重
合成分を組み合わせて共重合させ水可溶性の共重合体と
することによって、無色透明であると共に、（Ｉれた耐
塩性を有する水溶液増粘剤。In view of the current situation, this invention has been developed by copolymerizing a water-soluble copolymer by combining two types of copolymer components, which are colorless and transparent, and have excellent salt resistance. Aqueous thickener.
吸水剤、保水剤等に使用することのできるアクリル系共
重合体を提供せんとするものである。It is an object of the present invention to provide an acrylic copolymer that can be used as a water absorbing agent, a water retaining agent, and the like.
すなわち、この発明の水溶性アクリル系共重合体は、少
な（とも下記の（ａ）及び（ｂ）に示される化合物を架
橋剤を使用し、若しくは使用せずに共重合させることに
よって得られたことを特徴とするものである。That is, the water-soluble acrylic copolymer of the present invention can be obtained by copolymerizing a small amount of the compounds shown in (a) and (b) below with or without using a crosslinking agent. It is characterized by this.
（ａ）９０．０〜９８．５重量％のアクリル酸又は／及
びメタクリル酸。(a) 90.0-98.5% by weight of acrylic acid or/and methacrylic acid.
（ｂ）１０．０〜１．５ＩＥ量％の下記一般式。(b) 10.0 to 1.5 IE amount% of the following general formula.
−０−Ｘ で表される化合物。-0-X A compound represented by
ただし、Ｙは。However, Y.
（Ｒは水素又はメチル基である）で。(R is hydrogen or a methyl group).
Ｘは。X is.
（Ｘ式におけるＲ２は炭素数６〜３０個のアルキル基、
又はアルキルフェニル基を示し。(R2 in formula X is an alkyl group having 6 to 30 carbon atoms,
or alkylphenyl group.
１、ｍ、ｎは２ｍ又はｎが≧１．及び
２＜ｚ＋ｍ＋ｎ＜１００を満足するものである。）
この発明おける水不溶性のアクリル系共重合体は、その
単量体構成々分の主体は基本的には（ａ）化合物で示さ
れるアクリル酸又は／及びメタクリル酸であって、その
構成割合は９０．０〜９８．５％（重量％；以下同じ）
の範囲である。1, m, n is 2m or n is ≧1. and 2<z+m+n<100. ) In the water-insoluble acrylic copolymer of the present invention, the monomer components are basically acrylic acid and/or methacrylic acid represented by compound (a), and the constituent proportions thereof are as follows: 90.0-98.5% (weight%; same below)
is within the range of
その量が９０．０％を下回る場合は、増粘剤あるいは吸
水剤、又は保水剤としての本来の性能が低下すると共に
、９８．５％を超えると実質的に耐塩機能を発揮す’４
（ｂ）化合物の配合量が減少し。If the amount is less than 90.0%, the original performance as a thickener, water absorbing agent, or water retaining agent will decrease, and if it exceeds 98.5%, it will substantially exhibit salt resistance function.
(b) The amount of compound compounded is reduced.
その結果得られた共重合体の耐塩性が低下するため所期
の性能を有する共重合体を得ることができない。As a result, the salt resistance of the resulting copolymer decreases, making it impossible to obtain a copolymer with desired performance.
か＼る（ａ）化合物は、そのカルボキシル基の少なくと
も一部を２例えば水酸化ナトリウム、水酸化カリウム、
水酸化リチウム等のアルカリ金属の水酸化物、又はアン
モニア、若しくはトリエチルアミン、トリエタノールア
ミン等の揮発性アミンなどの中和剤で部分中和した中和
単量体であってもよい。The compound (a) has at least a portion of its carboxyl group 2, such as sodium hydroxide, potassium hydroxide,
It may be a neutralized monomer partially neutralized with a neutralizing agent such as an alkali metal hydroxide such as lithium hydroxide, or ammonia, or a volatile amine such as triethylamine or triethanolamine.
前記（ａ）化合物であるアクリル酸又は／及びメタクリ
ル酸に対する共重合成分の一つとして。As one of the copolymerization components for acrylic acid and/or methacrylic acid, which is the compound (a).
−０−Ｘ
で示されている（ｂ）化合物において、オキシエチレン
単位の！個、メチル基置換オキシエチレン単位のｍ個及
びエチル基置換オキシエチレン車位のｎ個は、ｍ、ｎが
共に１個又はそれ以上であって、ｊ、ｍ、ｎの総和が２
より大で、かつ１００より小であることが要件である。-0-X In the compound (b) represented by oxyethylene unit! , m methyl group-substituted oxyethylene units, and n ethyl group-substituted oxyethylene positions, m and n are both 1 or more, and the sum of j, m, and n is 2.
The requirement is that it be greater than and less than 100.
また、（ｂ）化合物におけるＸ中のＲ１としては、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ラウリル
、ステアリル、オクチルフェニル及びノニルフェニル等
が該当する。R1 in X in compound (b) includes hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, octylphenyl, nonylphenyl, and the like.
Ｘの式中のｌ、ｍ、ｎにおける前記
ｍ又はｎ≧１．及び２＜Ｊ＋ｍ＋ｎ＜１００の規定は、
この範囲を満足することにより得られる共重合体の水に
対する溶解性、透明性を顕著に向上させることができる
。In the formula of X, m or n≧1. and 2<J+m+n<100,
By satisfying this range, the water solubility and transparency of the resulting copolymer can be significantly improved.
か＼る（ｂ）化合物の中の代表的なものとし。(b) A typical compound among the compounds.
アリル・ポリオキシエチレン（β＝１０）ポリオキシプ
ロピレン（ｍ＝３）ノニルフェノールエーテル、アリル
・ポリオキシエチレン（Ａ＝７）ポリオキシプロピレン
（ｍ＝３） ラウリルエーテル。Allyl polyoxyethylene (β=10) polyoxypropylene (m=3) nonylphenol ether, allyl polyoxyethylene (A=7) polyoxypropylene (m=3) lauryl ether.
アリル・ポリオキシエチレンＢ ＝ １４）ポリオキシ
プロピレン（ｍ＝３）ステアリルエーテル等がある。Allyl polyoxyethylene B = 14) polyoxypropylene (m = 3) stearyl ether, etc.
なお、この発明においては架橋剤として以下に述べる化
合物を、前記（ａ）化合物と（ｂ）化合物に共重合させ
て共重合体を形成してもよい。In addition, in this invention, the compound described below as a crosslinking agent may be copolymerized with the above-mentioned (a) compound and (b) compound to form a copolymer.
すなわち、前記（ａ）化合物及び（ｂ）化合物と重合可
能な化合物であって２炭素数と水酸基とがそれぞれ２個
以上を含む母体多価アルコールの１分子当り２個以上の
アルケニルエーテル基を有する多価アルコールのポリア
ルケニルポリエーテルで、具体的にはアリルペンタエリ
スリトール。That is, a compound that is polymerizable with the compounds (a) and (b) and has two or more alkenyl ether groups per molecule of the parent polyhydric alcohol containing two or more carbon atoms and two or more hydroxyl groups. A polyalkenyl polyether of a polyhydric alcohol, specifically allylpentaerythritol.
トリメチロールプロパンジアリルエーテル、アリルサッ
カローズ等がある。Examples include trimethylolpropane diallyl ether and allyl saccharose.
この架橋剤として加える化合物は、単量体全構成々分に
対して５．０％以下の範囲で加えることが望ましい。The compound added as a crosslinking agent is desirably added in an amount of 5.0% or less based on the total monomer components.
さらに、この発明においては、前記（ａ）化合物、 （
ｂ）化合物及び必要に応じて加える前記の架橋剤に対し
て、これらの化合物との共重合性を有する他のビニル系
単量体を配合して共重合させてもよい。Furthermore, in this invention, the compound (a), (
b) Other vinyl monomers having copolymerizability with these compounds may be blended and copolymerized with the compound and the above-mentioned crosslinking agent added as necessary.
か＼る第４成分としての単量体には、アルキル基の炭素
数が１〜４個のアルキルアクリル酸エステル、又はアル
キルメタクリル酸エステルで、具体的にはアクリル酸エ
チル、アクリル酸ブチル。The monomer as the fourth component is an alkyl acrylate or alkyl methacrylate in which the alkyl group has 1 to 4 carbon atoms, specifically ethyl acrylate or butyl acrylate.
メタクリル酸メチル等がある。Examples include methyl methacrylate.
これらは、単量体全量に対して略１０％以下の範囲で使
用することが好ましい。It is preferable to use these in an amount of approximately 10% or less based on the total amount of monomers.
この発明の水溶性アクリル系共重合体は、前記した各単
量体を通常の析出重合法又は溶液重合法で共重合するこ
とによって容易に得ることができるもので、使用する触
媒としてはアゾ系、過酸化物系、レドックス系等のラジ
カル重合開始剤が好適である。The water-soluble acrylic copolymer of the present invention can be easily obtained by copolymerizing the above-mentioned monomers by a conventional precipitation polymerization method or solution polymerization method, and the catalyst used is an azo-based copolymer. , peroxide type, redox type, and other radical polymerization initiators are suitable.
この発明によって得られる水不溶性アクリル系共重合体
は１ （ａ）化合物であるアクリル酸又は／及びメタク
リル酸に対し、 （ｂ）化合物で示される３つの異なっ
たポリオキシエチレン単位の複数で構成された長鎖ビニ
ル系単量体を所定の範囲晋で共重合することにより、一
定の濃度水準において極めて高い粘度を与えることがで
き、増粘された水性媒体中においても、その中の塩に対
して左右されずに安定性を保つものである。The water-insoluble acrylic copolymer obtained by this invention is composed of (a) a compound of acrylic acid or/and methacrylic acid, and (b) a plurality of three different polyoxyethylene units represented by the compound. By copolymerizing long-chain vinyl monomers in a predetermined range, extremely high viscosity can be obtained at a certain concentration level, and even in thickened aqueous media, the salts therein can be copolymerized. It maintains stability without being influenced by
したがって、水性塗料のようなラテックス塗料組成物に
おける粘弾性改良剤として使用するときは、優れた流動
性と均質性を付与することができる。Therefore, when used as a viscoelastic modifier in latex coating compositions such as water-based coatings, it can impart excellent fluidity and homogeneity.
また、織物等の捺染ペーストの増粘に使用するときは、
調合の容易さ、顔料分散液との相溶性。Also, when used to thicken printing paste for textiles etc.
Ease of formulation, compatibility with pigment dispersions.
捺染物の光沢等においてその性能を著しく改良すること
ができる。It is possible to significantly improve the performance of printed materials in terms of gloss, etc.
さらに、この発明においては架橋に有効な多価アルコー
ルのポリアルケニルエーテルの５％以下における任意量
を、前記（ａ）及び（ｂ）化合物と共重合させることに
よって得られた共重合体を適宜の三次元網状構造の形態
とすることができ。Furthermore, in the present invention, a copolymer obtained by copolymerizing an arbitrary amount of 5% or less of the polyalkenyl ether of a polyhydric alcohol effective for crosslinking with the compounds (a) and (b) is used in an appropriate manner. It can be in the form of a three-dimensional network structure.
かくして得た共重合体は水性系中で膨潤して微小ゲルを
構成し、増粘、吸水、保水等に一層優れた効果を発揮す
る。The thus obtained copolymer swells in an aqueous system to form a microgel, and exhibits superior effects in thickening, water absorption, water retention, etc.
以下、実施例を掲げてこの発明をより具体的に説明する
。Hereinafter, this invention will be described in more detail with reference to Examples.
２立聞上ニユ
下記第１表に示す配合割合で、 （ａ）化合物としてア
クリル酸、 （ｂ）化合物としてアリル・ポリオキシエ
チレン（Ａ’＝１０）ポリオキシプロピレン（ｍ＝３）
ノニルフェノールエーテルの単量体組成物５０ｇを、ベ
ンゼン４５０ｇと共に１１のコンデンサー付フラスコ中
で攪拌しながら窒素置換し、ついで触媒としてペンゾー
ルパーオキサイドを３ｇ添加し温度７０℃に保って１５
時間反応させた。At the compounding ratio shown in Table 1 below, (a) acrylic acid as a compound, (b) allyl polyoxyethylene (A' = 10) and polyoxypropylene (m = 3) as a compound.
50 g of a monomer composition of nonylphenol ether was placed in a condenser-equipped flask (No. 11) with 450 g of benzene, and the atmosphere was replaced with nitrogen while stirring. Then, 3 g of penzole peroxide was added as a catalyst, and the temperature was kept at 70°C.
Allowed time to react.
これを冷却した後、析出した共重合体粉末を遠心分離機
で分離し、温度５５℃で乾燥させて共重合体を得た。（
実施例１）
同様にして第１表に記載したように、 （ａ）化合物と
してアクリル酸、 （ｂ）化合物としてアリル・ポリ
オキシエチレン（１＝７）ポリオキシプロピレン（ｍ＝
３）ラウリルエーテル、及び架橋剤（Ｃ）としてテトラ
アリルオキシエタンを共重合して共重合体を得た。（実
施例２）
また、 （ａ）化合物としてメタクリル酸、 （ｂ）
化合物としてアリル・ポリオキシエチレン（ｊ！＝１４
）ポリオキシプロピレン（ｒｉ＝３）ステアリルエーテ
ル、架橋剤（ｃ）としてアリル蔗糖エーテル、及び第４
成分として他の共重合可能な単量体（ｄ）としてアクリ
ル酸エチルを配合して共重合体を得た。（実施例３）
これらの共重合体１．０ｇを蒸溜水２００ｍ１中に投入
し、１ＯＮのＮａＯＨを１ｍｌ添加して溶解し、その溶
液の外観を観察し、ついでこの溶液中に食塩を添加して
その粘度を測定した。After cooling, the precipitated copolymer powder was separated using a centrifuge and dried at a temperature of 55° C. to obtain a copolymer. (
Example 1) Similarly, as described in Table 1, (a) acrylic acid as a compound, (b) allyl polyoxyethylene (1=7) polyoxypropylene (m=
3) A copolymer was obtained by copolymerizing lauryl ether and tetraallyloxyethane as a crosslinking agent (C). (Example 2) Also, (a) methacrylic acid as a compound, (b)
Allyl polyoxyethylene (j!=14
) polyoxypropylene (ri=3) stearyl ether, allyl sucrose ether as crosslinker (c), and a fourth
A copolymer was obtained by blending ethyl acrylate as another copolymerizable monomer (d). (Example 3) 1.0 g of these copolymers was put into 200 ml of distilled water, 1 ml of 1ON NaOH was added to dissolve it, the appearance of the solution was observed, and then common salt was added to this solution. The viscosity was measured.
これらの結果を第１表に示すと共に、対照として従来増
粘剤等として汎用されているポリアクリル酸、架橋型ポ
リアクリル酸の性能をこの第１表に併記する。These results are shown in Table 1, and as a control, the performance of polyacrylic acid and crosslinked polyacrylic acid, which have been commonly used as thickeners, is also shown in Table 1.
第 １ 表 〔以下余白〕 註）、第１表の単量体組成の略号は以下の成分である。Chapter 1 Table [Margin below] Note) The abbreviations for monomer compositions in Table 1 are as follows.
Ａ Ａ；アクリル酸
ＭＡＡ ；メタクリル酸
Ｅ Ａｉアクリル酸エチル
ＥＮＰ ：アリル・ポリオキシエチレン（１＝１０）ポ
リオキシプロピレン（ｍ＝３）
ノニルフェノールエーテル
Ｅ Ｌ、アリル・ポリオキシエチレン（ｌ＝７）ポリ
オキシプロピレン（ｍ＝３）ラ
ウリルエーテル
Ｅ Ｓ；アリル・ポリオキシエチレン（ｌ＝１４）ポリ
オキシプロピレン（ｍ＝３）
ステアリルエーテル
ＴＡＥ ；テトラアリルオキシエタン
ＡＳＥ、アリル蔗塘エーテル
註）２ 第１表の※印に該当する商品は次の商品である
。A A; acrylic acid MAA; methacrylic acid E Ai ethyl acrylate ENP: allyl polyoxyethylene (1=10) polyoxypropylene (m=3) nonylphenol ether E L, allyl polyoxyethylene (l=7) poly Oxypropylene (m=3) lauryl ether ES; allyl polyoxyethylene (l=14) polyoxypropylene (m=3) stearyl ether TAE; tetraallyloxyethane ASE, allyl shochu ether Note) 2 Table 1 The products marked with * are as follows.
※１；ジュリマーＡＣ−１０ＨＰ （日本紬薬■製ポ
リアクリル酸）
※２；シュンロンＰＷ−１１０（日本紬薬■製架橋型ポ
リアクリル酸）
註）、第１表の外観欄の結果は１食塩添加前の液の外観
である。*1: Julimar AC-10HP (polyacrylic acid manufactured by Nippon Tsumugi Pharmaceutical ■) *2: Shunron PW-110 (crosslinked polyacrylic acid manufactured by Nippon Tsumugi Pharmaceutical ■) Note) The results in the appearance column of Table 1 are 1 table salt. This is the appearance of the liquid before addition.
註）４ 第１表の粘度測定はブルックフィールドＢ型粘
度計による（温度２５℃、 １２ＰＰＭ）の測定値であ
る。Note) 4 The viscosity measurements in Table 1 are measured values using a Brookfield B type viscometer (temperature 25°C, 12 PPM).
この発明は、少なくとも前記（ａ）化合物であるアクリ
ル酸又は／及びメタクリル酸を主体として、これと（ｂ
）化合物を所定の量的割合で共重合することによって耐
塩作用、耐イオン作用に侵れた水溶性アクリル系共重合
体を簡単かつ容易に。This invention mainly consists of at least the compound (a), acrylic acid and/or methacrylic acid, and the compound (b).
) A water-soluble acrylic copolymer with salt resistance and ion resistance can be easily and easily produced by copolymerizing compounds in a predetermined quantitative ratio.
しかも経済的に得られるものであって、これにより得ら
れた耐塩性の水溶性アクル系共重合体は。Moreover, the salt-resistant water-soluble acrylic copolymer obtained thereby is economically obtainable.
多方面に亘る用途を有する。It has many uses.
すなわち、水分散の状態か、乾燥形態として増粘される
べき水性系に配合することによって優れた増粘効果を有
する捺染糊剤、また接着剤、塗料等のラテックスとして
使用することができる。That is, it can be used as a printing paste having an excellent thickening effect, or as a latex for adhesives, paints, etc. by blending it into an aqueous system to be thickened, either in the form of an aqueous dispersion or in a dry form.
また、セメントモルタルに対する改質に、セラミック、
釉薬等の陶磁器類の改質、ローションやヘアクリーム等
の化粧品の改質、軟膏、湿布薬等の医薬品の改質、更に
は洗剤類等に添加することによってその有用性を充分に
発揮するものである。In addition, ceramics,
Modification of ceramics such as glazes, modification of cosmetics such as lotions and hair creams, modification of medicines such as ointments and poultices, and addition to detergents etc. to fully demonstrate their usefulness. It is.
一方、得られた耐塩性の水溶性アクル系共重合体は吸水
剤、保水剤として２紙おむつ、ナプキン等の生理用品や
園芸用保水剤に、農業用として農薬、肥料の保持剤に、
水呼吸の壁材として建築関係に、さらには消防用として
火災における類焼防止、水損防止及び山林火災の拡散防
止等に使用することができる。On the other hand, the obtained salt-resistant water-soluble acrylic copolymer can be used as a water absorbing agent and water retaining agent in sanitary products such as disposable diapers and napkins, and as a water retaining agent for gardening, and as a retaining agent for pesticides and fertilizers for agricultural purposes.
It can be used in construction as a water-breathing wall material, and can also be used for firefighting to prevent the spread of fires, prevent water damage, and prevent the spread of forest fires.
Claims (4)
合物を架橋剤を使用し、若しくは使用せずに共重合させ
ることによって得られたことを特徴とする水溶性アクリ
ル系共重合体。 （ａ）９０．０〜９８．５重量％のアクリル酸又は／及
びメタクリル酸。 （ｂ）１０．０〜１．５重量％の下記一般式、Ｙ−Ｏ−
Ｘ で表される化合物。 ただし、Ｙは、 ▲数式、化学式、表等があります▼又はＣＨ＿２＝ＣＨ
−ＣＨ＿２− （Ｒは水素又はメチル基である）で、 Ｘは、 ▲数式、化学式、表等があります▼ （Ｘ式におけるＲ＿１は炭素数６〜３０個のアルキル基
、又はアルキルフェニル基を示し、ｌ、ｍ、ｎは、ｍ又
はｎが≧１、及び ２＜ｌ＋ｍ＋ｎ＜１００を満足するもので ある。）(1) A water-soluble acrylic copolymer obtained by copolymerizing at least the compounds shown in (a) and (b) below with or without a crosslinking agent. (a) 90.0-98.5% by weight of acrylic acid or/and methacrylic acid. (b) 10.0 to 1.5% by weight of the following general formula, Y-O-
A compound represented by X. However, Y is ▲There is a mathematical formula, chemical formula, table, etc.▼ or CH_2=CH
-CH_2- (R is hydrogen or methyl group), and X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 in the formula , l, m, and n satisfy m or n≧1 and 2<l+m+n<100.)
アンモニア、アミンより選ばれた化合物の１種若しくは
２種以上で中和されたものであることを特徴とする特許
請求の範囲第１項記載の水溶性アクリル系共重合体。(2) The compound (a) is an alkali metal hydroxide,
The water-soluble acrylic copolymer according to claim 1, which is neutralized with one or more compounds selected from ammonia and amines.
合物に対して、架橋剤として炭素数と水酸基とがそれぞ
れ２個以上を含む母体多価アルコールの１分子当り２個
以上のアルケニルエーテル基を有する多価アルコールの
ポリアルケニルポリエーテルを５重量％以下の割合で配
合して共重合したものであることを特徴とする特許請求
の範囲第１項記載の水溶性アクリル系共重合体。(3) The copolymer has two or more carbon atoms and two or more hydroxyl groups per molecule of the base polyhydric alcohol containing two or more carbon atoms and two or more hydroxyl groups as a crosslinking agent for the (a) compound and (b) compound. The water-soluble acrylic copolymer according to claim 1, which is a copolymer of a polyalkenyl polyether of a polyhydric alcohol having an alkenyl ether group in a proportion of 5% by weight or less. Combined.
びこれら（ａ）化合物と（ｂ）化合物に対し必要に応じ
て加える架橋剤に対して、これらと共重合可能な他の単
量体を配合して共重合したものであることを特徴とする
特許請求の範囲第１項乃至第３項記載の水溶性アクリル
系共重合体。(4) The copolymer is composed of (a) compound, (b) compound, and a crosslinking agent that is added as necessary to these (a) compound and (b) compound. 4. The water-soluble acrylic copolymer according to any one of claims 1 to 3, which is obtained by copolymerizing monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11408986A JPH0678395B2 (en) | 1986-05-19 | 1986-05-19 | Method for producing water-soluble acrylic copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11408986A JPH0678395B2 (en) | 1986-05-19 | 1986-05-19 | Method for producing water-soluble acrylic copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62270608A true JPS62270608A (en) | 1987-11-25 |
| JPH0678395B2 JPH0678395B2 (en) | 1994-10-05 |
Family
ID=14628818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11408986A Expired - Lifetime JPH0678395B2 (en) | 1986-05-19 | 1986-05-19 | Method for producing water-soluble acrylic copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678395B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03162479A (en) * | 1989-11-22 | 1991-07-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | Water-retaining agent for heat-generation composition |
| US5292828A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
| US5405900A (en) * | 1992-05-29 | 1995-04-11 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
| JP2006520832A (en) * | 2003-03-07 | 2006-09-14 | ビーエーエスエフ アクチェンゲゼルシャフト | Polymer products and their use in cosmetics |
| JP2010285556A (en) * | 2009-06-12 | 2010-12-24 | Kao Corp | Polymer builder for clothing detergent |
| JP2012132007A (en) * | 2010-12-17 | 2012-07-12 | Nippon Shokubai Co Ltd | Polyalkylene glycol-based polymer and method for producing the same |
-
1986
- 1986-05-19 JP JP11408986A patent/JPH0678395B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03162479A (en) * | 1989-11-22 | 1991-07-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | Water-retaining agent for heat-generation composition |
| US5292828A (en) * | 1992-05-29 | 1994-03-08 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
| US5352734A (en) * | 1992-05-29 | 1994-10-04 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
| US5401802A (en) * | 1992-05-29 | 1995-03-28 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing complex hydrophobic groups |
| US5405900A (en) * | 1992-05-29 | 1995-04-11 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers |
| JP2006520832A (en) * | 2003-03-07 | 2006-09-14 | ビーエーエスエフ アクチェンゲゼルシャフト | Polymer products and their use in cosmetics |
| JP2010285556A (en) * | 2009-06-12 | 2010-12-24 | Kao Corp | Polymer builder for clothing detergent |
| JP2012132007A (en) * | 2010-12-17 | 2012-07-12 | Nippon Shokubai Co Ltd | Polyalkylene glycol-based polymer and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0678395B2 (en) | 1994-10-05 |
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