JPS62262735A - Novel oily thickener - Google Patents
Novel oily thickenerInfo
- Publication number
- JPS62262735A JPS62262735A JP61104198A JP10419886A JPS62262735A JP S62262735 A JPS62262735 A JP S62262735A JP 61104198 A JP61104198 A JP 61104198A JP 10419886 A JP10419886 A JP 10419886A JP S62262735 A JPS62262735 A JP S62262735A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- acid
- thickener
- aluminum
- 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.)
- Pending
Links
- 239000002562 thickening agent Substances 0.000 title claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 239000000194 fatty acid Substances 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- -1 methallyl sulfonic acid alkali metal salt Chemical class 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 abstract description 6
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 abstract description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 abstract description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 abstract description 3
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 159000000011 group IA salts Chemical class 0.000 abstract 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 abstract 1
- 239000003209 petroleum derivative Substances 0.000 abstract 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- DIKJULDDNQFCJG-UHFFFAOYSA-M sodium;prop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-M 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000007883 water-soluble azo polymerization initiator Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、油性化粧品の増粘、インキ・塗料用添加剤、
グリス用濃稠剤、合成樹脂用添加剤、油の固化等に有用
な新規油系増粘剤に関する。[Detailed description of the invention] [Industrial application field] The present invention is applicable to thickening of oil-based cosmetics, additives for inks and paints,
This invention relates to a new oil-based thickener useful for thickening agents for grease, additives for synthetic resins, solidifying oils, etc.
従来、金属石鹸や硫酸セルロース四級アンモニウム塩、
デキストリン高級脂肪酸エステル等が所謂油系増粘剤と
して知られているが、金属石鹸は一般に増粘性不十分で
あり、デキス） ＩＪン高級脂肪酸エヌテルは石油系炭
化水素の増粘、ケ°ル化には必ずしも充分満足し得るも
のではない。又、同用途向けの硫酸セルロース四級アン
モニウム塩は極めて制限された条件でのみ製造可能であ
り、その供給はコスト的にも容易ではない。Conventionally, metal soaps, cellulose sulfate quaternary ammonium salts,
Dextrin higher fatty acid esters are known as so-called oil-based thickeners, but metal soaps generally have insufficient thickening properties, and dextrin higher fatty acid esters are used to thicken and kelize petroleum-based hydrocarbons. is not necessarily fully satisfactory. Furthermore, cellulose sulfate quaternary ammonium salt for the same purpose can be produced only under extremely limited conditions, and its supply is not easy in terms of cost.
本発明は、石油系炭化水素を容易に増粘、ケ°ル化し得
る油系増粘剤を提供することを目的とする。An object of the present invention is to provide an oil-based thickener that can easily thicken and kelize petroleum-based hydrocarbons.
本発明は、アクリル又はメタクリル酸とアリル又はメタ
リルスルホン酸アルカリ金属塩との共重合体のカルボキ
シル基を炭素数６以上の脂肪酸及びアルミニウム塩で架
橋し、且つスルホン酸基を四級アンモニウム塩化して成
る油系増粘剤の発明である。The present invention involves crosslinking the carboxyl groups of a copolymer of acrylic or methacrylic acid and an alkali metal salt of allyl or methallyl sulfonic acid with a fatty acid having 6 or more carbon atoms and an aluminum salt, and converting the sulfonic acid group into a quaternary ammonium salt. This is an invention of an oil-based thickener consisting of.
即ち、本発明者らは、石油系炭化水素を容易に増粘、ゲ
ル化し得る油系増粘剤に付鋭意研究の結果、アクリル酸
又はメタクリル酸とアリル又はメタリルスルホン酸アル
カリ金属塩との共重合体のカルボキシル基を脂肪酸及び
アルミニウム塩で架橋し、更にスルホン酸基を四級アン
モニウム塩化するときは、同目的を達成する優れた油系
増粘剤が容易に得られることを見出し、本発明を完成す
るに至った。That is, as a result of intensive research into oil-based thickeners that can easily thicken and gel petroleum-based hydrocarbons, the present inventors found that they have developed a combination of acrylic acid or methacrylic acid and an alkali metal salt of allyl or methallylsulfonic acid. We have discovered that when the carboxyl groups of the copolymer are cross-linked with fatty acids and aluminum salts, and the sulfonic acid groups are converted into quaternary ammonium salts, an excellent oil-based thickener that achieves the same purpose can be easily obtained. The invention was completed.
本発明で用いられるアクリル酸又はメタクリル酸とアリ
ル又はメタリルスルホン酸アルカリ金属塩との共重合体
は、常法によりこれらのモノマーを共重合させて得られ
たものを用いることで足りる。The copolymer of acrylic acid or methacrylic acid and alkali metal salt of allyl or methallylsulfonic acid used in the present invention may be one obtained by copolymerizing these monomers by a conventional method.
これらは通常、水溶性重合開始剤（例えば、過硫酸アン
モニウム、過硫酸カリウム等の過硫酸塩、Ｈ２０□−第
１鉄塩の如きレドックス系重合開始剤、２．２′−アゾ
ビス（２−アミジノプロパン）２塩酸塩 ２ 、２／−
アゾビス（Ｎ、Ｎ’−ノメチレンイソブチルアミノン）
２塩酸塩等の水溶性アゾ重合開始剤等）を用い、所要量
のアクリル酸又はメタクリル酸とアリルスルホン酸アル
カリ金属塩又はメタリルスルホン酸アルカリ金属塩とを
水溶媒中で重合反応させることにより容易に得られる。These are usually water-soluble polymerization initiators (for example, persulfates such as ammonium persulfate and potassium persulfate, redox polymerization initiators such as H20□-ferrous salts, 2,2'-azobis(2-amidinopropane) ) dihydrochloride 2,2/-
Azobis (N,N'-nomethyleneisobutylaminone)
By polymerizing the required amount of acrylic acid or methacrylic acid and an alkali metal salt of allylsulfonate or an alkali metal salt of methallylsulfonate in an aqueous solvent using a water-soluble azo polymerization initiator such as dihydrochloride, etc. easily obtained.
アクリル酸又はメタクリル酸とアリル又はメタリルスル
ホン酸アルカリ金属塩との使用割合は任意であり、特に
制約はないが、重量比で約１：１前後が、特に好ましく
用いられる。The ratio of acrylic acid or methacrylic acid and alkali metal salt of allyl or methallylsulfonic acid to be used is arbitrary and not particularly limited, but a weight ratio of about 1:1 is particularly preferably used.
本発明で用いられる炭素数６以上の脂肪酸としては、例
えば、カプリル酸、２−エチルヘキサン酸、カプリン酸
、パルミチン酸、オレイン酸等が挙げられるが、中でも
分枝を有する２−エチルヘキサン酸が特に好ましく用い
られる。本発明に係る上記脂肪酸の使用量は、通常ポリ
マー１ｇ当り０．２〜０．５１が好ましく用いられる。Examples of fatty acids having 6 or more carbon atoms used in the present invention include caprylic acid, 2-ethylhexanoic acid, capric acid, palmitic acid, oleic acid, etc. Among them, 2-ethylhexanoic acid having branches is exemplified. It is particularly preferably used. The amount of the fatty acid used in the present invention is preferably 0.2 to 0.51 per gram of polymer.
また、本発明で用いられるアルミニウム塩としては、例
えば、硝酸アルミニウム、硫酸アルミニウム、塩化アル
ミニウム等水溶性の無機塩が好ましく挙げられるが、こ
れらに限定されるものではない。これらアルミニウム塩
の使用量は、通常ポリマーＩＩ当りＡｔイオンとして０
．０３〜０．０７１である。Further, as the aluminum salt used in the present invention, for example, water-soluble inorganic salts such as aluminum nitrate, aluminum sulfate, and aluminum chloride are preferably mentioned, but the salt is not limited to these. The amount of these aluminum salts used is usually 0 as At ion per polymer II.
．． 03 to 0.071.
本発明に於てスルホン酸基を４級アンモニウム塩化する
目的で用いられる第４級アンモニウム塩としては、例え
ばジステアリルジメチルアンモニウムクロライＰが代表
的なものとして挙げられるが、特にこれに限定されるも
のではない。これら第４級アンモニウム塩の使用量につ
いては特に限定されないが、通常はアリル又はメタリル
スルホン酸アルカリ金属塩のモル数よりも多く用いられ
る。In the present invention, the quaternary ammonium salt used for the purpose of converting a sulfonic acid group into a quaternary ammonium salt includes, for example, distearyldimethylammonium chloride P, but is not particularly limited thereto. It's not a thing. Although the amount of these quaternary ammonium salts to be used is not particularly limited, it is usually used in an amount larger than the number of moles of the alkali metal salt of allyl or methallyl sulfonate.
本発明の油系増粘剤を得るには、例えば、常法により得
られたアクリル酸又はメタクリル酸とアリル又はメタリ
ルスルホン酸アルカリ金属塩との共重合体の重合液に、
要すれば水を追加した後、炭素数６以上の脂肪酸、例え
ば２−エチルヘキサン酸等を加え、更にこれにアルカリ
金属の水酸化物又は炭酸塩等を加えて共重合体及び脂肪
酸を共にアルカリ金属塩とし、然る後これにアルミニウ
ム塩、例えば硝酸アルミニウム等を加えて反応させれば
アルミニウム架橋体が得られる。次いで、このアルミニ
ウム架橋体のスルホン酸基を常法によりアルカリ金属塩
とした後、第４級アンモニウム塩と反応させれば、架橋
共重合体のスルホン酸基が４級アンモニウム塩化される
から、これを常法により単離し、乾燥すれば目的とする
増粘剤が得られる。To obtain the oil-based thickener of the present invention, for example, a polymer solution of a copolymer of acrylic acid or methacrylic acid and an alkali metal salt of allyl or methallylsulfonic acid obtained by a conventional method is added.
After adding water if necessary, add a fatty acid having 6 or more carbon atoms, such as 2-ethylhexanoic acid, and further add an alkali metal hydroxide or carbonate to this to make both the copolymer and the fatty acid alkali. A crosslinked aluminum product can be obtained by forming a metal salt, and then adding an aluminum salt, such as aluminum nitrate, to the metal salt and reacting it. Next, the sulfonic acid group of this crosslinked aluminum product is converted into an alkali metal salt by a conventional method and then reacted with a quaternary ammonium salt. The target thickener can be obtained by isolating and drying by a conventional method.
得られた本発明前系増粘剤は、石油系炭化水素を容易に
増粘、ケ°ル化することができ、増粘液は特に透明性に
優れている。The obtained thickener according to the present invention can easily thicken and kelize petroleum-based hydrocarbons, and the thickened liquid has particularly excellent transparency.
以下に実施例を示す。Examples are shown below.
実施例１
アクリル酸３０！ｊ、アリルスルホン酸ナトリウム塩３
０．９を水１４０ｍ／に溶解し、これに過硫酸アンモニ
ウム０．０６．９を添加して５０℃で４時間重合反応さ
せた。重合反応終了後、重合液６．７９をとり、これに
水５０ｍ１を加え、界面活性剤ツイーン２０を２滴添加
後、２−エチルへキサン酸０５ｍ１１及び１０％水酸化
す） ＩＪウム水溶液５ ｍｌを加え、次いで硝酸アル
ミニウム水溶Ｗ （Ａｔ（Ｎｏ３）３・９Ｈ２０ＬＯｆ
ｌ／水３Ｑｍｇ）を加えた。得られた沈殿を１０％水酸
化ナトリウム水溶液６．５ ｍｅに溶解し、ジステアリ
ルジメチルアンモニウムクロライドのメタノール溶液（
５，！７／６ｍｇ）を加えて一夜放置後、目的のコポリ
マーを分離し、乾燥した。このコポリマー〇、８Ｉをヘ
キサン２０ｒｎｌに溶解させると、液は透明に増粘した
。温度１５〜２０℃に於て、Ｂ型粘度計を用いて粘度を
測定したところ、粘度１０００ ｃｐｓを示した。ヘキ
サンをアイソ／４’ −Ｇ（エッソ社ｉｒ’：ｃＩｊｌ
：Ｉ ミネラルスピリット）に代え、コポリマー１．
０．９をアイツノＪ？−Ｇ２Ｑ７に溶解させると、液は
グル化した。シクロヘキサンでも同様の結果が得られた
。Example 1 Acrylic acid 30! j, allylsulfonic acid sodium salt 3
0.9 was dissolved in 140 m/ml of water, and ammonium persulfate 0.06.9 was added thereto, followed by a polymerization reaction at 50° C. for 4 hours. After the completion of the polymerization reaction, take 6.79 g of polymerization solution, add 50 ml of water to it, add 2 drops of surfactant Tween 20, and add 0.5 ml of 2-ethylhexanoic acid and 10% hydroxide) 5 ml of IJium aqueous solution. was added, and then aluminum nitrate aqueous solution W (At(No3)3.9H20LOof
l/3 Qmg of water) was added. The obtained precipitate was dissolved in 6.5 me of a 10% aqueous sodium hydroxide solution, and a methanol solution of distearyldimethylammonium chloride (
5,! After adding 7/6 mg) and leaving it overnight, the desired copolymer was separated and dried. When this copolymer 〇, 8I was dissolved in 20 rnl of hexane, the liquid became clear and thickened. When the viscosity was measured using a B-type viscometer at a temperature of 15 to 20°C, the viscosity was 1000 cps. Hexane iso/4'-G (Esso ir': cIjl
:I mineral spirit), copolymer 1.
0.9 Aitsuno J? - When dissolved in G2Q7, the liquid was glued. Similar results were obtained with cyclohexane.
実施例２
実施例１に於けるアクリル酸をメタクリル酸に、また、
アリルスルホン酸ナトリウム塩をメタリルスルホン酸ナ
トリウム塩に代えて実施例１と同様に重合反応し、処理
してコーリマーを得た。このコポリマーは実施例１のコ
ポリマー同様、ヘキサンを増粘し、またアイツノや−Ｇ
をグル化させた。Example 2 The acrylic acid in Example 1 was replaced with methacrylic acid, and
A polymerization reaction was carried out in the same manner as in Example 1 except that allylsulfonic acid sodium salt was replaced with methallylsulfonic acid sodium salt, and a colimer was obtained by treatment. This copolymer, like the copolymer of Example 1, thickens hexane and also
grouped.
本発明は、新規な油系増粘剤を提供するものであり、本
発明の増粘剤は、製造が容易で、特に石油系炭化水素を
容易に増粘、グル化し得る点に顕著な効果を奏するもの
である。The present invention provides a novel oil-based thickener, and the thickener of the present invention is easy to manufacture and has remarkable effects, particularly in that it can easily thicken and glue petroleum-based hydrocarbons. It is something that plays.
Claims (1)
リルスルホン酸アルカリ金属塩との共重合体のカルボキ
シル基を炭素数６以上の脂肪酸及びアルミニウム塩で架
橋し、且つスルホン酸基を四級アンモニウム塩化して成
る油系増粘剤。(1) The carboxyl group of the copolymer of acrylic acid or methacrylic acid and allyl or methallyl sulfonic acid alkali metal salt is crosslinked with a fatty acid having 6 or more carbon atoms and an aluminum salt, and the sulfonic acid group is converted into a quaternary ammonium salt. An oil-based thickener made of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104198A JPS62262735A (en) | 1986-05-06 | 1986-05-06 | Novel oily thickener |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104198A JPS62262735A (en) | 1986-05-06 | 1986-05-06 | Novel oily thickener |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62262735A true JPS62262735A (en) | 1987-11-14 |
Family
ID=14374278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61104198A Pending JPS62262735A (en) | 1986-05-06 | 1986-05-06 | Novel oily thickener |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62262735A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057745A1 (en) | 2001-12-27 | 2003-07-17 | Sanyo Chemical Industries, Ltd. | Non-aqueous absorbent and use thereof |
| WO2005121270A1 (en) * | 2004-06-08 | 2005-12-22 | Toagosei Co., Ltd. | Aqueous thickener and bleaching detergent |
| JP2008001762A (en) * | 2006-06-21 | 2008-01-10 | Sanyo Chem Ind Ltd | Non-aqueous electrically responsive gel and method for feeding non-aqueous liquid |
| WO2019044327A1 (en) * | 2017-08-28 | 2019-03-07 | 株式会社 資生堂 | Thickener for non-aqueous systems, and thickener composition |
-
1986
- 1986-05-06 JP JP61104198A patent/JPS62262735A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057745A1 (en) | 2001-12-27 | 2003-07-17 | Sanyo Chemical Industries, Ltd. | Non-aqueous absorbent and use thereof |
| CN1302021C (en) * | 2001-12-27 | 2007-02-28 | 三洋化成工业株式会社 | Non-aqueous absorbent and use thereof |
| US7470738B2 (en) | 2001-12-27 | 2008-12-30 | Sanyo Chemical Industries, Ltd. | Non-aqueous absorbent and use thereof |
| WO2005121270A1 (en) * | 2004-06-08 | 2005-12-22 | Toagosei Co., Ltd. | Aqueous thickener and bleaching detergent |
| JPWO2005121270A1 (en) * | 2004-06-08 | 2008-04-10 | 東亞合成株式会社 | Water-soluble thickener and bleach cleaner |
| JP4577308B2 (en) * | 2004-06-08 | 2010-11-10 | 東亞合成株式会社 | Water-soluble thickener and bleach cleaner |
| JP2008001762A (en) * | 2006-06-21 | 2008-01-10 | Sanyo Chem Ind Ltd | Non-aqueous electrically responsive gel and method for feeding non-aqueous liquid |
| WO2019044327A1 (en) * | 2017-08-28 | 2019-03-07 | 株式会社 資生堂 | Thickener for non-aqueous systems, and thickener composition |
| CN111032815A (en) * | 2017-08-28 | 2020-04-17 | 株式会社资生堂 | Nonaqueous thickener and thickening composition |
| JPWO2019044327A1 (en) * | 2017-08-28 | 2020-10-15 | 株式会社 資生堂 | Non-aqueous thickeners and thickening compositions |
| CN111032815B (en) * | 2017-08-28 | 2023-06-20 | 株式会社资生堂 | Thickening agent for nonaqueous system and thickening composition |
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