JPH0441718B2 - - Google Patents
Info
- Publication number
- JPH0441718B2 JPH0441718B2 JP62112192A JP11219287A JPH0441718B2 JP H0441718 B2 JPH0441718 B2 JP H0441718B2 JP 62112192 A JP62112192 A JP 62112192A JP 11219287 A JP11219287 A JP 11219287A JP H0441718 B2 JPH0441718 B2 JP H0441718B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- composition
- group
- tertiary amine
- 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
- 239000000203 mixture Substances 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- -1 polyoxyethylene Polymers 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 19
- 239000003945 anionic surfactant Substances 0.000 claims description 17
- 239000003599 detergent Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 238000005187 foaming Methods 0.000 description 21
- 150000003512 tertiary amines Chemical class 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007794 irritation Effects 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940031957 lauric acid diethanolamide Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000000691 measurement method Methods 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
- 238000010899 nucleation Methods 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
〔産業上の利用分野〕
本発明は組成物のPHが4.0〜6.0である弱酸性の
透明液体洗浄剤組成物、更に詳細には、優れた洗
浄力、豊かな起泡力を有し、かつ低温安定性に優
れた透明液体洗浄剤組成物に関するものである。
〔従来の技術〕
液体洗浄剤、例えば食器用液体洗浄剤は洗浄
力、起泡力、皮膚温和性、低温安定性等の諸性能
に優れていることが要求される。これらの諸性能
を発揮させる為、液体洗浄剤は、ポリオキシエチ
レンアルキルエーテル硫酸塩、アルキルベンゼン
スルホン酸塩の陰イオン性界面活性剤を主洗浄基
剤とし、この他に第３級アミンオキサイド、高級
脂肪酸アルカノールアミド等の補助界面活性剤が
併用されている。
例えば、ポリオキシエチレンアルキルエーテル
硫酸塩は皮膚温和性に優れた洗浄基剤であり為広
汎に利用されているが、刺激性を減少させる為ア
ルキレンオキサイド付加モル数を多くすると洗浄
力及び起泡力が低下する。この欠点を改良する
為、第３級アミンオキサイドを併用することによ
り皮膚刺激性を抑えながら洗浄力、起泡力を向上
させるという方法が、特開昭38−3264号公報や特
公昭38−17467号公報に開示されている。
〔発明が解決しようとする問題点〕
補助界面活性剤としての第３級アミンオキサイ
ドの添加効果は、その水溶液中で溶解挙動に起因
するものと考えられる。即ち第３級アミンオキサ
イドは水溶液中で下記の如き解離平衡にあり、
アルカリ側では非イオン性界面活性剤として、酸
側では陽イオン性界面活性剤としての挙動をとる
ことが知られている。
さらに、陰イオン性界面活性剤、例えばポリオ
キシエチレンアルキルエーテル硫酸塩との共存系
では下記の如き分子会合体を形成し活性剤イオン
の電荷を中和する。
この為ミセルを形成する活性剤分子間の電気的
反発力が減少しミセルを形成し易くなり、cmcは
減少し、会合数は増大する。この結果、より低濃
度で泡立つようになり、油性物質の可溶化量が増
大し、洗浄力は増大する。
上記のような第３級アミンオキサイドの性質を
考慮すれば、洗浄剤組成物のPHを酸性領域に調整
することにより、第３級アミンオキサイドと陰イ
オン性界面活性剤との分子会合体の形成は促進さ
れ、より有効に性能向上に寄与することが容易に
推察される。
しかしながら酸性領域においては、強固な分子
会合体の形成の為、著しい増粘が見られ、クラフ
ト点が上昇し低温安定性が悪化する。また系その
ものが疎水的になりすぎる為、油性汚れに対する
洗浄力は増大するが、逆に起泡力は著しく減少し
商品としての価値を損なう結果となる。
一般に、液体洗浄剤組成物は、容器からの出し
やすさを考慮して粘度を100〜500cp程度に調整
する必要があり、又冬季の溶液安定性の目安とし
て、−５℃程度までは外観変化しないことが要求
される。この目的の為、エタノール等の低級アル
コール類、ｐ−トリエンスルホン酸塩等の低級ア
ルキルベンゼンスルホン酸塩、エチレングリコー
ル、プロピレングリコール等のグリコール類、尿
素等が単独あるいは組み合わせて使用されてい
る。しかしながら、これらのハイドロトロープ剤
は上記の様な弱酸性の配合系においては効果が小
さく、多量に配合する必要があり不経済であつた
り、高温で保存した場合に分解し不快臭を発生し
たりする為必ずしも満足できるものではなかつ
た。又、たとえ減粘、低温安定化が達成されたと
しても、依然として起泡力の低下は免れ得なかつ
た。
〔問題点を解決するための手段〕
斯かる実状において、本発明者らは弱酸性領域
においても起泡力が減少せず、適度な粘度及び優
れた低温安定性を有する液体洗浄剤を得るべく鋭
意研究を行つた結果、陰イオン界面活性剤と第３
級アミンオキサイド及び高級脂肪酸アルカノール
アミドを併用した系において、特定の分子量を有
する、多価アルコールのポリプロピレンオキシド
付加物を添加すれば、適度な粘度を持ち、かつ低
温安定性に優れ、さらに驚くべきことに弱酸性に
おいて著しい増泡効果を発揮し、豊かな泡立ちを
付与しうることを見出し、本発明を完成した。
すなわち本発明は次の４成分(a)、(b)、(c)及び(d)
(a) ポリオキシエチレンアルキルエーテル硫酸
塩、アルキルベンゼンスルホン酸塩、α−オレ
フインスルホン酸塩及びアルカンスルホン酸塩
からなる群より選ばれる１種又は２種以上の陰
イオン性界面活性剤５〜25重量％
(b) モノ直鎖アルキル第３級アミンオキサイド１
〜10重量％
(c) 高級脂肪酸アルカノールアミド１〜15重量％
(d) 平均分子量が300〜4000のエチレングリコー
ル，グリセリン，トリメチロールプロパン，ペ
ンタエリスリトール又はソビトールのポリプロ
ピレンオキシド付加物0.5〜10重量％
を含有し、(a)成分と(b)成分のモル比〔(b)／(a)〕が
0.2〜１であり、かつ組成物のPHが4.0〜6.0である
ことを特徴とする透明液体洗浄剤組成物を提供す
るものである。
(a)成分として用いる陰イオン性界面活性剤はポ
リオキシエチレンアルキルエーテル硫酸塩、アル
キルベンゼンスルホン酸塩及びアルカンスルホン
酸塩からなる群より選ばれる１種又は２種以上の
陰イオン性界面活性剤の何れでも使用できるが、
手肌に対しマイルドな点で次の一般式（）
R1O（CH2CH2O）oSO3M （）
（式中、R1は炭素数９〜15の直鎖状もしくは分
岐状アルキル基又はアルケニル基を示し、ｎは平
均で0.5〜７の実数、Ｍはアルカリ金属、アルカ
リ土類金属、アンモニウム基又はアルカノール置
換アンモニウム基を示す）
で表わされるポリオキシエチレンアルキルエーテ
ル硫酸塩が好ましい。このR1の炭素数が９未満
では洗浄性能が不十分であり、16以上では組成物
の低温安定性が著しく悪化する為好ましくない。
特に好ましい炭素数は10〜13の範囲である。又
（）式中のエチレンオキサイド付加モリ数ｎは、
0.5未満では手肌に対する刺激性を増加させる為
好ましくなく、８以上では洗浄性能が著しく悪化
する為好ましくない。特に好ましいエチレンオキ
サイドの付加モル数の範囲は２〜5.5である。
本発明に於ける前記(a)成分の含有量は５〜25重
量％の範囲であつて、この含有が５重量％未満で
は洗浄力、起泡力が不十分であり、又25重量％を
超えると組成物の安定性が悪くなる。特に好まし
い含有量は10〜20重量％の範囲である。
本発明の組成物において(b)成分として用いられ
るモノ直鎖第３級アミンオキサイドは次の一般式
（）
（式中、R2は炭素数10〜16の直鎖状もしくは分
岐状アルキル基又はアルケニル基を示し、R3R4
メチル基又はエチル基を示す）で表されるモノ直
鎖第３級アミンオキサイドが好ましい。R2の炭
素数が10未満では組成物の洗浄性能が低く、16を
超えると低温安定性が著しく悪化する為好ましく
ない。このモノ直鎖第３級アミンオキサイドは洗
浄剤組成物中に１〜10重量％含有することが必要
であり、含有量が前記範囲を逸脱すると、(a)成分
との組合せに於いて洗浄力が低くなるか又は安定
性が損なわれる。
本発明の組成物において(c)成分として用いられ
る高級脂肪酸アルカノールアミドは、炭素数10〜
18の飽和あるいは不飽和の脂肪酸の１種又は２種
以上の混合物と、アルカノールアミンより合成さ
れたものが好ましく、このようなものとしては、
例えばヤシ油脂肪酸ジエタノールアミドが挙げら
れる。
高級脂肪酸アルカノールアミド（例えば、ラウ
リン酸ジエタノールアミドについて記す）は次の
ような共鳴構造をとると考られる。
この為、陰イオン性界面活性剤と静電的にゆる
く結合する性質がある。この相互作用は陰イオン
性界面活性剤と第３級アミンオキサイドの相互作
用程強くはなく、第３級アミンオキサイドのよう
に酸性領域で組成物の低温安定性を悪化させるこ
とはない。
高級脂肪酸アルカノールアミドを、陰イオン性
界面活性剤及び第３級アミンオキサイドと併用す
ると、陰イオン性界面活性剤と第３級アミンオキ
サイドの分子会合体形成を抑制する働きがあり、
陰イオン性界面活性剤と第３級アミンオキサイド
のみの組成物に比べ安定性が向上する。この為、
高級脂肪酸アルカノールアミドの含有量は１〜15
重量％、特に２〜８重量の範囲が好ましい。１重
量％未満では上記の効果が不十分であり、15重量
％を超えると逆に安定性を悪化させる。
本発明の組成物における(d)成分は、エチレング
リコール，グリセリン，トリメチロールプロパ
ン，ペンタエリスリトール又はソルビトールのポ
リプロピレンオキサイド付加物である。この中で
エチレングリコール又はグリセリンのポリプロピ
レンオキサイド付加物が特に望ましい。これらの
(d)成分は単独で又は２種以上を混合して用いられ
る。(d)成分は陰イオン性界面活性剤と第３級アミ
ンオキサイドを含有する弱酸性の洗浄剤組成物中
に、高級脂肪酸アルカノールアミドと共に添加す
ると著しい減粘・低温安定性向上効果、及び優れ
た増泡効果を発揮するが、効果発現の為には、多
価アルコールのポリプロピレンオキサイド付加物
の分子量が300〜4000、好ましくは500〜2000の範
囲内である必要があり、この範囲を逸脱した場合
には減粘・低温安定性向上効果は小さく、増泡効
果も発現しない。(d)成分は組成物中に0.5〜10重
量％、好ましくは２〜５重量％配合される。
本発明の組成物において、(a)成分である陰イオ
ン性界面活性剤と(b)成分である第３級アミンオキ
サイドは、前記の如く強固な分子会合体を形成す
る。この為、組成物中での(a)成分と(b)成分の混合
比率は組成物の洗浄性能に多大な影響を及ぼす。
本発明においては(a)成分と(b)成分の比率はモル
〔(b)／(a)〕で0.2〜１、特に0.3〜0.5であることが
好ましい。モル比が0.2未満であると、酸性領域
においても十分な洗浄性能が得られず、又１を超
える場合には、著しく低温安定性が悪化し、又組
成物中で陰イオン性界面活性剤と会合体を形成し
ないフリーな第３級アミンオキサイド分子が増
え、酸性領域でカチオン化する為、手肌に対する
刺激性が増大する。
本発明の組成物のPHは4.0〜6.0であり、PH4.0未
満では低温安定性も悪化し、手肌に対する刺激性
も増大する。又PH6.5を越える場合には洗浄力が
不十分である。
又、本発明の組成物は、泡立ちが研磨剤等の水
不溶性物質により阻害される為、これらを含むも
のであつてはならない。
本発明の組成物には、上記必須成分の他に、目
的とする性能を損じない範囲で必要に応じて公知
の液体洗浄剤用の界面活性剤を配合することがで
きる。斯かる界面活性剤としては、例えばポリオ
キシエチレン（平均付加モル数４〜20）アルキル
（C7〜C18の直鎖又は分岐）エーテル等の非イオン
性界面活性剤，アルキルベタイン等の両性界面活
性剤，α−スルホ脂肪酸エステル塩，Ｎ−アシル
グルタミン酸塩，モノアルキルリン酸塩等の陰イ
オン性界面活性が挙げられる。
さらに通常の液体洗浄剤組成物に用いられてい
る他の任意成分、例えば、エタノール等の低級ア
ルコール類，ｐ−トルエンスルホン酸塩等の低級
アルキルベンゼンスルホン酸塩，エチレングリコ
ール，プロピレングリコール等のグリコール類、
尿素等のハイドロトロープ剤，クエン酸，リンゴ
酸等のPH緩衝剤，有機又は無機ビルダー類、さら
に手荒れ防止剤，酵素，蛋白質誘導体，着色料、
香料，保存料などを配合することができる。
〔発明の効果〕
本発明の透明液体洗浄剤組成物は、優れた洗浄
力と豊かな起泡力を有し、適度な粘度を有し、低
温安定性に優れたものである。従つて台所用洗浄
剤、特に食器用洗浄剤として有用である。
〔実施例〕
次に、実施例によつて本発明をさらに詳細に説
明するが、本発明はこれらの実施例によつて限定
されるものではない。
実施例 １
表−１に示す組成物を調製し、各組成物の洗浄
力、起泡力、粘度、低温安定性を調べた。各例中
に於ける洗浄組成物の加種性能の測定及び評価は
次のようにして行つた。
＜試験法＞
（洗浄力）
牛脂に指示薬としてスダン（赤色色素）を
0.1重量％添加し、この５ｇを磁性の皿（直径25
cm）に塗布したものを洗剤、水をしみこませたス
ポンジでこすり洗いし、もはや皿より牛脂が清浄
にとれなくなるまでの洗浄された皿の枚数をもつ
て示す。
（起泡力）
汚れ成分として市販のバターを洗剤濃度0.5重
量％の洗剤溶液に0.1重量％添加したときの起泡
力を測定する。測定法は直径５cmのガラス円筒に
バターを添加した上記洗剤溶液を入れ、５分間回
転撹拌を行い、停止後の泡高を測定する。
（粘度）
各組成物を20℃に保つた粘度ビーカーに入れ、
Ｂ型粘度計（ローターNo.３、2000cpを超えると
きはローターNo.４；回転数60rpm）を用いて測定
する。
（低温安定性）
−５℃の恒温室に10日間試料を保存後評価す
る。
評価内容
○：変化なし
△：やや白濁
×：分離もしくは沈澱
実施例 ２
表−２に示す組成物を調製し、各組成物の洗浄
力、起泡力、粘度、低温安定性を調べた。
実施例 ３
表−３に示す組成物を調製し、各組成物の洗浄
力、起泡力、粘度、低温安定性を調べた。
[Industrial Application Field] The present invention relates to a weakly acidic transparent liquid cleaning composition having a pH of 4.0 to 6.0, more specifically, a composition having excellent cleaning power, rich foaming power, and The present invention relates to a transparent liquid detergent composition with excellent low-temperature stability. [Prior Art] Liquid detergents, such as liquid dishwashing detergents, are required to have excellent performance such as detergency, foaming power, skin gentleness, and low-temperature stability. In order to exhibit these various properties, the liquid cleaning agent uses anionic surfactants such as polyoxyethylene alkyl ether sulfate and alkylbenzene sulfonate as the main cleaning base, and also contains tertiary amine oxide, high grade Co-surfactants such as fatty acid alkanolamides are used in combination. For example, polyoxyethylene alkyl ether sulfate is a cleansing base with excellent skin gentleness and is therefore widely used, but in order to reduce irritation, increasing the number of moles of alkylene oxide added increases detergency and foaming power. decreases. In order to improve this drawback, a method of improving detergency and foaming power while suppressing skin irritation by using tertiary amine oxide in combination has been proposed in Japanese Patent Application Laid-open No. 38-3264 and Japanese Patent Publication No. 38-17467. It is disclosed in the publication No. [Problems to be Solved by the Invention] The effect of adding tertiary amine oxide as a co-surfactant is thought to be due to its dissolution behavior in an aqueous solution. That is, tertiary amine oxide is in the following dissociation equilibrium in an aqueous solution, It is known that it behaves as a nonionic surfactant on the alkaline side and as a cationic surfactant on the acid side. Furthermore, in a coexisting system with an anionic surfactant such as polyoxyethylene alkyl ether sulfate, the following molecular associations are formed to neutralize the charge of the surfactant ions. For this reason, the electrical repulsion between active agent molecules that form micelles decreases, making it easier to form micelles, decreasing cmc and increasing the number of associations. As a result, foaming occurs at a lower concentration, the amount of oily substances solubilized increases, and the cleaning power increases. Considering the properties of tertiary amine oxide as described above, by adjusting the pH of the cleaning composition to an acidic range, it is possible to form a molecular association between the tertiary amine oxide and the anionic surfactant. It can be easily inferred that this facilitates the improvement of performance and contributes more effectively to performance improvement. However, in an acidic region, due to the formation of strong molecular aggregates, significant thickening is observed, the Krafft point increases, and low temperature stability deteriorates. Furthermore, since the system itself becomes too hydrophobic, the detergency against oily stains increases, but on the contrary, the foaming power decreases significantly, resulting in a loss of value as a product. Generally, the viscosity of liquid cleaning compositions needs to be adjusted to about 100 to 500 cp to make it easier to take them out of the container, and as a guideline for solution stability in winter, the appearance will change up to about -5℃. required not to do so. For this purpose, lower alcohols such as ethanol, lower alkylbenzenesulfonates such as p-trienesulfonates, glycols such as ethylene glycol and propylene glycol, urea, etc. are used alone or in combination. However, these hydrotropes have little effect in weakly acidic formulation systems such as those mentioned above, are uneconomical as they must be formulated in large quantities, and may decompose and produce unpleasant odors when stored at high temperatures. However, it was not always satisfactory. Moreover, even if viscosity reduction and low-temperature stabilization were achieved, the foaming power still inevitably deteriorated. [Means for Solving the Problems] Under these circumstances, the present inventors aimed to obtain a liquid detergent that does not reduce its foaming power even in a weakly acidic region, has a suitable viscosity, and has excellent low-temperature stability. As a result of intensive research, we found that anionic surfactants and
If a polypropylene oxide adduct of a polyhydric alcohol with a specific molecular weight is added to a system that uses a lower amine oxide and a higher fatty acid alkanolamide in combination, it will have an appropriate viscosity and excellent low temperature stability, which is even more surprising. The present invention was completed based on the discovery that the foam exhibits a remarkable foaming effect in weakly acidic conditions and can provide rich foaming. That is, the present invention comprises the following four components (a), (b), (c) and (d) (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkanesulfonate. 5 to 25% by weight of one or more anionic surfactants selected from the group consisting of (b) monolinear alkyl tertiary amine oxide 1
-10% by weight (c) 1-15% by weight of higher fatty acid alkanolamide (d) 0.5-10% by weight of polypropylene oxide adducts of ethylene glycol, glycerin, trimethylolpropane, pentaerythritol or sobitol with an average molecular weight of 300-4000. The molar ratio of component (a) and component (b) [(b)/(a)] is
0.2 to 1, and the composition has a pH of 4.0 to 6.0. The anionic surfactant used as component (a) is one or more anionic surfactants selected from the group consisting of polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, and alkanesulfonates. You can use either, but
The following general formula () R 1 O (CH 2 CH 2 O) o SO 3 M () (in the formula, R 1 is a linear or branched alkyl having 9 to 15 carbon atoms) is mild to the skin of hands. polyoxyethylene alkyl ether sulfate is preferred. If the number of carbon atoms in R 1 is less than 9, the cleaning performance will be insufficient, and if it is 16 or more, the low temperature stability of the composition will be significantly deteriorated, which is not preferable.
The particularly preferred number of carbon atoms is in the range of 10 to 13. In addition, the number n of ethylene oxide added in the formula () is:
A value of less than 0.5 is undesirable because it increases the irritation to hand skin, and a value of 8 or more is unfavorable because the cleaning performance deteriorates significantly. A particularly preferred range of the number of moles of ethylene oxide added is 2 to 5.5. The content of component (a) in the present invention is in the range of 5 to 25% by weight, and if the content is less than 5% by weight, the cleaning power and foaming power will be insufficient, and if the content is less than 5% by weight, the detergency and foaming power will be insufficient. If the amount is exceeded, the stability of the composition will deteriorate. A particularly preferred content is in the range of 10 to 20% by weight. The monolinear tertiary amine oxide used as component (b) in the composition of the present invention has the following general formula () (In the formula, R 2 represents a linear or branched alkyl group or alkenyl group having 10 to 16 carbon atoms, and R 3 R 4
A monolinear tertiary amine oxide represented by a methyl group or an ethyl group is preferred. If the number of carbon atoms in R 2 is less than 10, the cleaning performance of the composition will be low, and if it exceeds 16, the low temperature stability will be significantly deteriorated, which is not preferable. This monolinear tertiary amine oxide must be contained in the cleaning composition in an amount of 1 to 10% by weight, and if the content deviates from the above range, the cleaning power in combination with component (a) will decrease. or stability is impaired. The higher fatty acid alkanolamide used as component (c) in the composition of the present invention has 10 to 10 carbon atoms.
Preferably, those synthesized from one or a mixture of two or more of the 18 saturated or unsaturated fatty acids and alkanolamines, such as:
For example, coconut oil fatty acid diethanolamide can be mentioned. Higher fatty acid alkanolamides (for example, lauric acid diethanolamide) are thought to have the following resonance structure. For this reason, it has the property of being electrostatically and loosely bonded to anionic surfactants. This interaction is not as strong as the interaction between anionic surfactants and tertiary amine oxides, and unlike tertiary amine oxides, does not deteriorate the low temperature stability of the composition in an acidic region. When higher fatty acid alkanolamide is used in combination with an anionic surfactant and tertiary amine oxide, it has the effect of suppressing the formation of molecular aggregates between the anionic surfactant and tertiary amine oxide.
Stability is improved compared to a composition containing only an anionic surfactant and tertiary amine oxide. For this reason,
The content of higher fatty acid alkanolamide is 1 to 15
% by weight, especially in the range from 2 to 8 weight % is preferred. If it is less than 1% by weight, the above effects are insufficient, and if it exceeds 15% by weight, the stability will be adversely affected. Component (d) in the composition of the present invention is a polypropylene oxide adduct of ethylene glycol, glycerin, trimethylolpropane, pentaerythritol or sorbitol. Among these, polypropylene oxide adducts of ethylene glycol or glycerin are particularly desirable. these
Component (d) may be used alone or in combination of two or more. When component (d) is added to a weakly acidic detergent composition containing an anionic surfactant and a tertiary amine oxide together with a higher fatty acid alkanolamide, it has a remarkable effect of reducing viscosity and improving low-temperature stability. It exhibits a foaming effect, but in order to exhibit the effect, the molecular weight of the polypropylene oxide adduct of polyhydric alcohol must be within the range of 300 to 4000, preferably 500 to 2000, and if it deviates from this range The effect of reducing viscosity and improving low-temperature stability is small, and the foaming effect does not appear. Component (d) is blended in the composition in an amount of 0.5 to 10% by weight, preferably 2 to 5% by weight. In the composition of the present invention, the anionic surfactant as component (a) and the tertiary amine oxide as component (b) form a strong molecular association as described above. Therefore, the mixing ratio of component (a) and component (b) in the composition has a great influence on the cleaning performance of the composition.
In the present invention, the ratio of component (a) to component (b) is preferably 0.2 to 1, particularly 0.3 to 0.5 in molar terms [(b)/(a)]. If the molar ratio is less than 0.2, sufficient cleaning performance cannot be obtained even in an acidic region, and if it exceeds 1, the low temperature stability will be significantly deteriorated, and the anionic surfactant may not be present in the composition. Free tertiary amine oxide molecules that do not form aggregates increase and become cationized in the acidic region, resulting in increased irritation to hand skin. The PH of the composition of the present invention is 4.0 to 6.0, and if the PH is less than 4.0, the low temperature stability deteriorates and the irritation to hand skin increases. Also, if the pH exceeds 6.5, the cleaning power will be insufficient. Furthermore, the composition of the present invention must not contain water-insoluble substances such as abrasives, since foaming is inhibited by these substances. In addition to the above-mentioned essential components, the composition of the present invention may optionally contain a known surfactant for liquid detergents within a range that does not impair the desired performance. Such surfactants include, for example, nonionic surfactants such as polyoxyethylene (average number of added moles of 4 to 20) alkyl (C 7 to C 18 linear or branched) ethers, amphoteric surfactants such as alkyl betaines, etc. Examples include activators, anionic surfactants such as α-sulfo fatty acid ester salts, N-acyl glutamates, and monoalkyl phosphates. Furthermore, other optional components used in ordinary liquid cleaning compositions, such as lower alcohols such as ethanol, lower alkylbenzenesulfonates such as p-toluenesulfonate, glycols such as ethylene glycol and propylene glycol, etc. ,
Hydrotropes such as urea, PH buffers such as citric acid and malic acid, organic or inorganic builders, agents to prevent rough hands, enzymes, protein derivatives, colorants,
Flavoring agents, preservatives, etc. can be added. [Effects of the Invention] The transparent liquid detergent composition of the present invention has excellent detergency and rich foaming power, moderate viscosity, and excellent low-temperature stability. Therefore, it is useful as a kitchen cleaner, especially as a dishwasher. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Compositions shown in Table 1 were prepared, and the detergency, foaming power, viscosity, and low-temperature stability of each composition were examined. The seeding performance of the cleaning compositions in each example was measured and evaluated as follows. <Test method> (Cleaning power) Sudan (red pigment) is added to beef tallow as an indicator.
0.1% by weight was added, and 5g of this was placed in a magnetic dish (diameter 25
cm) is scrubbed with a sponge soaked in detergent and water, and the number of dishes that have been cleaned is shown as the number of dishes that have been cleaned until the tallow can no longer be removed cleanly from the dishes. (Foaming power) The foaming power is measured when 0.1% by weight of commercially available butter is added as a staining ingredient to a detergent solution with a detergent concentration of 0.5% by weight. The measurement method is to put the above detergent solution to which butter has been added into a glass cylinder with a diameter of 5 cm, rotate and stir for 5 minutes, and measure the foam height after stopping. (Viscosity) Put each composition into a viscosity beaker kept at 20℃,
Measure using a B-type viscometer (rotor No. 3; if it exceeds 2000 cp, rotor No. 4; rotation speed 60 rpm). (Low temperature stability) Evaluate after storing the sample in a constant temperature room at -5°C for 10 days. Evaluation details ○: No change △: Slightly cloudy ×: Separation or precipitation Example 2 The compositions shown in Table 2 were prepared, and the detergency, foaming power, viscosity, and low-temperature stability of each composition were examined. Example 3 Compositions shown in Table 3 were prepared, and the detergency, foaming power, viscosity, and low-temperature stability of each composition were examined.
【表】
＊１ 数字は化合物の平均分子量を表す
＊２ エチレングリコールを出発原料とするPO付加物
[Table] *1 Number represents the average molecular weight of the compound *2 PO adduct using ethylene glycol as a starting material
【表】【table】
【表】
＊１ 数字は化合物の平均分子量を表す
＊２ エチレングリコールを出発原料とするPO付加物
[Table] *1 Number represents the average molecular weight of the compound *2 PO adduct using ethylene glycol as a starting material
【表】【table】
Claims (1)
塩、アルキルベンゼンスルホン酸塩、α−オレ
フインスルホン酸塩及びアルカンスルホン酸塩
からなる群より選ばれる１種又は２種以上の陰
イオン性界面活性剤 ５〜25重量％ (b) モノ直鎖アルキル第３級アミンオキサイド
１〜10重量％ (c) 高級脂肪酸アルカノールアミド １〜15重量
％ (d) 平均分子量が300〜4000のエチレングリコー
ル、グリセリン、トリメチロールプロパン、ペ
ンタエリスリトール又はソルビトールのポリプ
ロピレンオキシド付加物 0.5〜10％重量％を
含有し、(a)成分と(b)成分のモル比［(b)／(a)］が
0.2〜１であり、かつ組成物のPHが4.0〜6.0であ
ることを特徴とする透明液体洗浄剤組成物。 ２ (a)成分が次の一般式（） R1O（CH2CH2O）oSO3M （） （式中、R1は炭素数９〜15の直鎖状もしくは分
岐状アルキル基又はアルケニル基を示し、ｎは平
均で0.5〜７の実数、Ｍはアルカリ金属、アルカ
リ土類金属、アンモニウム基又はアルカノール置
換アモニウム基を示す） で表されるポリオキシエチレンアルキルエーテル
硫酸塩である特許請求の範囲第１項記載の透明液
体洗浄剤組成物。 ３ (d)成分がエチレングリコール又はグリセリン
のポリプロピレンオキシド付加物である特許請求
の範囲第１項記載の透明液体洗浄剤組成物。[Scope of Claims] 1. From the group consisting of the following four components (a) to (d): (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, and alkanesulfonate; One or more selected anionic surfactants 5-25% by weight (b) Monolinear alkyl tertiary amine oxide
1-10% by weight (c) Higher fatty acid alkanolamide 1-15% by weight (d) Polypropylene oxide adduct of ethylene glycol, glycerin, trimethylolpropane, pentaerythritol or sorbitol with an average molecular weight of 300-4000 0.5-10% by weight %, and the molar ratio of component (a) and component (b) [(b)/(a)] is
A transparent liquid detergent composition characterized in that the pH of the composition is 0.2 to 1 and the pH of the composition is 4.0 to 6.0. 2 (a) component has the following general formula () R 1 O (CH 2 CH 2 O) o SO 3 M () (wherein R 1 is a linear or branched alkyl group having 9 to 15 carbon atoms or a polyoxyethylene alkyl ether sulfate represented by alkenyl group, n is a real number of 0.5 to 7 on average, and M is an alkali metal, alkaline earth metal, ammonium group, or alkanol-substituted ammonium group) The transparent liquid cleaning composition according to item 1. 3. The transparent liquid detergent composition according to claim 1, wherein component (d) is a polypropylene oxide adduct of ethylene glycol or glycerin.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62112192A JPS63277300A (en) | 1987-05-08 | 1987-05-08 | Liquid detergent composition |
| GB8809175A GB2205578B (en) | 1987-05-08 | 1988-04-19 | Liquid detergent composition |
| MYPI88000471A MY103274A (en) | 1987-05-08 | 1988-05-05 | A liquid detergent composition |
| SG145/93A SG14593G (en) | 1987-05-08 | 1993-02-09 | Liquid detergent composition |
| HK404/93A HK40493A (en) | 1987-05-08 | 1993-04-29 | Liquid detergent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62112192A JPS63277300A (en) | 1987-05-08 | 1987-05-08 | Liquid detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63277300A JPS63277300A (en) | 1988-11-15 |
| JPH0441718B2 true JPH0441718B2 (en) | 1992-07-09 |
Family
ID=14580564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62112192A Granted JPS63277300A (en) | 1987-05-08 | 1987-05-08 | Liquid detergent composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS63277300A (en) |
| GB (1) | GB2205578B (en) |
| HK (1) | HK40493A (en) |
| MY (1) | MY103274A (en) |
| SG (1) | SG14593G (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY104998A (en) * | 1988-08-04 | 1994-07-30 | Kao Corp | Detergent composition |
| US5230835A (en) * | 1988-08-04 | 1993-07-27 | Kao Corporation | Mild non-irritating alkyl glycoside based detergent compositions |
| MY109460A (en) * | 1991-10-03 | 1997-01-31 | Kao Corp | Liquid detergent composition. |
| DE69320794T2 (en) * | 1992-02-19 | 1999-04-29 | The Procter & Gamble Co., Cincinnati, Ohio | AQUEOUS AQUEOUS DETERGENT COMPOSITIONS FOR HARD SURFACES |
| EP0623671A1 (en) * | 1993-05-06 | 1994-11-09 | The Procter & Gamble Company | Mixing order to prepare aqueous clear detergent compositions |
| ES2132631T5 (en) * | 1994-01-25 | 2011-02-17 | THE PROCTER & GAMBLE COMPANY | COMPOSITIONS OF LIQUID OR GELIFIED DETERGENTS FOR WASHING LOW SEVERE AND HIGH SOAPPED ACTION TABLETS CONTAINING OXIDES FROM LONG CHAIN AMINES. |
| WO1995035361A1 (en) * | 1994-06-17 | 1995-12-28 | The Procter & Gamble Company | Hand wash laundry compositions |
| JP6138355B2 (en) | 2013-05-24 | 2017-05-31 | ザ プロクター アンド ギャンブル カンパニー | Low pH detergent composition comprising nonionic surfactant |
| CA2910875C (en) | 2013-05-24 | 2018-11-06 | The Procter & Gamble Company | Low ph detergent composition |
| WO2014190130A1 (en) | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Concentrated surfactant composition |
| WO2016191238A1 (en) * | 2015-05-22 | 2016-12-01 | The Procter & Gamble Company | Surfactant and detergent compositions containing propoxylated glycerine |
| JP7278061B2 (en) * | 2018-11-27 | 2023-05-19 | ライオン株式会社 | Dishwashing detergent composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5335711A (en) * | 1976-09-14 | 1978-04-03 | Kao Corp | Neutral liquid detergent composition |
| JPS56112999A (en) * | 1980-02-08 | 1981-09-05 | Kao Corp | Detergent composition |
-
1987
- 1987-05-08 JP JP62112192A patent/JPS63277300A/en active Granted
-
1988
- 1988-04-19 GB GB8809175A patent/GB2205578B/en not_active Expired - Fee Related
- 1988-05-05 MY MYPI88000471A patent/MY103274A/en unknown
-
1993
- 1993-02-09 SG SG145/93A patent/SG14593G/en unknown
- 1993-04-29 HK HK404/93A patent/HK40493A/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5335711A (en) * | 1976-09-14 | 1978-04-03 | Kao Corp | Neutral liquid detergent composition |
| JPS56112999A (en) * | 1980-02-08 | 1981-09-05 | Kao Corp | Detergent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8809175D0 (en) | 1988-05-25 |
| SG14593G (en) | 1993-04-16 |
| JPS63277300A (en) | 1988-11-15 |
| GB2205578B (en) | 1991-07-31 |
| GB2205578A (en) | 1988-12-14 |
| HK40493A (en) | 1993-05-07 |
| MY103274A (en) | 1993-05-29 |
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