TW509721B - Liquid detergent composition - Google Patents

Abstract

The present invention provides a liquid detergent composition having high detergency without damaging styrene-based resin. The liquid detergent composition comprising (a) 0.1 to 50% by weight of a mixture of at least two different compounds from each other in view of their structural isomers and/or their number of carbon atoms, selected from glyceryl-ether compounds having the formula (I): R-OCH2CH(OH)CH2OH, wherein R is an alkyl or alkenyl group having 1 to 11 carbon atoms; (b) 0.01 to 30% by weight of a surfactant; (c) 0.01 to 30% by weight of a builder or an alkali agent; and (d) the balance of water.

Description

509721 _Case No. 87120648_Year_Month_Revision_ V. Description of the invention (1) Technical scope The present invention relates to a liquid detergent composition which has excellent cleaning power against oil stains and soap scales and has little damage to the substrate. Suitable as a cleaner for kitchens, bathrooms and toilets, and as a cleaner for strong dirt. In the prior art, in order to remove dirt that varies depending on a treatment object such as a bathroom, a kitchen, a floor, etc., a cleaning agent generally adapted to the composition of each dirt has been used. In addition to cleaning power, it is also required that the substrate to be cleaned does not cause damage. For example, if cleaning substrates such as styrene-based resins such as ABS resins that have recently been widely used as materials for various structures, or using styrene-based resins mixed with other materials such as metals, glass, etc. Damage can depend on the solvent to be added to the cleaner. The object of the present invention is to provide a liquid cleaner combination that does not damage various substrates, especially plastic substrates represented by styrene-based resins, and can demonstrate high cleaning power against various stains, especially modified oil stains and soap stains. Thing. The present inventors have previously proposed that a detergent composition for a hard surface contains a special range of a glyceryl ether solvent incorporated therein as a cleaner that can be applied to various uses to solve the trouble of selecting a cleaner for each use. Question (JP-A 7-3289). DISCLOSURE OF THE INVENTION In order to overcome the diversification of materials, the present inventors made intensive research based on the detergent composition disclosed in JP-A 7-3 2 8 9. As a result, the inventors have found that by incorporating glycerin in a special combination A composition obtained by replacing the glyceryl ether used in the prior art composition with an alkyl ether to improve the cleaning power without damaging the alkyl group

O: \ 56 \ 56347.ptc Page 5 509721 _Case No. 87120648_Year Month and Day_ί £ -_ V. Description of the Invention (2) Materials, thus completing the present invention. That is, the present invention provides a liquid detergent composition comprising: (a) a mixture of at least two mutually different compounds in a weight ratio of 0.1 to 50%, the differences of these compounds in view of their structural differences Structure and / or the number of C atoms contained therein, which is selected from glyceryl-ether compounds having the formula (I): R-〇CH2CH (OH) CH2OH (I) where R is 1 to 11 Alkyl or alkenyl group of C atom, (b) 0. 0 1 to 30% by weight surfactant, (c) 0. 01 to 30% by weight builder or alkali agent and (d ) The balance of water. The way of carrying out the present invention is as a component (a) the glyceryl ether used in the present invention is mixed with at least one kind of mixture satisfying the conditions represented by (i) or (ii): (i) glycerol represented by formula (I) A mixture of alkyl ethers, wherein the glyceryl ethers have alkyl or alkenyl groups (ie, R) with different numbers of C atoms each other; (ii) a structural isomer represented by formula (I). In particular, the mixture of glyceryl ethers is preferably a mixture of 2 or more. The mixing ratio of glyceryl scale is preferably in the range of 1: 9 to 9: 1, particularly preferably in the range of 2: 8 to 8: 2, and more preferably in the range of 3: 7 to 7: 3. As the condition (i), R s to be mixed are different from each other, then R is preferably an alkyl group having 3 to 8 C atoms, and particularly preferably 4 to 6. C atoms. As conditions (i i), R s are different from each other because R s are structural isomers of each other. Among them, R s to be mixed is preferably mixed with a linear alkyl group, a fluorenyl-branched alkyl group, and / or an ethyl-branched group, and particularly preferably, two or more members selected from these members are mixed. Good place

O: \ 56 \ 56347.ptc Page 6 509721 _Case No. 87120648_Year Month__ V. Description of the invention (3) Mixed linear alkyl and methyl-branched alkyl or linear alkyl and ethyl-branched Of alkyl. As the condition (i i 1), it is preferable to mix the glyceryl bond of (i) and (i i) ° The most preferable mixture is a glyceryl ether having 4 to 6 C atoms, or a mixture thereof, which satisfies the condition (1 1). As the component (a), the glyceryl ether can be prepared by force ul-chloro-2,3-epoxypropane to the alcohol corresponding to R in the presence of a Lewis acid catalyst, and then under basic conditions. The product is then ring-opened, and the epoxy group is ring-opened by hydrolysis. In order to provide sufficient cleaning power and improve stability in water systems, the content of component (a) in the liquid detergent composition is in the range of 0.1 to 50% by weight, preferably 0.5. To 30% by weight, more preferably 1 to 20% by weight. As the surfactant used in the component (b) of the present invention, an anionic surfactant, a non-ionic surfactant, an amphoteric surfactant, and a cationic surfactant are included. The anionic surfactant used may be described in jp-A 9-3 1 0 0 9 1, page 8, 13 rows, 41 to pages 9, 15 rows, 4 9 columns, which is preferred The local user is a linear alkylbenzene sulfonic acid with a C8 to (: 22 alkyl chain), an average of 1 to 10 mol of ethylene oxide polyoxyethylene alkyl ether sulfuric acid has been added, an average of 1 has been added Polyoxyethylene alkyl ether carboxylic acid to 10 mol of ethylene oxide, and polyoxyethylene alkyl amide ether carboxylic acid to which an average of 1 to 10 mol of ethylene oxide has been added, and its interaction with potassium, Sodium, magnesium and alkanolamine salts. The nonionic surfactants used can be described in JP-A 9-3 1 0 0 9 1, page 6, line 10, columns 35 to 8 In the 13th row and the 40th column, among the preferred users, C8 to C22 have been added with an average of 1 to 30 moles of ethylene oxide.

O: \ 56 \ 56347.ptc Page 7 509721 _Case No. 87120648 _ Month and Day__ V. Description of the invention (4) Polyoxyethylene alkyl ethers with alkyl chains have been added with an average of 1 to 30 moles Ethylene oxide, ethylene oxide and polyoxyethylene oxypropylene alkyl ethers with an average of 1 to 10 mole propylene oxide, have an average of 1 to 3 molecules of ethylene oxide (or propylene oxide). Fatty acid alkanolamides or derivatives thereof having 8 to 2 C atoms, in which amide bonds have long-chain C8 to (: 22 alkyloxyalkylamines and C8 to (: 22 alkyl chains) Glycanside, whose sugar has an average degree of condensation of 1.0 to 2.0. The amphoteric surfactant used may be described in JP-A 9-3 1 0 0 9 1, page 6, line 9, page Columns 1 to 10 and columns 34 to 34 include the alkylamidepropyl-N, N-dimethylglycine betaine, the alkylamidepropyl-N, N-difluorenyl-2 -Hydroxypropylsulfobetaine, alkyl-N, N-dimethylglycine betaine, alkylamidepropyl-N, N-dimethylpropylsulfobetaine, dodecyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, etc. Among these, dodecylamide-N, N- Betaine glycine betaine, myristyl amide propyl-N, N-dimethylglycine betaine, coca amide propyl-N, N-dimethylglycine betaine, dodecyl -N, N-Difluorenyl-2-hydroxypropylsulfobetaine, Dodecylamide-N, N-difluorenyl-2-hydroxypropylbetaine, etc., in terms of cleaning agents and foaming power The used cationic surfactant can be described in JP-A 9-3 1 0 0 9 1, page 3, line 4, line 11 to page 5, line 8, line 50 Cationic surfactants, and in the case of quaternary salts, the users are particularly preferably C6 to C24 long-chain two-membered dimers, pressing the salt 'long bond-carbon-based-base two-membered saddle salt and long-bond-yuan-two Phosphonium ammonium salts, which can have amide or lipid bonds therein, and the relative ions are preferably halogen atoms such as C 1 and B r atoms, sulfates, and sulfate residues containing alkyl groups such as fluorenyl and ethyl sulfate. Amine Cationic surfactants with long chain C8

O: \ 56 \ 56347.ptc Page 8 509721 _Case No. 87120648_Year_Month__ V. Description of the invention (5) Dialkyl-fluorenyl group with long chain to C24 alkyl group (with amide or ester bond) The amine salt is preferably in the form of the hydrochloride, sulfate or phosphate. In the present invention, a cationic surfactant can be incorporated to further improve the cleaning power. In the entire surfactant, the content of the cationic surfactant is preferably in the range of 5 to 80% by weight, and the content of the cationic surfactant in the composition is preferably 0.01 to 20% by weight, more preferably 0.1. To 10% by weight. For sufficient cleaning power, the content of component (b) in the liquid detergent composition ranges from 0.01 to 30% by weight, preferably from 0.05 to 20% by weight, more It is preferably from 0.1 to 10% by weight. As component (c) in the present invention, alkyl glycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, and serine-N, N-diacetic acid can be used. In JP-A 9-310091, JP-A 9-310098, JP-A 10-21929, etc., L-glutamic acid diacetic acid and (s, s) -ethylenediamine disuccinic acid. However, it is preferable to use hydroxycarboxylic acids such as citric acid and malic acid, dicarboxylic acids such as succinic acid and malonic acid, condensed conformation acids such as pyrofillic acid, and fruit acids such as ethane-1, meso-1, 1- Diphosphonic acid, aminotris (fluorenylphosphoric acid), ethylenediaminetetra (phosphonylenephosphoric acid), and aminocarboxylic acids such as ethylenediaminetetraacetic acid, nitrogentriacetic acid, hydroxyethylethylenediaminetriacetic acid, and Alkali metal salts such as its sodium salt, potassium salt, its salt, its alcohol amine salt and its water-soluble salt. For sufficient cleaning power, the content of the builder in component (c) is preferably from 0.1 to 20% by weight, and particularly preferably from 0.5 to 10% by weight. Preferable examples of the alkaline agent as the component (c) are hydroxides such as Na 〇 Η, Κ Ο Η, C a (Ο Η) 2 and the like, carbonates such as Na 2 C 03, K 2 C 03, half Sodium sesquicarbonate and the like, petrolates such as sodium crushed acid, potassium crushed acid and the like, and alcohol amines such as ethanol

O: \ 56 \ 56347.ptc Page 9 509721 _ Case No. 87120648 _ month and day ___ 5. Description of the invention (6) amines, 2-amino-2-fluorenyl-1-propanol, and so on, and what? And N-ethylmorpholine and ammonia. Among these, NaOH, KOH, Na2CO3, K2CO3, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, morpholine, and ammonia are particularly preferred. For cleaning power, the content of the alkaline agent as component (c) is preferably in the range of CL 1 to 20% by weight, more preferably 0.5 to 10% by weight. Other components than those described above may be added to the liquid detergent composition of the present invention to the extent that the object of the present invention can be satisfied. In particular, it is preferred to contain ethanol, ethylene glycol, or propylene glycol to improve phase stability, and a lower alkyl benzene sulfonate such as benzene sulfonate, toluene sulfonate, dibenzobenzene sulfonate or cumene Sulfonate is preferably added as a low-temperature stabilizer, and 3,5-di-tert-butyl-4-hydroxybenzone, 2,5-di-tert-butylhydroquinone, or DL-α-tocopherol is preferably added. As an antioxidant. In particular, flavors, colorants (dyestuffs) and preservatives can be mentioned as the basic ingredients in the product. Water is added with the above components to the liquid surfactant composition of the present invention. Water was added in an amount adjusted to 100% by weight. In addition, the liquid surfactant composition of the present invention is preferably adjusted to a range of ρ Η 3 to 13 to improve the cleaning power. This adjustment can be performed with NaoΗ, K0Η, or HC1 aqueous solution. Although the liquid surfactant composition of the present invention can be applied to various applications, it is particularly preferable as a surfactant composition for hardware. The term π hardware " refers to an object that maintains its predetermined shape regardless of whether it is a plane or a solid, and its hardness is not limited as long as it can be treated with a surfactant. Hardware includes not only those made of plastic, rubber, metal, tiles, bricks, concrete, cement, glass, wood, etc., but also those made by them, such as floors, stairs, and bile walls. Various items in contact such as instruments, tools, equipment,

O: \ 56 \ 56347.ptc Page 10 509721 _Case No. 87120648_Year_Month__ V. Description of the invention (7) Furniture, tableware, etc. Therefore, the liquid detergent composition of the present invention can be used as a detergent for kitchens, bathrooms, floors, tableware, automatic washing machines, drain pipes, and small items in kitchens and toilets. Brief Description of the Drawings Figure 1 shows a perspective view illustrating a substrate damage test method. Figure 2 shows a fragmentary view of an ABS resin test piece illustrating the substrate damage test method. Explanation of component symbols I, L: Parameters for calculating curvature Examples Examples 1 to 16 and Comparative Examples 1 to 1 2 Use the components shown in Tables 1 to 2 so that Examples 1 to 8 and Comparative Examples 1 to In 6, a liquid cleaner composition for surrounding a fire was prepared, and in Examples 9 to 16 and Comparative Examples 7 to 12, a liquid cleaner composition for a bathtub was prepared. Adjust p Η with Na 0 Η or HC 1. The glyceryl ether used as component (a) is a mixture of the following compounds 1 to 5. In the table, p is an average number of additions, and C η is an alkyl group having a number of C atoms of η. Compound 1: CH3CH2CH2CH2CH2-0CH2CH (0H) CH20H Compound 2: CH3CH (CH3) CH2CH2-OCH2CH (OH) CH2OH Compound 3: CH3CH2CH (CH3) CH2-0CH2CH (0H) CH20H Compound 4:

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CH3CH2CH2CH2CH2CH2CH2-0CH2CH (0H) CH20H In the evaluation method (1) described below, the properties of the substrates (the properties of the A B S resin) that are damaged by the respective liquid detergent compositions were investigated. In addition, according to the following evaluation methods (2) and (3), investigate the cleaning power of liquid cleaners used in these ranges to oil stains, and the cleaning power of liquid cleaners used in bathtubs to soap stains. The results are shown in Tables 1 to 2. Evaluation method (1) <damage properties of A B S resin> A test piece of AB S resin (Mitsubishi Mitsubishi (M ο n s a n t)) with a size of 230 × 3 5 × 2 mm was prepared. Make this test piece suitable for the surface shape of a vinyl chloride tube with a diameter of 276 mm and fix it as shown in Fig. 1 and twist it as shown in Fig. 2 (with a curvature of 0.74%). The formula determines: Curvature (%) two (IL) X100 / L, where I and L are defined in Figure 2. The test piece thus twisted (i.e. pressurized) was then rubbed 10 times with a commercial toilet paper (1 g dry weight) immersed in 1.7 g of the liquid detergent composition by rubbing 10 times. After that, the test piece was left at 20 ° C and 65% R for 24 hours, and the state of the surface was visually investigated, and the damage properties of the composition were evaluated according to the following criteria: 0: No abnormality X: Rupture evaluation method ( 2) <Cleaning power for oil stains> Apply cooking oil (fry oil) evenly on an iron plate and bake at 180 ° C for 30 minutes, then leave it at room temperature for 3 months to form almost The dried film is used as an oil stain board. About 0.5 milliliters of liquid detergent composition is dripped onto a horizontally fixed oil

O: \ 56 \ 56347.ptc Page 13 509721 _Case No. 87120648_Year Month and Day ___ V. Description of the invention (10) Stain the board and let it stand for 1 point. Thereafter, the oil slick was gently removed with absorbent cotton. This operation was performed for a total of 20 points, and the cleanliness levels were visually inspected, and evaluated according to the following criteria to display the average of 20 measurements. 5: Completely clean 4: Approximately 80% clean 3: Approximately 60% clean 2: Approximately 50% clean 1: Approximately 30% clean 0: No cleaning evaluation method (3) <Cleaning power to soap stain> 3 After one month of actual use, the soapy face wash box (made of polypropylene) was wiped 5 times with a polyurethane sponge of about 50 grams of a liquid cleaner for evaluation. This operation was performed 20 times in total. The cleanliness was visually checked and evaluated according to the following criteria, and the average of 20 measurements was displayed. 5: Extremely clean 4: Very clean 3: Incompletely clean 2: Slightly clean 1: Extremely clean

O: \ 56 \ 56347.ptc Page 14 509721 V. Description of the invention (11) R? -Dd GO as shanm _ ftr Ev \ ^ &gt; h〇 attached -ffi 1 1 ㈧ 隳 Μ · 11 隳 m &gt; a * 11¾ wif m ^ s mm mi 艰 4t 17¾ C = n ^ πισ to ^^ I 1 [N, ^ / m 11 11 31 [1 SMW 骠 \ l [N i 1 s MW m &amp;! &gt; pv 6i &gt; Ev n &gt; Ev ti &gt; n &gt; ^ r \ cS σ \ edge n ci LtJ ό edge to Lk)! o ^ r \ c # i— ^ 0 ο ^ r \ Ο ί〇_ ►— * &gt; — ί〇L〇LO 一 w 室 〇 ^ r \ Ο to Mu ^ r \ μ— ^ to uj UJ NJ 〇〇 to _ LT \ 1—i A to LO LO LO ο LT \ Ο ίο _ ^ r \ h— NJ to 〇 ^ ί \ Ο »—k U) _ Lk) H— ^ K) Ul H- ^ 〇ο fo _ U \ Κ) &gt; — * &gt; — ^ ON 〇 ^ Τ \ Ο to _ ^ r \ i —- * to, ►—a (0 Ο? 〇W) — ^ to K &gt; to oo 〇 * Κ) ro step W vyi AMC \ ry iw 〇 \ 〇to step W h— * to Os N- ) 〇! 〇Step Lr \ 1—k ΓΟ ON UJ -f ^ X UJ Κ) ΤΐΠ1ί &gt; ^ Η &gt; w to G \ X uj UJ Tmib- oj one 1- ^ to On X LO Ο fo w K ^ \ one Η- * K) 〇 \ Os mmu page ^ 509721 (l) damage properties of ABS substrate (3) used soap scale 淸Jie Li π: citrate EDTA-4Na cocaamide propyl-N, N-dimethylglycine betaine sodium dodecyl sulfate 爇 It deaf 1 1 .dodecyl maltol 1 fatty acid (Cl 2) Diethanolacyl alkyl (Cl 4) aminated oxygen dipropylene glycol ethyl ether diethylene glycol butyl ether Compound 5 (n-C6) | Compound 4 (n-C4) Compound 3 (2i-C5) Compound 2 ( 3i-C5) Compound 1 (n-C5) 〇〇 balance UJ to 一 ro LO Lk) so S | 〇〇 balance L ^ J to 一 ro oj OJ 〇〇 balance UJ to 一 K) LO LO) —A 〇〇 '-ο balance LO-one ro ro -4 ^ to 〇 ^ Τι 〇 balance OJ MH-*-LO H-^ 〇y \ ο balance UJ Η-^-LO Os 〇 〇 Balance r〇ro e; 〇Lh 〇 Os balance>-* b〇LO OJ 5; 〇4 ^ NJ '-o balance Lk) K) ro c \ Comparative Example 〇 Private 0 balance OJ hJ 、 * to 〇〇〇Private σ \ Margin LO ro-One K) On \ 〇 X k) Margin LO r〇 一 1 ~ k-h〇Os H— * X Lk) Lj Margin LO r〇j— ^ Η— * K) κ &gt; C \ &gt; — * X • NJ -ο balance LO K) NJ K) ο to IHffiil Page U 509721 _Case No. 87120648 _ ^^ _ Q_ {务 正 _ V. Explanation of the invention (13) Example 1 7 to 2 5 and Comparative Examples 1 to 3 8 Liquid cleaners (surfactants) for bathtubs prepared in Examples 1 7 to 2 5 and Comparative Examples 1 to 1 8 using the components shown in Table 3 . Adjust the value of ρ Na with NaO Η or HC 1. As the glyceryl ether of the component (a), a mixture of the above compounds 1 to 5 can be used. In the table, dodecyltrimethylammonium chloride is used as cation A, and octyldiphosphonium ammonium chloride is used as cation B. According to the above-mentioned evaluation methods (1) and (3), the respective liquid detergent compositions thus prepared were evaluated for their properties of damaging the substrate (A BS resin damage) and their cleaning power against soap stains. In addition, the following evaluation methods are used for additional evaluations: the evaluation method for evaluating the cleansing power of grease (4), the evaluation method for evaluating the cleansing power of scale (4), and the evaluation for evaluating the cleansing power of soap (No. 2) (6) without rubbing the dirt. The results are shown in Table 3. Evaluation method (4) <Cleaning power against grease stains> 10 adults bathed in an enamel bathtub with 400 warm water in the usual way, and left the bathtub overnight. Thereafter, the water was removed, and the dirt attached to the bathtub was regarded as fatty. Polyurethane sponge dipped in the prepared liquid detergent composition was gently wiped 5 times with the dirt, and the dirt was removed from the surface of the bath by visual evaluation according to the following criteria. The same evaluation was repeated 10 times, and the average is shown in the table. 5: Extremely clean 4: Very clean 3: Incompletely clean 2: Slightly clean

O: \ 56 \ 56347.ptc Page 17 509721 _Case No. 87120648_Year_Month_Revision_ V. Description of the invention (14) 1: Extremely clean evaluation method (5) <Cleaning power to scale> 6 adults in turn In a stainless steel bathtub filled with 200 liters of 40 ° C water, each person bathed for 15 minutes. After removing the water, let the bathtub stand for 1 day. 3 ml of the liquid detergent composition in a commercial sprayer was sprayed on the scale attached to the water-covered part of the inside of the bathtub, allowed to stand for 2 minutes, and then washed with water. Thereafter, the cleanliness was evaluated according to the following criteria. The same evaluation was repeated 10 times, and the average is shown in the table. 5: Extremely clean 4: Very clean 3: Incompletely clean 2: Slightly clean 1: Extremely clean evaluation method (6) <Cleaning power on soap scale (No. 2)> Put the polyester FRP board in a conventional bathroom, and let Let it stand for 3 months without detergent and use it as a dirt board. The soap stain on the board is difficult to remove by rubbing with sponge, and it is kept continuously. The dirt plate was fixed horizontally, and 3 ml of a liquid detergent composition in a commercial sprayer was sprayed thereon, left for 3 minutes, and then washed with water, and the cleanliness was evaluated according to the following criteria. The same evaluation was repeated 10 times, and the average is shown in the table. 5: Extremely clean 4: Very clean 3: Incompletely clean

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Claims (1)

509121 87120648 Amendment 1. A liquid detergent composition comprising (a) a mixture of at least two mutually different compounds in a weight ratio of 0.1 to 50%, the differences of these compounds in view of their structural isomers and / Or the number of C atoms contained therein, selected from glyceryl ether compounds having the formula (I): R-OCH2CH (OH) CH2OH (I) where R is an alkyl or alkenyl group having 4 to 6 C atoms And the mixture contains 2 different glyceryl ether compounds in a ratio ranging from 1: 9 to 9: 1, (b) 0 · 0 1 to 30% by weight of a surfactant, (c) 0 · 0 1 To 30% by weight of builder or alkaline agent and (d) the balance of water. 2. A composition according to item 1 of the scope of patent application, wherein (b) contains a cationic surfactant. O: \ 56 \ 56347.ptc Page 23