Free Answering Brief in Opposition - District Court of Delaware - Delaware

Case 1:04-cv-01507-SLR

Document 264-2

Filed 07/06/2006 [lll Patent Number: [45] Date of Patent:

Page 1 of 4 5,013,485 May 7, 1991

United States Patent [191
Tsukuda et al.
[54] LIQUID DETERGENT COMPOSITION CONTAINING TERPENE AND CALCIUM OR MAGNESIUM SALTS Inventors: Kazunori Tsukuda; Masakazu Toda, both of Utsunomiya; Masami Saito, Ichikai; Masaki Tsumadori, Utsunomiya, all of Japan Assignee: Kao Corporation, Tokyo, Japan Appl. No.: 373,278 Filed: Jun. 28, 1989 [56]

References Cited U.S. PATENT DOCUMENTS 4,414,128 11/1983 Goffinet .............................. 252/111

[75]

Primary Examiner--Prince E. Willis Assistant Examiner--John F. McNally Attorney, Agent, or Firm--Oblon, Spivak, McClelland, Maier & Neustadt [57] " ABSTRACT A liquid detergent composition for household use is disclosed. It comprises, as essential components, (A) 0.01-1.0% by weight of an anionic surface active agent, (B) 0.01-1.0% by weight of a terpene-type hydrocarbon solvent selected from monoterpenes and sesquiterpenes, and (C) 0.001-0.1% by weight of a water-soluble divalent metallic salt. The composition has superior detergency, exhibits a minimum adverse effect on surfaces which it contacts and a high degree of safety when in contact with the human body, and does not require rinsing. 7 Claims, No Drawings

[73] [21] [22]

Foreign Application Priority Data [30] Jul. 19, 1988 [JP] Japan ................................ 63-177996 [51] Int. CIP ......................... C11D 1/12; CllD 3/04; CI1D 3/18 [52] U.S. CI ..................................... 252/551; 252/550; 252/554; 252/162; 252/558 252/106, 107, 1 I1, 114, [58] Field of Search ............... 252/118, 122, 139, 153, 162, 170, 171,545, 546, 540, 551,550, 554

Case 1:04-cv-01507-SLR

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Accordingly, an object of the present invention is to provide a liquid detergent composition comprising as LIQUID DETERGENT COMPOSITION essential components: CONTAINING TERPENE AND CALCIUM OR (A) 0.01-1.0% by weight of an anionic surface active MAGNESIUM SALTS 5 agents, (B) 0.01-1.0% by weight of a terpene-type hydrocarBACKGROUND OF THE INVENTION bon solvent selected from monoterpenes and sesquiterI. Field of the Invention penes, and The present invention relates to a liquid detergent (C) 0.001-0.1% by weight of a water-soluble divalent composition, and, in particular, to a liquid detergent 10 metal salt. composition for household use having superior deterOther objects, features and advantages of the invengency, as well as exhibiting a minimum adverse effect tion will hereinafter become more readily apparent on surfaces which it contacts, a high degree of safety from the following description. when in contact with ~he human body, and which does DETAILED DESCRIPTION OF THE not require rinsing. 15 INVENTION AND PREFERRED 2. Description of the Background EMBODIMENTS In general, when a prolonged period of time elapses Examples of the anionic surface active agent used as after a solid surface gets soiled, washing becomes diffithe component (A) in the present invention include cult because the soiling material adheres strongly to the surface. For example, in the case where dirt adhering to 20 sulfonate-type anionic surface active agents and sulfatetype anionic surface active agents commonly 'used in exhaust fan blades, walls in the kitchen area, glass, refrigerator surfaces, and the like has accumulated over a detergent compositions. The sulfonate-type anionic surface active agents include linear or branched alkyl long period of time, this dirt changes to a highly viscous, oxidized form of degenerated oils. In e~di~.on, (C8-C23) benzene sulfonates, long chain alkyl (C8-C22) difficult-to-clean, oily-type soiling, such as that from 25 sulfonates, and long chain olefin (C8-C22) sulfonates. Examples of sulfate-type anionic surface active agents hand stains, cigarette tars, and the like exists throughout include long chain monoalkyl (C8-C22) sulfates, polythe household in locations other than the kitchen area. oxyethylene (1-6 mols) long chain alkyl (C8-C22) ether Commonly known detergents for removing such sulfates, polyoxyethylene (1-6 mols) alkyl (C8-C18) oily-type soiling include those containing a strong alka30 phenylether sulfates, and the like. As counter ions to line agent such as sodium hydroxide or the like, as a these anionic surface active agents, examples which can major component, and those containing an organic be given are alkali metal ions such as sodium, potassium, amhae, a water-soluble organic solvent (such as ethylene and the like, and alkanolamine, ions such as monoethaglycol monoalkyl ether, diethylene glycol monoalkyl nolamine, diethanolamine, triethanolamine, and the like. ether, or the like), and a surface active agent. 35 Among the above anionic surface active agents the However, the former type presents a safety problem, sulfonate-type anionic surface active agents are particuespecially with respect to skin irritation, while the latter larly desirable as the (A) component of the present type gives rise to discomfort because of having an offeninvention from the aspect of high resistance to hydrolysive odor of the organic solvent. sis. In addition, linear or branched alkylbenzene sulfoDetergents containing monoterpenes and sesquiter- 40 nares are desirable from the aspect of high detergency. penes have been proposed as detergents with a high The (A) component anionic surface active agents degree of safety and without an offensive odor of ormay be used individually or as a mixture of two or more types in the composition of the present invention. ganic solvents (Japanese Patent Laid-open Nos. The amount of the (A) component as a percentage by 14296/1986, 14297/1986, and 164798/1987). Although they have high detergency performance, their handling 45 weight (hereinafter referred to as wt %) of the total composition is in the range of 0.01 to 1.0 wt %; a particis sometimes cumbersome upon practical use. For examularly desirable amount is in the range of 0.1 to 0:5 wt ple, they must be diluted with water before use, or %. If the amount is less than 0.01 wt % bf the mixture, rinsed off with water after being used in the original the surface active agent exhibits insufficient emulsifying liquid form. This problem is caused by abrasive powders contained in the detergent or surface active agents 50 and dispersion action and the solubilizing activity is inadequate; if greater than 1.0 wt %, it leaves wiping contained in the emulsion type detergents. traces on the surface of the washed object after wiping, SUMMARY OF THE INVENTION which needs an undesirable rinsing step. The component (B) of the composition of the present The present inventors conducted extensive studies to 55 invention is a terpene-type hydrocarbon solvent seprovide, with due consideration to the drawbacks of lected from monoterpenes and sesquiterpenes. Examsuch conventional detergents, a liquid detergent comples of monoterpene-type hydrocarbon solvents are position for household use having superior detergency, D-limonene and L-limonene which are contained in exhibiting a minimum adverse effect on surfaces which orange oil, lemon oil, or the like, a-terpineol contained it contacts, and a high degree of safety when in contact 60 in pine oil or the like, and a-pinene,/3-pinene, myrcene, with the human body, and which does not require rinsand pocymene contained in turpentine oil or the like. ing, and found that a liquid detergent composition Examples of sesquiterpene°type hydrocarbon solvents which comprises an anionic surface active agent, a terwhich can be given are caryophyllene, cedrene, and the pene-type hydrocarbon selected from monoterpenes like, which are contained in substantial quantities in and sesquiterpenes, and a water-soluble divalent metal 65 cedar oil, clover oil, cananga oil, and the like. salt, did not require dilution prior to use, nor an afterThe (B) component which is a terpene-type hydrorinse, had a high degree of safety, and easily removed carbon solvent selected from monoterpenes and sesquitsoiling. erpenes may be used individually or as a mixture of two

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or more types in the composition of the present invenwindow glass. The detergency, wiping traces, and soltion. In addition, it is possible to incorporate their startvent odor were then evaluated. ing materials Of orange oil. turpentine oil, or pine oil as The object window glass was sprayed with I cc of a liquid detergent using a commercial sprayer, and wiped they are into the composition of the present invention. A desirable amount of the (B) component as a per- 5 with a dry towel. Sensory evaluations were then carried out, using the following evaluation criteria. centage of the total composition is in the range of 0.01 to 1.0 wt %; a particularly desirable amount is in the Evaluation Criteria Detergency range of 0.I to 0.5 wt %. If the amount is less than 0.01 O: 80% of soiling is removed wt % of the composition, action as a solvent cannot be expected; if greater than 1.0 wt %, a large amount of a 10 F: 20 to 50% of soiling is removed surface active agent is necessary to ensure stable solubiX: Almost no soiling removed lization of the compound. Because remnants remain on Wiping traces the surface of the washed object they must be rinsed O: Second wiping not necessary and wiped a second time, which is undesirable. F: Slight wiping traces remaining Water-soluble divalent metal salts which are suitable 15 X: Considerable wiping traces observed as the component (C) of the composition of the present Solvent odor O: No objectionable odor detected invention are, for example, calcium salts and magnesium salts. Of the calcium salts, the chloride and the sulfate F: Slight objectionable odor are particularly desirable; for the magnesium salts, the X: Objectionable odor noted sulfate is best used. 20 The results are shown in Table 1. TABLE 1
Components Sodium alkylbenzene sulfonate(1) Polyoxyethylenealkyl .... ether(2) D-limonene a-Pinene Ethyl cellosolve Butyl carbitol Calcium chloride .... Ion exchanged water Detergency Wiping traces Solvent odor 1 0.5 2 0.5 3 0.3 (wt %) 4 0.3 0.2 --1.0 ...... -Balance O O X --1.0 .... Balance O F F Balance F F O Balance F F O 0.01 Balance O X O 0.3 -~-0.5 5 1.5 -0.5 -6* 0.2 0.1 0.3 -0.01 Balance O O O 7* 0.3 --0.5 -0.01 Balance O O O

*Compositions of the present invention (I) An average cabon number in alkyl chain: (2) An average cabon number in alkyl chain: CI.,, An average ethylene oxide addition tools: 6

A desirable amount of the (C) component in a perExample 2 centage of the total composition is in the range of 0.001 to 0.1 wt %. The HLB value of the component (A) of Detergent compositions listed in the following Table the present invention can be freely adjusted correspond2 were prepared, and the detergency and wiping traces ing to the amount of the component (C) added. Addiwere evaluated using soiled models. tion of the component (C) also assists to solubilize the Soiled models used were 3 cm×8 cm glass plates to component (B). which cigarette tars were adhered. The glass plates In addition, as required, components other than the 45 were immersed in test solutions for 2 minutes and the essential components (A), (B), and (C) can be added to elimination of the soiling was evaluated to determine the liquid detergent composition of the present inventhe detergency according to the following criteria. The tion. These optional components include nonionic surglass plates were wiped with dry towel and the comface active agents, alkaline agents, dispersing agents, pleteness after drying was sensorially evaluated accordsolvents, acids, perfumes, dyes, pigments, preservatives, 50 ing to the following criteria to determine wiping traces. germicides, and the like. Detergency Other features of the invention will become apparent O: 80% of soiling is removed in the course of the following description of the exemF: 20 to 50% of soiling is removed plary embodiments which are given for illustration of X: Almost no soiling removed Wiping traces the invention and are not intended to be limiting55 thereof. O: Second wiping not necessary F: Slight wiping traces remaining EXAMPLES X: Considerable wiping traces observed Example I Results are shown in Table 2. Detergent compositions listed in the following Table I were prepared and actually used to wash a household TABLE 2 (wt %)
Components Sodium alkylbenzene solfonate(1) Polyoxyeth ylenealkyl8" 9* 0.3 0.1 10* 11" 0.3 0.1 12* 0.3 0.1 13 14 0.3 0.1 15 0.5 0.5 0.3 0. I 0.3 0.1 2.5 2.5

Case 1:04-cv-01507-SLR 5
Components ether(2) Orange oil (Major component: D-limonene) Turpentine oil (Major component: ct,/3-pinene) Cananga oil (Major component: a, /~-caryophyllene) a-terpineol Butyl carbitol ..... Ethanol ...... Diethanolamine Calcium chloride Ion exchanged water Detergency Wiping traces 8* 0.5 ---0.5 0.01 Balance O O

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TABLE 2-continued (wt %) 9* 10" 11" 12" -0.5 .... --0.5 0.01 Balance O O 0.5 -0.5 0.01 Balance O O -0.5 0.5 0.01 Balance O O --0.1 0.01 Balance O O --1.0

13 --

14

15
I0.0

--3.0
10.0

0.5 -Balance O F

0.5
Balance F O Balance O X

*Compositions of the present invention (1) An average eabon number in alkyl chain: C]2 (2) An average cabon number in alkyt chain: C12, An average ethylene oxide addition mols: 6

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings, it is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described 25 herein. What is claimed is: 1. A liquid detergent composition comprising as essential components: (A) 0.01-1.0% by weight of an anionic surface active 30 agent, (B) 0.01-1.0% by weight of a terpene hydrocarbon ¯ solvent selected from monoterpenes and sesqueterpenes; and (C) 0.001-0.1% by weight of a water-soluble divalent 35 metallic salt selected from the group consisting of CaCI2, CaSO4 and MgSO4. 2. The liquid detergent composition of claim 1, wherein the anionic surface active agent is selected from the group consisting of the linear or branched 40 alkyl C8-C23 benzene sulfonates, long chain alkyl C8-C22 sulfonates, long chain olefin C8-C2~ sulfonates, long chain monoalkyl C8-C22 sulfates, polyoxyethylene (1-6 mol) long chain alkyl C8-C2~ ether sulfates and 45

polyoxyethylene (1-6 mols) alkyl C8-C18 phenylether sulfates or mixtures thereof. 3. The liquid detergent composition of claim 1, wherein the anionic s.,rface active agent is present in from 0.1-0.5% by weight. 4. The liquid detergent composition of claim 1, wherein the terpene hydrocarbon solvent is selected from the group consisting of D-limonene, L-limonen," orange oil, lemon oil, a-terpineol, pine oil, ct-pinene, /3-pinene, myrcene, p-cymene, terpentine oil, caryophyllene, cedrene, cedar oil, clover oil, and cananga oil or mixtures thereof. 5. The liquid detergent composition of claim 1, wherein the terpene hydrocarbon is present in from 0.1-0.5% by weight. 6. The liquid detergent composition of claim 1, wherein the counterion of the anionic surface active agent is selected from the group consisting of alkali metal ions, alkanolamine ions. 7. The liquid detergent composition of claim 1, wherein the anionic surface active agent is a linear or branched alkyl benzene sulfonate.

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