JP2006290942A - Hard surface detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard surface detergent composition which does not use a nitrogen compound having a high nitrogen content, has good intimacy with staining, excels in detergency, and has high safety to humans and the nature. <P>SOLUTION: The hard surface detergent composition comprises (A) a polyether amine compound having a nitrogen content of 0.1-3 mass% and (B) a water soluble polyether solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a detergent composition that is excellent in removing dirt components present on hard surfaces such as metals, plastics, glass, ceramics, and concrete, and that is highly safe for humans and nature.

  In general households, kitchen fans, gas ranges, bath tubs, toilets, tableware, vehicles, buildings, etc. are made of metal, plastic, glass, ceramics, concrete or the like. Various stains adhere to these hard surfaces due to wind and rain, foods, emissions, oils, exhaust gases, and the like. In order to remove such dirt, it is only necessary to use a surfactant for washing. However, in many cases, the composite dirt cannot be completely removed with the surfactant alone.

（式中Ｒ_１は炭素原子数１〜４のアルキル基、Ｒ_２は水素原子、メチル基またはエチル基 ｎ＝１〜１０）で示されるアルキルポリアルキレングリコールエーテル（ＩＶ）１〜２０重量部（質量部）を含有することを特徴とする液体洗浄剤組成物が開示されている。 Therefore, as a cleaning composition that solves the above problem, for example, in Patent Document 1, as an essential component, surfactant (I) 0.1 to 50 parts by weight (parts by mass) Alkali Builder (II) 1 to 20 parts by weight Part (mass part) 0.5-20 parts by weight (mass part) of one or more aliphatic carboxylates (III) having 6 to 10 carbon atoms One or more general formulas

(Wherein R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is a hydrogen atom, a methyl group or an ethyl group n = 1 to 10) 1 to 20 parts by weight of an alkyl polyalkylene glycol ether (IV) ( A liquid detergent composition containing a mass part) is disclosed.

Patent Document 2 discloses that (A) one or more surfactants are 0.1 to 20 wt% (mass%).
(B) Solvent 1-20 wt% (mass%) represented by the following general formula (I)
_{RO [(C 2 H 4 O} ) m (C 3 H 6 O) n] R '(1)
In the formula, when either m or n is 0, R and R ′ are alkyl groups having 1 to 4 carbon atoms, and when m and n> 0, R and R ′ are H or 1 carbon atom. And R and R ′ are not H. However, m and n are 0-4 and m + n = 1-6. [] Is a polyoxyalkylene chain formed by bonding oxyethylene groups and oxypropylene groups randomly and / or in blocks.
(C) One or two or more alkali substances selected from organic amines such as alkanolamine and / or caustic alkali 0.1 to 15 wt% (mass%)
(D) The liquid detergent composition characterized by including water balance is disclosed.

JP-A-56-047496 Patent Claim JP 61-151300 A Claims

  The cleaning composition disclosed in Patent Documents 1 and 2 is one of the cleaning compositions suitable for removing various stains by the solvent dissolving ability against dirt and the detergency of alkaline agent. It has been broken. However, when a strong alkali agent such as sodium hydroxide or potassium hydroxide is used, it may not be familiar with dirt and may cause uneven cleaning. Here, “cleaning unevenness” means that dirt remains in the mottle after cleaning. It is also known to use a surfactant and a strong alkali agent in order to eliminate this washing unevenness, but the effect is not sufficient.

  In addition, when low molecular alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine are used, the water content is improved when the nitrogen content in the cleaning agent increases and is discharged into the environment as wastewater, although it is well-suited to dirt. Problems such as contamination and eutrophication may occur. At present, local governments and the like also regulate emission of nitrogen compounds, and a cleaning agent having a low nitrogen content is desired. In addition, low molecular weight alkanolamines have a problem that they are strongly irritating to the skin, and monoethanolamine may be changed to nitrosamine, and there is a movement to limit this use.

  Accordingly, an object of the present invention is to provide a hard detergent composition that does not use a nitrogen compound having a high nitrogen content, has a good cleaning power that is well-familiar with dirt, and is highly safe for humans and nature. It is to provide.

  Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors use a polyetheramine compound, so that the safety of the human body is high, the familiarity with dirt, and the nitrogen content with excellent detergency. The present inventors have found that a hard detergent composition having a low viscosity can be obtained, and have reached the present invention.

  That is, the present invention comprises a hard surface cleaner composition comprising a polyetheramine compound (A) having a nitrogen content of 0.1 to 3% by mass and a water-soluble polyether solvent (B). It is a thing.

  The effect of the present invention is to provide a hard cleaning composition that does not use a nitrogen compound having a high nitrogen content, has a good cleaning power, is well-familiar with dirt, and is highly safe for humans and nature. There is.

（式中、ＰＯは、−Ｃ_３Ｈ_６Ｏ−基を表し、ＥＯは、−Ｃ_２Ｈ_４Ｏ−基を表し、ｋ、ｐ、ｒ及びｔは、それぞれ３〜５０の数を表し、ｍ、ｑ、ｓ及びｗは、それぞれ１〜１００の数を表す。） The component (A) that can be used in the present invention is a polyetheramine compound having a nitrogen content of 0.1 to 3% by mass, such as an alkylene oxide adduct of ammonia, an alkylene oxide adduct of ethylenediamine, or an alkylene oxide of diethylenetriamine. Examples include an adduct, an alkylene oxide adduct of triethylenetetramine, and the like, in which an alkylene oxide is added to an amine compound having active hydrogen. Such a polyetheramine compound is alkaline, and has the advantage of good compatibility with dirt as well as the effect of alkali cleaning. Among such polyetheramine compounds, water-soluble polyetheramine compounds are preferable from the viewpoint of familiarity with dirt and detergency, and polyetheramine compounds represented by the following general formula (1) are more preferable. Here, “water-soluble” means that when water and a polyetheramine compound are mixed one-to-one at room temperature, the entire amount is dissolved or emulsified:

(Wherein, PO _represents -C _{3 H} 6 O- groups, EO _represents -C _{2 H} 4 O- group, k, p, r and t each represent the number of 3 to 50, m, q, s, and w each represent a number from 1 to 100.)

  In the said General formula (1), k, p, r, and t represent the polymerization degree of an oxypropylene group, respectively, respectively represent the number of 3-50, Preferably it is 5-40, More preferably, it is 5-30. It is. Here, if the number of k, p, r, and t is less than 3, it is not preferable because the detergency may be inferior, and if it exceeds 50, the blending stability may be deteriorated. M, q, s and w each represent the degree of polymerization of the oxyethylene group, each representing an independent number of 1 to 100, preferably 3 to 80, more preferably 5 to 60, still more preferably 5 to 5. 50. In addition, since the cleaning power may be inferior when the number of m, q, s, and w becomes larger than 100, it is not preferable.

  The polyetheramine compound represented by the general formula (1) is preferably dissolved or dispersed in water, and the ratio of the oxyethylene group to the total mass of the oxypropylene group and the oxyethylene group is preferably 10 to 80% by mass. 20-70 mass% is more preferable, and 30-60 mass% is still more preferable. Here, if the ratio of the oxyethylene group is less than 10% by mass, it may not be water-soluble, and if it exceeds 80% by mass, uneven cleaning may occur.

  The polyetheramine compound of the general formula (1) can be produced by any method, but the most general method is, for example, adding propylene oxide in an amount necessary for ethylenediamine in the presence of a catalyst, Thereafter, a necessary amount of ethylene oxide may be added. As the catalyst, for example, hydroxides and oxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide barium oxide are preferable, hydroxides are more preferable, and water Sodium oxide and potassium hydroxide are more preferable.

  Since the polyetheramine compound (A) is an amine compound, nitrogen is contained in the hard surface cleaning composition of the present invention. A large amount of nitrogen outflow induces problems such as water pollution in the river and eutrophication, so it is preferable that it be as small as possible. Therefore, in order to reduce the nitrogen content, it is better that the nitrogen content in the polyetheramine compound (A) is small, and the nitrogen content in the polyetheramine compound (A) must be 0.1 to 3% by mass. , Preferably it is 0.3-1 mass%, More preferably, it is 0.5-0.8 mass%. Here, when the nitrogen content exceeds 3% by mass, the nitrogen content in the hard cleaning composition is increased, which may be a problem in drainage regulations and the like. If it is less than%, the cleaning power may be inferior or uneven cleaning may occur.

（式中、Ｒは、炭素数１〜４のアルキル基を表し、平均重合度ｘ及びｙは、０〜４の数を表し、ｘ＋ｙ＝１〜６の数を表す。） Next, the water-soluble polyether solvent (B) will be described. Here, “water-soluble” has the same meaning as the above-mentioned water-solubility, and means that when water and a polyether solvent are mixed one-to-one at room temperature, the entire amount is dissolved or emulsified. . Examples of the water-soluble polyether compound as the component (B) of the present invention include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, diglycerin, triglycerin, and alkylene having 1 to 4 carbon atoms. Examples thereof include oxide adducts, alkyl glyceryl ethers having 1 to 4 carbon atoms, and lower fatty acid esters of the above polyether compounds. Among these, an alkylene oxide adduct of a lower alcohol having 1 to 4 carbon atoms is preferable, and a compound represented by the following general formula (2) is particularly preferable:

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and the average degree of polymerization x and y represents a number of 0 to 4 and x + y = 1 to 6).

  In General formula (2), R removes a hydroxyl group from alcohol represented by ROH, and represents an alkyl group having 1 to 4 carbon atoms. Examples of these alkyl groups include a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group and the like. Among these alkyl groups, an alkyl group having 2 to 4 carbon atoms is preferable and an alkyl group having 4 carbon atoms is more preferable because of good cleaning properties.

  x represents the average degree of polymerization of the oxyethylene group, and y represents the average degree of polymerization of the oxypropylene group. x and y each represents an independent number of 0 to 4, and preferably 0.5 to 3 respectively. It is not preferred that x and y are numbers greater than 4 because water solubility may be lost or cleaning properties may be poor. Moreover, it must be x + y = 1-6, and it is preferable that x + y = 1.5-4.5. If the sum of x and y is greater than 6, it is not preferable because water solubility may be lost or cleaning properties may be poor.

  The compound represented by the general formula (2) can be produced by an arbitrary method. As the most general method, for example, an ethylene oxide is added to an alcohol represented by ROH using the above-described catalyst. In this method, the required amount of propylene oxide is added. Usually, since the polyether compound produced in this way has molecular weight distribution, x and y may become numbers other than an integer as mentioned above.

  In the hard surface cleaning composition of the present invention, the blending ratio of the component (A) and the component (B) is such that the ratio of the component (B) is 0.05 to 50 parts by weight with respect to 1 part by weight of the component (A). More preferably, it is 0.1-30 mass parts, More preferably, it is 0.2-10 mass parts, Most preferably, it is 0.3-3 mass parts. Here, it is not preferable that the component (B) is less than 0.05 parts by mass and exceeds 50 parts by mass with respect to 1 part by mass of the component (A) because the cleaning power may be reduced.

  Furthermore, the hard surface cleaning composition of this invention can add a nonionic surfactant as (C) component. In addition, although (A) component may be classified as a nonionic surfactant, (C) component of this invention is a nonionic surfactant except (A) component. Examples of such nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers (the addition form of ethylene oxide and propylene oxide may be random or block). Good)), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or ethylene oxide adduct thereof, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or ethylene thereof Oxide adduct, fatty acid-N-methylmonoethanolamide or its ethylene oxide adduct, fatty acid die Noramide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl (poly) glycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, N-long chain alkyldimethylamine oxide, etc. The hard surface cleaning composition of the invention can contain one or more selected from these (C) components.

  Among the nonionic surfactants as described above, nonionic surfactants that do not contain nitrogen atoms are preferred, and nonionics that use two types of alkylene oxides, ethylene oxide and propylene oxide, from the viewpoint of suppressing foaming during washing. A surfactant is more preferable, and polyoxyethylene polyoxypropylene alkyl ether (random addition) is still more preferable. The alkyl group that can be used in the polyoxyethylene polyoxypropylene alkyl ether (random addition) preferably has 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms, and still more preferably 10 to 14 carbon atoms. Moreover, 5-20 mol is preferable and, as for the addition mole number of ethylene oxide and propylene oxide, 7-15 mol is more preferable. Furthermore, the molar ratio of ethylene oxide to the total added alkylene oxide is preferably from 50 to 99 mol%, more preferably from 60 to 95 mol%, still more preferably from 65 to 90 mol%. These components (C) are preferably added in an amount of 0 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight with respect to 1 part by weight of the component (A). .

  Furthermore, the hard surface cleaning composition of the present invention can contain a builder as the component (D). Examples of the builder include oxycarboxylic acids such as lactic acid, citric acid, gluconic acid, tartaric acid and malic acid or salts thereof (sodium, potassium, ammonium salts, etc.); dicarboxylic acids such as succinic acid, glutaric acid and malonic acid, or These salts (sodium, potassium, ammonium salts, etc.); aminocarboxylic acids such as ethylenediaminetetraacetic acid and hydroxyethylenediamineacetic acid or salts thereof (sodium, potassium, ammonium salts, etc.); phosphorus such as trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid Salts of acid compounds (sodium, potassium, ammonium salts, etc.); carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate; borate salts such as potassium borate and sodium borate; sodium hydrogen sulfate, Potassium hydrogen sulfate Sulfates such as magnesium hydrogen sulfate; inorganic alkali metal salts such as sodium silicate, sodium metasilicate, potassium silicate, potassium metasilicate and zeolite; alkali metal or alkaline earth metal water such as sodium hydroxide and potassium hydroxide Oxides; organic alkali metal salts such as sodium formate, sodium acetate and sodium oxalate can be mentioned. The hard surface cleaning composition of this invention can contain 1 type, or 2 or more types chosen from these (D) components.

  Among the above builders, oxycarboxylic acids or salts thereof, phosphates, aminocarboxylic acids or salts thereof, alkali metal or alkaline earth metal hydroxides and carbonates are preferred, oxycarboxylates, Alkali metal or alkaline earth metal hydroxides and carbonates are more preferred. These components (D) are preferably added in an amount of 0 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and still more preferably 0.1 to 1 part by weight with respect to 1 part by weight of the component (A). .

  Furthermore, the hard surface cleaning composition of the present invention can be used in combination with other components as long as the effects of the present invention are not impaired. Examples of other components include alcohols such as ethanol, butanol, ethylene glycol, and propylene glycol; low-temperature stabilizers such as lower alkyl sulfonates such as benzene sulfonate and toluene sulfonate; caproic acid and isoheptanoic acid Lower fatty acids having 5 to 10 carbon atoms such as caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid; 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxy Antioxidants such as phenol, 2,5-di-t-butylhydroquinone, DL-α-tocophenol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,9-nona Diol, 1,8-alkylene glycol-based solvents such as octanediol, limonene, can pinene, terpene hydrocarbon solvents such as dipentene, perfumes, dyes, be incorporated together a preservative, and the like.

  The hard surface cleaning composition of the present invention may be used at a high concentration, but is preferably diluted with water. When diluting with water, it is preferable to use after diluting so that the combined concentration of the component (A) and the component (B) is 0.1 to 50% by mass, and 0.2 to 30% by mass. More preferably, 0.3-10 mass% is still more preferable, and 0.5-5 mass% is the most preferable. When the concentration of the component (A) and the component (B) is less than 0.1% by mass, the detergency may be deteriorated. When the concentration exceeds 50% by mass, there is almost no change in performance and the concentration is increased. This is because the meaning of doing so fades economically. If the purpose is distribution, etc., there is no problem even if it exceeds 50% by mass.

  The hard surface cleaning composition of the present invention can be used for cleaning concrete, tile, metal, synthetic resin, rock, glass, enamel, or a paint applied on them, and also for cleaning rubber products, automobile bodies, etc. It can be used, and is particularly useful for household cleaners such as kitchen fans and gas ranges, bath tubs, toilets, and tableware. The hard surface cleaning composition of the present invention can be used in any conventionally known method. For example, the hard surface cleaning composition of the present invention is applied and brushed, and then washed with water. Dirt can be removed by wiping or wiping. Examples of the application method include a method of soaking in a cloth or a brush and applying as it is, a method of spraying by hand spray or mechanical spray, and the like. Examples of the brushing method include a method of brushing by hand or machine using a waste cloth, a cloth brush, a metal brush, a resin brush, or the like. As a wiping method, it may be wiped off with a waste cloth or the like, and may be washed away with tap water. Moreover, the washing | cleaning method using an automatic cleaning apparatus or an ultrasonic wave may be sufficient, and also processing, such as a rinse agent, may be performed after washing | cleaning.

Hereinafter, the hard surface cleaning composition of the present invention will be described more specifically with reference to examples. In the following examples and the like, “%” and “ppm” are based on mass unless otherwise specified.
The cleaning liquid, test plate preparation and test method are described below.
<Adjustment of cleaning liquid>
In Examples 1 to 6, 700 ml of water was put into a 1000 ml beaker equipped with a stirrer, and then each component was sequentially added with stirring according to the recipe shown in Table 1. After all components were added, the mixture was stirred for 30 minutes to prepare a uniform cleaning solution. About Examples 7 and 8, after adding a washing | cleaning liquid only with each component, without putting water, it diluted so that it might become the density | concentration of a recipe. Note that both of the cleaning liquids without water were stable and uniform liquids.

<Cleaning test plate>
The following two types of slate plates were prepared as cleaning test plates.
(1) A 10 cm × 20 cm slate plate was placed outdoors for 3 months to attach water scale.
(2) Carbon black (Mitsubishi Chemical: MA100) 10 parts by mass, mineral oil (Mitsubishi Mitsubishi: Super Oil N22) 45 parts by mass, and soybean oil 45 parts by mass are pseudo-stained and 10 cm × 20 cm I painted it on a slate board. Thereafter, the slate plate coated with pseudo-stain was placed in a high-temperature bath at 150 ° C. for 6 hours to degrade the oil stain and adhere to the slate plate.

<Washing method>
The two types of soiled slate plates were rubbed 5 times on a urethane sponge (110 mm × 65 mm × 30 mm) containing a cleaning agent for evaluation under a load of about 500 g. Subsequent dirt on the slate plate was visually evaluated in the following five stages.
1 ... very good removal of dirt 2 ... good removal of dirt 3 ... some dirt that couldn't be removed 4 ... some unevenness in removing dirt 5 ... some dirt was removed

<Protein denaturation test>
In order to evaluate skin irritation, a protein denaturation test was performed according to the following method according to the method of Miyazawa et al. [Japan Cosmetics Engineers Journal 18 (2), 96-105 (1984)]. That is, a solution 10 obtained by further dissolving 0.025% by mass of ovalbumin (manufactured by Wako Pure Chemical Industries, Ltd.) in an aqueous solution containing sodium sulfate 0.15 mol / liter and sodium phosphate 0.05 mol / liter as a pH 7 buffer solution. 1 mg of the product of the present invention and the comparative product shown in Table 1 were mixed with each milliliter. Immediately after preparation of this solution and after standing at 25 ° C. for 48 hours, the protein denaturation rate was determined by quantifying the amount of ovalbumin using liquid chromatography under the following conditions.
<Conditions>
Column: manufactured by Tosoh Corporation, trade name G-3000
Detector: UV detector, detection wavelength 220 nm
Eluent: Protein denaturation rate (%) of aqueous solution containing sodium sulfate 0.15 mol / liter and sodium phosphate 0.05 mol / liter = 100 × (A−B) / A
A: Ovalbumin amount immediately after preparation B: Ovalbumin amount after standing for 48 hours

<Compound used>
(A) Component A-1: In general formula (1), k, p, r, and t are each 10, m, q, s, and w are each 10 and the nitrogen content is 0.68 mass%. Polyether amine compounds.
A-2: A polyetheramine compound in which k, p, r, and t are 15 in the general formula (1), m, q, s, and w are each 20 and the nitrogen content is 0.40% by mass. .
(B) Component B-1: Polyether solvent of R: propyl group, x: 2.0, y: 1.3 in the general formula (2).
B-2: Polyether solvent of general formula (2): R: n-butyl group, x: 1.0, y: 2.0.
B-3: Diglycerin (C) component C-1:
_{C 12 H 25 -O- (EO)} 8 (PO) 3 -H block copolymer products C-2:
_{C 12 H 25 -O - [(} EO) 8 (PO) 3] -H random copolymer product (D) Component D-1: Sodium citrate D-2: sodium bicarbonate D-3: Sodium hydroxide

Other components E-1: Diethanolamine Nitrogen content 13.3% by mass

  The hard surface cleaning composition of the present invention is used for cleaning concrete, tiles, metals, synthetic resins, rocks, glass, enamel, or those coated with paints, rubber products, automobile bodies, etc. can do.

Claims (5)

  A hard surface cleaning composition comprising a polyetheramine compound (A) having a nitrogen content of 0.1 to 3% by mass and a water-soluble polyether solvent (B). The polyetheramine compound (A) is represented by the following general formula (1)

(Wherein, PO _represents -C _{3 H} 6 O- groups, EO _represents -C _{2 H} 4 O- group, k, p, r and t each represent the number of 3 to 50, The hard surface cleaning composition according to claim 1, wherein m, q, s, and w each represent a number of 1 to 100. The water-soluble polyether solvent (B) is represented by the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and the average degree of polymerization x and y represents a number of 0 to 4 and x + y = 1 to 6). The hard surface cleaning composition according to claim 1 or 2.   Furthermore, the hard surface cleaning composition of any one of Claim 1 thru | or 3 which contains a nonionic surfactant as (C) component.   Furthermore, the hard surface cleaning composition of any one of Claims 1 thru | or 4 which contains a builder as (D) component.