JP2021169556A - Cleaning agent - Google Patents

Abstract

To provide a cleaning agent having excellent detergency under both high and low temperature conditions, and having a small change in viscosity even when the operating temperature changes.SOLUTION: A cleaning agent containing (a) a polyoxyalkylene isodecyl ether-based nonionic surfactant having an average number of added moles of oxyethylene groups of 1 to 6 and an average number of added moles of oxypropylene groups of 1 to 6, (b) a carboxyvinyl polymer, and (c) abrasive material. The cleaning agent has a viscosity change rate of 0.25 or less at a temperature of 10 to 35°C.SELECTED DRAWING: None

Description

The present invention relates to a cleaning agent.

In the industrial field, detergents containing a surfactant and a water-insoluble abrasive are used to remove strong stains such as cutting oil and grease from the skin of hands and feet. This detergent is required to have good detergency and usability, and various studies have been made to improve these performances.

For example, Patent Document 1 describes a non-polyoxyalkylene ether-based non-polyoxyalkylene ether having a hydrophilic group consisting of a polyoxyethylene residue and an oxypropylene residue for the purpose of providing a cosmetic for body cleaning that does not leave a sticky feeling after use. A cosmetic for body cleaning, which comprises an ionic surfactant and scrub particles of a synthetic polymer, is disclosed.

Further, Patent Document 2 describes a copolymer of (meth) acrylic acid and (meth) acrylic acid ester and biodegradable polishing for the purpose of reducing the slimy feeling at the time of washing and improving the rinsing property. A body cleanser containing the material and polyoxyethylene polyoxypropylene propyl heptyl ether is disclosed.

Further, Patent Document 3 has an inorganic value of 350 or more and 500 or less and an organic value of 350 or more and an organic value for the purpose of providing a body detergent having excellent detergency of stains derived from engine oil or cutting oil. Contains a polyoxyethylene polyoxypropylene propyl heptyl ether-based nonionic surfactant having an average addition molar number of oxypropylene residues of 400 or more and 550 or less and an average number of moles of oxypropylene residues of 2.5 or less, and an abrasive. Body cleansers are disclosed.

Japanese Unexamined Patent Publication No. 2006-16402 Japanese Unexamined Patent Publication No. 2012-233128 JP-A-2019-189820

Although the above-mentioned cleaning agents have excellent effects, there is still room for improvement in their detergency. In addition, if the viscosity of the cleaning agent changes significantly depending on the temperature, problems may occur when the cleaning agent is used under low temperature or high temperature conditions. Therefore, an object of the present invention is to provide a cleaning agent having excellent detergency under both high temperature conditions and low temperature conditions and having a small change in viscosity even when the operating temperature changes.

As a result of diligent studies by the present inventors, by using a specific surfactant and a specific thickener in combination, the detergency is excellent under both high temperature and low temperature conditions, and the operating temperature is high. It has been found that a cleaning agent having a small change in viscosity can be provided even if the temperature changes.

The present invention includes the following embodiments.
[1]
A polyoxyalkylene isodecyl ether-based nonionic surfactant having an average number of moles of oxyethylene groups added of 1 to 6 and an average number of moles of oxypropylene groups added of 1 to 6
With carboxyvinyl polymer
Abrasive and
A detergent having a viscosity change rate of 0.25 or less between 10 ° C. and 35 ° C.
[2]
The cleaning agent according to [1], wherein the carboxyvinyl polymer is a carbomer.
[3]
The cleaning agent according to [1] or [2], wherein the carboxyvinyl polymer has a viscosity of 2,000 to 35,000 mPa · s when it is used as a 0.2% neutralized solution.
[4]
The cleaning agent according to any one of [1] to [3] for use on the body.
[5]
The cleaning agent according to any one of [1] to [4] for cleaning oil stains.
[6]
The cleaning agent according to any one of [1] to [5], wherein the average particle size of the abrasive is 1 to 500 μm.
[7]
The cleaning agent according to any one of [1] to [6], wherein the abrasive contains biodegradable particles.

According to the present invention, it is possible to provide a cleaning agent having excellent detergency under both high temperature conditions and low temperature conditions and having a small change in viscosity even when the operating temperature changes.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof.

<Cleaning agent>
In one embodiment of the present invention, a polyoxyalkylene isodecyl ether-based nonionic surfactant having an average number of moles of oxyethylene groups added of 1 to 6 and an average number of moles of oxypropylene groups added of 1 to 6 It contains an agent (hereinafter sometimes abbreviated as "isodecyl-based surfactant"), a carboxyvinyl polymer, and an abrasive, and has a viscosity change rate of 0.25 or less between 10 ° C. and 35 ° C. There is a cleaning agent.

By using the isodecyl-based surfactant in combination with the carboxyvinyl polymer, the detergency can be improved under both low temperature and high temperature conditions, and the temperature-dependent viscosity change can be suppressed. can. When the viscosity of the cleaning agent changes depending on the temperature, for example, when the viscosity becomes high, there arises a problem that the cleaning agent is difficult to come out of the container. On the other hand, when the viscosity is low, the fluidity of the cleaning agent is increased and it becomes difficult to hold the cleaning agent in the soiled portion, and as a result, there arises a problem that cleaning cannot be performed well. Since the cleaning agent according to the present embodiment suppresses the temperature-dependent viscosity change, such a problem can be avoided.

The viscosity of the cleaning agent according to the present embodiment has a viscosity change rate of 0.25 or less, preferably 0.2 or less, and more preferably 0. It is 15 or less. Within this range, the viscosity of the cleaning agent set under the room temperature condition of about 20 ° C., which is normally supplied, does not change much depending on the usage conditions, and excellent handleability and cleaning property can be obtained in the low temperature to high temperature region. ..
This viscosity change rate is calculated by the following formula (1) by calculating the difference between the maximum viscosity and the minimum viscosity when the viscosity is measured in a measurement environment of 5 ° C. between 10 ° C. and 35 ° C. Will be done.
Viscosity change rate = (maximum viscosity-minimum viscosity) / minimum viscosity (1)

The cleaning agent according to the present embodiment preferably has both a maximum viscosity and a minimum viscosity of 3,000 to 16,000 mPa · s in an environment of 10 ° C. to 35 ° C., preferably 5,000 to 13 It is more preferably 000 mPa · s, and even more preferably 7,000 to 11,000 mPa · s. By setting the viscosity of the cleaning agent within the above range, there is an advantage that it is easy to use regardless of the season.

(Surfactant)
The cleaning agent according to the present embodiment has a polyoxyalkylene isodecyl ether-based nonionic surfactant having an average number of moles of oxyethylene groups added of 1 to 6 and an average number of moles of oxypropylene groups added of 1 to 6. Contains activator. By containing an isodecyl-based surfactant, excellent detergency can be exhibited. The isodecyl-based surfactant is preferably one obtained by addition-polymerizing ethylene oxide and propylene oxide to isodecyl alcohol.

As used herein, the term "isodecyl" is a branched alkyl group of _{C 10} H _{21 having a branched methyl group.} The number of branched methyl groups is not particularly limited, but is, for example, 1, 2, 3 or 4. The location of the branched methyl group is not particularly limited.

The average number of moles of oxyethylene groups added is 1 to 6, preferably 2 to 5, and more preferably 3 or 4. The average number of moles of the oxypropylene group added is 1 to 6, preferably 2 to 5, and more preferably 3 or 4. By setting the average number of moles of the oxyethylene group and the oxypropylene group within the above range, the detergency tends to be further improved. In the present specification, the "average number of added moles" means the value of the weighted average when the cleaning agent contains two or more kinds of isodecyl-based surfactants.

The following formulas (1) and (2) can be exemplified as specific structures of the isodecyl-based surfactant, but the structure is not limited thereto.
(IDe) -O- (PO) _n- (EO) _m- H ... (1)
(IDe) -O- (EO) _m- (PO) _n- H ... (2)
[During the ceremony,
iDe is an isodecyl group and
PO is an oxypropylene group
EO is an oxyethylene group
n is 1 to 6, preferably 2 to 5, and more preferably 3 or 4.
m is 1 to 6, preferably 2 to 5, and more preferably 3 or 4. ]

The content of the isodecyl-based surfactant is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and further preferably 7 to 12% by mass, based on the mass of the cleaning agent. By setting the content of the isodecyl-based surfactant to 3% by mass or more, the detergency tends to be further improved. Further, by setting the content of the isodecyl-based surfactant to 20% by mass or less, skin irritation and slimy feeling can be reduced.

The cleaning agent of the present embodiment may further contain a surfactant other than the isodecyl-based surfactant as long as the effect is not adversely affected. Examples of other surfactants include cationic surfactants, amphoteric surfactants, anionic surfactants, and nonionic surfactants (excluding isodecyl-based surfactants).

Examples of cationic surfactants include alkyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium bromide, alkylpentaethoxyammonium chloride, lanolin fatty acid ethylsulfate aminopropylethyldimethylammonium, and cations. Ammonium-based surfactants such as cellulose chemicals; amide-based surfactants such as acyldiethylaminoethylamide, acyldimethylaminopropylamide, and polyoxyethylene fatty acid amide; myristyldimethylamine oxide and the like can be mentioned.

Examples of the amphoteric surfactant include betaine-based surfactants such as alkyldimethylaminoacetate betaine and acylamide propyldimethylaminoacetic acid betaine having 13 or more carbon atoms in the fatty acid residue; N-alkyl-N-carboxymethyl. Imidazolinium-based surfactants such as -N-hydroxyethyl imidazolinium betaine, N-alkyl-N-carboxymethyl-N-hydroxyethylethylenediamine-lauryl sulfate and salts thereof; glycine-based surfactants such as polyoctylpolyaminoethylglycine Activator: Aminopropionic acid-based surfactants such as alkylaminopropionic acid and alkylaminodipropionic acid can be mentioned.

Examples of anionic surfactants include sodium soap having 17 or less carbon atoms; acylsarcosine having 17 or less carbon atoms as a fatty acid residue and a salt thereof, acyl amino acids and salts thereof, acylated peptides and salts thereof, and the like. Amino acid-based surfactants; polyoxyethylene alkyl ether carboxylic acids and salts thereof, polyoxyethylene alkyl ether sulfates and salts thereof, polyoxyalkylene additives such as polyoxyethylene alkyl ether sulfonic acids and salts thereof; alkyl phosphoric acid and its salts. Phosphoric acid-based surfactants such as potassium salt, alkanolamine salt, polyoxyethylene alkyl ether phosphoric acid and its salts; sulfosuccinic acid-based surfactants such as dialkyl sulfosuccinate and its salts, polyoxyethylene sulfosuccinate alkyl ether and its salts Agents; alkylphenol-based surfactants such as alkylphenol ether phosphoric acid esters and salts thereof; sodium laureth sulfate and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene sorbit beeswax, polyoxyethylene castor oil, polyoxyethylene sterol, polyoxyethylene hydrogenated sterol, polyoxyethylene lanolin, and polyoxyethylene lanolin. Polyoxyalkylene ether-based surfactants such as alcohol and polyoxyethylene alkylphenyl formaldehyde condensate; phospholipids such as lecithin; propylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbitan fatty acid esters having 17 or less carbon atoms in fatty acid residues, polyoxyethylene sorbit fatty acid esters in which fatty acid residues are saturated carbon chains, and ester-based surfactants such as polyethylene glycol fatty acid esters. ..

The content of the surfactant other than the isodecyl-based surfactant is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10 based on the mass of the detergent. It is mass%.

(Thickener)
The cleaning agent according to this embodiment contains a carboxyvinyl polymer. By including the carboxyvinyl polymer, the temperature-dependent viscosity change can be suppressed. Examples of the carboxyvinyl polymer include a polymer of acrylic acid and a salt thereof, a compound called carbomer according to the International Nomenclature of Cosmetic Raw Materials (INCI), and the like. In order to suppress the temperature-dependent viscosity change of the cleaning agent containing the isodecyl-based surfactant, it is particularly preferable to use carbomer.

The carboxyvinyl polymer preferably has a viscosity of 2,000 to 35,000 mPa · s when it is used as a 0.2% neutralized solution. The carboxyvinyl polymer having a viscosity in such a range can further suppress the temperature-dependent viscosity change of the cleaning agent. The viscosity of the 0.2% neutralized solution is more preferably 10,000 to 32,500 mPa · s, still more preferably 15,000 to 30,000 mPa · s. A particularly preferred carboxyvinyl polymer is a carbomer having a viscosity within the above range. In addition, in this specification, "0.2% neutralizing solution" is neutralized by adding 18W / W% sodium hydroxide solution to 0.25W / W% thickener solution in an environment of 20 degreeC. , The pH is adjusted to 7.0, purified water is added, and the concentration of the thickener is adjusted to 0.2 W / W%, which means the viscosity of the solution.

The content of the carboxyvinyl polymer is preferably 0.1 to 2.0% by mass, more preferably 0.2 to 1.0% by mass, and further preferably 0. It is 25 to 0.5% by mass. By setting the content of the carboxyvinyl polymer to 0.1% by mass or more, the temperature-dependent viscosity change tends to be further suppressed, and the stability of the cleaning agent (for example, separation suppression, prevention of precipitation of the abrasive material) ) Can be improved. Further, by setting the content of the carboxyvinyl polymer to 2.0% by mass or less, the cleaning agent can be easily taken out of the container.

The cleaning agent of the present embodiment may further contain a thickener other than the carboxyvinyl polymer as long as the effect is not adversely affected. Examples of other thickeners include synthetic polymers (excluding carboxyvinyl polymers) and natural polymers.

Examples of the synthetic polymer include acrylic acid / alkyl methacrylate copolymer, polyvinyl alcohol, polyvinylpyrrolidone, carboxyalkyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and methyl hydroxy. Propyl cellulose, propylene glycol alginate, methoxyethylene maleic anhydride copolymer, polydimethylmethylene piperidinium chloride, vinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, nitrocellulose, polyethylene glycol fatty acid ester, polyethylene distearate Examples thereof include polyoxyethylene fatty acid esters such as glycol, polyoxyethylene fatty acid esters such as methyl glucoside polyoxyethylene dioleate, and methyl glycosides.

Natural polymers include, for example, starch, soluble starch, carboxymethyl starch, methyl starch, cellulose, gelatin, arabic gum, xanthan gum, guar gum, locust bin gum, quince seed, carrageenan, galactan, pectin, mannan, dextran, succinoglucan. , Curdlan, casein, albumin, collagen and the like.

The content of the thickener other than the carboxyvinyl polymer is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, still more preferably 0 to 10% by mass, based on the mass of the cleaning agent. Is.

(Abrasive)
The cleaning agent according to this embodiment contains an abrasive. By using an abrasive, the detergency can be enhanced by the physical friction effect, and dirt can be adsorbed on the particle surface. The polishing material (scrub material) is not particularly limited, and conventionally known materials can be appropriately selected and used. As the polishing material, for example, inorganic particles such as porous silica particles, crystalline cellulose particles, cellulose acetate particles, cellulose particles such as chitosan / cellulose / starch mixture particles, walnut shell particles, corn cochlear particles, apricots. Nuclear particles, polyhydroxybutyrate particles, poly (hydroxybutyrate / hydroxyhexanoate) particles, esterified starch particles, cellulose, cellulose acetate particles, chitosan / cellulose / starch mixture particles, polybutylene succinate particles, polybutylene succin Nate adipate particles, polylactic acid particles, polyethylene succinate particles, polycaprolactone resin particles, polyglycolic acid particles, polytetramethylene adipate co-terephthalate particles, polybutylene adipate terephthalate particles, polybutylene succinate co-adipate co -Telephthalate particles, polybutylene succinate carbonate particles, polybutylene succinate terephthalate particles, polyethylene particles and the like can be mentioned. As the abrasive, one type may be used alone, or two or more types may be used in combination.

The abrasive is preferably biodegradable particles. Since it is a biodegradable particle, it is excellent in degradability when released into the environment, and tends to further improve its environmental suitability. Biodegradable particles include, for example, walnut shell particles, corn cochlear particles, apricot nuclei particles, polyhydroxybutyrate particles, poly (hydroxybutyrate / hydroxyhexanoate) particles, esterified starch particles, cellulose, and the like. Cellulose acetate particles, chitosan / cellulose / starch mixture particles, polybutylene succinate particles, polybutylene succinate adipate particles, polylactic acid particles, polyethylene succinate particles, polycaprolactone resin particles, polyglycolic acid particles, polytetramethylene adipate. Examples thereof include co-terephthalate particles, polybutylene adipate terephthalate particles, polybutylene succinate co-adipate co-terephthalate particles, polybutylene succinate carbonate particles, and polybutylene succinate terephthalate particles.

The average particle size of the abrasive is preferably 1 to 500 μm, more preferably 50 to 400 μm, and even more preferably 100 to 300 μm. By setting the average particle size of the abrasive material within the above range, the detergency tends to be further improved. The average particle size can be measured by a dry particle size distribution meter (Robot Shifter RPS-105M manufactured by Seishin Enterprise Co., Ltd., etc.) in accordance with JIS Z 8801.

The content of the abrasive is preferably 1 to 10% by mass, more preferably 2 to 7% by mass, and further preferably 3 to 5% by mass, based on the mass of the cleaning agent. By setting the content of the abrasive material within the above range, the detergency tends to be further improved. When the content of the abrasive is 1% by mass or more, the detergency tends to be further improved. Further, when the content of the abrasive is 10% by mass or less, physical irritation when used on the body can be suppressed.

(Arbitrary ingredient)
The cleaning agent according to the present embodiment may further contain other optional components in addition to the surfactant, the carboxyvinyl polymer and the abrasive. Examples of the optional component include a pH adjuster, a moisturizer, a solvent and the like. Water is preferable as the solvent.

(PH regulator)
By using a pH adjuster, irritation to the skin can be reduced. The pH adjuster is not particularly limited as long as it is usually used for cleaning agents, but for example, inorganic substances such as sodium hydroxide, potassium hydroxide and aqueous ammonia; trimethylamine, diethanolamine, diethylamine, triethanolamine and the like. Organic amines can be mentioned.

The content of the pH adjuster is preferably 0.1 to 20% by mass, more preferably 0.15 to 5.0% by mass, and further preferably 0.2 to 5.0% by mass, based on the mass of the cleaning agent. It is 3.0% by mass.

(Moisturizer)
By using a moisturizer, it is possible to prevent rough skin due to excessive degreasing, which contributes to an improvement in usability. The moisturizer is not particularly limited as long as it is usually used for cleaning agents, and for example, trimethylglycine, glycerin, hyaluronic acid, urea, uric acid, ammonia, lecithin, lanolin, squalane, squalane, glucosamine, creatinine, etc. Nucleic acid-related substances such as DNA and RNA can be mentioned.

The content of the moisturizer is preferably 0.01 to 20% by mass, more preferably 0.03 to 10% by mass, and further preferably 0.05 to 10% by mass, based on the mass of the cleaning agent. Is.

<Use>
The cleaning agent according to this embodiment is preferably used on the body. The body part is not particularly limited, but it is preferable to use it on the hand. The cleaning agent according to this embodiment is preferably used for cleaning oil stains. The type of oil stain is not particularly limited, and examples thereof include stains caused by engine oil, grease, cutting oil, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited thereto.

<Manufacturing of cleaning agent>
Each component shown in Table 1 below (the unit of the numerical value in the table is mass%) was weighed in a beaker so that the total amount was 500 g, and stirred with a magnetic stirrer for 15 minutes to obtain a cleaning agent. The detergency and temperature-dependent viscosity change of the obtained detergent were evaluated as shown below.

The properties of the thickener used in this example and / or comparative example are shown below.
・ AQUPEC HV-805EG, Sumitomo Seika Chemical Co., Ltd. product, composition: carbomer, 0.2% neutralized solution viscosity: 22,000 mPa ・ s
・ AQUPEC HV-701EDR, Sumitomo Seika Chemical Co., Ltd. product, composition: acrylic acid / alkyl methacrylate copolymer, 0.2% neutralized solution viscosity: 32,000 mPa · s
-Carbopol 980, Lubrizol product, composition: carbomer, 0.2% neutralized solution viscosity: 18,500 mPa · s

<Evaluation method of cleaning agent>
(Cleaning power)
Detergent: Detergent obtained in Examples 1 to 6 and Comparative Examples 1 to 6 Oil model Dirt: Silicon grease (Shin-Etsu Chemical Co., Ltd.) per 1 part by mass of carbon black (SEAST KH N-339 manufactured by Tokai Carbon Co., Ltd.) HIVAC-G manufactured by Kogyo Co., Ltd.) 10 parts by mass mixed well.
Artificial leather A and B: Soft semery 1003 Color: 1
Cleaning evaluation equipment: Martindale wear tester (JAMES H.HEAL & CO.LTD.HALIFAX ENGLAND) Mode: 0.5, number of rubbing 20 times

Set the white artificial leather A cut into a circle with a diameter of 4 cm and the white artificial leather B cut into a circle with a diameter of 13 cm in the Martindale wear tester, and add 0.03 g of the above oil model stain to the artificial leather A. After coating, 0.2 ml of the cleaning agent was applied to the artificial leather B, the artificial leathers A and B were rubbed together using a Martindale wear tester under the above conditions, and then the artificial leather A was washed with water for 10 seconds. The artificial leather after washing with water was captured as an image on a PC by a scanner, and the degree of blackness was visually evaluated as the washed state on the artificial leather according to the following evaluation criteria.
[Evaluation criteria]
AA: Very high detergency A: High detergency B: Low detergency C: Very low detergency

(Temperature-dependent viscosity change)
Put 50 ml of detergent in a beaker, adjust the temperature to 10, 15, 20, 25, 30, 35 ° C in a constant temperature bath, and use Spindle No. 5 using an RVDV-IB type viscometer (manufactured by Brookfield). Then, the viscosity was measured at 20 rpm and evaluated according to the following evaluation criteria.
[Evaluation criteria]
Among the measurements under all 6 temperature conditions, the viscosity change rate by the following formula (1) was measured from the difference between the maximum viscosity and the minimum viscosity, and evaluated according to the following criteria.
A: Viscosity change rate is 0.2 or less B: Viscosity change rate is 0.25 or less and more than 0.2 C: Viscosity change rate is more than 0.25 Viscosity change rate = (maximum viscosity-minimum viscosity) / minimum viscosity (1) )

(Scrub feeling)
Ten panelists were asked to wash their hands using the obtained detergent, and the "scrub feeling" during hand washing was evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: Good scrubbing B: Slightly good scrubbing C: Poor scrubbing

<Evaluation result>
Table 1 shows the evaluation results of the cleaning agent.

Claims (7)

A polyoxyalkylene isodecyl ether-based nonionic surfactant having an average number of moles of oxyethylene groups added of 1 to 6 and an average number of moles of oxypropylene groups added of 1 to 6
With carboxyvinyl polymer
Abrasive and
A detergent having a viscosity change rate of 0.25 or less between 10 ° C. and 35 ° C. The cleaning agent according to claim 1, wherein the carboxyvinyl polymer is a carbomer. The cleaning agent according to claim 1 or 2, wherein the carboxyvinyl polymer has a viscosity of 2,000 to 35,000 mPa · s when it is used as a 0.2% neutralized solution. The cleaning agent according to any one of claims 1 to 3, for use on the body. The cleaning agent according to any one of claims 1 to 4, for cleaning oil stains. The cleaning agent according to any one of claims 1 to 5, wherein the average particle size of the abrasive is 1 to 500 μm. The cleaning agent according to any one of claims 1 to 6, wherein the abrasive contains biodegradable particles.