JP2007154038A - Detergent composition for dry cleaning, cleaning solution for dry cleaning and method for dry cleaning using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning solution for dry cleaning which is not only excellent in detergency and resoiling resistance but also safe and little affects the skin and is easily disposed of after cleaning, moreover prevents discoloration of the solvent. <P>SOLUTION: This detergent composition for dry cleaning used together with a 10-13C cyclic monoterpene and/or a derivative thereof as the solvent is characterized in that the composition comprises at least either of an anionic surfactant and a nonionic surfactant, a cationic surfactant and at least either of a phosphorus-based antioxidant and a sulfur-based antioxidant. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning composition for dry cleaning and a cleaning liquid for dry cleaning that are preferably used for dry cleaning, and a dry cleaning method using the same.

  Conventionally, as a cleaning agent for dry cleaning, one obtained by adding an anionic surfactant or a nonionic surfactant to a petroleum solvent is known (Patent Document 1).

JP 2000-192085 A

  By the way, in dry cleaning, in addition to removing dirt on the object to be cleaned (detergency), for example, preventing once removed dirt from adhering to the object to be cleaned (anti-contamination prevention) and use It is required to satisfy many demands at the same time, such as the high flash point of the solvent to be used, high safety, that the cleaning liquid remaining on the object to be cleaned does not adversely affect the skin, and that the used solvent can be easily treated. It has been.

  However, when a conventional dry cleaning detergent composition mainly composed of a so-called petroleum solvent as described in Patent Document 1 is used, it is difficult to satisfy such many demands in a balanced manner. It was.

Furthermore, the present inventors not only have excellent cleanability and anti-recontamination property in such dry cleaning, but also are safe, have little adverse effect on the skin, and can be used as a cleaning agent that can facilitate post-treatment of the cleaning liquid. , Using a cyclic monoterpene and / or its derivative called a so-called natural citrus solvent as a solvent, and simultaneously adding at least one of a cationic surfactant and a nonionic surfactant and an anionic surfactant Thus, the inventors have found that the cleaning liquid can satisfy various demands as described above in a well-balanced manner and filed a patent application.
That is, the dry cleaning method according to the application uses a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof as a solvent, and includes at least one of an anionic surfactant and a nonionic surfactant, and a cation. A cleaning composition for dry cleaning containing a surfactant is used together with the solvent.

  However, as a result of further research on the dry cleaning as described above, the phenolic antioxidant used together with the solvent and the cleaning composition as described above exhibits an antioxidant function in the long-term operation of the dry cleaning. As a by-product was formed, the new problem was found that the by-product gradually colored the solvent yellow or the like.

  Therefore, the present invention is not only excellent in cleanability and anti-recontamination property in dry cleaning, but also safe and easy after-treatment of the cleaning liquid, and in addition, prevents coloring of the solvent. Let it be an issue.

  In order to solve such a problem, the present invention provides (1) dry cleaning for use in combination with a solvent in which dry monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is used as a solvent. A cleaning composition comprising at least one of an anionic surfactant and a nonionic surfactant, a cationic surfactant, and at least one of a phosphorus-based and sulfur-based antioxidant. (2) As a solvent, a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is blended as a solvent, and the detergent composition includes an anionic surfactant and a nonionic surfactant. At least one of the surfactant, the cationic surfactant, and at least one of the phosphorus-based and sulfur-based antioxidants are arranged. (3) A cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is used as a solvent, and an anionic surfactant and a non-detergent are used as a cleaning composition. There is provided a dry cleaning method characterized by using at least one of an ionic surfactant, a cationic surfactant, and at least one of a phosphorus-based and sulfur-based antioxidant.

  A cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof not only has an excellent detergency, but also has a high flash point and is excellent in safety, and is a natural component. Therefore, it has the characteristic that there is little irritation | stimulation to skin and the process after use is easy. Therefore, by using the solvent as a solvent for dry cleaning, a cleaning liquid for dry cleaning using the solvent has these characteristics.

  Further, by using such a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof as a solvent and using a cationic surfactant as a cleaning agent composition, it is possible to prevent recontamination during cleaning. Is extremely excellent. This is because the soil component separated from the object to be cleaned is stabilized by the action of the cationic surfactant in the solvent and the action of at least one of the anionic surfactant and the nonionic surfactant. This is thought to be easier.

In the present invention, in addition to such a solvent and cleaning composition, at least one of a phosphorus-based and sulfur-based antioxidant can be added to prevent the solvent from being oxidized and to prevent coloring. it can.
In addition, when a phenolic antioxidant is added in the dry cleaning, a synergistic action of the phenolic antioxidant and at least one of a phosphorus-based and sulfur-based antioxidant is used in combination with the solvent. On the other hand, it exhibits an excellent anti-oxidation function and an excellent effect of preventing the coloring of the solvent by the phenolic antioxidant.

  Thus, according to the present invention, in dry cleaning, it is excellent in the washability of the object to be cleaned, prevents recontamination of the object to be cleaned, and has an effect that the used solvent can be easily treated, In addition, there is an extremely excellent effect that oxidation and coloring of the solvent can be prevented in a long-term operation.

Hereinafter, embodiments of the present invention will be described.
The cleaning composition for dry cleaning according to the present invention contains a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof, an anionic surfactant, a cationic surfactant, and a nonionic surfactant. To do.

Cyclic monoterpenes are those in which two isoprenes are bonded in a cyclic manner. Boranes represented by the following formula (1), curans represented by the following formula (2), and compounds represented by the following formula (3): Fencans, p-menthanes represented by the following formula (4), pinanes represented by the following formula (5), and thujans represented by the following formula (6).
In the formulas (1) to (6), R1, R2 and R3 represent a saturated or unsaturated hydrocarbon group having 1 to 2 carbon atoms and may be the same or different from each other.
In the formulas (1) to (6), at least two or more double bonds are included at arbitrary positions that are not adjacent to each other, and a hydroxyl group may be added at an arbitrary position.

  Specific examples of the bornanes represented by the formula (1) include bornane, bornyl, borneol, isoborneol, camphor, camphorquinone, norbornane, norbornyl, camphene and the like.

  Specific examples of the curans represented by the formula (2) include carran, caryl, norcalane, norcaryl and the like.

  Specific examples of the fencans represented by the formula (3) include fencan, fenquil alcohol, fencon and the like.

  Specific examples of the p-menthanes represented by the formula (4) include p-menthane, p-menthyl, limonene, α-terpinene, γ-terpinene, menthol, carveol, perillyl alcohol, α-terpineol, and peryl. Examples include aldehyde, menthone, carvone, piperiton, and plegon.

  Specific examples of the pinanes represented by the formula (5) include pinane, α-pinane, chrysanthenone, berbenone, and norpinane.

  Specific examples of the tsujangs represented by the formula (6) include tsujang, tujiru, and tsujion.

The cyclic monoterpene having 10 to 13 carbon atoms as described above has both sufficient cleaning power and drying property of the object to be cleaned after cleaning, and further, there is little damage to the object to be cleaned at the time of cleaning, There are few restrictions in use, and since it has a high flash point, it has an excellent effect of high safety.
Among them, the cyclic monoterpene having 10 to 11 carbon atoms has a good balance of cleaning power, drying property and safety as described above, and can constitute a cleaning composition with little damage to the object to be cleaned. It can be particularly preferably used.

  When the number of carbon atoms is 9 or less, it is no longer a cyclic monoterpene in the first place, and it has both sufficient detergency and dryness of the object to be washed, but the molecular polarity increases. The object to be cleaned becomes more damaged during cleaning. Moreover, the flash point is lowered by the decrease in the molecular weight, and a highly safe cleaning composition cannot be obtained.

  On the other hand, when the number of carbon atoms is 14 or more, the object to be cleaned is less damaged at the time of cleaning, and the safety is higher, but the cleaning power is lowered and the drying property of the object to be cleaned after cleaning is inferior. It is not preferable in terms. Moreover, when the molecular weight of cyclic monoterpene becomes large, it is not preferable at the point that biodegradability falls and disposal processing becomes difficult.

Furthermore, the derivative of the cyclic monoterpene refers to one in which R1 to R3 in the formulas (1) to (6) are groups having 1 to 2 carbon atoms, excluding the cyclic monoterpene. .
Specific examples of R1 to R3 include an alkyl group, a vinyl group, an alkoxyl group, and an aldehyde group, and an alkyl group and a vinyl group are preferably used. When an alkyl group or a vinyl group is used, there is an effect that cleaning of dirt becomes more effective without damaging the fibers of the object to be cleaned.

Of the cyclic monoterpenes and / or derivatives thereof as described above, p-menthanes (formula 4) and tsujans (formula 6) in which the side chain is coordinated to the carbocyclic ring in the para position are preferred. ). Since these p-menthanes (Formula 4) and Tsujang (Formula 6) are liquid, they are in a form suitable as a cleaning composition for dry cleaning, are easy to handle and have relatively little irritation to the skin. There is an advantage of less.
In particular, among p-menthanes (Formula 4), p-menthane, p-menthyl, limonene, and γ-terpinene are more preferably used, and among the tsujangs (Formula 6), tsujang is more preferably used.

  Examples of the cationic surfactant used in the cleaning composition for dry cleaning of the present invention include alkylamine salt type cationic surfactants, acylamine salt type cationic surfactants, and quaternary ammonium salt type cationic surfactants. Agents, amide bond-containing ammonium salt type cationic surfactants, ester bond or ether bond-containing ammonium salt type cationic surfactants, imidazoline or imidazolium salt type cationic surfactants, and the like. These may be used alone or in combination of two or more.

The alkyl amine salt type cationic surfactants, specific examples of acyl amine salt type cationic surfactants, for example, primary amine salts having an alkyl group of C ₁₂ ~ ₁₈ (hydrochloride, acetate, etc.), C ₁₇ alkyl group or an acyl aminoethyl diethylamine salt having an alkenyl group (hydrochloride, formate, acetate, lactate salts), N- alkyl polyalkylene polyamine salt (hydrochloride having an alkyl group of C ₁₂ ~ _18, acetates , C number of alkylene group is 2 to 3, repeating number of alkylene amine group is 1 to 3), fatty acid polyethylene polyamide salt having C ₁₇ alkyl group or alkenyl group (hydrochloride, repeating number of ethylene amine group is 2) , diethylaminoethyl amide salt having an alkyl group of C ₁₇ (hydrochloride, acetate, lactate salts). These may be used alone or in combination of two or more.

The quaternary ammonium salt type cationic surfactants, specific examples of the amide bond-containing ammonium salt type cationic surfactants, for example alkyl or alkenyl trimethyl ammonium salt having an alkyl or alkenyl group of C ₁₈ of C ₁₂ ~ ₁₈ (anion _{^{Cl -, Br -, C 2}} H 5 SO 4 -, CH 3 SO 4 - , etc.), alkyl or alkenyl dimethylethyl ammonium salts (anions having an alkyl or alkenyl group of C ₁₈ of C ₁₂ ~ ₁₈ ions _{^{Cl -, Br -, C 2}} H 5 SO 4 -, CH 3 SO 4 - , etc.), a dialkyl or dialkenyl dimethyl ammonium salts (anions having an alkyl or alkenyl group of C ₁₈ of C ₁₂ ~ ₁₈ are _{^{Cl -, Br -, C 2}} H 5 SO 4 -, CH 3 SO 4 -), alkyl or alkenyl group C ₁₈ of C ₁₂ ~ ₁₈ Alkyl or alkenyl dimethyl benzyl ammonium salts having (anion ^{_{Cl -), C 12 ~ 18}} ( anion Cl ^-, Br -) alkyl pyridinium salts having an alkyl ^group, alkenyl group or C ₁₇ of C ₁₇ Acylaminoethylmethyldiethylammonium salt having a group (an anion is CH ₃ SO ₄ ⁻ ), acylaminopropyldimethylbenzylammonium salt having an alkyl group of C ₁₃ (an anion is Cl ⁻ ), having an alkyl group of C ₁₇ acyl aminopropyl dimethyl hydroxyethyl ammonium salts (anions Cl ^-) - diacyl which have an alkyl or alkenyl group of C ₁₇ of C _17, acyl aminoethyl pyridinium salt having an alkyl group of C ₁₁ (anion ^Cl) Aminoethyldimethylammonium salt (anion is C l ^-, Note that one of the methyl groups may be made to the hydroxyethyl group). Moreover, the compound etc. which cationized tertiary amines, such as a trialkyl or an alkenyl dialkylamine, using quaternizing agents, such as a xylenyl dichloride, etc. are mentioned. These may be used alone or in combination of two or more.

Specific examples of the ester bond or an ether bond-containing ammonium salt type cationic surfactants, for example, Zia siloxy ethyl methyl hydroxyethyl ammonium salt (anion having an alkyl or alkenyl group of C ₁₇ of C ₁₇ is CH ₃ SO ₄ ^-), alkyloxy pyridium salt (anion having an alkyl group of C ₁₆ is Cl ^-) and the like. These may be used alone or in combination of two or more.

Specific examples of the imidazoline or imidazolium salt type cationic surfactant include, for example, alkyl or alkenyl imidazoline having an alkyl group of C ₁₁ to ₁₇ or an alkenyl group of C ₁₇ (acetates, carbonates, quaternized compounds). , C ₁₁ (also quaternary compound) 1-hydroxyethyl 2-alkyl or alkenyl imidazoline having an alkenyl group of alkyl or C ₁₇ to _17, 1-acyl aminoethyl having an alkyl or alkenyl group of C ₁₇ -2-alkylimidazolium salts (anions are CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , an alkyl group at the 2-position is a methyl group or an ethyl group), and the like. These may be used alone or in combination of two or more.

  The said cationic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. Of these cationic surfactants, quaternary ammonium salt type cationic surfactants are particularly preferable from the viewpoint of excellent solubility and stability in cyclic monoterpenes and / or derivatives thereof.

  Examples of the anionic surfactant used in the cleaning composition for dry cleaning of the present invention include a carboxylic acid type anionic surfactant, a sulfate ester type anionic surfactant, a sulfonic acid type anionic surfactant, and a phosphate ester type. Anionic surfactants and the like can be mentioned. These may be used alone or in combination of two or more.

  Specific examples of the carboxylic acid type anionic surfactant include fatty acid salts, rosinates, naphthenates, ether carboxylates, alkenyl succinates, N-acyl glutamates, and the like. These may be used alone or in combination of two or more.

  Specific examples of the sulfate ester type anionic surfactant include a first alkyl sulfate, a second alkyl sulfate, an alkyl polyoxyethylene sulfate, an alkylphenyl polyoxyethylene sulfate, a monoacylglycerol sulfate, and an acylaminosulfate. Salts, olive oil, castor oil, cottonseed oil, rapeseed oil, sulfated oils in which the double bonds and hydroxyl groups in the fats and oils are sulfated salts (partially acylglycerin is hydrolyzed and sulfated) Examples thereof include a sulfated fatty acid alkyl ester which is a salt of a sulfated product such as a double bond such as oleic acid or ricinoleic acid or a propyl or butyl ester of a fatty acid having a hydroxyl group. These may be used alone or in combination of two or more.

A sulfonic acid type anion Specific examples of surfactants, for example C ₁₄ ~ is ₁₉ α- olefin sulfonated α- olefin sulfonate (AOS) salts, SO ₂ to n- paraffins C ₈ ~ _20, second alkane sulfonates obtained a sulfoxy compound or Suruhokuroru products of Cl ₂ and neutralized with an alkali, methyl fatty acid C ₁₂ ~ _18, a salt of alpha-sulfonated or isopropyl esters, alpha-sulfo fatty acid ester salt , Acyl isethionate, N-acyl-N-methyl taurate, dialkyl sulfosuccinate, alkyl benzene sulfonate (ABS, LAS), alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, petroleum sulfonate, lignin sulfone Examples include acid salts. These may be used alone or in combination of two or more.

  Specific examples of the phosphate ester type anionic surfactant include, for example, an alkyl phosphate salt ((1) phosphate monoester salt, (2) diester salt, (3) a mixture of (1) and (2) ), Alkyl polyoxyethylene salt of phosphate (usually present as a mixture with diester salt), alkyl polyoxyethylene salt of phosphate (usually present as a mixture of monoester salt and diester salt), etc. . Moreover, the sulfate ester salt (Na salt, K salt, etc.) of the said styrenated phenol polyalkylene oxide adduct, the sulfate ester salt (Na salt, K salt, etc.) of the said benzylated phenol polyalkylene oxide adduct, etc. are mentioned.

  The said anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. Among these anionic surfactants, alkylbenzene sulfonates and dialkylsulfosuccinates are particularly preferable from the viewpoint of excellent solubility and stability in cyclic monoterpenes and / or derivatives thereof.

  Specific examples of the nonionic surfactant used in the cleaning composition for dry cleaning of the present invention include, for example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, fatty acid alkanolamide compounds, polyalkylene polyamine polyalkylenes. Examples include oxide adducts, polyhydric alcohol fatty acid esters, and polyhydric alcohol fatty acid ester polyalkylene oxide adducts.

  These may be used alone or in combination of two or more. Of these nonionic surfactants, polyoxyalkylene alkyl ethers are particularly preferred from the viewpoint of excellent solubility and stability in cyclic monoterpenes and / or derivatives thereof.

  As the formulation of the cleaning composition for dry cleaning of the present invention, the cationic surfactant is contained in an amount of 1 to 90% by weight, preferably 10 to 40% by weight, and the anionic surfactant is contained in an amount of 0 to 60% by weight, preferably 1 to 30% by weight and 0 to 60% by weight, preferably 1 to 30% by weight of a nonionic surfactant.

  Examples of phosphorus antioxidants used in the present invention include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, diphenyl diisooctyl phosphite, diphenyl diisodecyl phosphite. Phyto, triphenyl phosphite, trisnonylphenyl phosphite, tris-di-nonylphenyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, distearyl-pentaerythritol diphosphite, bis ( Nonylphenyl) pentaerythritol diphosphite, 4,4′-isopropylidene diphenol alkyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl di-tridecyl phosphite), 1,1 , 3-Tris 2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) butane, tetrakis (2,4-di-tert-butylphenyl) -4,4′-bisphenylene diphosphite, 3,4 , 5,6-dibenzo-1,2-oxaphosphan-2-oxide, trilauryl trithiophosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl di (tridecyl) phosphite, diphenyl tridecyl phosphite Phyto, phenyl-bisphenol A pentaerythritol diphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid diethyl ester, and the like.

  Further, as the sulfur-based antioxidant used in the present invention, dilauryl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester, distearyl-3,3′- Thiodipropionate, ditridecyl-3,3′-thiodipropionate, lauryl stearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole and the like.

  The phosphorus-based or sulfur-based antioxidants may be used alone, or two or more phosphorus-based antioxidants, two or more sulfur-based antioxidants, or a combination of two or more phosphorus-based and sulfur-based antioxidants. Good.

The phosphorus-based or sulfur-based antioxidant is preferably added so as to have a concentration of 1 to 10,000 ppm in the solvent to be used, and is added so as to have a concentration of 50 to 200 ppm. It is more preferable.
In addition, since the phosphorus-based or sulfur-based antioxidant is consumed in dry cleaning together with the cleaning composition for dry cleaning, it is usually used for dry cleaning in order to maintain the concentration in the solvent as described above. It is preferable to add 0.001-1 weight part with respect to 100 weight part of cleaning composition, and adding 0.01-0.1 weight part is more preferable.
When the addition amount is less than 0.001 part by weight, the antioxidant effect cannot be expected so much. Moreover, since the price will become high when the addition amount exceeds 1 part by weight, it is not preferable.

  In the present invention, a phenol-based antioxidant and a phosphorus-based or sulfur-based antioxidant can be used in combination. By using this phenolic antioxidant in combination, it becomes possible to prevent the oxidation of the solvent more effectively, and since it is used in combination with a phosphorus-based or sulfur-based antioxidant, the phenolic antioxidant is prevented. It is possible to prevent the solvent from being colored due to the antioxidant function of the agent.

  Examples of the phenolic antioxidant include 2,6-di-t-butylphenol, 2-t-butyl-4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, and 2,4-diethyl-6- t-butylphenol, 2,6-di-t-butyl-p-cresol (BHT), 4,6-bis (octylthiomethyl) -o-cresol, 2,6-di-t-butyl-4-ethylphenol 2,6-di-t-butyl-4-hydroxymethylphenol, 2,6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, n-octadecyl-β- (4′- Hydroxy 3 ', 5-di-t-butylphenyl) propionate, 2,4- (n-octylthio) -6- (4-hydroxy 3', 5'-di-t-butylanilino) -1,3,5- Triazine Styrenated phenol, styrenated cresol, tocophenol, 2-t-butyl-6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,2′- Methylene bis (4-methyl-6-tert-butylphenol), 2,2′-methylene bis (4-ethyl-6-tert-butylphenol), 2,2′-methylene bis (4-methyl-6-cyclohexylphenol), 2, 2′-dihydroxy-3,3′-di (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2,2′-ethylidene-bis (2,4-di-tert-butylphenol), 2,2 ′ -Butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylide Bis (3-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis-3- (-T-butyl-4-hydroxy-5-methylphenyl) propionate, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N '-Hexamethylenebis- (3,5-di-t-butyl-4-hydroxy) hydrocinnamide, 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2-thiodiethylenebis- [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-t Butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-4-hydroxybenzyl) ) Isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) -4-hydroxyphenyl) propionate] methane, calcium (3,5-di-t-butyl-4-hydroxybenzylmonoethyl phosphonate), propyl gallate, octyl gallate , Lauryl gallate, 2,4,6-tri-t-butylphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,1,3-tris- (2 -Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,8,10-tetraoxaspiro [5 , 5] undecane and the like, and one or more of these can be used.

Moreover, it is preferable to add the said phenolic antioxidant so that it may become a density | concentration of 1-10000 ppm in the solvent used, and it is more preferable to add so that it may become a density | concentration of 50-200 ppm. preferable.
In addition, since the phenolic antioxidant is consumed in the dry cleaning together with the cleaning composition for dry cleaning, in order to maintain the concentration in the solvent as described above, the cleaning composition for dry cleaning is usually used. It is preferable to add at a ratio of 0.001 to 1 part by weight with respect to 100 parts by weight of the product, and it is more preferable to add at a ratio of 0.01 to 0.1 part by weight.

Further, in the cleaning composition for dry cleaning according to the present invention, other components can be added within a range not impairing the effects of the present invention. Other components include, for example, cyclic monoterpenes and / or derivatives thereof used as a solvent and other petroleum solvents (hereinafter, the solvent in the cleaning composition is also referred to as “solvent component”), as a dissolution aid. Examples include high-boiling alcohol solvents such as functional glycol ethers, silicone oils that function as smoothing agents, water, and rust inhibitors.
By adding a solvent component, there is an effect that the viscosity of the cleaning composition for dry cleaning is lowered and it is easy to use.
When the solvent component is added to the cleaning composition for dry cleaning according to the present invention, the solvent component is preferably added so that the total amount of the solvent component is 1 to 90% by weight, and is added so as to be 30 to 60% by weight. More preferably.
When the total amount of the solvent components is less than 1% by weight, it tends to be difficult to maintain stability and viscosity, and when it exceeds 90% by weight, the cleaning effect as a detergent tends to be weakened.

  The cleaning liquid for dry cleaning according to the present invention contains the cyclic monoterpene and / or a derivative thereof as a solvent, and at least one of the anionic surfactant or the nonionic surfactant as a cleaning composition, It contains a cationic surfactant and at least one of the phosphorus-based or sulfur-based antioxidant.

  The cleaning liquid for dry cleaning of the present invention may contain a petroleum solvent in addition to the cyclic monoterpene and / or its derivative. By adding petroleum solvent, the solvent unit price can be reduced. The blending amount of the petroleum solvent is not particularly limited as long as it does not hinder the effects of the cyclic monoterpene and / or derivative thereof and the surfactant, which are solvents, but is usually 80% by weight with respect to the total amount of the solvent. It is preferable to make it less than%.

The petroleum solvent, for example, those composed mainly of hydrocarbon oils C ₉ ~ ₁₁ such as naphthene and paraffin.
Of these, normal decane is particularly preferable from the viewpoint of low drying properties and odor.

  The composition of the cleaning liquid for dry cleaning according to the present invention usually comprises 95 to 99.99% by weight of the solvent and 0.01 to 5% by weight of the cleaning composition, preferably 99 to 99.99% of the solvent. 9% by weight, and the cleaning composition comprises 0.1 to 1% by weight.

The dry cleaning method of the present invention is a method of cleaning an object to be cleaned using the above-described cleaning liquid for dry cleaning.
Specifically, first, an object to be cleaned is immersed in the cleaning liquid, and further cleaned by applying physical external force such as stirring, rotation, dropping, vibration, or the like. Dirt components adhering to the object to be cleaned can be eluted in the cleaning liquid by dipping, and by applying a physical external force, the cleaning liquid penetrates into the details of the object to be cleaned and promotes separation of fibers and dirt components. As a result, the cleaning efficiency can be improved.

  Further, in cleaning, the cleaning liquid can be heated, and preferably by heating to about 25 ° C., the solubility of the soil component in the cleaning agent can be improved and the cleaning efficiency can be improved. . In addition, from the viewpoint of the risk of ignition and damage to clothing, when the temperature exceeds 25 ° C., the cleaning liquid can be appropriately cooled.

  After the cleaning, the object to be cleaned and the cleaning liquid from which the soil components are eluted are separated, and the object to be cleaned is dried. This separation and drying can prevent the cleaning liquid from remaining in the object to be cleaned and reduce the risk of chemical burns. As a separation method, a method using squeezing or centrifugal force can be employed. Moreover, as a drying method, although it is based on normal temperature or by heating, any method is possible, However, The method by heating is preferable from a viewpoint of accelerating drying. As heating temperature, 40-80 degreeC is preferable, and if it is this temperature range, it will become a thing with few damages of a to-be-cleaned object, promoting drying.

The cleaning liquid separated from the object to be cleaned can be used again for dry cleaning. In this case, the cleaning power can be maintained by adding a new cleaning liquid according to the amount of the soil component in the cleaning liquid.
In addition, the cleaning solution from which the soil components are eluted may be used again after being distilled or filtered through a cartridge filter. A cleaning solution containing almost no dirt component can be obtained by distillation or filtration with a cartridge filter.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Preparation of cleaning liquid for dry cleaning Based on the blending ratio shown in Table 1 below, a cleaning liquid for dry cleaning was prepared. In addition, about the solvent and surfactant, the following were used.

Cationic surfactant: Alkyldimethylethylammonium salt solubilizer: 3-methoxy-3-methyl-1-butanol Nonionic surfactant: Sorbitan fatty acid ester solvent: Limonene (in formula (4), R1 to R3 are all CH ₃ is a cyclic monoterpene)
Phenol antioxidant: 2,6-di-t-butyl-p-cresol (BHT)
Phosphorous antioxidant A: 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite
(Product name “ADKSTAB HP-10” manufactured by Asahi Denka Kogyo Co., Ltd.)
Sulfur-based antioxidant: dimyristyl-3,3-thiodipropionic acid ester

Solvent coloring test method and evaluation method The dry cleaning cleaning liquids of Examples and Comparative Examples were added at a ratio of 2% by weight with respect to the solvent, and 1 g of activated carbon was added to 25 ml of the solvent, and left for 8 days. Then, the presence or absence of discoloration of the liquid was evaluated by measuring the liquid transmittance using a transmittance meter (GEMBU PHOTO COLORIMTER MODEL GC-111).
The results of the above test are shown in Table 1.

  As shown in Table 1, in the case of the comparative example to which the phenolic antioxidant was added, the solvent was colored yellow and the transmittance was reduced to 78%, whereas the phosphoric or sulfur antioxidant was used. In the case of the Example which used the agent together, it turns out that coloring of the solvent is suppressed.

(Reference test)
Furthermore, the presence or absence of coloring by addition of the following phosphorus antioxidant was evaluated with respect to the mixture of the solvent and phenolic antioxidant mentioned above.

Phosphorous antioxidant B: Tris (2,4-di-t-butylphenyl) phosphite
(Brand name "IRGAFOS 168" manufactured by Chivas Health Chemical)
In addition, about the test method and evaluation method of coloring, it carried out like the above except having made the test days into 6 days. The results are shown in Table 2.

  The above test is positioned as a reference example because it does not contain at least one of a phosphorus-based or sulfur-based antioxidant, but when a different type of phosphorus-based antioxidant is used than in the above examples Even in this case, it was confirmed that coloring of the cleaning liquid can be prevented.

Claims (3)

In a dry cleaning in which a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is used as a solvent, a cleaning composition for dry cleaning used together with the solvent,
A cleaning for dry cleaning comprising at least one of an anionic surfactant and a nonionic surfactant, a cationic surfactant, and at least one of a phosphorus-based and sulfur-based antioxidant Agent composition.   As the solvent, a cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is blended, and as the detergent composition, at least one of an anionic surfactant and a nonionic surfactant, a cationic surfactant, A cleaning liquid for dry cleaning, comprising at least one of phosphorus-based and sulfur-based antioxidants.   A cyclic monoterpene having 10 to 13 carbon atoms and / or a derivative thereof is used as a solvent, and at least one of an anionic surfactant and a nonionic surfactant as a cleaning composition, a cationic surfactant, A dry cleaning method comprising using at least one of phosphorus-based and sulfur-based antioxidants.