Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/325—Amines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/402—Amides imides, sulfamic acids
  • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/46—Compounds containing quaternary nitrogen atoms
  • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups

Definitions

• the present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softener composition having excellent storage stability.
• Cationic surfactants are known to be useful as softeners because they have the effect of imparting a texture to the fibers. It is also known that when silicone is combined with a cationic surfactant, the texture-imparting effect is further improved.
• silicones amino-modified silicones are known to act on wet articles after dehydration during washing and to provide excellent texture imparting effects (Patent Documents 1 to 3). .
• softeners containing silicone are known to have insufficient storage stability.
• Patent Document 3 blending urea
• Patent Document 4 blending a compound capable of generating hydrogen peroxide
• Patent Document 5 blending a compound capable of generating hydrogen peroxide
• Patent Document 6 blending a compound capable of generating hydrogen peroxide
• Nonionic surfactant and carboxylic acid type amphoteric surfactant
• blend urea is known.
• softening agent containing ester quaternary ammonium it is known to mix
• JP 2008-150756 A JP 2000-110077 A Japanese Patent Laid-Open No. 4-50373 JP 2007-284843 A Japanese Patent Laid-Open No. 2003-3378 JP 2002-515551 A JP 2004-211230 A Japanese Patent Laid-Open No. 2004-21112 JP 2012-202000 A JP 2007-284843 A
• the inventors combined amino-modified silicone, a specific type of cationic surfactant, and urea at a specific ratio, and preserved the function as a softening agent. It has been found that stability can be improved (especially, changes in scent formation, scent quality, yellowing, viscosity and fluidity during storage) can be suppressed, and the present invention has been completed. That is, the present invention relates to the following 1 to 7.
• A one or more cationic surfactants selected from the group consisting of an amine compound containing at least one hydrocarbon group having 10 to 24 carbon atoms in the molecule, a neutralized product thereof, and a quaternized product thereof.
• the hydrocarbon group may be separated by one or more groups selected from the group consisting of an ester group, an ether group and an amide group, (B) amino-modified silicone, and (C) urea, its double salt, and general formula (C):
• R a is a methyl group, an ethyl group or a hydroxyalkyl group having 1 to 2 carbon atoms
• R b , R c and R d are each independently a hydrogen atom, a methyl group or an ethyl group.
• (A) is represented by the following general formulas (A-III), (A-IV) and (A-V): (In each of the general formulas, R 1 is a hydrocarbon group having 15 to 17 carbon atoms which may be the same or different.) Agent composition.
• liquid softener composition as described in any one of 1 to 3 above, wherein (B) is an emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at a terminal with a surfactant. .
• liquid softener composition as described in any one of 1 to 5 above, further comprising (L) trehalose.
• liquid softener composition as described in any one of 1 to 6 above, further comprising (N) a highly branched cyclic dextrin.
• the liquid softener composition as described in any one of 1 to 7 above.
• the liquid softener composition of the present invention improves the storage stability while maintaining the function as a softener (especially the fragrance during storage, the quality of the fragrance, the yellowing, The change in viscosity and fluidity can be sufficiently suppressed). Furthermore, as shown in the examples described later, the liquid softener composition of the present invention has the above-mentioned storage stability and is washed at a low bath ratio (particularly, drying using a dryer is used in combination). In this case, it is possible to suppress the deterioration of the texture of the object to be washed and the generation of odor. Therefore, the present invention is useful as a softener having an added value not found in conventional liquid softener compositions.
• the component (A) contained in the liquid softener composition of the present invention, together with the component (B) described later, has an effect of imparting a texture (including smoothness) to the fibers (that is, the original function of the softener). Is added to the liquid softener composition.
• the component (A) is selected from the group consisting of an amine compound containing one or more hydrocarbon groups having 10 to 24 carbon atoms in the molecule, a neutralized product thereof, and a quaternized product thereof, and as a cationic surfactant. It functions. In the amine compound, the hydrocarbon group is bonded to a nitrogen atom, and the number of hydrocarbon groups bonded to the nitrogen atom is 1 to 3.
• the hydrocarbon group has 10 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and particularly preferably 14 to 18 carbon atoms. Further, the hydrocarbon group may be separated by one or more groups selected from the group consisting of an ester group, an ether group and an amide group. Among ester groups, ether groups and amide groups, ester groups are particularly preferred. When the group to be split is an ester group or an amide group, the number of groups to be split is one for each hydrocarbon group. In the case where the group to be split is an ether group, the number is one per hydrocarbon group.
• the neutralized product is a compound obtained by neutralizing the above amine compound with an acid.
• the acid used for neutralization examples include hydrochloric acid, sulfuric acid, methyl sulfuric acid, and paratoluenesulfonic acid.
• the neutralized product is preferably in the form of an amine salt.
• the neutralized product is produced by dispersing an amine compound that has been neutralized with an acid in advance, adding a liquid or solid amine compound into an aqueous acid solution, or simultaneously adding an amine compound and an acid into water, etc. Can be performed.
• a quaternized product is a compound obtained by treating a compound having 3 hydrocarbon groups bonded to a nitrogen atom (tertiary amine) with a quaternizing agent among the above amine compounds.
• a quaternizing agent examples include methyl chloride and dimethyl sulfate.
• Examples of the amine compound of component (A) include compounds represented by any one of the following general formulas (AI) to (A-VII), neutralized products thereof, or quaternized products thereof.
• R 1 may be the same or different from a hydrocarbon group having 15 to 17 carbon atoms (in other words, from a fatty acid having 16 to 18 carbon atoms). Residue derived by removing the carboxyl group).
• Preferred fatty acids for inducing R 1 include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, partially hydrogenated palm oil fatty acid (iodine value 10-60), and partially hydrogenated beef tallow fatty acid (iodine). Valence 10-60) and the like.
• it is a mixture of stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid and linolenic acid, and the mass ratio of saturated fatty acid / unsaturated fatty acid is 95/5 to 50/50, cis isomer / trans isomer Is 40/60 to 80/20, iodine value is 10 to 50, and the fatty acid content of 18 carbon atoms is 80% by mass or more based on the total mass of the mixture, and the total amount of linoleic acid and linolenic acid is the total amount of the mixture
• the mixture is 2% by mass or less based on the mass.
• the said composition is said fatty acid mixture or
• the methyl esterified product can be synthesized by a condensation reaction of methyldiethanolamine.
• methyl chloride or the like is used as the quaternizing agent.
• dimethyl sulfate can be used, methyl chloride is preferred because it has a low molecular weight and can reduce the amount required for quaternization.
• the quaternized product in which the mass ratio of each quaternized product is (A-II) / quaternary product in (AI) 99 / It is preferable to synthesize so as to be 1 to 50/50.
• the component (A) a composition comprising a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a compound represented by the general formula (A-V)
• the composition can be synthesized by subjecting the fatty acid composition or its methyl esterified product to a condensation reaction with triethanolamine.
• a composition containing dimethylsulfate, methyl chloride, dimethyl sulfate, or the like can be used as the quaternizing agent, but dimethyl sulfate is preferred from the viewpoint of the reactivity of the quaternization reaction.
• an unreacted product that is, a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a general formula (A-V) The compound represented
• A-III a compound represented by the general formula (A-IV)
• A-V general formula
• the said composition is the said fatty acid composition, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine (Adduct of N-methylethanolamine and acrylonitrile according to the method described in J. Org. Chem., 26, 3409 (1960)) Can be synthesized by a condensation reaction.
• compositions a quaternized product of the compound represented by the general formula (A-III), a quaternized product of the compound represented by the general formula (A-IV), and the general formula (A-V).
• a composition containing a quaternized product of the compound represented by is such that the quaternized product of the compound represented by (A-III) is based on the total mass of the composition.
• the quaternized product of the compound represented by (A-III) is 10 to 55% by mass with respect to the total mass of the composition, and the quaternized product of the compound represented by (A-IV) is 30%.
• the quaternized product of the compound represented by (A-V) is 5 to 35% by mass.
• a component may be used individually by 1 type and may be used as a mixture which consists of 2 or more types. When used as a mixture, if the content of the amine compound having 2 or 3 hydrocarbon groups bonded to the nitrogen atom is 50% by mass or more based on the total mass of the mixture, the function as a softener is further enhanced. This is preferable.
• the blending amount of the component (A) is not particularly limited, but is preferably 10 to 30% by mass, more preferably 10 to 25% by mass with respect to the total mass of the liquid softening agent composition.
• (B) component contained in the liquid softening composition of this invention is mix
• the amino-modified silicone as component (B) is a compound formed by introducing amino groups at both ends or side chains of the dimethyl silicone skeleton.
• Preferred amino-modified silicones have the following general formula (B):
• R is independently selected from the group consisting of —H, —OH, —CH 3 and —Si (CH 3 ) 3
• X is — (CH 2 ) a —NH 2 , or , — (CH 2 ) a —NH (CH 2 ) b NH 2 (a is an integer from 0 to 3, b is an integer from 1 to 3), n is from 1 to 1500, and m is 1 to 20, and a compound obtained by introducing an amino group into the side chain X.
• the amino-modified silicone may be in the form of oil (silicone oil), or may be in the form of an emulsion (silicone emulsion) emulsified by using a nonionic surfactant or a cationic surfactant as an emulsifier.
• the kinematic viscosity at 25 ° C. is preferably 50 to 20000 mm 2 / s, and more preferably 500 to 10,000 mm 2 / s.
• the kinematic viscosity can be measured with an Ostwald viscometer.
• the amino equivalent of the silicone oil is preferably 100 to 10,000 g / mol, more preferably 1200 to 4000 g / mol. An amino equivalent within this range is preferable because the function as a softening agent is good.
• the amino equivalent can be determined by dividing the weight average molecular weight of the amino-modified silicone by the number of nitrogen atoms contained in the amino-modified silicone. The number of nitrogen atoms can be determined by elemental analysis.
• the viscosity of the base silicone oil is 1,000 mm 2 / s or more, more preferably 10,000 mm 2 / s or more.
• the emulsifier in the emulsion include a cationic surfactant and a nonionic surfactant, and a cationic surfactant is preferable.
• a particularly preferred component (B) is an emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at the terminal with a surfactant.
• This emulsion is preferable because the degree of yellowing during storage of the liquid softening agent composition is the smallest and the effect of improving the texture is excellent.
• This emulsion preferably has a kinematic viscosity at 25 ° C. of 100 to 20,000 mm 2 / s and an amino equivalent of 400 to 8000 g / mol.
• a commercially available amino-modified silicone can be used.
• silicone oils are those sold under the trade names: SF-8417, BY16-849, BY16-892, FZ-3785, or BY16-890 from Toray Dow Corning Co., Ltd., or from Shin-Etsu Chemical Co., Ltd.
• Product names: KF-864, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867 or those sold under KF-869, KF-861, KF-8010, etc. can give. Silicone emulsions sold by Toray Dow Corning Co., Ltd.
• PolonMF- 14 Polon MF-29
• Polon MF-14D Polon MF-44
• Polon MF-14EC Polon MF-52
• a component may be used individually by 1 type and may be used as a mixture which consists of 2 or more types.
• the blending amount of the component (B) is 0.1 to 15% by mass, preferably 0.5 to 15% by mass with respect to the total mass of the liquid softening agent composition. When it is 0.1% by mass or more, the blending effect of the component (B) can be sufficiently exhibited. When it is 15% by mass or less, yellowing during storage of the liquid softening agent composition can be sufficiently suppressed, and an increase in production cost can be suppressed.
• the component (C) contained in the liquid softening composition of the present invention is yellowing, fragrance and fragrance quality during storage of the liquid softening composition resulting from the blending of the components (A) and (B). It is blended in order to suppress the deterioration.
• Urea is a compound represented by the chemical formula: (NH 2 ) 2 C ⁇ O.
• urea HNO 3 ⁇ CO (NH 2 ) 2, H 3 PO 4 ⁇ CO (NH 2) 2, H 2 C 2 O 4 ⁇ 2 CO (NH 2) 2, Ca (NO 3) 2 ⁇ 4CO (NH 2) 2, CaSO 4 ⁇ 4CO (NH 2) 2, Mg (NO 3) 2 ⁇ CO (NH 2) 2 ⁇ 2H 2 O, CaSO 4 ⁇ (5 ⁇ 6) 4CO (NH 2) 2 -2H 2 O and the like.
• urea is particularly preferred.
• the urea derivative is the following general formula (C):
• R a is a methyl group, an ethyl group or a hydroxyalkyl group having 1 to 2 carbon atoms
• R b , R c and R d are each independently a hydrogen atom, a methyl group or an ethyl group. .
• Specific examples include 1,3-dimethylurea and N- (2-hydroxyethyl) urea. Of these, 1,3-dimethylurea is preferred.
• component (C) is particularly preferable.
• the urea, the double salt of urea and the urea derivative of the general formula (C) are all readily available on the market or can be synthesized.
• a component may be used individually by 1 type, and may be used as a mixture which consists of 2 or more types.
• the blending amount of the component (C) is 0.5 to 10% by mass, preferably 1 to 10% by mass, and more preferably 1 to 5% by mass with respect to the total mass of the liquid softening agent composition.
• it is 0.5% by mass or more, yellowing, storage of fragrance, and deterioration of fragrance quality during storage of the liquid softening agent composition can be sufficiently suppressed.
• it is 10% by mass or less, deterioration in usability due to an increase in viscosity during storage of the liquid softening agent composition can be suppressed.
• the yellowing that occurs during storage of the liquid softening agent composition occurs because the amine group and amino group contained in the component (A) and the component (B) are thermally oxidized to form an azo bond and turn yellow. It is considered a phenomenon. Although yellowing involves both the component (A) and the component (B), it is thought that the component (B) is more involved.
• the fragrance standing and the deterioration of the scent quality that occur during storage of the liquid softener composition are phenomena that occur because the (A) component and the (B) component decompose at a high temperature, and the (A) component and the (B) component. All of these are considered to be involved. Although both the component (A) and the component (B) are involved in the fragrance standing and the deterioration of the quality of the scent, it is considered that the component (A) is more involved.
• the mass ratio is preferably 1 to 20, and more preferably 1 to 5.
• the mass ratio is preferably 20 or less, and more preferably 0.2 to 5.
• (L) component which is a trehalose can be mix
• Component (L) is for improving the decrease in texture and odor generation (especially the decrease in texture and generation of odor that occurs when a dryer is used after washing at a low bath ratio). Blended.
• the component (L) can be added to further suppress an increase in viscosity after storage of the liquid softening agent composition and increase usability.
• Trehalose used in the present invention is a non-reducing disaccharide in which two molecules of glucose are linked by 1,1.
• Trehalose having an ⁇ , ⁇ structure ( ⁇ -D-glucopyranosyl ⁇ -D-glucopyranoside), ⁇ , ⁇ type (neotrehalose), and ⁇ , ⁇ type (isotrehalose).
• any type may be used, and one type may be used alone, or two or more types may be used in appropriate combination, and ⁇ and ⁇ types are particularly preferable.
• Trehalose may be a commercially available product, and examples of the commercially available product include Treha (manufactured by Hayashibara Co., Ltd.).
• the blending amount of the component (L) is not particularly limited as long as the blending effect of the component (L) can be sufficiently obtained, but is 0.01 to 10.0 with respect to the total mass of the liquid softener composition of the present invention. % By mass is preferable, 0.1 to 5% by mass is more preferable, and 1 to 5% by mass is still more preferable. When the blending amount is 0.01% by mass or more, it is possible to sufficiently obtain an effect of suppressing the odor generated in the clothes when the clothes that are repeatedly worn and washed are dried with a dryer of a drum type washing machine. Furthermore, a sufficient inhibitory effect on viscosity increase after storage of the liquid softening agent composition can also be obtained.
• the mass ratio of the (L) component to the sum of the (A) component and the (B) component is within such a range, in addition to the above blending effect, the viscosity stability of the liquid softener composition after storage is increased. It can be improved further.
• the liquid softening agent composition of the present invention can contain an (M) component that is an antibacterial agent as an optional component.
• Component (M) imparts a good deodorizing property to the object to be washed (inhibition of the growth of unpleasant odor-producing bacteria in the object to be washed. In particular, the washing that occurs when a dryer is used after washing at a low bath ratio. For the purpose of suppressing the generation of odors.
• Component (M) is one or more antibacterial agents selected from the group consisting of biguanide antibacterial agents and N, N-bis (3-aminoalkyl) alkylamines.
• the biguanide antibacterial agent has the following structure: Or a compound derived from a biguanide having antibacterial action.
• the biguanide antibacterial agent includes the following general formula (M-1): -[R 11 -NH-C (NH) -NH-C (NH) -NH] n -n.HY (M-1) (Wherein R 11 is an alkylene group having 2 to 8 carbon atoms, n is 2 to 14, and HY is an organic acid or an inorganic acid). R 11 is preferably an alkylene group having 4 to 8 carbon atoms, and particularly preferably a hexamethylene group. n is preferably 10 to 14, more preferably 11 to 13, and particularly preferably 12. HY is preferably hydrochloric acid, gluconic acid or acetic acid, and particularly preferably hydrochloric acid.
• the component (M) is preferably a compound in which R 11 is a hexamethylene group in the general formula (M-1), n is 10 to 14, and HY is hydrochloric acid. Particularly preferred are compounds in which R 11 is a hexamethylene group, n is 11 to 13, and HY is hydrochloric acid.
• a compound (poly (hexamethylene biguanide) hydrochloride in which R 11 is a hexamethylene group in the general formula (M-1), n is 12, and HY is hydrochloric acid trade name: Proxel IB ( Registered trademark) (Lonza).
• biguanide antibacterial agents include the following structures: And chlorohexidine hydrochloride (1,1′-Hexamethylene bis [5- (4-chlorophenyl) biguanide] dihydrochloride).
• a biguanide antibacterial agent may be used alone or as a mixture of two or more.
• R 12 As the component (M), the following general formula (M-2): R 12 —N [(CH 2 ) n —NH 2 ] 2 (M-2) (Wherein R 12 represents an alkyl group having 8 to 18 carbon atoms and n is a number of 1 to 4) (N, N-bis (3-aminoalkyl) alkylamine) Can also be used.
• R 12 may be linear or branched, but is preferably linear. When R 12 is a straight chain, the deodorizing property of the article to be washed can be further improved.
• R 12 has 8 to 18 carbon atoms, preferably 8 to 14 carbon atoms, and more preferably 12 carbon atoms.
• R 12 has 8 or more carbon atoms, an excellent antibacterial action can be exhibited.
• the number of carbon atoms in R 12 is 14 or less, it is possible to avoid a decrease in compoundability in the softener composition due to a decrease in water solubility.
• n is 1 to 4, preferably 2 to 4, and more preferably 3. When n is 1 to 4, an excellent antibacterial action can be exhibited.
• N N-bis (3-amino) such as N, N-bis (3-aminomethyl) octylamine, N, N-bis (3-aminomethyl) decylamine, N, N-bis (3-aminomethyl) dodecylamine, etc.
• Aminomethyl) alkylamine N, N-bis (3-aminoethyl) octylamine, N, N-bis (3-aminoethyl) decylamine, N, N-bis (3-aminoethyl) dodecylamine, etc.
• Aminoethyl) alkylamine N, N-bis (3-amino) such as N, N-bis (3-aminopropyl) octylamine, N, N-bis (3-aminopropyl) decylamine, N, N-bis (3-aminopropyl) dodecylamine, etc.
• Aminopropyl) alkylamines N, N-bis (3-amino (butylamino) octylamine, N, N-bis (3-aminobutyl) decylamine, N, N-bis (3-aminobutyl) dodecylamine, etc. Aminobutyl) alkylamine and the like.
• N, N-bis (3-aminopropyl) alkylamine is preferable, and N, N-bis (3-aminopropyl) dodecylamine is more preferable.
• M-2 the compound represented by the general formula (M-2), one type may be used alone, or a mixture of two or more types may be used.
• the above component (M) is easily available on the market or can be synthesized.
• component (M) one kind selected from the group consisting of a biguanide antibacterial agent and a compound represented by the above general formula (M-2) may be used alone, or a mixture of two or more kinds may be used. Also good.
• the blending amount of the component (M) is not particularly limited as long as the blending effect of the component (M) can be sufficiently obtained.
• the liquid softening agent composition can be further improved in the deodorizing property of the washing object.
• the amount is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1% by mass with respect to the total mass.
• the mass ratio of the component (B) to the component (M) is 1/1 to 100/1, preferably 2/1. ⁇ 50/1.
• mass of (B) / (M) is 1/1 to 100/1, the deodorizing property can be imparted to the article to be washed at a higher level.
• (N) component which is a highly branched cyclic dextrin can further be mix
• Highly branched cyclic dextrin is a substance also called cluster dextrin.
• the component (N) includes the odor that could not be suppressed by the component (L) (trehalose), thereby further enhancing the deodorizing and deodorizing effects of the liquid softening agent composition, It is blended to further improve odor and deodorization properties (particularly, deodorization and deodorization of sebum oxidation odor).
• the highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000.
• the inner branched cyclic structure portion refers to a cyclic structure portion formed by an ⁇ -1,4-glucoside bond and an ⁇ -1,6-glucoside bond.
• the outer branched structure portion means an acyclic structure portion bonded to the inner branched cyclic structure portion.
• the highly branched cyclic dextrin has a specific structure as described above and has a high degree of polymerization (molecular weight).
• Specific examples of the highly branched cyclic dextrin of component (N) include an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104, and the degree of polymerization is in the range of 50 to 10,000. Glucan is mentioned. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.
• the molecular weight is about 30,000 to 1,000,000 and the molecule has one cyclic structure (inner branched cyclic structure portion) composed of about 10 to 100 glucoses, and the cyclic structure.
• the degree of polymerization of glucose in the highly branched cyclic dextrin is, for example, in the range of 50 to 5000.
• the degree of polymerization of glucose in the inner branched cyclic structure portion of the highly branched cyclic dextrin is, for example, in the range of 10-100.
• the degree of polymerization of glucose in the outer branched structure portion of the highly branched cyclic dextrin is, for example, 40 or more.
• the average polymerization degree of glucose in each unit chain constituting the outer branched structure portion is 10 to 20.
• the highly branched cyclic dextrin of component (N) is produced, for example, using starch as a raw material and an enzyme called branching enzyme.
• Starch which is a raw material, is composed of amylose in which glucose is linearly linked by ⁇ -1,4-glucoside bonds and amylopectin having a structure that is complicatedly branched by ⁇ -1,6-glucoside bonds. It is a macromolecule with many connected structures.
• Branching enzyme an enzyme used, is a glucan chain transferase widely distributed in animals and plants and microorganisms, and acts on the seam portion of the cluster structure of amylopectin to catalyze the reaction of cyclizing it.
• (N) component is easily available in the market or can be synthesized. Specific examples include “Cluster Dextrin” (registered trademark) of Glico Nutrition Foods, Inc.
• one highly branched cyclic dextrin may be used alone, or a mixture of two or more may be used.
• the blending amount of the component (N) is not particularly limited as long as the blending effect of the component (N) can be sufficiently obtained, but is preferably 0.01 to 10% by mass with respect to the total mass of the liquid softening agent composition, More preferably, it is 0.05 to 5% by mass, and still more preferably 0.1 to 2% by mass.
• the blending amount of the component (N) is 0.01% by mass or more, an excellent deodorizing effect and deodorizing effect can be exhibited.
• the blending amount of the component (N) is 10% by mass or less, while suppressing the increase in the viscosity of the liquid softening agent composition while obtaining the blending effect, the dischargeability from the container and the insertion into the inlet of the washing machine Usability such as ease can be maintained.
• the pH of the liquid softening agent composition of the present invention is not particularly limited, but the pH is set in the range of 1 to 6 for the purpose of suppressing hydrolysis of the ester group contained in the molecule of the component (A) accompanying storage aging. It is preferable to adjust, and more preferably in the range of 2 to 4.
• a regulator can be used.
• the viscosity of the liquid softening agent composition of the present invention is preferably less than 1000 mPa ⁇ s. Considering the increase in viscosity due to storage aging, the viscosity immediately after blending is more preferably less than 800 mPa ⁇ s, and even more preferably less than 500 mPa ⁇ s. When it is in such a range, it is preferable because the usability such as handling property when being put into a washing machine is good. From the viewpoint of usability, the lower limit of the viscosity is not particularly limited.
• the viscosity of the liquid softening agent composition in the present invention refers to a value measured at 25 ° C. using a B-type viscometer (for example, an analog viscometer T manufactured by Brookfield).
• the component normally used for a liquid softening agent composition can be arbitrarily mix
• the optional component include those shown below.
• nonionic active agent (D) component is mix
• the component (D) is a nonionic surfactant obtained by adding an alkylene oxide to a primary or secondary alcohol. Specifically, a nonionic interface obtained by adding an average of 5 to 100 moles of alkylene oxide to a primary or secondary alcohol having a branched alkyl group or branched alkenyl group having 8 to 20, preferably 10 to 14 carbon atoms. It is an activator.
• ethylene oxide is preferably used alone, but propylene oxide may be added together with ethylene oxide. When both are added, any order may be added first.
• the average number of moles of alkylene oxide added is preferably 10 to 80 moles, particularly preferably 20 to 60 moles.
• the average number of moles of propylene oxide added can be 1 to 5 moles, preferably 1 to 3 moles.
• Specific examples of the component (D) include those obtained by adding an average of 60 mol of ethylene oxide (EO) to primary isotridecyl alcohol, those obtained by adding an average of 40 mol of ethylene oxide (EO) to primary isotridecyl alcohol, and alkyl group carbon. Examples include those obtained by adding 50 moles of EO to an average of 10 to 14 linear secondary alcohols.
• the component (D) is prepared, for example, by using propylene or butylene as a raw material and preparing an n-mer thereof (3 to 6-mer in the case of propylene, 2 to 4-mer in the case of butylene, etc.) Then, it can be prepared by adding alkylene oxide to a primary or secondary alcohol obtained by hydrogenation by a conventional method known to those skilled in the art.
• the blending amount of the component (D) is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and most preferably 1% with respect to the total mass of the liquid softening agent composition. 0.0 mass% to 7 mass%.
• the stability with respect to freezing of a liquid softening agent composition can be improved as it is 0.1 mass% or more. When it is 15% by mass or less, the stability of the liquid softening agent composition during high-temperature storage can be improved.
• component fragrance
• a component is mix
• a general perfume can be used in the technical field and is not particularly limited.
• a list of perfume raw materials that can be used is various documents such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and “Synthetic fragrance chemistry and commercial knowledge”, Motoichi Into, Kagaku Kogyo Nipposha (1996) and “Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co.
• the blending of the component (C) sufficiently suppresses fragrance formation and deterioration of the fragrance quality during storage of the liquid softening agent composition, so that the scenting effect by the component (E) is higher. It becomes.
• the amount of component (E) is preferably 0.1 to 5% by mass relative to the total mass of the liquid softening agent composition.
• (F) component A solvent (F) component is mix
• the component (F) is one or more aqueous solvents selected from the group consisting of alcohols having 1 to 4 carbon atoms, glycol ether solvents and polyhydric alcohols.
• ethanol isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and the following general formula (X): R—O— (C 2 H 4 O) y — (C 3 H 6 O) z —H (X) (Wherein R is an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, y and z are average added mole numbers, and y is 1 to 10, preferably 2 to 5, z represents a number of 0 to 5, preferably 0 to 2.)
• the solvent component chosen from the water-soluble solvent represented by these is mention
• Preferable examples include ethylene glycol, butyl carbitol, propylene glycol, glycerin and the like, and glycerin is particularly preferable from the viewpoint of viscosity stabilization at a low temperature.
• the amount of component (F) is 0 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the liquid softening agent composition.
• the function as a solvent can be effectively exhibited as the mass is 0.1% or more. When it is 10% by mass or less, stability can be secured effectively and efficiently.
• (G) component antiseptic
• the preservative is blended in order to maintain the antiseptic property of the liquid softener composition during long-term storage.
• preservative those known in the art can be used and are not particularly limited. Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, alcohol-based 2-bromo-2-nitropropane-1,3-diol, and iodine-based compounds.
• isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3 -Isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3-one, and mixtures thereof.
• a more preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by weight of 5
• a water-soluble mixture of chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one examples include benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio- 2,2-bis (benzmethylamide) and the like can also be used. Of these, 1,2-benzisothiazolin-3-one is particularly preferred.
• benzisothiazoline-based organic sulfur compounds When a plurality of types of benzisothiazoline-based organic sulfur compounds are used, they can be used in any mixing ratio.
• An example of an iodine compound is 3-iodo-2-propynyl N-butylcarbamate.
• the benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like. it can.
• the compounding amount of the preservative is preferably 0.0001 to 1% by mass with respect to the total mass of the liquid softening agent composition.
• the function as a preservative can be exhibited as it is 0.0001 mass% or more. When the content is 1% by mass or less, it is possible to suppress a decrease in storage stability of the liquid softening agent composition
• Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the composition.
• inorganic or organic water-soluble salts include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, etc., alkali metal salts or alkaline earth metal salts of sulfuric acid or nitric acid, p-toluenesulfonic acid, glycolic acid, lactic acid, etc.
• alkali metal salts of organic acids Preferably, they are calcium chloride, magnesium chloride, and sodium chloride.
• the amount of the inorganic or organic water-soluble salt is 0 to 3% by mass, preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, based on the total amount of the composition.
• the addition of inorganic or organic water-soluble salts may be added at any step in the production of the composition.
• antioxidant other than the aforementioned component (L) (trehalose) can be blended as the component (I). Antioxidant is mix
• antioxidant both natural antioxidants and synthetic antioxidants known in the art can be used.
• ascorbic acid ascorbyl palmitate, propyl gallate, BHT (butylated hydroxytoluene), particularly dibutylhydroxytoluene, BHA (butylated hydroxyanisole), a mixture of propyl gallate and citric acid, hydroquinone, three Grade butyl hydroquinone, natural tocopherol compounds, long chain esters of gallic acid (C8 to C22) such as dodecyl gallate, irganox compounds available from Ciba Specialty Chemicals, citric acid and / or isopropyl citrate 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoid, furans, amino acids and the like.
• BHT butylated hydroxytoluene
• BHA butylated hydroxyanisole
• the blending amount of the antioxidant is preferably 0.01 to 1% by mass with respect to the total mass of the liquid softening agent composition.
• the function as an antioxidant can be exhibited as it is 0.01 mass% or more. When the content is 1% by mass or less, it is possible to suppress a decrease in storage stability of the liquid softening agent composition due to excessive blending.
• the dye those known in the technical field can be used and are not particularly limited.
• a water-soluble dye is preferable from the viewpoint of ease of blending, and among these, one or more water-soluble dyes selected from acidic dyes and direct dyes are more preferable.
• Specific examples of dyes that can be added include, for example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, issued July 20, 1970, Maruzen Co., Ltd.), Dye Note 22nd Edition (Color Dye Co., Ltd.), Legal Dye Handbook (Edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuho Nippo Co., Ltd.).
• the compounding amount of the dye is preferably 0.01 to 50 ppm, more preferably 0.1 to 30 ppm, based on the mass, with respect to the liquid softening agent composition. By setting it as such a compounding quantity, it can prevent that the color colored by the liquid softening agent composition becomes very thin, and can make a coloring effect sufficient, On the other hand, in a liquid softening agent composition It is possible to prevent the colored color from becoming too dark.
• Component (K) Other additives
• enzymes such as cellulase, amylase, protease, lipase, keratinase, foam suppressor, and the like can be blended.
• the liquid softener composition of the present invention is preferably an aqueous composition.
• water is mix
• water to be mixed tap water, ion exchange water, pure water, distilled water, etc. can be used. In view of cost, ion exchange water is most preferable.
• the liquid softener composition of the present invention can be produced using various methods generally used for the production of liquid softener compositions.
• the methods described in JP-A-68137, JP-A-10-237762, JP-A-5-310660, JP-A-5-310661, and JP-A-5-310661 are preferred.
• (C) component dissolved in water add a part of the mixture consisting of other aqueous phase components, or add the oil phase to a part of the aqueous phase to form a liquid crystal phase of a cationic surfactant, Next, the liquid crystal phase and the remaining aqueous phase are mixed to invert the liquid crystal phase, or 2)
• the oil phase and the aqueous phase of 1) above are mixed together and emulsified and dispersed. be able to.
• blend (B) component when (B) component is an emulsion, you may mix
• those having high water solubility are preferably added to the aqueous phase, and those having low water solubility are preferably added to the oil phase.
• the water-soluble (M) component is preferably blended in the aqueous phase or at the end of production, and the oil-soluble (M) component is blended in the oil phase.
• Component (N) may be blended at the end of production.
• the stirring force and shearing force of the mixing apparatus are such that the average particle size of the oil phase of the obtained liquid softening agent composition is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, still more preferably.
• the thickness is preferably set to 0.1 to 1 ⁇ m. When in such a range, the dispersion stability of the oil phase becomes good.
• liquid softener composition of the present invention can be used in the same manner as a general liquid softener composition.
• a method of softening a washing object by dissolving the liquid softener composition of the present invention in rinse water at the stage of rinsing or water in a container such as a tub with the liquid softener composition of the present invention.
• a method in which the product is dissolved, and further, an article to be cleaned is put in and immersed.
• the bath ratio (mass ratio of the liquid softener composition to the article to be washed) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, it is preferably used in such an amount that the concentration of the component (A) is 5 ppm to 1000 ppm, more preferably 10 ppm to 300 ppm, with respect to the total amount of water used.
• a Cationic surfactant (component (A))
• (A-1) A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471.
• Amino-modified silicone (component (B))
• (B-1) An emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at its terminal, obtained from Toray Dow Corning Co., Ltd. under the trade name: SM8904.
• (B-7) was obtained as a component to be blended into the comparative example not containing amino-modified silicone.
• (B-7) A polyether-modified silicone described as (B-2) in Example 2 of JP-A-2005-187987.
• (C-1) Urea obtained as a product name: urea (special grade) manufactured by Pure Chemical Co., Ltd. Urea is a compound represented by the chemical formula: (NH 2 ) 2 C ⁇ O, and corresponds to urea which is the component (C) of the present invention.
• Dimethylurea is a compound represented by the general formula (C) (wherein R a is a methyl group, R b and R c are hydrogen atoms, and R d is a methyl group), and the present invention This corresponds to the urea derivative which is the component (C).
• Nonionic activator (component (D))
• (D-1) and (D-2) were obtained as nonionic active agents.
• component B is an emulsion (use (B-1), (B-2), (B-3) as component (B))
• the liquid softening agent composition was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation). First, (A) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, component (C) and component (J) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture.
• the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the components (B), (F), (H), and hydrochloric acid from 980 g.
• the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred.
• the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was.
• component (H) is added, and thereafter component (B) and component (F) are added, and hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L) as necessary.
• Kanto Chemical was added in an appropriate amount to adjust the pH to 2.5, and ion exchange water was added so that the total mass became 1,000 g to obtain a target liquid softener composition.
• component B is oil (use component (B-4), (B-5), (B-6) or (B-7) as component (B))
• the liquid softening agent composition was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation). First, (A) component, (B) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, component (C) and component (J) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture.
• the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the component (F) and the component (H) from 980 g.
• the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred.
• the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was.
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softener composition is shown in the “smoothness” column of Table 2.
• the fragrance and quality of the scent 100 mL of each liquid softener composition was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 50 ° C. for 4 weeks.
• the scent was evaluated.
• As a control those stored under the same conditions except that the temperature during storage was 5 ° C. were used.
• the scent of the control and the quality of the scent after storage were the same as the scent and quality of the scent before storage (immediately after preparation). Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softening agent composition is shown in the column of “scent after storage” in Table 2.
• ⁇ Evaluation criteria> 5 Equivalent to the control 4: Very slightly yellow compared to the control 3: Slightly yellow compared to the control 2: Very yellow compared to the control 1: Very yellow compared to the control
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softening agent composition is shown in the column “Appearance after storage” in Table 2.
• Viscosity and flowability after storage 100 mL of each liquid softener composition was put into a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 40 ° C. for 6 months. The fluidity was evaluated from the appearance. As a control, those stored under the same conditions except that the temperature during storage was room temperature were used. In addition, the viscosity and fluidity of the control after storage were the same (invariable) as the viscosity and fluidity before storage (immediately after preparation). Evaluation was carried out by five expert panelists in accordance with the following evaluation criteria.
• (A-1) A cationic surfactant synthesized according to the procedure described in Example 4 of JP-A-2003-12471.
• Amino-modified silicone (component (B))
• (B-1) An emulsion obtained by emulsion polymerization of an amino-modified silicone having a —H group and / or —OH group at its terminal, obtained from Toray Dow Corning Co., Ltd. under the trade name: SM8904.
• (B-7) was obtained as a component to be blended into the comparative example not containing amino-modified silicone.
• (B-7) A polyether-modified silicone described as (B-2) in Example 2 of JP-A-2005-187987.
• (C-1) Urea obtained as a product name: urea (special grade) manufactured by Pure Chemical Co., Ltd. Urea is a compound represented by the chemical formula: (NH 2 ) 2 C ⁇ O, and corresponds to urea which is the component (C) of the present invention.
• Dimethylurea is a compound represented by the general formula (C) (wherein R a is a methyl group, R b and R c are hydrogen atoms, and R d is a methyl group), and the present invention This corresponds to the urea derivative which is the component (C).
• Nonionic activator (component (D))
• (D-1) and (D-2) were obtained as nonionic active agents.
• Trehalose (L) component)
• L Trehalose (manufactured by Hayashibara Co., Ltd.)
• Antibacterial agent component (M))
• M-1 A compound obtained from Lonza Corporation under the trade name: Proxel IB (registered trademark), in which R 11 is a hexamethylene group, n is 12, and HY is hydrochloric acid in the general formula (M-1).
• the main component of Cluster Dextrin (Registered Trademark) has a molecular weight of about 30,000 to 1,000,000, and has one cyclic structure (inner branched cyclic structure) composed of about 10 to 100 glucose in the molecule. Furthermore, it was a dextrin having a weight average degree of polymerization of about 2500, in which a large number of acyclic glucan chains (outer branched structure portions) were bonded to the cyclic structure portion.
• Liquid softener compositions of Examples 26 to 55 and Comparative Examples 5 to 8 having the compositions shown in Table 4 to be described later were prepared according to the following procedure.
• the numerical units of the components (A) to (N) are mass% with respect to the total mass of the liquid softener composition, and the numerical unit of the component (J) is ppm (based on the liquid softener composition). Mass basis).
• component B is an emulsion (use (B-1), (B-2), (B-3) as component (B))
• the liquid softening agent composition was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation). First, (A) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (C), the component (J) and, if necessary, the component (L) were dissolved in ion-exchange water for balance to obtain an aqueous phase mixture.
• the mass of ion-exchange water for balance was obtained by subtracting the total mass of the oil phase mixture, the component (B) and the component (F), the component (H), the component (M), the component (N) and hydrochloric acid from 900 g. It was equivalent to the rest.
• the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred.
• the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, the component (H) is added, and then the components (B) and (F) are added. If necessary, the components (M) and (N) are added, and hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added to adjust the pH to 2.5, and ion exchange water is added so that the total mass becomes 1,000 g. A liquid softener composition was obtained.
• component B is oil (use component (B-4), (B-5), (B-6) or (B-7) as component (B))
• the liquid softening agent composition was prepared by the following procedure using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation). First, (A) component, (B) component, (D) component, (E) component, (G) component, and (I) component were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (C), the component (J) and, if necessary, the component (L) were dissolved in balance ion-exchanged water to obtain an aqueous phase mixture.
• the mass of ion-exchange water for balance corresponded to the balance obtained by subtracting the total mass of the oil phase mixture, the component (F) and the component (H) from 950 g.
• the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred.
• the division ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was.
• (F) component and (H) component are added, and then (M) component and (N) component are added as necessary, hydrochloric acid (reagent 1 mol / L, Kanto Chemical), or sodium hydroxide.
• (Reagent 1 mol / L, Kanto Chemical) was added in an appropriate amount to adjust the pH to 2.5, and ion-exchanged water was further added so that the total mass became 1,000 g to obtain the target liquid softener composition. .
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softener composition is shown in the “Smoothness” column of Table 4.
• the fragrance and quality of the scent 100 mL of each liquid softener composition was placed in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.), sealed, and stored at 50 ° C. for 4 weeks.
• the scent was evaluated.
• As a control those stored under the same conditions except that the temperature during storage was 5 ° C. were used.
• the scent of the control and the quality of the scent after storage were the same as the scent and quality of the scent before storage (immediately after preparation). Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softening agent composition is shown in the column of “scent after storage” in Table 4.
• ⁇ Evaluation criteria> 5 Equivalent to the control 4: Very slightly yellow compared to the control 3: Slightly yellow compared to the control 2: Very yellow compared to the control 1: Very yellow compared to the control
• the average score of 10 panelists was taken, and an average score of 3.0 or more was determined to be acceptable in terms of commercial value as a softener.
• the average score of each liquid softener composition is shown in the column “Appearance after storage” in Table 4.
• PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd. The viscosity increase of the agent composition and the ease of pouring of the liquid softener composition when weighed into the measuring cap were evaluated. Evaluation was performed by 10 professional panelists in accordance with the following evaluation criteria.
• Deodorant evaluation 1 of sebum odor of skin shirts worn repeatedly 1. Washing treatment after wearing After wearing a commercially available cotton shirt (BVD) for 9 hours, it was washed using a drum-type washing machine (Toshiba TW-4000VFL) at the course / setting (use detergent “Top NANOX” (Lion Corporation), 15 minutes of washing, 1 rinse, 5 minutes of dehydration, 1.5 kg of items to be washed). At the time of rinsing, each liquid softener composition was charged from an automatic charging port. The amount of detergent used was 10 mL, and the amount of liquid softener composition used was 5.0 mL. After washing, the cotton-skin shirt was dried at the left setting. This cycle of wearing, washing (softener treatment) and drying was repeated 5 times under the same conditions. A cotton skin shirt after the fifth cycle was used as a test cloth.
• Deodorant evaluation of sebum odor of skin shirts worn repeatedly 2 Washing treatment after wearing The cotton shirt after completion of the above-mentioned deodorant evaluation 1 was further subjected to each step of wearing and washing described in the column of deodorant evaluation 1. After the washing process, a cotton skin shirt was put in a plastic bag and left at 30 ° C. for 12 hours to obtain a test cloth for evaluating deodorization.
• the present invention can be used in the field of liquid softeners for clothing.

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