WO2008018186A1 - Liquid softener composition - Google Patents

Liquid softener composition Download PDF

Info

Publication number
WO2008018186A1
WO2008018186A1 PCT/JP2007/050112 JP2007050112W WO2008018186A1 WO 2008018186 A1 WO2008018186 A1 WO 2008018186A1 JP 2007050112 W JP2007050112 W JP 2007050112W WO 2008018186 A1 WO2008018186 A1 WO 2008018186A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone
liquid softener
polymer compound
softener composition
water
Prior art date
Application number
PCT/JP2007/050112
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroshi Akimoto
Takehiko Miyahara
Kiyoshi Mizuno
Noriko Takahashi
Original Assignee
Lion Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006214569A external-priority patent/JP5328084B2/en
Application filed by Lion Corporation filed Critical Lion Corporation
Priority to KR1020097002263A priority Critical patent/KR101358540B1/en
Publication of WO2008018186A1 publication Critical patent/WO2008018186A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • 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
    • D06M15/55—Epoxy resins
    • 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
    • D06M15/61—Polyamines polyimines

Definitions

  • the present invention when clothes are air-dried, especially when they are worn and washed repeatedly for a long time, even when clothes are air-dried, or when they are air-dried under high humidity conditions such as in the rainy season, it is possible to provide a liquid softener composition that can eliminate unpleasant odors such as “freshly dried”, and that makes it difficult to leave the scent of clothes after drying.
  • the liquid softening agent composition of the present invention has a transparent or translucent appearance, and can exhibit excellent flexibility for textiles such as clothing. In addition, there is little irritation to the skin.
  • the component (A) of the present invention is a silicone polymer compound.
  • the silicone polymer compound preferably has a viscosity of 10 to 100000000 mm 2 / s (B-type viscometer, 25 ° C.). There is no particular limitation as long as flexibility and smoothness can be imparted when adsorbed on a fiber product.
  • Silicone polymer compounds generally used for fiber treatment include dimethyl silicone, polyether-modified silicone, methylphenol silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrosilicone silicone, and fluorine-modifying silicone. Examples thereof include silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, and amino-modified silicone, and one of these can be used alone or as a mixture of two or more.
  • the molecular structure of this silicone polymer compound is linear or branched or crosslinked. May be.
  • the modified silicone polymer compound may be modified with one kind of organic functional group, or may be modified with two or more kinds of organic functional groups.
  • the silicone compound can be used as an oil or an emulsion dispersed with any emulsifier.
  • a silicone polymer compound containing no amino group is preferable.
  • dimethylsilicone which is preferably nonionic, is preferred because it enhances the effect of adsorbing the silicone polymer compound of component (A) on the fiber by component (B), which will be described later, and increases flexibility and slipping power.
  • Carbinol-modified silicone, epoxy-modified silicone, polyether-modified silicone, dimethyl silicone and polyether-modified silicone are more preferred.
  • particularly preferable silicone polymer compounds include polyether-modified silicones from the viewpoint of imparting flexibility and making the liquid softener composition transparent or translucent, thereby increasing commercial value.
  • the term “transparent” means that when a glass cell having an optical path length of 10 mm is used and ion-exchanged water is added to the control side cell, the light transmittance at a wavelength of 660 nm is 95% or more.
  • the term “translucent” means that the transmittance is 30% or more and less than 95%.
  • the silicone is suitable for obtaining a transparent liquid softening agent composition with less flexibility and good flexibility as compared with dimethyl silicone having no polyether group.
  • Preferable polyether-modified silicone includes a copolymer of alkyl (1 to 3 carbon atoms) siloxane and polyoxyalkylene (preferably having 2 to 5 carbon atoms of an alkylene group). Of these, dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene,
  • Coalescence is preferred.
  • Examples of such compounds include compounds represented by the following general formula (I) or ( ⁇ ).
  • M, N, a and b are average degrees of polymerization, R represents hydrogen or an alkyl group.
  • M is 10 to: LOOOO, preferably ⁇ is 50 to: LOOO, More preferably ⁇ is 100 to 300, N is 1 to 1000, preferably 5 to 300, more preferably 5 to 100, and M> N, ai or 2 to 100, preferably ⁇ or 5 ⁇ 50, more preferably ⁇ or 5 to 20, bi or 0 to 50, preferably ⁇ or 0 to 10.
  • R is more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • the polyether-modified silicone represented by the above general formula (I) generally has an organohydrogenpolysiloxane having a Si— group and a carbon-carbon double bond such as polyoxyalkylene aryl ether. It can be produced by addition reaction with a terminal polyoxyalkylene alkyl ether.
  • A is from 5 to: L0000
  • B is from 2 to: L0000 S is preferable
  • h is from 2 to 100
  • i is preferably from 0 to 50.
  • R is preferably an alkyl group having 1 to 5 carbon atoms.
  • R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • the weight average molecular weight of the block copolymer represented by the formula ( ⁇ ), the softness, and the smoothness are preferably 15,000 to 100,000,000.
  • SILWET FZ— 2104 SILWET FZ— 2120, SILWET FZ— 2161, SI LWET FZ — 2162, SILWET FZ— 2164, SILWET FZ— 2171, SILWET FZ2222, ABN SILWET FZ— Fl— 009— 01, ABN SILWET FZ— Fl— O 09— 02, ABN SILWET FZ— Fl— 009— 03, ABN SILWET FZ — Fl— O 09— 05, ABN SILWET FZ— Fl— 009— 09, ABN SILWET FZ— Fl— O 09— 11, ABN SILWET FZ— Fl— 009— 13, ABN SILWET FZ— Fl— O 09— 54,
  • the component (B) of the present invention is transparent when the water-soluble polymer compound lg is added to 100 g of water at 25 ° C. It has the effect of adsorbing compounds to fibers.
  • the water-soluble polymer compound having a cationic property a compound having a cationic property when dissolved in water can be used.
  • the water-soluble polymer compound having a cationic property includes an amino group, an amine group, a quaternary ammonia.
  • a water-soluble polymer compound having one or more cationic groups is also preferred.
  • Low molecular weight force Compared to thionic surfactants, the effect of adsorbing the fragrance component on the fiber surface is high, which is preferable.
  • the water-soluble polymer compound having a cationic property as component (B) preferably has a degree of cationization of 0.1% or more, for example 0.1 to 35, particularly 1.5% or more.
  • a good example is 2. 0-15.
  • the degree of cation is a polymer of a cationic monomer, a copolymer of a cationic monomer and a non-on monomer, and a part of a non-on polymer.
  • the polymer compound is a copolymer of a cationic monomer and a ionic monomer, and a cationic monomer.
  • a copolymer of an ionic monomer and a nonionic monomer it is defined as a value calculated by the following formula (2).
  • the Z-ion group of Z includes a carboxyl group and a sulfonic acid group contained in a monomer unit in a polymer chain. Specifically, it is a carboxylic acid in acrylic acid, etc. Does not include counter ion of cationic group.
  • MERQUAT 280 represented by the following formula (III):
  • NALCO made by NALCO
  • the degree of cationization of the polymer of the non-ionic monomer and the polymer of the cation monomer becomes zero.
  • the water-soluble polymer of component (B) preferably has a weight average molecular weight of 1,000 to 5,000,000 as measured by gel permeation chromatography using polyethylene glycol as a standard substance. More preferably, it is 3, 000-1, 000, 000, and still more preferably 5,000-500, 000. As a result, it is possible to effectively prevent odors, and it is possible to suppress the increase in viscosity and to improve the usability.
  • component (B) examples include MERQUAT 100 (manufactured by NALCO), Ade Kachi-Ace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidoru EC-004, Daidoru HEC, Daidoru EC (Daido Polymers of salt dimethyl diallyl ammonium such as Kasei Kogyo Co., Ltd., dimethyl chloride ammonium acrylamide such as MERQUAT 550, JL5 (NALCO), etc.
  • c and d each represent an average degree of polymerization and are each preferably in the range of 6 to 30000, more preferably in the range of 20 to 6000, and still more preferably in the range of 30 to 3000.
  • Examples of such polymers are MERQUAT 100 (manufactured by NALCO), Ade force Katsioace PD-50 (manufactured by Asahi Denki Kogyo Co., Ltd.), Daidoru EC-004, Daidoru HEC And Dydoll EC (manufactured by Daido Kasei Kogyo Co., Ltd.).
  • the above water-soluble polymer compound having a cationic property may be used alone or as a mixture.
  • the blending amount of the component (B) is not particularly limited, but it is preferable that the range is not imparted with rigidity to the fiber product.For example, on the basis of the total mass of the composition, 0.1 to 30% by mass is more preferable, and 0.5 to 15% by mass is more preferable.
  • the blending amount of component (B) in such a range, the effect of promoting the adsorption of the silicone polymer compound to the fiber product surface will be enhanced, and the effects such as flexibility and smoothness will be sufficient. Possible and In addition, the increase in viscosity can be suppressed and the usability can be improved.
  • the mass ratio of the component (A) to the component (B) is in the range of 99: 1 to 50:50. Preferably it is 95: 5-60: 40, More preferably, it is the range of 90: 10-70: 30.
  • the ratio is within such a range, functions having excellent texture such as flexibility and smoothness can be obtained for clothing such as polyester and cotton.
  • the adsorptivity of silicone to fibers can be improved.
  • Component (C) of the present invention is a fragrance composition containing a fragrance component having a boiling point of 250 ° C or lower.
  • the boiling point of fragrance components generally ranges from about 20 ° C to about 500 ° C, but when a boiling point of 250 ° C or less is used, residual fragrance is suppressed while suppressing unpleasant room drying odor.
  • a fragrance composition having low properties is obtained.
  • a fragrance composition containing one or more kinds selected from the group power consisting of citronellol, dihydromilucenol, tetrahydral linalool, beta-nonone, gera-ol and limonene is preferable.
  • these perfume ingredients commercially available ones can be used.
  • the present invention further includes (D) liquids such as antibacterial agents, deodorant bases, nonionic surfactants, water, water-soluble solvents, dyes, antioxidants, antifoaming agents, inorganic salts, and other additives.
  • Ingredients usually blended in the softener composition can be contained within a range not impairing the effects of the present invention.
  • the temperature from room temperature to the solvent reflux temperature is 0.5 to Soak for 24 hours, preferably 1-10 hours.
  • R 1 is an alkyl or alkyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms
  • R 2 is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group.
  • R 1 has the same meaning as described above, and r is the average number of moles added, and is a number from 2 to 50, preferably 5 to 30.
  • R 1 has the same meaning as described above, s and t are the average number of moles added, s is 2 to 40, preferably Preferably, it is a number from 5 to 30, and t is a number from 1 to 20, preferably from 1 to 10.
  • s is 2 to 40, preferably Preferably, it is a number from 5 to 30, and t is a number from 1 to 20, preferably from 1 to 10.
  • the storage stability is further improved, which is preferable.
  • the blending amount is preferably 0.1 to 20% by mass based on the total mass of the composition, particularly preferably 0.5 to 15% by mass, and more preferably 1 to LO mass%.
  • water ion-exchanged water or distilled water, which is preferably water from which hardness components such as calcium and magnesium present in trace amounts and heavy metals such as iron are removed, can be used.
  • Water-soluble solvents that can contain a small amount of chlorine for the purpose of sterilizing or sterilizing water include ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, and polyoxy It is preferable to blend a solvent component selected from ethylene vinyl ether and a water-soluble solvent represented by the following general formula (X).
  • R 3 is an alkyl group or a alkenyl group having 1 to 8, preferably 2 to 6 carbon atoms.
  • Y and z are the average number of moles attached, and y is 2 to 50, preferably Is a number between 2 and 30, z is a number between 0 and 50, and preferably is a number between 20 and 20).
  • preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycolenomonopropylene glycolenomonobutylino ether H (C H O) (C H O) H] and the like.
  • the blending amount of these components is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the composition. It can
  • the dye is not particularly limited, but may be one or more of water-soluble dyes selected from acid dyes and direct dyes, even though water-soluble dyes are preferred because of their ease of addition. Like That's right. 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 (Shokusha Co., Ltd.), Legal Dye Handbook (Edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuho Nippo Co., Ltd.), etc. are incorporated herein by reference.
  • the combined amount of the dye is preferably 0.01 to 50 ppm, more preferably 0.1 to 30 ppm, based on the total mass of the composition.
  • Isopropyl acid 1-hydroxyethylidene 1,1-diphosphonic acid (ethidronic acid), 4,5 dihydroxy —m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoids, furans, amino acids, etc. Can be mentioned.
  • the blending amount of the antioxidant is preferably in the range of 0.01 to 1% by mass based on the total amount of the composition.
  • the antifoaming agent examples include silicone-based antifoaming agents such as dimethyl silicone containing fine powder such as silica, alcohol-based antifoaming agents, ester-based antifoaming agents, mineral oil-based antifoaming agents, and vegetable oil-based antifoaming agents.
  • Antifoaming agents, synthetic oil-based antifoaming agents, and the like can be mentioned.
  • Silicone-based antifoaming agents are also preferable because they suppress foaming during measurement of the softening agent and improve the meterability.
  • Silicone defoamer Examples include oil-type antifoaming agents, compound-type antifoaming agents, self-emulsifying antifoaming agents, emulsion-type antifoaming agents, powder-type antifoaming agents, and solid-type antifoaming agents. ⁇ Type defoamer and emulsion type defoamer are preferred.
  • the blending amount of the antifoaming agent is not particularly limited, but can be 0.1 ppm to 1% by mass, more preferably 1 ppm to 0.05% by mass, based on the total mass of the composition. be able to.
  • the liquid softener composition of the present invention can contain an inorganic salt.
  • Inorganic salt is selected from salt-sodium, salt-potassium, salt-calcium and salt-magnesium strength.
  • LOOOppm preferably It is preferable to add 10 to 500 ppm.
  • the raw material of the composition may contain sodium salt and potassium salt, but the inorganic salt mixed in by these is not subject to the above restriction.
  • additives include cationic surfactants, partially esterified products of hexanoic acid and glycerin or pentaerythritol, sodium chloride, ammonium chloride, calcium chloride
  • Water-soluble salts such as magnesium chloride and potassium chloride, oils such as liquid paraffin and higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives, UV screening agents, fluorescent brighteners, pH adjusters described later, etc. .
  • the inclusion of the cationic polymer compound (B) Less than the amount! /, It is better to mix in the amount.
  • additives and the like used in ordinary household finishes can be used as long as the effects of the present invention are not hindered.
  • additives include cationic surfactants, partially esterified products of hexanoic acid and glycerin or pentaerythritol, water-soluble salts such as ammonium chloride, liquid paraffin, and higher grades.
  • oils such as alcohol, urea, hydrocarbons, nonionic cellulose derivatives, ultraviolet absorbers, fluorescent brighteners, and pH adjusters described later.
  • the cationic polymer compound of component (B) is lower than the content of bismuth!
  • the pH of the liquid softening agent composition of the present invention is not particularly limited, but is preferably in the range of 3-8, more preferably in the range of 4-6. It is diluted in the rinse solution and enters the neutral zone.
  • the viscosity of the liquid softening agent composition of the present invention is not particularly limited, but is preferably 5 to 50 mPa's (B type viscometer (Piscometer (TOKIMEC), 25 ° C)). In this case, it is preferable because the usability is good.
  • the liquid softener composition of the present invention is preferably used in such an amount that the concentration of the component (A) is 5 ppm to 5000 ppm with respect to the total amount of water used when the textile product is actually subjected to soft finishing. More preferably, it is used in an amount such that it is 10 ppm to 300 ppm, and the concentration of component (B) is preferably used in such an amount that it is 0.5 ppm to 100 ppm. Is used in an amount of 3 ppm to 30 ppm.
  • BBD Skin shirt worn for more than 1 year at home is cut in half, and commercial detergent “Top” (manufactured by Lion Co., Ltd., ingredients: surfactant (sodium alpha-olefin sulfo fatty acid ester, sodium fatty acid, direct (Chain alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent) for 5 minutes (detergent is used in standard amount, bath ratio 30 times, using tap water at 25 ° C) ), And rinsed twice for 3 minutes.
  • surfactant sodium alpha-olefin sulfo fatty acid ester, sodium fatty acid, direct (Chain alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent
  • Average point is 1.1 to 2.0, ⁇ , 0.1 to 1.0, ⁇ , -1.0, 0 to 0, ⁇ , 2.00 to 1 1.1, and X to half IJ decided.
  • the control has a clear odor, less! / ⁇
  • Half-finished new skin shirt (BVD), commercial detergent “Top” (manufactured by Lion Co., Ltd.), ingredients: surfactant (sodium alpha-olefin sulfofatty acid ester, sodium fatty acid, linear alkylbenzene, polyoxyethylene alkyl) Ether), water softener, al Washed with potash, enzyme, fluorescent brightening agent) for 5 minutes (standard amount of detergent used, 30 times bath ratio, using 25 ° C water) and rinsed twice for 3 minutes.
  • 10 g of the liquid softener composition shown in the table was added to 30 liters of water, and the clothing was softened (30 times the bath ratio, using tap water at 25 ° C, 3 minutes). Then, after dehydrating and drying for 24 hours at 40% humidity and 25 ° C, the remaining fragrance was judged by 10 panelists according to the following criteria, and the average score was obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Disclosed is a liquid softener composition which can inhibit unpleasant odor formed from laundry and whose perfume is less likely to remain on cloths. The liquid softener composition comprises: (A) a silicone polymeric compound; (B) a cationic water-soluble polymeric compound; and (C) a perfume composition comprising a perfume component having a boiling point of 250˚C or lower.

Description

液体柔軟剤組成物  Liquid softener composition
技術分野  Technical field
[0001] 本発明は、衣類等の繊維製品等に使用できる液体柔軟剤組成物に関する。  [0001] The present invention relates to a liquid softener composition that can be used for textiles such as clothing.
背景技術  Background art
[0002] 通常の洗濯で衣類などを洗濯して室内に干す場合、特に、梅雨時など微生物の繁 殖しゃすい環境で衣類を室内に乾燥又は保存すると、菌に由来する不快な臭いが 発生する問題がある。この不快な臭いとは、洗濯しても完全に落としきれない皮脂や タンパク質などの汚れが原因で、菌による分解や作用で発生すると考えられる。特に 長期間着用 ·洗濯を繰り返した衣類を梅雨時や室内で洗濯物干しをした時のような 高湿度条件で発生しやすく、蓄積した汚れに含まれる皮脂やタンパク質が空気酸ィ匕 や皮膚常在菌の代謝によって次第に分解し、中鎖脂肪酸、中鎖アルデヒド、中鎖ァ ルコール、ケトン、短鎖脂肪酸、窒素化合物および硫黄化合物などを構成する複合 臭を発生する (非特許文献 1)。しかしながら、未だ不明な点も多ぐ完全に解明され てはいない。この問題を解決するために、ジ長鎖型 4級アンモ-ゥム塩を主体とする 柔軟剤化合物に抗菌化合物を併用した液体柔軟剤組成物が開示されている (特許 文献 1〜4)が、ジ長鎖型 4級アンモ-ゥム塩を主体とした組成物を用いて繊維製品を 処理すると、菌の増殖を抑制する効果は高いものの、風合い面ではぬめり感が生じ たり、滑らかさを付与する効果が小さくなる。  [0002] When clothes are washed in a normal laundry and dried indoors, especially when clothes are dried or stored indoors in a microorganism-prone environment such as during a rainy season, an unpleasant odor derived from bacteria is generated. There's a problem. This unpleasant odor is considered to be caused by decomposition and action by bacteria due to sebum such as sebum and protein that cannot be completely removed even after washing. Especially when worn for long periods of time ・ Wearing clothes that have been washed repeatedly are likely to occur in high humidity conditions such as during the rainy season or when the laundry is dried indoors. It is gradually decomposed by the metabolism of the fungus and generates a composite odor that constitutes medium chain fatty acids, medium chain aldehydes, medium chain alcohols, ketones, short chain fatty acids, nitrogen compounds and sulfur compounds (Non-patent Document 1). However, many unclear points have not yet been fully elucidated. In order to solve this problem, a liquid softener composition in which an antibacterial compound is used in combination with a softener compound mainly composed of a di-long chain type quaternary ammonium salt has been disclosed (Patent Documents 1 to 4). When a textile product is treated with a composition mainly composed of di-long-chain quaternary ammonium salt, the effect of inhibiting the growth of fungi is high, but a feeling of sliminess is produced on the texture and smoothness is achieved. The effect to give becomes small.
一方、特許文献 2では高残香性の香料と抗菌剤の併用により、衣類洗濯後の室内 乾燥中に発生する不快なにおいを抑制するというものである力 乾燥後にも衣類に 香料が多く残ってしまう。近年、清潔志向の高まりや好みの香水を使用する等の理由 カゝら香りの少ない製品が望まれており、微香性、無香性が好まれている。  On the other hand, in Patent Document 2, a combination of a high-perfume fragrance and an antibacterial agent suppresses unpleasant odors that occur during indoor drying after washing clothes. A large amount of fragrance remains in clothes even after drying. . In recent years, a product with little fragrance has been desired because of an increase in cleanliness and the use of favorite perfume, and a slight fragrance and an unscented property are preferred.
[0003] 特許文献 1 :特開 2001— 192967  [0003] Patent Document 1: JP 2001-192967 A
特許文献 2 :特開 2004— 143638  Patent Document 2: JP 2004-143638
特許文献 3：特開 2004 - 211215  Patent Document 3: JP 2004-211215 A
特許文献 4：特開 2004 - 211230 非特許文献 1 :埴原、園田、香料 No.233、 p.109-116、 2004年 Patent Document 4: Japanese Patent Laid-Open No. 2004-211230 Non-Patent Document 1: Sugawara, Sonoda, Fragrance No.233, p.109-116, 2004
発明の開示  Disclosure of the invention
[0004] 本発明の目的は、洗濯物力も発生する不快な臭いを抑制でき、衣類に香料が残り にく ヽ液体柔軟剤組成物を提供することである。  [0004] An object of the present invention is to provide a liquid softener composition that can suppress an unpleasant odor that also generates laundry power and leaves no fragrance in the clothes.
本発明者らは、特定の低残香性香料を、カチオン性を有する水溶性高分子化合物 と共に、シリコーン高分子化合物を含有する液体柔軟剤組成物に加えることにより、「 生乾き」のような不快な臭いを臭わなくすることができ、且つ乾燥後の衣類の香りは残 りに《することが可能であるとの知見を得た。従って、本発明は、（A)シリコーン高分 子化合物、（B)カチオン性を有する水溶性高分子化合物、及び (C)沸点が 250°C以 下の香料成分を含有する香料組成物を含有する液体柔軟剤組成物を提供する。 本発明によれば、衣類等を部屋干ししたとき、特に長期間着用 ·洗濯を繰り返した 衣類を部屋干ししたときや、梅雨時のような高湿度条件下で部屋干ししたときであつ ても、「生乾き」のような不快な臭いを臭わなくすることができ、且つ乾燥後の衣類の 香りは残りにくくすることが可能である液体柔軟剤組成物を提供することができる。本 発明の液体柔軟剤組成物は、透明又は半透明の外観を有し、衣類などの繊維製品 に対して優れた柔軟性を発揮することができる。また、皮膚への刺激も少ない。  The present inventors have added an unpleasant sensation such as “freshly dried” by adding a specific low residual fragrance fragrance to a liquid softener composition containing a silicone polymer compound together with a water-soluble polymer compound having a cationic property. It was found that the odor can be eliminated and that the scent of the clothes after drying can be left behind. Accordingly, the present invention includes (A) a silicone polymer compound, (B) a water-soluble polymer compound having cationic properties, and (C) a fragrance composition containing a fragrance component having a boiling point of 250 ° C. or lower. A liquid softener composition is provided. According to the present invention, when clothes are air-dried, especially when they are worn and washed repeatedly for a long time, even when clothes are air-dried, or when they are air-dried under high humidity conditions such as in the rainy season, It is possible to provide a liquid softener composition that can eliminate unpleasant odors such as “freshly dried”, and that makes it difficult to leave the scent of clothes after drying. The liquid softening agent composition of the present invention has a transparent or translucent appearance, and can exhibit excellent flexibility for textiles such as clothing. In addition, there is little irritation to the skin.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0005] 〔液体柔軟剤組成物〕 [Liquid softener composition]
本発明の (A)成分は、シリコーン高分子化合物である。このシリコーン高分子化合 物は、 10〜100000000 mm2/s (B型粘度計、 25°C)の粘度を有するのが好ましい。繊 維製品に吸着した時に、柔軟性、滑らかさを付与することが可能であれば特に限定さ れない。一般的に繊維処理に使用されているシリコーン高分子化合物としては、ジメ チルシリコーン、ポリエーテル変性シリコーン、メチルフエ-ルシリコーン、アルキル変 性シリコーン、高級脂肪酸変性シリコーン、メチルハイドロジ ンシリコーン、フッ素変 性シリコーン、エポキシ変性シリコーン、カルボキシ変性シリコーン、カルビノール変 性シリコーン、及びアミノ変性シリコーンなどが挙げられ、これらの 1種を単独で又は 2 種以上の混合物として使用することができる。 The component (A) of the present invention is a silicone polymer compound. The silicone polymer compound preferably has a viscosity of 10 to 100000000 mm 2 / s (B-type viscometer, 25 ° C.). There is no particular limitation as long as flexibility and smoothness can be imparted when adsorbed on a fiber product. Silicone polymer compounds generally used for fiber treatment include dimethyl silicone, polyether-modified silicone, methylphenol silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrosilicone silicone, and fluorine-modifying silicone. Examples thereof include silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, and amino-modified silicone, and one of these can be used alone or as a mixture of two or more.
このシリコーン高分子化合物の分子構造は、直鎖状であっても分岐や架橋してい てもよい。また、変性シリコーン高分子化合物は 1種類の有機官能基により変性され て ヽても構わな 、し、 2種以上の有機官能基により変性されて 、てもよ 、。 The molecular structure of this silicone polymer compound is linear or branched or crosslinked. May be. The modified silicone polymer compound may be modified with one kind of organic functional group, or may be modified with two or more kinds of organic functional groups.
シリコーンィ匕合物はオイルとして使用でき、また任意の乳化剤によって分散された 乳化物としても使用できる。柔軟処理した繊維製品の黄変を防止するために、ァミノ 基を含有しないシリコーン高分子化合物であることが好ましい。さらに、後述する（B) 成分による (A)成分のシリコーン高分子化合物を繊維へ吸着させる効果を高め、柔 軟性、滑ら力さを高める点から、非イオン性であることが好ましぐジメチルシリコーン 、カルビノール変性シリコーン、エポキシ変性シリコーン、ポリエーテル変性シリコーン 力 り好ましぐジメチルシリコーン、ポリエーテル変性シリコーンが更に好ましい。  The silicone compound can be used as an oil or an emulsion dispersed with any emulsifier. In order to prevent yellowing of the textile product subjected to softening treatment, a silicone polymer compound containing no amino group is preferable. Furthermore, dimethylsilicone, which is preferably nonionic, is preferred because it enhances the effect of adsorbing the silicone polymer compound of component (A) on the fiber by component (B), which will be described later, and increases flexibility and slipping power. Carbinol-modified silicone, epoxy-modified silicone, polyether-modified silicone, dimethyl silicone and polyether-modified silicone are more preferred.
[0006] このなかでも特に好ましいシリコーン高分子化合物として、柔軟性付与及び液体柔 軟剤組成物を透明ないし半透明にし、商品価値を高めることができる等の観点から、 ポリエーテル変性シリコーンを挙げることができる。なお、本明細書において、透明と は、測定セルの光路長 10mmのガラスセルを使用し、対照側セルにイオン交換水を 入れた場合に、 660nmの波長の光透過率が 95%以上であることを意味し、半透明 とは、前記透過率が 30%以上 95%未満であることを意味する。該シリコーンは、ポリ エーテル基を有しな ヽジメチルシリコーンに比べ、キシミ感が少なく良好な柔軟性を 有するとともに、透明な液体柔軟剤組成物を得るのに好適である。好ましいポリエー テル変性シリコーンとしては、アルキル (炭素数 1〜3)シロキサンとポリオキシアルキ レン (アルキレン基の炭素数 2〜5が好ましい）の共重合体が挙げられる。このうち、ジ メチルシロキサンとポリオキシアルキレン（ポリオキシエチレン、ポリオキシプロピレン、 [0006] Among these, particularly preferable silicone polymer compounds include polyether-modified silicones from the viewpoint of imparting flexibility and making the liquid softener composition transparent or translucent, thereby increasing commercial value. Can do. In this specification, the term “transparent” means that when a glass cell having an optical path length of 10 mm is used and ion-exchanged water is added to the control side cell, the light transmittance at a wavelength of 660 nm is 95% or more. The term “translucent” means that the transmittance is 30% or more and less than 95%. The silicone is suitable for obtaining a transparent liquid softening agent composition with less flexibility and good flexibility as compared with dimethyl silicone having no polyether group. Preferable polyether-modified silicone includes a copolymer of alkyl (1 to 3 carbon atoms) siloxane and polyoxyalkylene (preferably having 2 to 5 carbon atoms of an alkylene group). Of these, dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene,
合体が好ましい。このようなものとして、下記一般式 (I)又は (Π)で表される化合物が 挙げられる。 Coalescence is preferred. Examples of such compounds include compounds represented by the following general formula (I) or (Π).
[0007] [化 1]
Figure imgf000005_0001
[0007] [Chemical 1]
Figure imgf000005_0001
[0008] (式中、 M、 N、 a及び bは平均重合度であり、 Rは水素又はアルキル基を表す。 ) ここで、 Mは 10〜： LOOOO、好まし <は 50〜： LOOO、より好まし <は 100〜300、 Nは 1 〜1000、好ましくは 5〜300、より好ましくは 5〜100、かつ M>Nであることが好まし く、 aiま 2〜100、好ましく ίま 5〜50、より好ましく ίま 5〜20、 biま 0〜50、好ましく ίま 0〜 10が好ましい。 Rとしては水素又は炭素数 1〜4のアルキル基が好ましぐ水素である のがより好ましい。 [0008] (In the formula, M, N, a and b are average degrees of polymerization, R represents hydrogen or an alkyl group.) Here, M is 10 to: LOOOO, preferably <is 50 to: LOOO, More preferably <is 100 to 300, N is 1 to 1000, preferably 5 to 300, more preferably 5 to 100, and M> N, ai or 2 to 100, preferably ί or 5 ~ 50, more preferably ί or 5 to 20, bi or 0 to 50, preferably ί or 0 to 10. R is more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
上記一般式 (I)で表されるポリエーテル変性シリコーンは、一般に、 Si— Η基を有す るオルガノハイドロジェンポリシロキサンと、例えばポリオキシアルキレンァリルエーテ ル等の、炭素 炭素二重結合を末端に有するポリオキシアルキレンアルキルエーテ ルとを付加反応させることにより製造することができる。  The polyether-modified silicone represented by the above general formula (I) generally has an organohydrogenpolysiloxane having a Si— group and a carbon-carbon double bond such as polyoxyalkylene aryl ether. It can be produced by addition reaction with a terminal polyoxyalkylene alkyl ether.
[0009] [化 2] ヽ [0009] [Chemical 2] ヽ
CH3 CH3  CH3 CH3
R '0(C2H40)h(C3HeO)i - -SI-R-0 (C2H40) h (C3H80) I - R" ( Π ) R '0 (C2H40) h (C3HeO) i--SI-R-0 (C2H40) h (C3H80) I- R "(Π)
CH3 CH3  CH3 CH3
み Β  Β
[0010] (式中、 A、 B、 h、及び iは平均重合度であり、 Rはアルキル基を表し、 R'は水素又は アルキル基を表す。 ) [Wherein, A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group.]
ここで、 Aは 5〜： L0000、 Bは 2〜： L0000であること力 S好ましく、 hは 2〜100、 iは 0〜 50が好ましい。 Rとしては炭素数 1〜5のアルキル基が好ましい。 R'としては水素又 は炭素数 1〜4のアルキル基が好ましい。また、式 (Π)で表わされるブロック共重合体 の重量平均分子量 ίま、柔軟' 14、滑ら力さの観^;力ら 15, 000〜100, 000, 000であ ることが好ましい。  Here, A is from 5 to: L0000, B is from 2 to: L0000 S is preferable, h is from 2 to 100, and i is preferably from 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. Further, the weight average molecular weight of the block copolymer represented by the formula (Π), the softness, and the smoothness are preferably 15,000 to 100,000,000.
上記線状ポリシロキサン ポリオキシアルキレンブロック共重合体は、反応性末端 基を有するポリオキシアルキレン化合物と、該化合物の反応性末端基と反応する末 端基を有するジヒドロカルビルシロキサンとを反応させることにより製造することができ る。 The linear polysiloxane polyoxyalkylene block copolymer has a reactive terminal It can be produced by reacting a polyoxyalkylene compound having a group with a dihydrocarbylsiloxane having an end group that reacts with a reactive end group of the compound.
[0011] 本発明で用いることのできるポリエーテル変性シリコーンオイルの具体的な例として は、東レ，ダウ コ一-ング (株）製の CF1188HV、 BY22— 029、 SH3772M, SH 3775M, SH3748, SH3749, SF8410、 SH8700、 BY22— 008、 SF8421、 SI LWET L— 7001、 SILWET L— 7002、 SILWET L— 7602、 SILWET L— 7 604, SILWET FZ— 2104、 SILWET FZ— 2120、 SILWET FZ— 2161、 SI LWET FZ— 2162、 SILWET FZ— 2164、 SILWET FZ— 2171、 SILWET FZ2222, ABN SILWET FZ— Fl— 009— 01、 ABN SILWET FZ— Fl— O 09— 02、ABN SILWET FZ— Fl— 009— 03、 ABN SILWET FZ— Fl— O 09— 05、 ABN SILWET FZ— Fl— 009— 09、 ABN SILWET FZ— Fl— O 09— 11、 ABN SILWET FZ— Fl— 009— 13、 ABN SILWET FZ— Fl— O 09— 54、 ABN SILWET FZ— 2222、信越化学工業 (株）製の KF352A、 KF60 08、 KF615A、 KF6016、 KF6017、 GE東芝シリコーン (株）製の TSF4450、 TS F4452等が挙げられ、これらを 1種単独で又は 2種以上の混合物として用いることが できる。  Specific examples of the polyether-modified silicone oil that can be used in the present invention include CF1188HV, BY22-029, SH3772M, SH 3775M, SH3748, SH3749, manufactured by Toray, Dow Corning Co., Ltd. SF8410, SH8700, BY22-008, SF8421, SI LWET L— 7001, SILWET L— 7002, SILWET L— 7602, SILWET L— 7 604, SILWET FZ— 2104, SILWET FZ— 2120, SILWET FZ— 2161, SI LWET FZ — 2162, SILWET FZ— 2164, SILWET FZ— 2171, SILWET FZ2222, ABN SILWET FZ— Fl— 009— 01, ABN SILWET FZ— Fl— O 09— 02, ABN SILWET FZ— Fl— 009— 03, ABN SILWET FZ — Fl— O 09— 05, ABN SILWET FZ— Fl— 009— 09, ABN SILWET FZ— Fl— O 09— 11, ABN SILWET FZ— Fl— 009— 13, ABN SILWET FZ— Fl— O 09— 54, ABN SILWET FZ-2222, KF352A, KF60 08, KF615A, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd., TSF4450, TS F4452 manufactured by GE Toshiba Silicone Co., Ltd., etc. In or can be used as a mixture of two or more thereof.
本発明で用いる (A)成分のシリコーン高分子化合物の配合量は特に限定されない 力 柔軟性、滑ら力さ及び組成物の粘度の点から、組成物の全質量を基準として、 3 〜70質量％が好ましぐさらに好ましくは 5〜50質量％、特に好ましくは 6〜40質量 %である。これにより、柔軟性、滑らかさなどの効果を優秀なものとすることができ、か つ、粘度の上昇を抑えて使用性を良好なものとすることができる。  The blending amount of the silicone polymer compound of component (A) used in the present invention is not particularly limited. From the viewpoint of flexibility, sliding strength and viscosity of the composition, 3 to 70% by mass based on the total mass of the composition. Is more preferably 5 to 50% by mass, particularly preferably 6 to 40% by mass. Thereby, the effects such as flexibility and smoothness can be made excellent, and the usability can be made good by suppressing the increase in viscosity.
[0012] 本発明の（B)成分は、 25°Cの水 100gに対し、水溶性高分子化合物 lgを加えたと きに、その液が濁らず透明であり、（A)成分のシリコーン高分子化合物を繊維へ吸着 させる効果を有するものである。カチオン性を有する水溶性高分子化合物としては、 水に溶解した時にカチオン性を有するものが使用し得る力 特にカチオン性を有する 水溶性高分子化合物としては、アミノ基、アミン基、第 4級アンモ-ゥム基カも選ばれ る 1種以上のカチオン性基を有する水溶性高分子化合物が好ま 、。低分子量の力 チオン性界面活性剤に比べて、香料成分を繊維表面に吸着させる効果が高 ヽので 好ましい。 [0012] The component (B) of the present invention is transparent when the water-soluble polymer compound lg is added to 100 g of water at 25 ° C. It has the effect of adsorbing compounds to fibers. As the water-soluble polymer compound having a cationic property, a compound having a cationic property when dissolved in water can be used. Particularly, the water-soluble polymer compound having a cationic property includes an amino group, an amine group, a quaternary ammonia. A water-soluble polymer compound having one or more cationic groups is also preferred. Low molecular weight force Compared to thionic surfactants, the effect of adsorbing the fragrance component on the fiber surface is high, which is preferable.
(B)成分のカチオン性を有する水溶性高分子化合物は、カチオン化度が 0. 1%以 上のものが好ましぐ例えば 0. 1〜35であるのがよぐ特に 1. 5%以上が好ましぐ例 えば 2. 0〜15であるのがよい。カチオンィ匕度がこのような条件を満たすことにより、共 存するシリコーン高分子化合物を繊維へ吸着させる効果を優秀なものとすることがで き、かつ、多量の配合が必要となって経済的でないケースを防止することができる。  The water-soluble polymer compound having a cationic property as component (B) preferably has a degree of cationization of 0.1% or more, for example 0.1 to 35, particularly 1.5% or more. A good example is 2. 0-15. When the cation density satisfies these conditions, the effect of adsorbing the coexisting silicone polymer compound on the fiber can be made excellent, and a large amount of compounding is required, which is not economical. Can be prevented.
[0013] ここで、カチオンィ匕度とは、高分子化合物がカチオン性モノマーの重合体、カチォ ン性モノマーとノ-オン性モノマーの共重合体、及びノ-オン性重合体の一部をカチ オン性基で変性又は置換したもの（カチオンィ匕セルロースなど）の場合には下記数式 (1)により、また、高分子化合物がカチオン性モノマーとァ-オン性モノマーの共重 合体、及びカチオン性モノマーとァ-オン性モノマーとノ-オン性モノマーの共重合 体の場合には、下記数式（2)により算出される値と定義する。 [0013] Here, the degree of cation is a polymer of a cationic monomer, a copolymer of a cationic monomer and a non-on monomer, and a part of a non-on polymer. For those modified or substituted with an ionic group (such as cationic cellulose), the polymer compound is a copolymer of a cationic monomer and a ionic monomer, and a cationic monomer. In the case of a copolymer of an ionic monomer and a nonionic monomer, it is defined as a value calculated by the following formula (2).
カチオンィ匕度（％) =XXYX 100 · · ·数式（1)  Cation degree (%) = XXYX 100 · · · · Formula (1)
[X:高分子化合物のカチオン性基中のカチオン化された原子 (窒素等)の原子量 [X: atomic weight of cationized atoms (nitrogen, etc.) in the cationic group of the polymer compound
Υ:高分子化合物 lg中に含まれるカチオン性基のモル数] Υ: Number of moles of cationic group contained in polymer compound lg]
カチオン化度（％) = (Y-Z) X 100 · · ·数式（2)  Degree of cationization (%) = (Y-Z) X 100 · · · Formula (2)
[X:高分子化合物のカチオン性基中のカチオン化された原子 (窒素等)の原子量 [X: atomic weight of cationized atoms (nitrogen, etc.) in the cationic group of the polymer compound
Y：高分子化合物 lg中に含まれるカチオン性基のモル数 Y: Number of moles of cationic group contained in polymer compound lg
Z:高分子化合物 lg中に含まれるァ-オン性基のモル数  Z: Number of moles of ionic group contained in polymer compound lg
(Zのァ-オン性基とは、高分子鎖中のモノマー単位に含まれるカルボキシル基、ス ルホン酸基などが挙げられる。具体的には、アクリル酸中のカルボン酸などである。た だし、カチオン性基の対イオンは含まない。 ) ]  (The Z-ion group of Z includes a carboxyl group and a sulfonic acid group contained in a monomer unit in a polymer chain. Specifically, it is a carboxylic acid in acrylic acid, etc. Does not include counter ion of cationic group.
[0014] カチオン化度の算出例として、下記式（III)で表されるマーコート（MERQUAT) 280 [0014] As an example of calculating the degree of cationization, MERQUAT 280 represented by the following formula (III):
(ナルコ（NALCO)社製)の場合を示す。  The case of NALCO (made by NALCO) is shown.
X： 14 (窒素原子の原子量）  X: 14 (atomic weight of nitrogen atom)
Y:4. 95 X 10— 3 (カチオン性基の lg中の重量： 0. 8gとカチオン性基の分子量より 算出) Z: 2. 78 X 10 (ァ-オン性基の lg中の重量： 0. 2gとァ-オン性基の分子量より 算出) Y:. 4 95 X 10- 3 ( weight in lg cationic groups: calculated from the molecular weight of 0. 8 g and the cationic groups) Z: 2. 78 X 10 (weight of lg-on group in lg: calculated from 0.2 g and molecular weight of ar-on group)
式 (2)より、  From equation (2)
カチオンィヒ度（％) =  Cation degree (%) =
14 X (4. 95 X 10 —2. 78 X 10— X 100 = 3. 0  14 X (4. 95 X 10 —2. 78 X 10— X 100 = 3.0
である。  It is.
[0015] [化 3] [0015] [Chemical 3]
Figure imgf000008_0001
Figure imgf000008_0001
[0016] m:n=65 : 35 [0016] m: n = 65: 35
塩化ジメチルジァリルアンモ-ゥムとアクリル酸との質量比 = 80： 20  Mass ratio of dimethyldiallyl ammonium chloride to acrylic acid = 80:20
よって、上記記載のカチオンィ匕度の算出法によれば、ノ-オン性モノマーの重合体 ゃァ-オン性モノマーの重合体のカチオン化度は 0となる。  Therefore, according to the above-described method for calculating the cation degree, the degree of cationization of the polymer of the non-ionic monomer and the polymer of the cation monomer becomes zero.
[0017] (B)成分の水溶性高分子は、ポリエチレングリコールを標準物質としてゲルパーメ ーシヨンクロマトグラフィ法で測定される重量平均分子量が、 1, 000〜5, 000, 000 であること力 S好ましく、より好ましくは 3, 000-1, 000, 000であり、さらに好ましくは 5 , 000-500, 000である。これにより臭気を良好に防止すること力 Sでき、かつ、粘度 の上昇を抑えて使用性を優秀なものとすることが可能となる。 [0017] The water-soluble polymer of component (B) preferably has a weight average molecular weight of 1,000 to 5,000,000 as measured by gel permeation chromatography using polyethylene glycol as a standard substance. More preferably, it is 3, 000-1, 000, 000, and still more preferably 5,000-500, 000. As a result, it is possible to effectively prevent odors, and it is possible to suppress the increase in viscosity and to improve the usability.
(B)成分の例としては、マーコート（MERQUAT) 100 (ナルコ（NALCO)社製）、アデ 力カチォエース PD— 50 (旭電化工業 (株））、ダイドール EC— 004、ダイドール HEC 、ダイドール EC (大同化成工業 (株)製)等の塩ィ匕ジメチルジァリルアンモ-ゥムの重 合体、マーコート (MERQUAT) 550、 JL5 (ナルコ（NALCO)社製）等の塩化ジメチル ジァリルアンモ-ゥム 'アクリルアミド共重合体、マーコート (MERQUAT) 280 (ナルコ（ NALCO)社製)等の塩ィ匕ジメチルジァリルアンモ-ゥム ·アクリル酸共重合体、レオガ ード KGP (ライオン (株）製）等のカチオン化セルロース、ルビカット（LUVIQUAT) -FC905 (B · Α· S 'F社製）等の塩化イミダゾリ-ゥム ·ビュルピロリドン共重体、ルガ ルバン（LUGALVAN)— G15000 (B'A' S 'F社製）等のポリエチレンィミン、ポバ ール CM318 ( (株）クラレ製）等のカチオン化ポリビュルアルコール、キトサン等のアミ ノ基を有する天然系の高分子誘導体、ジェチルァミノメタタリレート'エチレンォキシド 等が付加された親水基を有するビュルモノマーとの共重合体等が挙げられるが、水 に溶解時にカチオン性を有する高分子化合物であればよぐ本例に限定されるもの ではない。 Examples of component (B) include MERQUAT 100 (manufactured by NALCO), Ade Kachi-Ace PD-50 (Asahi Denka Kogyo Co., Ltd.), Daidoru EC-004, Daidoru HEC, Daidoru EC (Daido Polymers of salt dimethyl diallyl ammonium such as Kasei Kogyo Co., Ltd., dimethyl chloride ammonium acrylamide such as MERQUAT 550, JL5 (NALCO), etc. Polymer, MERQUAT 280 (Nalco ( NALCO)) and other cationized cellulose such as Leogard KGP (Lion Corporation), LUVIQUAT -FC905 (B · Imidazolium chloride such as S · S 'F) · polyethylenepyrroline such as Bulpyrrolidone copolymer, LUGALVAN — G15000 (made by B'A' S 'F), poval Cationized polybulal alcohol such as CM318 (manufactured by Kuraray Co., Ltd.), a natural polymer derivative having an amino group such as chitosan, and a hydrophilic group with addition of jetylamino metatalylate 'ethylene oxide, etc. Examples thereof include a copolymer with a butyl monomer, but are not limited to this example as long as the polymer compound has a cationic property when dissolved in water.
この中で、シリコーンの付与する柔軟性などの風合いを妨げない観点から、（B)成 分単独で吸着した時に繊維に付与する剛性の小さ ヽものが好ま ヽ。塩化ジメチル ジァリルアンモ-ゥムの重合体、塩化イミダゾリ-ゥム 'ビュルピロリドン共重体、カチ オン化セルロースが好まし!/、。  Among these, from the viewpoint of not hindering the texture such as flexibility imparted by the silicone, those having a small rigidity imparted to the fiber when adsorbed by the component (B) alone are preferred. Preference is given to polymers of dimethyldiarylammonium chloride, imidazolium chloride butylpyrrolidone copolymer, and cationized cellulose!
特に好ま 、高分子としては、下記一般式 (IV)に示すジメチルジァリルアンモ-ゥ ム塩を重合して得られるカチオン性高分子である。この高分子の構造は、通常、下記 一般式 (V)又は下記一般式 (VI)で表わされる。また、一般式 (V)の構造単位と一般 式 (VI)の構造単位が共に含まれて 、てもよ!/、。  Particularly preferred as the polymer is a cationic polymer obtained by polymerizing a dimethyl diallyl ammonium salt represented by the following general formula (IV). The structure of this polymer is usually represented by the following general formula (V) or the following general formula (VI). In addition, both the structural unit of the general formula (V) and the structural unit of the general formula (VI) may be included!
[0018] [化 4] [0018] [Chemical 4]
Figure imgf000009_0001
Figure imgf000009_0001
(式中 X—は、塩ィ匕物イオン、臭化物イオンなどの任意のマイナスイオンを示す。 )(In the formula, X— represents any negative ion such as salt or bromide ions.)
[0019] [化 5]
Figure imgf000010_0001
[0019] [Chemical 5]
Figure imgf000010_0001
[0020] [化 6] [0020] [Chemical 6]
Figure imgf000010_0002
Figure imgf000010_0002
[0021] 式中、 c、 dは、各々平均重合度であり、各々 6〜30000の範囲であること力 子ましく 、より好ましくは 20〜6000、さらに好ましくは 30〜3000の範囲である。 [0021] In the formula, c and d each represent an average degree of polymerization and are each preferably in the range of 6 to 30000, more preferably in the range of 20 to 6000, and still more preferably in the range of 30 to 3000.
このような高分子の例としては、マーコート（MERQUAT) 100 (ナルコ（NALCO)社 製）、アデ力カチォエース PD— 50 (旭電ィ匕工業 (株)製）、ダイドール EC— 004、ダイ ドール HEC、ダイドール EC (大同化成工業 (株)製)等が挙げられる。  Examples of such polymers are MERQUAT 100 (manufactured by NALCO), Ade force Katsioace PD-50 (manufactured by Asahi Denki Kogyo Co., Ltd.), Daidoru EC-004, Daidoru HEC And Dydoll EC (manufactured by Daido Kasei Kogyo Co., Ltd.).
本発明の (B)成分としては、上記のカチオン性を有する水溶性高分子化合物を 1 種単独で用いてもょ ヽし、混合物として用いることもできる。  As the component (B) of the present invention, the above water-soluble polymer compound having a cationic property may be used alone or as a mixture.
(B)成分の配合量は特に限定されな 、が、繊維製品に剛性を付与しな 、範囲のも のとするのが好ましぐ例えば、組成物の全質量を基準として、 0. 1〜30質量％とす るのがよぐさらに好ましくは 0. 5〜15質量％とするのがよい。（B)成分の配合量をこ のような範囲のものとすることにより、シリコーン高分子化合物の繊維製品表面への 吸着促進効果を高め、柔軟性、滑らかさなどの効果を十分なものとすることが可能と なり、かつ、粘度の上昇を抑えて使用性の面で良好なものとすることができる。 The blending amount of the component (B) is not particularly limited, but it is preferable that the range is not imparted with rigidity to the fiber product.For example, on the basis of the total mass of the composition, 0.1 to 30% by mass is more preferable, and 0.5 to 15% by mass is more preferable. By making the blending amount of component (B) in such a range, the effect of promoting the adsorption of the silicone polymer compound to the fiber product surface will be enhanced, and the effects such as flexibility and smoothness will be sufficient. Possible and In addition, the increase in viscosity can be suppressed and the usability can be improved.
[0022] 本発明の液体柔軟剤組成物中において、（A)成分：（B)成分の質量比は、 99 : 1 〜50： 50の範囲内である。好ましくは 95 : 5〜60 :40、さらに好ましくは 90 : 10〜70： 30の範囲である。このような範囲内の比とすることにより、ポリエステル、綿等の衣類 に対し柔軟性、滑らかさ等の風合いの優れた機能が得られる。尚、（B)成分の割合 力 の範囲内にあることにより、シリコーンの繊維への吸着性を良好なものとすること ができる。  [0022] In the liquid softening composition of the present invention, the mass ratio of the component (A) to the component (B) is in the range of 99: 1 to 50:50. Preferably it is 95: 5-60: 40, More preferably, it is the range of 90: 10-70: 30. By setting the ratio within such a range, functions having excellent texture such as flexibility and smoothness can be obtained for clothing such as polyester and cotton. In addition, when the ratio is within the range of the ratio force of the component (B), the adsorptivity of silicone to fibers can be improved.
[0023] 本発明の（C)成分は、沸点が 250°C以下の香料成分を含有する香料組成物である 。香料成分の沸点は、一般的に、約 20°C〜約 500°Cまで広範囲に亘るが、そのうち、 沸点が 250°C以下のものを用いると、不快な部屋干し臭を抑制しつつ、残香性の低い 香料組成物が得られる。このような香料成分としては、具体的には、ギ酸ェチル (沸点 54°C、以下同様)、酢酸ェチル (77°C)、プロピオン酸ェチル (99°C)、酪酸ェチル (121 °C)、へキシルアルデヒド (131°C)、トランス- 2-へキセナール (146°C)、ヘプチルアルデ ヒド (153°C)、ピルビン酸ェチル (144°C)、アルファピネン (156°C)、シス- 3-へキセノー ル (157°C)、プロピオン酸イソアミル (161°C)、ベータピネン (166°C)、酢酸-トランス- 2- へキセ-ル (166°C)、酪酸ブチル (165°C)、酢酸-シス- 3-へキセニル (169°C)、ォクチ ルアルデヒド (170°C)、酢酸へキシル (172°C)、メチルヘプテノン (174°C)、 1,8-シネオ一 ル (177°C)、パラクレジルメチルエーテル (175°C)、リモネン (178°C)、 p-シメン (177°C)、 ベンズアルデヒド (179°C)、 2,6-ノナジェナール (196°C)、ノニルアルデヒド (191°C)、テト ラハイド口リナロール (197°C)、リナロール (198°C)、フエ-ル酢酸メチル (218°C)、スチラ リルアルコール (204°C)、ラバンジュロール (203°C)、シトロネラール (206°C)、カンファー (208°C)、ジハイドロミルセノール (215°C)、デシルアルデヒド (209°C)、メントン (207°C)、 酢酸パラクレジル (212°C)、テトラヒドロゲラ-オール (213°C)、ミルセノール (213°C)、酢 酸スチラリル (212°C)、酢酸べンジル (215°C)、エストラゴール (216°C)、ジメチルベンジ ルカルビノール (215°C)、タービネオール (219°C)、酢酸リナリル (220°C)、フエ-ルェチ ルアルコール (220°C)、シトロネロール (225°C)、ジハイドロアネトール (225°C)、酢酸 n- ボル-ル (226°C)、酢酸イソボル-ル (227°C)、ネロール (227°C)、シトラール (228°C)、 酢酸シトロネリル (229°C)、ゲラ-オール (230°C)、ジヒドロジヤスモン (230°C)、カルボン ( 231°C)、ゥンデシルアルデヒド (223°C)、酢酸フエ-ルェチル (232°C)、ベルテネックス（ 232°C)、メチルノニルァセトアルデヒド (232°C)、ァネトール (236°C)、ゥンデシレンアル デヒド (235°C)、アルファョノン (237°C)、力ルバクロール (238°C)、ベータョノン (239°C)、 ヒドロキシシトロネラール (241°C)、プロピオン酸シトロネリル (242°C)、酢酸ゲラ -ル (24 5°C)、シス-ジャスモン (248°C)等があげられる。このうち、シトロネロール、ジハイドロミ ルセノール、テトラハイド口リナロール、ベータョノン、ゲラ-オールおよびリモネンから 成る群力も選ばれる 1種又は 2種以上を含有する香料組成物が好ましい。特に、ジハ イドロミルセノール、テトラハイド口リナロール、リモネンを含有するのが好ましい。これ らの香料成分としては、商業的に入手できるものを使用することができる。 [0023] Component (C) of the present invention is a fragrance composition containing a fragrance component having a boiling point of 250 ° C or lower. The boiling point of fragrance components generally ranges from about 20 ° C to about 500 ° C, but when a boiling point of 250 ° C or less is used, residual fragrance is suppressed while suppressing unpleasant room drying odor. A fragrance composition having low properties is obtained. Specific examples of such perfume ingredients include ethyl formate (boiling point 54 ° C, the same applies hereinafter), ethyl acetate (77 ° C), ethyl propionate (99 ° C), ethyl butyrate (121 ° C), Hexylaldehyde (131 ° C), trans-2-hexenal (146 ° C), heptylaldehyde (153 ° C), ethyl pyruvate (144 ° C), alphapinene (156 ° C), cis-3 -Hexanol (157 ° C), Isoamyl propionate (161 ° C), Betapinene (166 ° C), Acetic acid-trans-2-Hexane (166 ° C), Butyl butyrate (165 ° C), Acetic acid-cis-3-hexenyl (169 ° C), octyl aldehyde (170 ° C), hexyl acetate (172 ° C), methylheptenone (174 ° C), 1,8-cineole (177 ° C) ), Paracresyl methyl ether (175 ° C), limonene (178 ° C), p-cymene (177 ° C), benzaldehyde (179 ° C), 2,6-nonagenal (196 ° C), nonylaldehyde ( 191 ° C), Tetra Hyde Linalool (197 ° C), linalool (198 ° C), methyl acetate (218 ° C), styryl alcohol (204 ° C), lavandrol (203 ° C), citronellal (206 ° C), Camphor (208 ° C), dihydromyrcenol (215 ° C), decylaldehyde (209 ° C), menthone (207 ° C), paracresyl acetate (212 ° C), tetrahydrogeraol (213 ° C) , Milsenol (213 ° C), Styraryl acetate (212 ° C), Benzyl acetate (215 ° C), Estragole (216 ° C), Dimethyl benzyl carbinol (215 ° C), Turbineol (219 ° C), Linalyl acetate (220 ° C), vinyl alcohol (220 ° C), citronellol (225 ° C), dihydroanethole (225 ° C), n-bol acetate (226 ° C), isobol acetate (227 ° C), nerol (227 ° C), citral (228 ° C), citronellyl acetate (229 ° C), geraol (230 ° C), dihydrodiasmon (230 ° C), Carvone ( 231 ° C), undecyl aldehyde (223 ° C), ferroethyl acetate (232 ° C), vertenex (232 ° C), methylnonylacetaldehyde (232 ° C), anethole (236 ° C) , Undecylenaldehyde (235 ° C), alpha-nonone (237 ° C), force rubachlor (238 ° C), beta-nonone (239 ° C), hydroxycitronellal (241 ° C), citronellyl propionate (242 ° C), Examples include gallate acetate (24 5 ° C), cis-jasmon (248 ° C), and the like. Among these, a fragrance composition containing one or more kinds selected from the group power consisting of citronellol, dihydromilucenol, tetrahydral linalool, beta-nonone, gera-ol and limonene is preferable. In particular, it is preferable to contain dihydromyrcenol, tetrahydrin linalool, and limonene. As these perfume ingredients, commercially available ones can be used.
沸点が 250°C以下の香料成分力 香料組成物の全量を基準にして好ましくは 10〜4 5質量％、より好ましくは 15〜35質量％、さらに好ましくは 20〜35質量％の量で含まれ るのが好ましい。このような範囲内で含まれると、部屋干し臭抑制効果が高まるので 好ましい。なお、本明細書において、沸点は、 latmにおける標準沸点をいう。  Perfume component power having a boiling point of 250 ° C. or less It is preferably contained in an amount of 10 to 45% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 35% by mass based on the total amount of the fragrance composition. It is preferable. If it is included within such a range, the effect of suppressing room-drying odor is enhanced, which is preferable. In this specification, the boiling point refers to the normal boiling point at latm.
(C)成分の配合量は特に限定されないが、例えば、組成物の全量を基準にして、 好ましくは 0.01〜2.5質量0 /0、より好ましくは 0.05〜0.5質量％の量で含まれるのがよい 。このような範囲で含まれると、部屋干し臭抑制効果の点で好ましい。 Blend quantity of the component (C) is not particularly limited, for example, based on the total amount of the composition, preferably from 0.01 to 2.5 mass 0/0, and more preferably be included in an amount of 0.05 to 0.5 mass% . If it is included in such a range, it is preferable in terms of the effect of suppressing room drying odor.
本発明はさらに、（D)抗菌剤、消臭基剤、ノ-オン性界面活性剤、水、水溶性溶剤 、染料、酸化防止剤、消泡剤、無機塩、その他の添加剤等の液体柔軟剤組成物に 通常配合されている成分を本発明の効果を損なわない範囲で含有することができる  The present invention further includes (D) liquids such as antibacterial agents, deodorant bases, nonionic surfactants, water, water-soluble solvents, dyes, antioxidants, antifoaming agents, inorganic salts, and other additives. Ingredients usually blended in the softener composition can be contained within a range not impairing the effects of the present invention.
(D)成分の抗菌剤は、不快な臭いを抑制する効果を高める目的で配合することが できる。抗菌剤としては、「香粧品、医薬品防腐 '殺菌剤の科学」吉村孝一、滝川博 文著、フレグランスジャーナル社 1990年 4月 10日発行 501頁〜 564頁に記載され ているものを使用することができ、好ましいものとしては、トリクロサン、ビス一（2—ピリ ジルチオ一 1ーォキシド）亜鉛、 2, 4, 5, 6—テトラクロ口イソフタロニトリル、トリクロ口 力ルバ-リド、 2- (4ーチオシァノメチルチオ）ベンズイミダゾール、ポリへキサメチレ ンビグァ-ジン塩酸塩、グルクロン酸クロルへキシジン、 8—ォキシキノリン、塩化ベン ザルコ-ゥム、塩ィ匕セタルコ-ゥム、塩ィ匕ジデシルジメチルアンモ -ゥム等が挙げられ 、好ましくはトリクロサン、塩化ベンザルコ-ゥム、塩化ジデシルジメチルアンモ -ゥム 力も選ばれる 1種以上が好ましい。 The antibacterial agent (D) can be blended for the purpose of enhancing the effect of suppressing unpleasant odors. As antibacterial agents, use the ones described in pages 501 to 564 of “Cosmetics, Pharmaceutical Preservation, Science of Bactericides”, Koichi Yoshimura, Hirofumi Takikawa, and Fragrance Journal, published April 10, 1990. Preferred are triclosan, bis (2-pyridylthio-1-oxide) zinc, 2,4,5,6-tetrachloroisophthalonitrile, triclohydrate rubalide, 2- (4-thio). Cyanomethylthio) benzimidazole, polyhexamethylbiguanidine hydrochloride, chlorhexidine glucuronate, 8-oxyquinoline, benzalkonium chloride, salt cetalum, salt decidyldimethylammonium chloride Can be mentioned Preferably, at least one selected from triclosan, benzalkonium chloride, and didecyldimethylammonium chloride force is preferable.
配合量は、 0.05〜5質量％、更に 0.2〜5質量％が不快な臭いを抑制する効果の点 で好ましい。  The blending amount is preferably 0.05 to 5% by mass, and more preferably 0.2 to 5% by mass from the viewpoint of suppressing an unpleasant odor.
[0025] 本発明では、不快な臭いを抑制する効果を更に高める目的で、上記成分に加えて 消臭基材を含有することが好ましい。消臭基材とは、悪臭物質の濃度を減じることが できる物質、および悪臭物質の濃度は減じな!、ものの悪臭強度を低減させたと感じさ せる物質である。具体的には、ベタイン化合物などの化学的消臭法に属する消臭基 材、シクロデキストリン、金属石けんなどの包接系消臭基材、香料などの主に感覚的 消臭法に属する消臭基材などが挙げられる。その中でも感覚的消臭機構と化学的消 臭機構をいずれも有する植物抽出系の消臭基材が不快な臭いを抑制する効果の観 点から好ましい。該消臭基材は、その抽出物が消臭作用を有するものであれば、上 記植物の種類が特に制限されるものではなぐ具体的には、ローズマリー、セージ、 ォゥゴン、ォレガ入マジョラム、ブラックミント、メボウキ、タチジヤコゥ、タイム、メリッサ 、ナギナタコウジュ、セボリーなどのシソ科植物、グローブ、ユーカリ等のフツモモ科植 物、バラ科植物、ヒノキ科植物、レンギヨゥ等のモクセィ科植物、スォゥ、モウセンゴケ 、コブシ、ホオノキ、ダイォゥ、ヘンナ、フキタンポポ、ホップ、ャロウ等の植物からの抽 出物が挙げられる。これらの中でも、本発明において特に好ましい消臭基材は、ロー ズマリー、セージ、ヘンナ、フキタンポポカもの抽出物である。上記植物抽出物は、 1 種単独で又は 2種以上を適宜組み合わせて使用することができる。  In the present invention, in order to further enhance the effect of suppressing unpleasant odor, it is preferable to contain a deodorizing base material in addition to the above components. A deodorant base material is a substance that can reduce the concentration of malodorous substances, and a substance that does not reduce the concentration of malodorous substances! Specifically, deodorizing bases belonging to chemical deodorizing methods such as betaine compounds, inclusion deodorizing base materials such as cyclodextrins and metal soaps, and fragrances mainly belonging to sensory deodorizing methods Examples include base materials. Among these, a plant extraction-type deodorizing base material having both a sensory deodorizing mechanism and a chemical deodorizing mechanism is preferable from the viewpoint of suppressing an unpleasant odor. The deodorant base material is not particularly limited in terms of the type of the plant as long as the extract has a deodorizing action. Specifically, rosemary, sage, ougon, olega marjoram, Black mint, Meuboki, Tajijiakou, Thyme, Melissa, Naginata Koju, Sevorie and other Lamiaceae plants, Globe, Eucalyptus and other Fusumidae plants, Rosaceae, Cypress family, Forsythia and other Moxae family plants, Sou, Mousengoke, Examples include extracts from plants such as kobushi, honoki, daioh, henna, dandelion, hops, and gallows. Among these, a particularly preferred deodorizing base material in the present invention is an extract of rosemary, sage, henna, or squirrel poppoca. The above plant extracts can be used singly or in appropriate combination of two or more.
[0026] また、本発明において、これらの植物からの抽出方法は、特に限定されないが、例 えば以下のような方法で得ることができる。  In the present invention, the extraction method from these plants is not particularly limited, and for example, it can be obtained by the following method.
即ち、原料となる植物の全部又は根部、茎部、葉部、種子部、花部などをそのまま 、あるいは粉状にして極性溶媒に浸漬し、室温から溶媒還流温度までの温度で 0. 5 〜24時間、好ましくは 1〜10時間浸漬する。必要に応じて加熱する上記極性溶媒と しては、水、エタノール、プロピレングリコール、ジプロピレングリコール、ジォキサン、 メタノール、アセトン、ジェチルエーテル、エチレンクロライド及びイソプロパノールな どの有機溶媒、又はこれらの有機溶媒と水との混合物 (例えば、有機溶媒:水 = 10 : 9 0〜90 : 10 (体積比））が挙げられる。水、メタノール、エタノールが好ましぐ特に水 を溶媒として抽出した消臭基剤が消臭効果において優れている。必要に応じて加熱 後、すぐに又は数日間室温でさらに浸漬した後、濾過、遠心分離などの方法で抽出 液を残查カも分離する。得られた抽出液をそのまま消臭基剤として用いてもよいが、 好ましくは蒸留等で溶媒を除去する方法である。 That is, all or the root part, stem part, leaf part, seed part, flower part, etc. of the plant as the raw material are left as it is or powdered and immersed in a polar solvent, and the temperature from room temperature to the solvent reflux temperature is 0.5 to Soak for 24 hours, preferably 1-10 hours. Examples of the polar solvent to be heated as necessary include water, ethanol, propylene glycol, dipropylene glycol, dioxane, methanol, acetone, jetyl ether, ethylene chloride, isopropanol, and organic solvents such as these, Mixture with water (e.g. organic solvent: water = 10: 9 0 to 90:10 (volume ratio)). Water, methanol, and ethanol are preferred, and deodorant bases extracted with water as a solvent are particularly excellent in deodorizing effect. If necessary, immediately after heating, or after further immersion at room temperature for several days, separate the residue from the extract by methods such as filtration and centrifugation. Although the obtained extract may be used as a deodorant base as it is, a method of removing the solvent by distillation or the like is preferable.
本発明の組成物において、上記植物カゝら抽出した消臭基剤の配合量は、特に制 限されるものではないが、通常、組成物の全質量をベースとして、 0. 01〜10質量％ とするのがよぐ好ましくは 0. 1〜5質量％、更に好ましくは 0. 5〜2質量％が好適で ある。  In the composition of the present invention, the amount of the deodorant base extracted from the plant moss is not particularly limited, but usually 0.01 to 10 mass based on the total mass of the composition. % Is more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 2% by mass.
[0027] ノ-オン性界面活性剤としては、例えば炭素数 8〜20のアルキル基又はァルケ- ル基を 1つ以上有するポリオキシアルキレンアルキルエーテルが好ましぐ特にォキ シアルキレン基が平均 2〜50モル付加されたものが好ましい。さらに下記一般式 (VI I)で表されるノ-オン性界面活性剤が好まし ヽ。  [0027] As the nonionic surfactant, for example, a polyoxyalkylene alkyl ether having one or more alkyl groups or alkyl groups having 8 to 20 carbon atoms is preferred, and in particular, an oxyalkylene group has an average of 2 Those added with ~ 50 mol are preferred. Furthermore, a nonionic surfactant represented by the following general formula (VI I) is preferred.
R1— T [ (R20) — H] (VII) R 1 — T [(R 2 0) — H] (VII)
P Q  P Q
(式中、 R1は、炭素数 10〜18、好ましくは 12〜 18のアルキル基又はァルケ-ル基で あり、 R2は炭素数 2又は 3のアルキレン基であり、好ましくはエチレン基である。 (In the formula, R 1 is an alkyl or alkyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R 2 is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. .
Pは平均付加モル数であり、 2〜50、好ましくは 5〜30、特に好ましくは 5〜20の数を 示す。 Tは O 、 一 N 、 一 NH 、 一 N (C H OH) 一、 CON 、 一 CONH—  P is an average number of moles added, and represents a number of 2 to 50, preferably 5 to 30, particularly preferably 5 to 20. T is O, 1 N, 1 NH, 1 N (C H OH) 1, CON, 1 CONH—
2 4  twenty four
又は CON (C H OH)—であり、 Tが— O—、— NH―、— N (C H OH)―、—CON  Or CON (C H OH) — and T is — O—, — NH—, — N (C H OH) —, —CON
2 4 2 4  2 4 2 4
H—、又は— CON (C H OH)—の場合は、 qは 1であり、 Tが— N 又は— CON—  In the case of H— or —CON (C H OH) —, q is 1 and T is —N or —CON—
2 4  twenty four
の場合は、 qは 2である。 )  In the case, q is 2. )
[0028] 上記一般式 (VII)の化合物の具体例として、下記一般式 (VIII)、 (IX)で表される 化合物を挙げることができる。 [0028] Specific examples of the compound of the general formula (VII) include compounds represented by the following general formulas (VIII) and (IX).
R1— O—（C H O)— H (VIII) R 1 — O— (CHO) — H (VIII)
2 4 r  2 4 r
(式中、 R1は前記と同じ意味であり、 rは平均付加モル数であり、 2〜50、好ましくは 5 〜30の数である。 ) (Wherein R 1 has the same meaning as described above, and r is the average number of moles added, and is a number from 2 to 50, preferably 5 to 30.)
R1— O— (C H O) (C H O) H (IX) R 1 — O— (CHO) (CHO) H (IX)
2 4 s 3 6 t  2 4 s 3 6 t
(式中、 R1は前記と同じ意味であり、 s及び tは平均付加モル数であり、 sは 2〜40、好 ましくは 5〜30の数であり、 tは 1〜20、好ましくは 1〜10の数である。 (C H O)と（C (Wherein R 1 has the same meaning as described above, s and t are the average number of moles added, s is 2 to 40, preferably Preferably, it is a number from 5 to 30, and t is a number from 1 to 20, preferably from 1 to 10. (CHO) and (C
2 4 3 2 4 3
H O)はランダム又はブロック付加体であってもよい。 ) H 2 O) may be random or block adducts. )
6  6
ノ-オン活性剤を含有することにより、保存安定性がさらに向上するので好ましい。 その配合量は、組成物の全質量を基準として、 0. 1〜20質量％とするのが好ましぐ 特に 0. 5〜15質量％、更に 1〜： LO質量％が好ましい。このような配合量とすることに より、保存安定性の向上効果を十分なものとすることができ、かつ、効果が飽和に達 した際の余分な添加を抑えて経済性を図ることが可能となり、さらに柔軟処理時の泡 立ちの点力もも好ましいものとすることができる。  By containing a non-active agent, the storage stability is further improved, which is preferable. The blending amount is preferably 0.1 to 20% by mass based on the total mass of the composition, particularly preferably 0.5 to 15% by mass, and more preferably 1 to LO mass%. By using such a blending amount, the effect of improving storage stability can be made sufficient, and it is possible to achieve economic efficiency by suppressing excessive addition when the effect reaches saturation. In addition, the point power of foaming at the time of the flexible processing can be made preferable.
[0029] 水としては、水中に微量に存在するカルシウム、マグネシウムなどの硬度成分や鉄 などの重金属を除去した水が好ましぐイオン交換水又は蒸留水を用いることができ る。また、水を殺菌あるいは滅菌する目的から少量の塩素を含有しても差し支えない 水溶性溶剤としては、エタノール、イソプロパノール、グリセリン、エチレングリコール 、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、へキシレング リコール、ポリオキシエチレンフエ-ルエーテル、及び下記一般式 (X)で表わされる 水溶性溶剤から選ばれる溶媒成分を配合することが好ましい。 [0029] As water, ion-exchanged water or distilled water, which is preferably water from which hardness components such as calcium and magnesium present in trace amounts and heavy metals such as iron are removed, can be used. Water-soluble solvents that can contain a small amount of chlorine for the purpose of sterilizing or sterilizing water include ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, and polyoxy It is preferable to blend a solvent component selected from ethylene vinyl ether and a water-soluble solvent represented by the following general formula (X).
R3— O— (C H O) 一（C H O) 一 H (X) R 3 — O— (CHO) One (CHO) One H (X)
2 4 y 3 6 z  2 4 y 3 6 z
(式中、 R3は、炭素数 1〜8、好ましくは 2〜6のアルキル基又はァルケ-ル基である。 y及び zは平均付カ卩モル数であり、 yは 2〜50、好ましくは 2〜30、 zは 0〜50、好まし くは。〜 20の数を示す。 ) (In the formula, R 3 is an alkyl group or a alkenyl group having 1 to 8, preferably 2 to 6 carbon atoms. Y and z are the average number of moles attached, and y is 2 to 50, preferably Is a number between 2 and 30, z is a number between 0 and 50, and preferably is a number between 20 and 20).
中でも好ましい例としては、エタノール、エチレングリコール、ブチルカルビトール、 プロピレングリコール、ジエチレングリコーノレモノプロピレングリコーノレモノブチノレエー テル H (C H O) (C H O) H]等が挙げられる。  Among them, preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycolenomonopropylene glycolenomonobutylino ether H (C H O) (C H O) H] and the like.
4 9 3 6 2 4 2  4 9 3 6 2 4 2
これらの成分の配合量は、組成物の全質量を基準として、 0. 1〜30質量％とする のがよぐ好ましくは 2〜20質量％、さらに好ましくは 5〜15質量％とすることができる  The blending amount of these components is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the composition. it can
[0030] 染料としては特に限定されないが、添加の容易さから水溶性染料が好ましぐ中で も酸性染料、直接染料カゝら選ばれる水溶性染料の 1種又は 2種以上であることが好ま しい。添加できる染料の具体例は、例えば染料便覧 (有機合成化学協会編,昭和 45 年 7月 20日発行,丸善 (株) )、染料ノート第 22版（ (株)色染社)、法定色素ハンドブッ ク（日本化粧品工業連合会編、 1988年 11月 28日発行、（株)薬事日報社)等に記 載されており、それらを引用することにより本明細書の開示の一部とされる。染料の配 合量は、組成物の全質量をベースとして、好ましくは 0. 01〜50ppm、より好ましくは 0. l〜30ppmとすることができる。このような配合量とすることにより、液体柔軟剤組 成物に着色された色が非常に薄くなるのを防止でき、着色効果を充分なものとするこ とができる一方で、液体柔軟剤組成物に着色された色が濃くなりすぎるのを防止でき る。 [0030] The dye is not particularly limited, but may be one or more of water-soluble dyes selected from acid dyes and direct dyes, even though water-soluble dyes are preferred because of their ease of addition. Like That's right. 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 (Shokusha Co., Ltd.), Legal Dye Handbook (Edited by the Japan Cosmetic Industry Association, published on November 28, 1988, Yakuho Nippo Co., Ltd.), etc. are incorporated herein by reference. The combined amount of the dye is preferably 0.01 to 50 ppm, more preferably 0.1 to 30 ppm, based on the total mass of the composition. By using such a blending amount, it is possible to prevent the color colored in the liquid softener composition from becoming very thin and to achieve a sufficient coloring effect. It is possible to prevent the color of the object from becoming too dark.
[0031] 本発明では、組成物の香気安定性や色調安定性向上のため、酸化防止剤を添カロ することができる。酸ィ匕防止剤としては、一般に知られている天然系酸ィ匕防止剤、合 成系酸ィ匕防止剤ともに使用できる。具体的には、ァスコルビン酸、ァスコルビン酸パ ルミテート、没食子酸プロピルの混合物、 BHT (ブチル化ヒドロキシトルエン）、 BHA( ブチル化ヒドロキシァ-ソール）、没食子酸プロピル、及びクェン酸の混合物、ハイド ロキノン、三級ブチルハイドロキノン、天然のトコフエロール系化合物、没食子酸の長 鎖エステル（C8〜C22)、例えば没食子酸ドデシル、チバスペシャルティケミカル (株） カゝら入手可能なィルガノックス系化合物、クェン酸及び Zまたはクェン酸イソプロピル 、 1ーヒドロキシェチリデン 1, 1ージホスホン酸（ェチドロン酸）、 4, 5 ジヒドロキシ —m—ベンゼンスルホン酸/ナトリウム塩、ジメトキシフエノール、カテコール、メトキシ フエノール、カロチノイド、フラン類、アミノ酸類等が挙げられる。  [0031] In the present invention, an antioxidant can be added to improve the aroma stability and the color tone stability of the composition. As the acid / antioxidant, generally known natural acid / antioxidant and synthetic acid / antioxidant can be used. Specifically, ascorbic acid, ascorbyl palmitate, a mixture of propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyasol), propyl gallate, and citrate, hydroquinone, Tertiary butyl hydroquinone, natural tocopherol compounds, long-chain esters of gallic acid (C8 to C22) such as dodecyl gallate, Ciba Specialty Chemicals Co., Ltd. Isopropyl acid, 1-hydroxyethylidene 1,1-diphosphonic acid (ethidronic acid), 4,5 dihydroxy —m-benzenesulfonic acid / sodium salt, dimethoxyphenol, catechol, methoxyphenol, carotenoids, furans, amino acids, etc. Can be mentioned.
この中で、液体柔軟剤組成物の外観や保存安定性の観点から、 BHT (プチル化ヒ ドロキシトルエン）、メトキシフエノール、トコフエロール系化合物等が好ましい。  Among these, from the viewpoints of the appearance and storage stability of the liquid softening agent composition, BHT (ptylated hydroxytoluene), methoxyphenol, tocopherol compounds and the like are preferable.
酸化防止剤の配合量は、組成物の全量を基準にして 0. 01〜1質量％の範囲で使 用されることが好ましい。  The blending amount of the antioxidant is preferably in the range of 0.01 to 1% by mass based on the total amount of the composition.
[0032] 消泡剤としては、例えば、シリカ等の微粉を含有するジメチルシリコーン等のシリコ 一ン系消泡剤、アルコール系消泡剤、エステル系消泡剤、鉱油系消泡剤、植物油系 消泡剤、及び合成油系消泡剤等が挙げられるが、柔軟剤計量時の泡立ちを抑えて 計量性を向上させる観点力もシリコーン系の消泡剤が好ましい。シリコーン系消泡剤 としては、オイル型消泡剤、コンパゥンド型消泡剤、自己乳化型消泡剤、エマルシヨン 型消泡剤、粉末型消泡剤及び固形型消泡剤等が挙げられ、この中でも、自己乳ィ匕 型消泡剤及びエマルシヨン型消泡剤が好まし 、。消泡剤の配合量は特に限定されな いが、組成物の全質量を基準として、 0. lppm〜l質量％とすることができ、さらに好 ましくは lppm〜0. 05質量％とすることができる。 [0032] Examples of the antifoaming agent include silicone-based antifoaming agents such as dimethyl silicone containing fine powder such as silica, alcohol-based antifoaming agents, ester-based antifoaming agents, mineral oil-based antifoaming agents, and vegetable oil-based antifoaming agents. Antifoaming agents, synthetic oil-based antifoaming agents, and the like can be mentioned. Silicone-based antifoaming agents are also preferable because they suppress foaming during measurement of the softening agent and improve the meterability. Silicone defoamer Examples include oil-type antifoaming agents, compound-type antifoaming agents, self-emulsifying antifoaming agents, emulsion-type antifoaming agents, powder-type antifoaming agents, and solid-type antifoaming agents.匕 Type defoamer and emulsion type defoamer are preferred. The blending amount of the antifoaming agent is not particularly limited, but can be 0.1 ppm to 1% by mass, more preferably 1 ppm to 0.05% by mass, based on the total mass of the composition. be able to.
本発明の液体柔軟剤組成物には、無機塩を含有することができる。無機塩としては 、塩ィ匕ナトリウム、塩ィ匕カリウム、塩ィ匕カルシウム及び塩ィ匕マグネシウム力 選ばれる 少なくとも 1種が貯蔵安定性の点力も好ましぐ組成物中 0〜： LOOOppm、好ましくは 1 0〜500ppm添加することが良好である。ただし、組成物の原料には、ナトリウム塩や カリウム塩が含まれることがあるが、これらにより混入する無機塩は上記制限を受ける ものではない。  The liquid softener composition of the present invention can contain an inorganic salt. Inorganic salt is selected from salt-sodium, salt-potassium, salt-calcium and salt-magnesium strength. In the composition in which at least one kind is also preferred in terms of storage stability, 0 to: LOOOppm, preferably It is preferable to add 10 to 500 ppm. However, the raw material of the composition may contain sodium salt and potassium salt, but the inorganic salt mixed in by these is not subject to the above restriction.
その他の添加剤として、カチオン性界面活性剤、へキサン酸とグリセリンまたはペン タエリスリトールとの部分エステル化物や、食塩、塩化アンモ-ゥム、塩化カルシウム Other additives include cationic surfactants, partially esterified products of hexanoic acid and glycerin or pentaerythritol, sodium chloride, ammonium chloride, calcium chloride
、塩化マグネシウム、塩化カリウム等の水溶性塩、流動パラフィン、高級アルコールな どの油剤、尿素、炭化水素、非イオン性セルロース誘導体、紫外線遮蔽剤、蛍光増 白剤、後述する pH調整剤等が挙げられる。なお、ァ-オン性界面活性剤、ァ-オン 性高分子化合物は、配合する場合には、シリコーン高分子化合物の吸着効果を考 慮して、 (B)成分のカチオン性高分子化合物の含有量よりも少な!/、量で配合するの がよい。 Water-soluble salts such as magnesium chloride and potassium chloride, oils such as liquid paraffin and higher alcohols, urea, hydrocarbons, nonionic cellulose derivatives, UV screening agents, fluorescent brighteners, pH adjusters described later, etc. . In addition, in the case of blending the ionic surfactant and the ionic polymer compound, in consideration of the adsorption effect of the silicone polymer compound, the inclusion of the cationic polymer compound (B) Less than the amount! /, It is better to mix in the amount.
本発明の液体柔軟剤組成物には、本発明の効果を妨げない範囲で、通常の家庭 用仕上げ剤に使用されている添加剤などを使用することができる。そのような添加剤 として、具体的には、カチオン性界面活性剤、へキサン酸とグリセリンまたはペンタエ リスリトールとの部分エステルイ匕物や、塩化アンモ -ゥム等の水溶性塩、流動パラフィ ン、高級アルコールなどの油剤、尿素、炭化水素、非イオン性セルロース誘導体、紫 外線吸収剤、蛍光増白剤、後述する pH調整剤等が挙げられる。なお、ァ-オン性界 面活性剤、ァ-オン性高分子化合物は、配合する場合には、シリコーンィ匕合物の吸 着効果を考慮して、 (B)成分のカチオン性高分子化合物の含有量よりも低!、量で配 合するのがよい。 [0034] 本発明の液体柔軟剤組成物の pHは特に限定されないが、 3〜8の範囲であること が好ましぐ 4〜6の範囲であることがより好ましい。すすぎ液中では希釈され中性領 域にはいります。必要に応じて、塩酸、硫酸、リン酸、アルキル硫酸、安息香酸、パラ トルエンスルホン酸、クェン酸、リンゴ酸、コハク酸、乳酸、グリコール酸、ヒドロキシェ タンジホスホン酸、フィチン酸、エチレンジァミン四酢酸、トリエタノールァミン、ジエタ ノールァミン、ジメチルァミン、 N—メチルエタノールァミン、 N—メチルジェタノールァ ミン等の短鎖アミンィ匕合物、水酸化ナトリウム等のアルカリ金属水酸化物、アルカリ金 属炭酸塩、アルカリ金属珪酸塩などの pH調整剤を用いることができる。 In the liquid softener composition of the present invention, additives and the like used in ordinary household finishes can be used as long as the effects of the present invention are not hindered. Specific examples of such additives include cationic surfactants, partially esterified products of hexanoic acid and glycerin or pentaerythritol, water-soluble salts such as ammonium chloride, liquid paraffin, and higher grades. Examples thereof include oils such as alcohol, urea, hydrocarbons, nonionic cellulose derivatives, ultraviolet absorbers, fluorescent brighteners, and pH adjusters described later. In addition, when compounding the ionic surfactant, the ionic polymer compound, in consideration of the adsorption effect of the silicone compound, the cationic polymer compound of component (B) The content is lower than the content of bismuth! [0034] The pH of the liquid softening agent composition of the present invention is not particularly limited, but is preferably in the range of 3-8, more preferably in the range of 4-6. It is diluted in the rinse solution and enters the neutral zone. As required, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, para-toluenesulfonic acid, citrate, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytic acid, ethylenediamine tetraacetic acid, trimethyl Short chain amine compounds such as ethanolamine, diethylanolamine, dimethylamine, N-methylethanolamine, N-methylethanolamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkalis A pH adjuster such as a metal silicate can be used.
本発明の液体柔軟剤組成物の粘度は特に限定されな!、が、 5〜50mPa' s (B型 粘度計（ピスコメーター（TOKIMEC)、 25°C)であるのが好ましい。このような範囲にあ ると、使用性が良好であるので好ましい。  The viscosity of the liquid softening agent composition of the present invention is not particularly limited, but is preferably 5 to 50 mPa's (B type viscometer (Piscometer (TOKIMEC), 25 ° C)). In this case, it is preferable because the usability is good.
[0035] 本発明の液体柔軟剤組成物は、上記 (A)〜 (C)成分及び場合により任意成分を 含有し、通常、残部は水である。本発明の液体柔軟剤組成物の製造は、上記各成分 を容器に充填し、これを十分に撹拌した後に水を添加して均一になるまで十分に撹 拌することにより行うことができる。これらの成分の添カ卩は、一緒に又は任意の順序で 行うことができるが、例えば、（A)成分及び (C)成分を添加'撹拌した後、水を添加し て撹拌し、次いで、成分 (B)及び必要により（D)を添加'撹拌することにより本発明の 液体柔軟剤組成物を製造することができる。また、本発明の液体柔軟剤組成物は、 適度な濃度に希釈して使用される。使用方法は特に限定されないが、衣料を通常の 洗濯を行い、すすぎの段階ですすぎ水に本発明の組成物を溶解させて処理を行う、 また、たらいのような容器を用い本発明の組成物を水に溶解させ、更に衣料を入れて 浸漬処理する方法などが挙げられる。繊維製品の処理は 、ずれの方法で行ってもよ いが、浴比 (繊維製品に対する処理液の比率）は 3〜： LOO倍、特に 5〜50倍であるこ とが好ましい。  [0035] The liquid softener composition of the present invention contains the components (A) to (C) and optionally an optional component, and the balance is usually water. The liquid softener composition of the present invention can be produced by filling each of the above components in a container, sufficiently stirring the mixture, and then adding water to sufficiently stir until uniform. The addition of these components can be performed together or in any order. For example, after adding (A) component and (C) component and stirring, water is added and stirred, and then The liquid softener composition of the present invention can be produced by adding and stirring the component (B) and, if necessary, (D). The liquid softener composition of the present invention is used after diluting to an appropriate concentration. The method of use is not particularly limited, but the laundry is usually washed, and the composition of the present invention is dissolved in the rinse water at the rinsing stage, and the composition of the present invention is used in a container such as a tub. A method of soaking in water and further immersing with clothing. The treatment of the textile product may be carried out by a deviation method, but the bath ratio (ratio of the treatment liquid to the textile product) is preferably 3 to: LOO times, particularly 5 to 50 times.
また、本発明の液体柔軟剤組成物は、実際に繊維製品の柔軟仕上げを行う際の全 使用水量に対し、 (A)成分の濃度が 5ppm〜5000ppmとなるような量で使用するの が好ましぐさらに好ましくは 10ppm〜300ppmとなるような量で使用され、（B)成分 の濃度は 0. 5ppm〜100ppmとなるような量で使用するのが好ましぐさらに好ましく は 3ppm〜30ppmとなるような量で使用される。 The liquid softener composition of the present invention is preferably used in such an amount that the concentration of the component (A) is 5 ppm to 5000 ppm with respect to the total amount of water used when the textile product is actually subjected to soft finishing. More preferably, it is used in an amount such that it is 10 ppm to 300 ppm, and the concentration of component (B) is preferably used in such an amount that it is 0.5 ppm to 100 ppm. Is used in an amount of 3 ppm to 30 ppm.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明はこれに 限定されるものではない。なお、下記例で％は質量％を示す。  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to this. In the following examples,% indicates mass%.
実施例  Example
[0036] 以下の表 1に記載の (A)シリコーンィ匕合物、（C)香料成分、及び場合により後記の 共通成分 1〜4のいずれかを、夫々所定量を 500mlビーカーに充填し、撹拌羽を用 いて十分に撹拌した。次に、撹拌しながら、イオン交換水を添加し、さらに撹拌しなが ら、表 2に記載の（B)カチオン性を有する水溶性高分子化合物および表 4に記載の（ D)抗菌剤を添加し撹拌後、均一になるまで十分に撹拌して、 400gの液体柔軟剤組 成物を調製した。尚、特に断りが無い限り、配合温度は 25± 2°Cで行った。各成分の 配合量は、表 5に示す通りである。  [0036] (A) Silicone compound, (C) perfume ingredient, and optionally any one of the following common ingredients 1 to 4 shown in Table 1 below, each in a predetermined amount filled into a 500 ml beaker, The mixture was sufficiently stirred using a stirring blade. Next, with stirring, ion-exchanged water is added, and while further stirring, the (B) cationic water-soluble polymer compound described in Table 2 and the (D) antibacterial agent described in Table 4 are added. After adding and stirring, the mixture was sufficiently stirred until it was uniform to prepare 400 g of a liquid softener composition. The mixing temperature was 25 ± 2 ° C unless otherwise specified. Table 5 shows the amount of each component.
このようにして得た各液体柔軟剤組成物（実施例 1〜16及び比較例 1〜3)につい て、以下に記載する部屋干し臭評価法に従って、部屋干し臭抑制の効果を評価した 。結果を表 5に記載する。  About each liquid softening agent composition (Examples 1-16 and Comparative Examples 1-3) obtained in this way, the effect of room-dried odor suppression was evaluated according to the room-dried odor evaluation method described below. The results are listed in Table 5.
[0037] [表 1]  [0037] [Table 1]
Figure imgf000019_0001
Figure imgf000019_0001
[0038] [(A- 4)ポリエーテル変性シリコーンの製造]  [0038] [(A-4) Production of polyether-modified silicone]
(CH ) SiO(CH CH SiO) (CH HSiO) Si(CH )で表されるハイドロジェンシロキサン Hydrogen siloxane represented by (CH) SiO (CH CH SiO) (CH HSiO) Si (CH)
3 3 3 3 210 3 9 3 3 3 3 3 3 210 3 9 3 3
828g、平均組成 CH =CHCH 0(CH CH O) Hで表されるァリル化ポリエーテル 210g  828 g, average composition CH = CHCH 0 (CH CH O) H
2 2 2 2 9  2 2 2 2 9
、エチルアルコール 726g及び塩化白金酸の C1を中和したものを白金がァリル化ポリ エーテルに対して重量で 5ppmとなるように秤量して、反応温度 80°Cで攪拌し 5時間 反応させた。反応終了後溶媒を減圧留去することにより下記式 (I)で表されるポリエ 一テル変性シリコーンを得た。  Then, 726 g of ethyl alcohol and neutralized C1 of chloroplatinic acid were weighed so that platinum was 5 ppm by weight with respect to the arylated polyether, and stirred at a reaction temperature of 80 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a polyether-modified silicone represented by the following formula (I).
[0039] [化 7]
Figure imgf000020_0001
[0039] [Chemical 7]
Figure imgf000020_0001
[0040] [表 2][0040] [Table 2]
Figure imgf000020_0002
Figure imgf000020_0002
[0041] [表 3] [0041] [Table 3]
c成分：香料組成物 c component: perfume composition
Figure imgf000021_0001
Figure imgf000021_0001
*：へ"ンシ ンソ'ヱ トの 50%溶液  *: 50% solution of water
**：シ"フ' p f レンク- ' コールの 10%溶液  **: 10% solution of Shifu "p f lenk-" call
[0042] [表 4]
Figure imgf000021_0002
[0042] [Table 4]
Figure imgf000021_0002
[0043] (共通成分 1) [0043] (Common component 1)
下記の成分は、〔 〕内に示した量 (有姿での配合量、組成物の全量を基準とする。 以下同様。）を添加した。 1-1 ケーソン CG— ICP (ローム &ハース社製） [lOOppm] The following components were added in the amounts shown in [] (based on the total amount of the composition and the total amount of the composition, the same shall apply hereinafter). 1-1 Caisson CG—ICP (Rohm & Haas) [lOOppm]
1-2 ソフタノール 50 (C12- 14第 2級アルコール E05付加物、 日本触媒 (株)製）〔4%〕 1-2 Softanol 50 (C12-14 secondary alcohol E05 adduct, manufactured by Nippon Shokubai Co., Ltd.) [4%]
1- 3 95%合成未変性エタノール（日本合成アルコール (株)製） 〔10%〕 1-3 95% synthetic unmodified ethanol (manufactured by Nippon Synthetic Alcohol Co., Ltd.) [10%]
[0044] (共通成分 2) [0044] (Common component 2)
下記の成分は、〔 〕内に示した量 (有姿での配合量)を添加した。  The following ingredients were added in the amount shown in [] (the amount blended in solid form).
2- 1 プロキセル BDN (アビシァ（株）製） 〔5ppm〕  2-1 Proxel BDN (manufactured by Abyssia) [5ppm]
2-2 ァミゼット 5C (ヤシ油脂肪酸モノエタノールアミド E05付加物、川研ファインケミ カル (株)）〔4%〕  2-2 Amizzet 5C (coconut oil fatty acid monoethanolamide E05 adduct, Kawaken Fine Chemical Co., Ltd.) [4%]
2-3 95%合成未変性エタノール（日本合成アルコール (株)製） 〔10%〕  2-3 95% synthetic unmodified ethanol (manufactured by Nippon Synthetic Alcohol Co., Ltd.) [10%]
2-4 X-50-963 (シリコーン系エマルシヨン型消泡剤、信越化学工業 (株)製） [15ppm 2-4 X-50-963 (Silicone-based emulsion type antifoam, manufactured by Shin-Etsu Chemical Co., Ltd.) [15ppm
] ]
2-5 C丄アシッド イェロー 3(B.A.S.F社製、キノリンイェロー WS 〔3ppm〕  2-5 C 丄 Acid Yellow 3 (B.A.S.F, Quinoline Yellow WS (3ppm)
2- 6 クレモーゲン（CREMOGEN)ローズマリーエキス（ノヽ一マンアンドライマー（株）〔 0.5 %]  2- 6 Cremogen (CREMOGEN) Rosemary Extract (Noichi Mann Andrimer Co., Ltd. [0.5%]
[0045] (共通成分 3)  [0045] (Common ingredient 3)
下記の成分は、〔 〕内に示した量 (有姿での配合量)を添加した。  The following ingredients were added in the amount shown in [] (the amount blended in solid form).
3- 1 プロテクトール（Protectol) BN (BASF (株）製）〔20ppm〕  3-1 Protectol BN (manufactured by BASF Corp.) [20ppm]
3-2 ルテンゾール（Lutensol) TO 5 (イソトリデカノール E05付カ卩物、 BASF (株） 製）〔4%〕  3-2 Lutensol TO 5 (a product with isotridecanol E05, manufactured by BASF Corp.) [4%]
3-3 95%合成未変性エタノール（日本合成アルコール (株)製）〔10%〕  3-3 95% synthetic unmodified ethanol (manufactured by Nippon Synthetic Alcohol Co., Ltd.) [10%]
3-4 X-50-963 (シリコーン系エマルシヨン型消泡剤、信越化学工業 (株)製）〔15pp m]  3-4 X-50-963 (Silicone-based emulsion type antifoaming agent, manufactured by Shin-Etsu Chemical Co., Ltd.) [15pp m]
3-5 CIダイレクト レッド 225(日本化薬 (株）製、カャフヱクトレッド B)〔3ppm〕 3-5 CI Direct Red 225 (Nippon Kayaku Co., Ltd., CAFECT RED B) [3ppm]
3- 6 ェクストラポンローズマリー P (EXTRAPONE ROSEMARY P、ローズマリー抽出 物、シムライズ (株）〔1%〕 3-6 EXTRAPONE ROSEMARY P, rosemary extract, Simrise (1%)
(共通成分 4)  (Common ingredient 4)
下記の成分は、〔 〕内に示した量 (有姿での配合量)を添加した。  The following ingredients were added in the amount shown in [] (the amount blended in solid form).
4- 1 ケーソンじ0—1じ 〔20 111〕 4-2 ソフタノール 90 (C12- 14第 2級アルコール E09付加物、日本触媒 (株)製）〔3%〕4- 1 Caisson 0-1 (20 111) 4-2 Softanol 90 (C12-14 secondary alcohol E09 adduct, manufactured by Nippon Shokubai Co., Ltd.) [3%]
4-3 95%合成未変性エタノール（日本合成アルコール (株)製）〔10%〕 4-3 95% synthetic unmodified ethanol (manufactured by Nippon Synthetic Alcohol Co., Ltd.) [10%]
4-4 X-50-963 (シリコーン系エマルシヨン型消泡剤、信越化学工業 (株)製） [15ppm 4-4 X-50-963 (Silicone-based emulsion type defoamer, manufactured by Shin-Etsu Chemical Co., Ltd.) [15ppm
] ]
4-5 C丄アシッド ブルー 9((株)洛東ィ匕学工業製、ラタトーブリリアントブル- FCF)〔3 ppm]  4-5 C 丄 Acid Blue 9 (Ratoto Brilliant Bull-FCF, manufactured by Totoi Engineering Co., Ltd.) [3 ppm]
[0046] 〔部屋干し臭評価方法〕  [0046] [Dry odor evaluation method]
家庭で 1年以上着用した肌シャツ (BVD)を半裁し、市販衣料用洗剤「トップ」（ライォ ン (株)製、成分:界面活性剤 (アルファオレフインスルホ脂肪酸エステルナトリウム、脂 肪酸ナトリウム、直鎖アルキルベンゼン系、ポリオキシエチレンアルキルエーテル）、 水軟化剤、アルカリ剤、酵素、蛍光増白剤)で 5分洗浄し (洗剤は標準使用量、浴比 3 0倍、 25°Cの水道水使用）、ためすすぎを 3分間 2回行なった。その際、半裁した一 方のみためすすぎ 2回目に、表に示す液体柔軟剤組成物を水量 30リットルに対して 10gカ卩えて、衣料の柔軟処理 (浴比 30倍、 25°Cの水道水使用、 3分)を行った。又、 半裁したもう一方はためすすぎ 2回目〖こも柔軟剤を使用せずに水道水のみで処理を 行なった。その後、脱水し、湿度 99%、 25°Cで 5時間乾燥した後の衣料の臭いを 10 人のパネラーにより下記の基準で判定し、平均点を求めた。  Skin shirt (BVD) worn for more than 1 year at home is cut in half, and commercial detergent “Top” (manufactured by Lion Co., Ltd., ingredients: surfactant (sodium alpha-olefin sulfo fatty acid ester, sodium fatty acid, direct (Chain alkylbenzene, polyoxyethylene alkyl ether), water softener, alkali agent, enzyme, fluorescent whitening agent) for 5 minutes (detergent is used in standard amount, bath ratio 30 times, using tap water at 25 ° C) ), And rinsed twice for 3 minutes. At that time, rinse only for one half-finished, and for the second time, add 10g of the liquid softener composition shown in the table to 30 liters of water and soften the clothing (30 times the bath ratio, tap water at 25 ° C). Used, 3 minutes). In addition, the other half-finished was rinsed for the second time and was treated with tap water only without using a softener. Then, after dehydrating and drying at 99% humidity and 25 ° C for 5 hours, the smell of the clothing was judged by 10 panelists according to the following criteria, and the average score was obtained.
平均点が 1. 1〜2. 0点を◎、 0. 1〜1. 0点を〇、 - 1. 0〜0点を△、—2. 0〜一 1. 1点、を Xとして半 IJ定した。  Average point is 1.1 to 2.0, ◎, 0.1 to 1.0, ◯, -1.0, 0 to 0, △, 2.00 to 1 1.1, and X to half IJ decided.
+ 2：対照 (柔軟剤未処理)よりはっきり臭 、が少な!/ヽ  + 2: Clearly less odor than control (no softener treatment)! / ヽ
+ 1：対照よりややや臭!、が少な!/、  + 1: Slightly less odor than the control! /,
0 ：対照とほぼ同じ  0: almost the same as the control
1：対照の方がやや臭!、が少な!/ヽ  1: Slightly less odor in the control! / ヽ
2：対照の方がはっきり臭 、が少な!/ヽ  2: The control has a clear odor, less! / ヽ
[0047] 〔残香性評価方法〕 [0047] [Residual odor evaluation method]
新品の肌シャツ (BVD)を半裁し、市販衣料用洗剤「トップ」（ライオン (株)製、成分： 界面活性剤（アルファオレフインスルホ脂肪酸エステルナトリウム、脂肪酸ナトリウム、 直鎖アルキルベンゼン系、ポリオキシエチレンアルキルエーテル）、水軟化剤、アル カリ剤、酵素、蛍光増白剤)で 5分洗浄し (洗剤は標準使用量、浴比 30倍、 25°Cの水 道水使用）、ためすすぎを 3分間 2回行なった。その際、表に示す液体柔軟剤組成物 を水量 30リットルに対して 10gカ卩えて、衣料の柔軟処理 (浴比 30倍、 25°Cの水道水 使用、 3分)を行った。その後、脱水し、湿度 40%、 25°Cで 24時間乾燥した後の残 香性を 10人のパネラーにより下記の基準で判定し、平均点を求めた。 Half-finished new skin shirt (BVD), commercial detergent “Top” (manufactured by Lion Co., Ltd.), ingredients: surfactant (sodium alpha-olefin sulfofatty acid ester, sodium fatty acid, linear alkylbenzene, polyoxyethylene alkyl) Ether), water softener, al Washed with potash, enzyme, fluorescent brightening agent) for 5 minutes (standard amount of detergent used, 30 times bath ratio, using 25 ° C water) and rinsed twice for 3 minutes. At that time, 10 g of the liquid softener composition shown in the table was added to 30 liters of water, and the clothing was softened (30 times the bath ratio, using tap water at 25 ° C, 3 minutes). Then, after dehydrating and drying for 24 hours at 40% humidity and 25 ° C, the remaining fragrance was judged by 10 panelists according to the following criteria, and the average score was obtained.
平均点力^). 0〜1. 5点を◎、 1. 6〜3. 0点を〇、 3. 1〜4. 0点を△、 4. 1〜5. 0 点を Xとして判定した。  Average point force ^). Judged 0 to 1.5 as ◎, 1.6 to 3.0 as ◯, 3.1 to 4.0 as △, 4.1 to 5.0 as X .
0:無臭  0: Odorless
1 :やっと感知できる二オイ  1: At last it can be detected
2：何の-オイであるかわかる弱!、二オイ  2: Weak-you can see what is oy!
3 :楽に感知できる-オイ  3: Easy to detect-Oy
4:強い二オイ  4: Strong two oysters
5 :強烈な二オイ  5: Intense two oysters
[表 5] [Table 5]
Figure imgf000025_0001
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0002

Claims

請求の範囲 The scope of the claims
[1] (A)シリコーン高分子化合物、  [1] (A) silicone polymer compound,
(B)カチオン性を有する水溶性高分子化合物、及び  (B) a water-soluble polymer compound having cationic properties, and
(C)沸点が 250°C以下の香料成分を含有する香料組成物、  (C) a fragrance composition containing a fragrance component having a boiling point of 250 ° C or lower,
を含有する液体柔軟剤組成物。  A liquid softener composition comprising:
[2] 沸点が 250°C以下の香料成分力 香料組成物の全量を基準にして 10〜45重量％ で含まれる請求項 1項記載の液体柔軟剤組成物。  [2] The liquid softener composition according to claim 1, which is contained in an amount of 10 to 45% by weight based on the total amount of the fragrance composition, having a boiling point of 250 ° C. or less.
[3] 沸点が 250°C以下の香料成分力 シトロネロール、ジハイドロミルセノール、テトラハ イド口リナロール、ベータョノン、ゲラ-オールおよびリモネン力 成る群力 選ばれる 請求項 1又は 2記載の液体柔軟剤組成物。 [3] Perfume component strength with a boiling point of 250 ° C or less Citronellol, dihydromyrcenol, tetrahydral linalool, beta-nonone, gera-ol and limonene strength are selected. Liquid softener composition according to claim 1 or 2 object.
[4] (A)シリコーン高分子化合物と (B)カチオン性を有する水溶性高分子化合物との 質量比が（A)： (B) = 99 : 1〜50 : 50の割合で含有する、請求項 1〜3のいずれか 1 項記載の液体柔軟剤組成物。 [4] The mass ratio of (A) silicone polymer compound to (B) cationic water-soluble polymer compound is (A): (B) = 99: 1 to 50:50 Item 4. The liquid softener composition according to any one of Items 1 to 3.
[5] (A)シリコーン高分子化合物力 ジメチルシリコーン、ポリエーテル変性シリコーン、 メチルフエ-ルシリコーン、アルキル変性シリコーン、高級脂肪酸変性シリコーン、メ チルハイドロジェンシリコーン、フッ素変性シリコーン、エポキシ変性シリコーン、カル ボキシ変性シリコーン、カルビノール変性シリコーン、及びアミノ変性シリコーンからな る群力 選ばれる請求項 1〜4のいずれか 1項記載の液体柔軟剤組成物。 [5] (A) Silicone polymer compound strength dimethyl silicone, polyether-modified silicone, methylphenol silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified The liquid softener composition according to any one of claims 1 to 4, which is selected from the group consisting of silicone, carbinol-modified silicone, and amino-modified silicone.
[6] (A)シリコーン高分子化合物力 ポリエーテル変性シリコーンである請求項 5記載の 液体柔軟剤組成物。 6. The liquid softener composition according to claim 5, which is (A) silicone polymer compound strength polyether-modified silicone.
[7] ポリエーテル変性シリコーンが、下記式 (I)で表される化合物である請求項 6記載の 液体柔軟剤組成物。  [7] The liquid softener composition according to [6], wherein the polyether-modified silicone is a compound represented by the following formula (I):
Figure imgf000026_0001
Figure imgf000026_0001
(式中、 M、 N、 a及び bは各々平均重合度を表し、 Mは 10〜： LOOOOの数、 Nは 1〜1 000の数、 aは 2〜： L00の数、及び bは 0〜50の数を表す。 Rは水素又は炭素数 1〜4 のアルキル基を表す。 ) (In the formula, M, N, a and b each represent an average degree of polymerization, M is 10 to: the number of LOOOO, N is 1 to 1 The number of 000, a is 2 to: the number of L00, and b is the number of 0 to 50. R represents hydrogen or an alkyl group having 1 to 4 carbon atoms. )
[8] (B)カチオン性を有する水溶性高分子化合物力 カチオン化度が 0. 1 %以上の重 合体もしくは共重合体である請求項 1〜7の 、ずれか 1項記載の液体柔軟剤組成物  [8] (B) Water-soluble polymer compound having cationic property The liquid softener according to any one of claims 1 to 7, which is a polymer or copolymer having a cationization degree of 0.1% or more. Composition
[9] (B)カチオン性を有する水溶性高分子化合物が、下記式 (V)又は (VI)で表される 構造単位を含み、重量平均分子量が 1 , 000〜5, 000, 000の重合体もしくは共重 合体である請求項 1〜8のいずれか 1記載の液体柔軟剤組成物。 [9] (B) The water-soluble polymer compound having a cationic property includes a structural unit represented by the following formula (V) or (VI), and has a weight average molecular weight of 1,000 to 5,000,000. The liquid softener composition according to any one of claims 1 to 8, which is a polymer or a copolymer.
[化 2]  [Chemical 2]
( VI)
Figure imgf000027_0001
(VI)
Figure imgf000027_0001
(式中、 c及び dは、各々平均重合度を表し、各々 6〜30000の範囲の数である。 X— は、マイナスィ才ンを示す。 )  (In the formula, c and d each represent an average degree of polymerization, and each represents a number in the range of 6 to 30000. X— represents a minus value.)
さらに (D)抗菌剤を含有する請求項 1〜9の 、ずれか 1項記載の液体柔軟剤組成 物。  The liquid softener composition according to any one of claims 1 to 9, further comprising (D) an antibacterial agent.
PCT/JP2007/050112 2006-08-07 2007-01-10 Liquid softener composition WO2008018186A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020097002263A KR101358540B1 (en) 2006-08-07 2007-01-10 Liquid softener composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-214569 2006-08-07
JP2006214569A JP5328084B2 (en) 2005-08-05 2006-08-07 Liquid softener composition

Publications (1)

Publication Number Publication Date
WO2008018186A1 true WO2008018186A1 (en) 2008-02-14

Family

ID=39032726

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/050112 WO2008018186A1 (en) 2006-08-07 2007-01-10 Liquid softener composition

Country Status (2)

Country Link
KR (1) KR101358540B1 (en)
WO (1) WO2008018186A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021086364A1 (en) * 2019-10-31 2021-05-06 Colgate-Palmolive Company Fabric care compositions having improved microbiological robustness and methods for the same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101988072B1 (en) * 2012-06-29 2019-06-11 라이온 가부시키가이샤 Liquid fabric softener composition
KR101880558B1 (en) * 2016-06-10 2018-07-23 (주)엔바이오 Fabric treatment composition having anti-bacterial and anti-static function
KR102430221B1 (en) * 2018-02-21 2022-08-05 주식회사 엘지생활건강 Cleansing composition for removal of organic acid
KR101975550B1 (en) * 2018-02-26 2019-05-07 주식회사 대원지에스아이 Antibacterial and deodorant fiber Softening Composition comprising chaff vinegar

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004503670A (en) * 2000-07-13 2004-02-05 ザ、プロクター、エンド、ギャンブル、カンパニー Perfume composition and detersive composition containing this perfume composition
WO2004025017A1 (en) * 2002-09-13 2004-03-25 Lion Corporation Liquid fabric softener composition
JP2004211215A (en) * 2002-12-27 2004-07-29 Lion Corp Liquid softening agent composition
JP2004269791A (en) * 2003-03-11 2004-09-30 Tsumura & Co Perfume composition for hard surface detergent
JP2005187973A (en) * 2003-12-25 2005-07-14 Lion Corp Liquid softener composition
JP2006077336A (en) * 2004-09-07 2006-03-23 Lion Corp Transparent or translucent liquid softening agent composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004503670A (en) * 2000-07-13 2004-02-05 ザ、プロクター、エンド、ギャンブル、カンパニー Perfume composition and detersive composition containing this perfume composition
WO2004025017A1 (en) * 2002-09-13 2004-03-25 Lion Corporation Liquid fabric softener composition
JP2004211215A (en) * 2002-12-27 2004-07-29 Lion Corp Liquid softening agent composition
JP2004269791A (en) * 2003-03-11 2004-09-30 Tsumura & Co Perfume composition for hard surface detergent
JP2005187973A (en) * 2003-12-25 2005-07-14 Lion Corp Liquid softener composition
JP2006077336A (en) * 2004-09-07 2006-03-23 Lion Corp Transparent or translucent liquid softening agent composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021086364A1 (en) * 2019-10-31 2021-05-06 Colgate-Palmolive Company Fabric care compositions having improved microbiological robustness and methods for the same

Also Published As

Publication number Publication date
KR101358540B1 (en) 2014-02-05
KR20090037912A (en) 2009-04-16

Similar Documents

Publication Publication Date Title
JP5034078B2 (en) Liquid softener composition
JP5995294B2 (en) Liquid softener composition
JP2009161866A (en) Liquid finishing agent composition
WO2008018186A1 (en) Liquid softener composition
JP4381306B2 (en) Liquid softener composition
JP5863114B2 (en) Liquid treatment composition for textile products
JP5328084B2 (en) Liquid softener composition
JP4712411B2 (en) Textile treatment composition
JP2008002024A (en) Liquid treating agent composition for textile product and method for treating textile product
JP5245149B2 (en) Liquid finish composition for textile products
JP4589622B2 (en) Liquid softener composition
JP5396642B2 (en) Liquid finish composition for textile products
JP2007321272A (en) Liquid softener composition
JPWO2014185454A1 (en) Liquid treatment composition for textile products
JP4841275B2 (en) Finishing composition
JP4055544B2 (en) Liquid softener composition
JP6175359B2 (en) Textile treatment agent
JP4956822B2 (en) Liquid finish composition
JP5025994B2 (en) Liquid softener composition
JP7437894B2 (en) Fiber processing articles consisting of fiber processing products and fragrance-containing products
JP7150587B2 (en) Fiber treatment composition
JP5256529B2 (en) UV-absorbing fiber treatment agent composition
JP2006077336A (en) Transparent or translucent liquid softening agent composition
JP5536342B2 (en) Aqueous acidic flavoring composition
JP2007321271A (en) Finishing agent composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07706459

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1020097002263

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07706459

Country of ref document: EP

Kind code of ref document: A1