Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/46—Compounds containing quaternary nitrogen atoms
  • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
  • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
  • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
  • C07C321/20—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
• • 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
  • 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
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/12—Aldehydes; Ketones
  • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/325—Amines
  • D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/325—Amines
  • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
• • 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
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
  • D06M15/11—Starch or derivatives thereof

Definitions

• the present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softening agent composition that can continuously exhibit the scent intended at the time of design while suppressing the generation of off-flavors and is excellent in storage stability at low temperatures.
• Patent Documents 1 to 3 a technique using a fragrance precursor obtained by chemically combining a fragrance and a non-volatile substrate is known in the fields of softeners, bleaches and detergents.
• the perfume precursor continuously releases a scent by being disconnected by a trigger such as light, heat, water or the like.
• a sulfur-containing fragrance precursor formed by bonding a thiol and an ⁇ , ⁇ -unsaturated ketone type fragrance is excellent in scent sustainability (Patent Document 1).
• the softeners that are blended may give off an odor or decrease the storage stability of the softener at low temperatures, especially the freeze-recoverability (liquid softener in winter) Have been frozen and then thawed, it does not return to the viscosity before freezing), and techniques for solving these problems are known (Patent Documents 4 to 8).
• JP-T-2005-511710 Special table 2014-511414 gazette International Publication No. 2015/073223 Japanese Patent Laying-Open No. 2015-4145 Japanese Patent Laid-Open No. 7-18777 Japanese Patent Laid-Open No. 7-18575 JP-A-9-310276 JP-A-7-18572
• the present inventors have found that a sulfur-like off-flavor derived from the sulfur-containing fragrance precursor is generated, and the pleasant fragrance intended at the time of design cannot be realized. I found. Furthermore, the present inventor shows that the liquid softening agent composition containing a sulfur-containing fragrance precursor has a large increase in viscosity after freezing (in other words, low freezing and restoring properties), and storage stability at low temperatures. I found that it was not enough.
• the present inventor suppresses the generation of sulfur-like odor when a metal scavenger is further added to a liquid softener composition containing a specific type of softening base and a sulfur-containing fragrance precursor. Furthermore, it has been found that an increase in viscosity after restoration from freezing can be suppressed. The present invention has been made based on this finding.
• a liquid softener composition The following components (A) to (C): (A) an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), At least one compound selected from the group consisting of a salt and a quaternized product thereof, (B) a sulfur-containing fragrance precursor, and (C) a metal scavenger, A liquid softener composition comprising: [2] The liquid softener composition according to [1], wherein the mass ratio of the component (B) to the component (C) ((B) / (C)) is 0.05 to 50.
• the component (A) is at least one compound selected from the group consisting of compounds represented by general formulas (A1-1) to (A1-8), salts thereof, and quaternized compounds thereof.
• R 7 and R 8 are each independently a hydrocarbon group having 10 to 26 carbon atoms
• R 9 and R 10 are each independently a hydrocarbon group having 7 to 21 carbon atoms.
• YSGQ (B-1) [Where, Y represents a group selected from the group consisting of the following groups (Y-1) to (Y-7) or an isomer thereof, (In the formulas (Y-1) to (Y-7), the wavy line represents the position of the YS bond, and the dotted line represents the position of the single bond or the double bond).
• S represents a sulfur atom
• G represents a divalent or trivalent group derived from a linear or branched alkyl group or alkenyl group having 2 to 15 carbon atoms (the divalent or trivalent group is One optionally selected from the group consisting of —OR 11 , —NR 11 2 , —COOR 11 and R 11 groups, wherein R 11 represents a hydrogen atom or a C1-C6 alkyl group or alkenyl group.
• Q represents a hydrogen atom, a —S—Y group or a —NR 12 —Y group (in each group, Y is defined as described above, and R 12 is a hydrogen atom or a methyl group).
• the compound represented by the general formula (B-1) is 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone and 4
• the liquid softener composition according to [7] which is selected from the group consisting of-(dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone.
• the liquid softener composition of the present invention can continuously exhibit the scent intended at the time of design while suppressing the generation of a sulfur-like odor (excellent scent property). . Furthermore, the liquid softening agent composition of the present invention is excellent in storage stability (particularly freeze-recoverability) at low temperatures. Therefore, the present invention is useful as a liquid softener composition having added value not found in conventional liquid softener compositions.
• the liquid softener composition of the present invention comprises the following components (A) to (C): (A) an amine compound having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), At least one compound selected from the group consisting of a salt and a quaternized product thereof, (B) a sulfur-containing fragrance precursor, and (C) a metal scavenger, Containing.
• the component (A) has “1 to 3 hydrocarbon groups having 10 to 26 carbon atoms, which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—) in the molecule.
• a cationic surfactant which is “at least one compound selected from the group consisting of an amine compound, a salt thereof and a quaternized product thereof”.
• the component (A) is a softening base and is blended in order to give the liquid softening agent the effect of giving softness (texture) to the fiber product (that is, the original function of the softening agent).
• the hydrocarbon group having 10 to 26 carbon atoms (hereinafter sometimes referred to as “long-chain hydrocarbon group” in the present specification) has 10 to 26, preferably 17 to 26, more preferably 19 to 24. .
• the long chain hydrocarbon group may be saturated or unsaturated.
• the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is the long chain carbonization.
• the center of the hydrogen group is preferably distributed around the median.
• the long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group.
• the chain hydrocarbon group may be linear or branched.
• an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
• the long chain hydrocarbon group may be separated by an ester group (—COO—) and / or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.
• the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places.
• each splitting group may be the same or different.
• the carbon atom which a splitting group shall count to the carbon number of a long chain hydrocarbon group.
• the long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
• a secondary amine compound (the number of long-chain hydrocarbon groups is 2) or a tertiary amine compound (the number of long-chain hydrocarbon groups is 3) is preferable, and a tertiary amine compound is more preferable.
• R 1 to R 3 are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH 2 CH (Y) OCOR 4 (Y is a hydrogen atom or CH 3 , and R 4 is 7 carbon atoms) -(CH 2 ) n NHCOR 5 (n is 2 or 3, R 5 is a hydrocarbon group having 7 to 21 carbon atoms), hydrogen atom, carbon number 1 to 4 alkyl groups, —CH 2 CH (Y) OH (Y is a hydrogen atom or CH 3 ), or — (CH 2 ) n NH 2 (n is 2 or 3); At least one of R 1 to R 3 is a hydrocarbon group having 10 to 26 carbon atoms, —CH 2 CH (Y) OCOR 4 , or — (CH 2 ) n NHCOR 5 . ]
• the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R 1 to R 3 is preferably 17 to 26, and more preferably 19 to 24.
• the hydrocarbon group may be saturated or unsaturated.
• the hydrocarbon group is preferably an alkyl group or an alkenyl group.
• Y is a hydrogen atom or CH 3 , and a hydrogen atom is particularly preferable.
• R 4 is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms.
• Hydrocarbon group R 4 is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R 4 COOH) (fatty acid residues), R 4 Nomoto become fatty (R 4 COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as the R 4 is preferably 90/10 to 0/100, more preferably 80/20 to 0 / 100 is more preferable.
• R 4 is an unsaturated fatty acid residue
• a cis isomer and a trans isomer exist, and the mass ratio of cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.
• fatty acids based on R 4 include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), Examples include partially hydrogenated beef tallow fatty acid (iodine value 10 to 60).
• fatty acids prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c): It is preferable to use a composition.
• the ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100.
• the cis / trans ratio (mass ratio) is 40/60 to 100/0, more preferably 70/30 to 90/10.
• the fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, the fatty acid having 20 carbon atoms is less than 2% by mass, and the fatty acid having 21 to 22 carbon atoms is less than 1% by mass. .
• R 5 is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms.
• R 5 may be R 5 of said plurality of mutually identical, may be different. Specific examples of R 5 include the same as R 4 .
• R 1 to R 3 is a long-chain hydrocarbon group (hydrocarbon group having 10 to 26 carbon atoms), —CH 2 CH (Y) OCOR 4 , or — (CH 2 ) n NHCOR 5 ), preferably two are long-chain hydrocarbon groups.
• R 1 to R 3 are long-chain hydrocarbon groups, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH 2 CH (Y) OH or — (CH 2 ) n NH 2 , preferably an alkyl group having 1 to 4 carbon atoms, —CH 2 CH (Y) OH, or — (CH 2 ) n NH 2 .
• alkyl group having 1 to 4 carbon atoms a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
• Y in —CH 2 CH (Y) OH is the same as Y in —CH 2 CH (Y) OCOR 4 .
• N in — (CH 2 ) n NH 2 is the same as n in — (CH 2 ) n NHCOR 5 .
• Preferable examples of the compound represented by the general formula (A1) include compounds represented by the following general formulas (A1-1) to (A1-8).
• R 7 and R 8 are each independently a hydrocarbon group having 10 to 26 carbon atoms.
• R 9 and R 10 are each independently a hydrocarbon group having 7 to 21 carbon atoms.
• Examples of the hydrocarbon group for R 7 and R 8 include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R 1 to R 3 in the general formula (A1).
• Examples of the hydrocarbon group having 7 to 21 carbon atoms in R 9 and R 10 include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R 4 of the general formula (A1).
• R 9 of the plurality of it may be the same as each other, may be different.
• the component (A) may be a salt of an amine compound.
• the salt of an amine compound can be obtained by neutralizing the amine compound with an acid.
• the acid used for neutralization of the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be performed by a known method.
• the component (A) may be a quaternized amine compound.
• a quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent.
• the quaternizing agent used for quaternizing the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acids such as dimethyl sulfate.
• alkyl halides such as methyl chloride
• dialkyl sulfuric acids such as dimethyl sulfate.
• the alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• the quaternization of the amine compound can be performed by a known method.
• At least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof, and a quaternized product thereof is preferable. More preferred is at least one selected from the group consisting of compounds represented by the general formulas (A1-1) to (A1-8), salts thereof and quaternized products thereof, Particularly preferred is at least one selected from the group consisting of compounds represented by general formulas (A1-4) to (A1-6), salts thereof and quaternized products thereof. In particular, a quaternized product of the compound represented by the general formula (A1-4), a quaternized product of the compound represented by (A1-5), and a quaternized product of the compound represented by (A1-6). It is preferable to use together.
• a compound represented by the general formula (A1-2) (hereinafter referred to as “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter referred to as “compound (A1-3)”).
• the fatty acid composition described in the R 4 column of the general formula (A1), or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid, and methyl It can be synthesized by a condensation reaction with diethanolamine.
• the abundance ratio represented by “compound (A1-2) / compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.
• the abundance ratio represented by “a quaternized compound (A1-2) / a quaternized compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize so that
• a compound represented by the general formula (A1-4) (hereinafter referred to as “compound (A1-4)”) and a compound represented by the general formula (A1-5) (hereinafter referred to as “compound (A1-5)”)
• a compound represented by the general formula (A1-6) (hereinafter referred to as “compound (A1-6)”) is a fatty acid composition described in the R 4 column of the general formula (A1) or It can be synthesized by a condensation reaction between a fatty acid methyl ester composition and triethanolamine. At that time, the content ratio of each component to the total mass of the compounds (A1-4), (A1-5) and (A1-6) is 1 to 60 for the compound (A1-4) from the viewpoint of imparting flexibility.
• the compound (A1-5) is preferably 5 to 98% by mass, the compound (A1-6) is preferably 0.1 to 40% by mass, the compound (A1-4) is 30 to 60% by mass, the compound More preferably, (A1-5) is 10 to 55% by mass, and compound (A1-6) is 5 to 35% by mass.
• dimethyl sulfate it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction proceeds sufficiently.
• the abundance ratio of each of the quaternized compounds (A1-4), (A1-5) and (A1-6) is a mass ratio from the viewpoint of imparting flexibility, and the quaternized compound (A1-4) is 1
• the quaternized product of the compound (A1-5) is preferably 5 to 98% by mass, and the quaternized product of the compound (A1-6) is preferably 0.1 to 40% by mass.
• the quaternized product of 4) is 30 to 60% by mass, the quaternized product of compound (A1-5) is 10 to 55% by mass, and the quaternized product of compound (A1-6) is 5 to 35% by mass. More preferred.
• esteramine which is not quaternized generally remains after the quaternization reaction.
• the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.
• a compound represented by the general formula (A1-7) (hereinafter referred to as “compound (A1-7)”) and a compound represented by the general formula (A1-8) (hereinafter referred to as “compound (A1-8)”) From the fatty acid composition described in the R 4 column of the general formula (A1) and the adduct of N-methylethanolamine and acrylonitrile, J. Org. Org. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method.
• the abundance ratio represented by “compound (A1-7) / compound (A1-8)” is 99/1 to 50/50 by mass ratio.
• methyl chloride is preferably used as the quaternizing agent, which is expressed by “a quaternized compound (A1-7) / a quaternized compound (A1-8)”.
• the abundance ratio is preferably 99/1 to 50/50 by mass ratio.
• one type of amine compound, a salt thereof or a quaternized product thereof may be used alone, or a mixture of two or more types, for example, in the general formulas (A1-4) to (A1-6) You may use as a mixture of the compound represented.
• the blending amount of the component (A) is not particularly limited as long as it can achieve the blending purpose, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass with respect to the total mass of the liquid softening agent composition. More preferably, it is 10 to 20% by mass.
• Component (B) A component is a sulfur containing fragrance
• the “sulfur-containing fragrance precursor” refers to a compound obtained by chemically combining a fragrance and a non-volatile substrate containing sulfur.
• the sulfur-containing fragrance precursor itself does not give a fragrance, but when the bond between the fragrance and the substrate is cut by a trigger such as heat, light, water, etc., the fragrance is released to give a fragrance. Therefore, it is known that when clothing is treated with a sulfur-containing fragrance precursor, the effect as a fragrance is exhibited even in the latter half of the usage scene, such as after wearing or storage of the clothing.
• a component is mix
• flavor precursor As a sulfur containing fragrance
• it is a sulfur-containing fragrance precursor represented by the following general formula (B-1).
• Y represents a group selected from the group consisting of the following groups (Y-1) to (Y-7) or an isomer thereof, (In the formulas (Y-1) to (Y-7), the wavy line represents the position of the YS bond, and the dotted line represents the position of the single bond or the double bond).
• S represents a sulfur atom
• G represents a divalent or trivalent group derived from a linear or branched alkyl group or alkenyl group having 2 to 15, preferably 10 to 14 carbon atoms (the divalent or trivalent group).
• the trivalent group is optionally a group consisting of —OR 11 , —NR 11 2 , —COOR 11 and R 11 groups (wherein R 11 represents a hydrogen atom, a C1-C6 alkyl group or an alkenyl group).
• R 11 represents a hydrogen atom, a C1-C6 alkyl group or an alkenyl group.
• Q represents a hydrogen atom, a —S—Y group or a —NR 12 —Y group (in each group, Y is defined as described above, and R 12 is a hydrogen atom or a methyl group).
• “isomers” of the groups represented by the formulas (Y-1) to (Y-7) in the general formula (B-1) are isomers that each group can adopt on the chemical structure. For example, stereoisomers.
• one type may be used alone, or two or more types may be appropriately combined.
• Preferred examples of the compound represented by the general formula (B-1) include methyl or ethyl 2- (4-oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butane. -2-ylamino) -3- (4-oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butan-2-ylthio) propanate, methyl or ethyl 2- (4- Oxo-4- (2,6,6-trimethylcyclohex-2-en-1-yl) butan-2-ylamino) -3- (4-oxo-4- (2,6,6-trimethylcyclohexa-) 2-En-1-yl) butan-2-ylthio) propanate, methyl or ethyl 2- (2-oxo-4- (2,6,6-trimethylcyclohex-1-en-1-yl) butane-4 -Ilamino) -3- (2-Oki -4- (2,6,6-tri
• the sulfur-containing fragrance precursor can be easily obtained on the market or can be synthesized by a known method.
• one type of sulfur-containing fragrance precursor may be used alone, or a mixture of two or more types may be used.
• the blending amount of component (B) is not particularly limited as long as it can achieve the blending purpose, but is preferably 0.0001 to 1% by mass, more preferably 0.005, based on the total mass of the liquid softening agent composition. Is 0.5 to 0.5% by mass, more preferably 0.01 to 0.2% by mass.
• Component (C) is a metal scavenger.
• component (C) component suppresses generation of sulfur-like off-flavor derived from component (B) (sulfur-containing fragrance precursor) and improves the storage stability (freezing / restoring property) of the liquid softener composition at low temperatures. It is used for the purpose.
• the metal scavenger a compound generally known to have a metal scavenging effect can be used without any particular limitation.
• Component (C) may be a free acid or a salt thereof.
• the salt is preferably an alkali metal salt, and more preferably a sodium salt.
• the component (C) may be a hydrate.
• component (C) examples include aminocarboxylic acids and salts thereof, inorganic phosphoric acids and salts thereof, organic phosphoric acids and salts thereof, hydroxy acids and salts thereof, and the like. Of these, aminocarboxylic acids are preferred.
• aminocarboxylic acid examples include the following acids and alkali metal salts thereof.
• DEG N, N-Di- (2-hydroxyethyl) glycine
• HEIDA N- (2-hydroxyethyl) iminodiacetic acid
• HEDTA N- (hydroxyethyl) ethylenediamine tetraacetic acid)
• NTA Nitrilo Triacetic Acid
• DTPA Diethylene Triamine Pentaacetic Acid
• HEDTA Hydroxyethyl Ethylene Diamine Triacetic Acid
• EDTA Ethylene Diamine Tetraacetic Acid
• MGDA Metalglycine Diacetic Acid
• GLDA Dicarboxymethyle Glutamic Acid
• ASDA Aspartate Diacetic Acid
• EDDS Ethylenediamine
• inorganic phosphoric acid and its salt include tripolyphosphoric acid and its salt, pyrophosphoric acid and its salt, and the like.
• organic phosphoric acid and its salt include 1-hydroxyethane-1,1-diphosphonic acid and its salt, polyphosphonic acid and its salt, phytic acid and its salt, and the like.
• hydroxy acid and its salt include citric acid and its salt (for example, trisodium salt of citric acid) and malic acid and its salt (for example, disodium salt of malic acid). Of these, citric acid and its salts are preferred.
• the component (C) can be easily obtained on the market or can be synthesized by a known method.
• a component may be used individually by 1 type and may combine 2 or more types suitably.
• the blending amount of component (C) is not particularly limited as long as it can achieve the blending purpose, but is preferably 0.001 to 5% by mass, more preferably 0.01%, based on the total mass of the liquid softening agent composition. It is ⁇ 2% by mass, more preferably 0.05 to 1% by mass. When the blending amount is 0.001 to 5% by mass, an excellent blending effect can be obtained.
• the mass ratio of the component (A) to the component (C) is preferably 0.1 to 500, more preferably 1 to 200, still more preferably 10 to 100. It is.
• (A) / (C) is set to 0.1 to 500, a higher blending effect (a sulfur-like off-flavor generation suppressing effect and freezing / restoring property) can be obtained.
• the mass ratio of the component (B) to the component (C) is preferably 0.05 to 50, more preferably 0.1 to 10, and still more preferably 0. .2 to 5, particularly preferably 0.2 to 1.
• (B) / (C) is 0.05 to 50, it is possible to obtain a higher blending effect of component (C) (a sulfur-like off-flavor generation suppressing effect and freezing / restoring property).
• Optional Components in the liquid softener composition of the present invention optional components other than the essential components (A) to (C) described above may be blended as necessary within the range not impairing the effects of the present invention.
• the component generally mix
• Specific examples include highly branched cyclic dextrin (component (D)), water, nonionic surfactant, fragrance, water-soluble salt, dye, water-soluble solvent, preservative, ultraviolet absorber, antibacterial agent, deodorant, Examples include skin care ingredients.
• component (D) highly branched cyclic dextrin
• Component (D) is a highly branched cyclic dextrin.
• component (D) component is mix
• the highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000.
• the inner branched cyclic structure portion refers to a cyclic structure portion formed by an ⁇ -1,4-glucoside bond and an ⁇ -1,6-glucoside bond
• the outer branched structure portion refers to the inner branched cyclic portion.
• Highly branched cyclic dextrins are also called cluster dextrins.
• the highly branched cyclic dextrin in the present invention has a weight average molecular weight of about 30,000 to 1,000,000, has one cyclic structure (inner branched cyclic structure portion) in the molecule, and a number of glucan chains in the cyclic structure portion.
• the inner branched cyclic structure portion of the highly branched cyclic dextrin in the present invention is composed of about 10 to 100 glucose, and the inner branched cyclic structure portion includes an outer branched structure portion composed of a large number of acyclic branched glucan chains. Are connected.
• the degree of polymerization of the highly branched cyclic dextrin in the present invention is in the range of 50 to 5000.
• the polymerization degree of the inner branched cyclic structure portion of the highly branched cyclic dextrin in the present invention is in the range of 10-100.
• the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin in the present invention is 40 or more.
• the polymerization degree of each unit chain of the outer branched structure portion of the highly branched cyclic dextrin in the present invention is 10 to 20 on average.
• the highly branched cyclic dextrin in the present invention is produced, for example, by using starch as a raw material and acting on an enzyme called a branching enzyme.
• Starch which is a raw material, is composed of amylose in which glucose is linearly linked by ⁇ -1,4-glucoside bonds and amylopectin having a structure that is complicatedly branched by ⁇ -1,6-glucoside bonds. It is a macromolecule with many connected structures.
• Branching enzyme an enzyme used, is a glucan chain transferase widely distributed in animals, plants, and microorganisms. It acts on the seam portion of the cluster structure of amylopectin and catalyzes the reaction of cyclizing it.
• the highly branched cyclic dextrin in the present invention is a glucan having an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104 and having a polymerization degree in the range of 50 to 10,000. .
• the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.
• Specific examples of the highly branched cyclic dextrin contained in the liquid softening agent composition of the present invention include “Cluster Dextrin” (registered trademark) manufactured by Glico Nutrition Foods, Inc.
• the blending amount of the component (D) is not particularly limited as long as it is an amount that can achieve the blending purpose, but is preferably 0.05 to 0.5 relative to the total mass of the liquid softener composition. It is 5% by mass, more preferably 0.2-2% by mass, and still more preferably 0.3-1% by mass. When the blending amount is 0.05 to 5% by mass, an excellent blending effect can be obtained.
• Liquid softener composition of the water present invention is preferably an aqueous composition comprising water.
• water any of tap water, purified water, pure water, distilled water, ion exchange water and the like can be used. Of these, ion-exchanged water is preferred.
• the blending amount of water is not particularly limited, and can be appropriately blended in order to achieve a desired component composition.
• Nonionic surfactant (hereinafter also referred to as “component (E)”)
• component (E) a nonionic surfactant can be mix
• a nonionic surfactant When a nonionic surfactant is blended, freeze recovery stability at a level sufficient for commercial value can be easily secured.
• the nonionic surfactant for example, those derived from polyhydric alcohols, higher alcohols, higher amines or higher fatty acids can be used.
• a glycerin fatty acid ester or pentaerythritol in which a glycerin or pentaerythritol is ester-bonded with a fatty acid having 10 to 22 carbon atoms; an alkyl group or an alkenyl group having 10 to 22 carbon atoms; Polyoxyethylene alkyl ether having 10 to 100 moles; polyoxyethylene fatty acid alkyl (1 to 3 carbon atoms of the alkyl) ester; polyoxyethylene alkylamine having an average addition mole number of ethylene oxide of 10 to 100 moles; Examples thereof include alkyl polyglucosides having 8 to 18 alkyl groups or alkenyl groups; hydrogenated castor oil having an average addition mole number of ethylene oxide of 10 to 100 moles.
• polyoxyethylene alkyl ethers having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 20 to 80 moles are preferred.
• a nonionic surfactant may be used individually by 1 type, and may be used as a mixture which consists of 2 or more types.
• the blending amount of the nonionic surfactant is not particularly limited as long as it can achieve the blending purpose, but is preferably 0.01 to 10% by mass, more preferably 0.1%, based on the total mass of the liquid softening agent composition. It is ⁇ 8% by mass, more preferably 0.5 to 5% by mass.
• a fragrance other than the component (B) can be blended as an optional component.
• a general-purpose fragrance can be used in the technical field and is not particularly limited.
• a list of fragrance raw materials that can be used is various documents such as “Perfume and Flavor Chemicals”, Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994) and “Synthetic fragrance chemistry and commercial knowledge”, Motoichi Into, Kagaku Kogyo Nipposha (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co.
• the fragrance one type of fragrance may be used alone, or a mixture of two or more types may be used.
• the blending amount of the fragrance is not particularly limited as long as it is an amount that can achieve the blending purpose, but is preferably 0.1 to 3% by mass with respect to the total mass of the liquid softening agent composition, and more preferably 0.8%. It is 5 to 2% by mass, more preferably 0.5 to 1.5% by mass.
• the mass ratio of the component (B) to the component (F) is preferably 0.01 to 2, more preferably 0.02 to 1, and still more preferably 0.8. 1 to 0.5.
• (B) / (F) is set to 0.01 to 2
• a preferable fragrance strength can be maintained from after dehydration in the washing step to after drying.
• Water-soluble salts can be blended for the purpose of controlling the viscosity of the liquid softener composition.
• component (G) Water-soluble salts
• both inorganic salts and organic salts can be used.
• calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, and the like can be used, among which calcium chloride and magnesium chloride are preferable.
• One type of water-soluble salt may be used alone, or a mixture of two or more types may be used.
• the blending amount of the water-soluble salt is not particularly limited as long as it can achieve the blending purpose, but is 0.01 to 1% by mass with respect to the total mass of the liquid softening agent composition. In addition, you may mix
• the pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is in the range of 1 to 6 from the viewpoint of suppressing hydrolysis of the ester group contained in the molecule of the component (A) that accompanies storage days. It is preferable to adjust, and it is more preferable to adjust to the range of 2-4. Further, for the purpose of further suppressing the decomposition of the sulfur-containing fragrance precursor of component (B), the pH of the liquid softener composition at 25 ° C. is preferably 7 or less, and more preferably 3 or less.
• pH adjusters such as hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, sodium hydroxide and other alkali metal hydroxides, alkali metal carbonates and alkali metal silicates are used. Can be used.
• Viscosity of liquid softening agent composition The viscosity of the liquid softening agent composition is not particularly limited as long as its usability is not impaired, but the viscosity at 25 ° C is preferably less than 800 mPa ⁇ s. Considering the increase in viscosity due to storage aging, the viscosity of the liquid softener composition immediately after production at 25 ° C. is more preferably less than 500 mPa ⁇ s, and even more preferably less than 300 mPa ⁇ s. When it is in such a range, the usability such as handling property at the time of loading into the washing machine is good.
• the viscosity of the liquid softening agent composition can be measured using a B-type viscometer (manufactured by TOKIMEC).
• the liquid softener composition of the present invention can be produced by a known method, for example, a method similar to a conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
• a cationic surfactant as a main agent.
• an oil phase containing the component (A), the component (B), the component (E) and the component (F) and the aqueous phase are mixed under a temperature condition equal to or higher than the melting point of the component (A) to obtain an emulsion. It can be manufactured by preparing and then adding and mixing the components (C), (D) and (G) and other components as required, to the obtained emulsion.
• the oil phase can be prepared by mixing the component (A), the component (B), the component (E), the component (F) and an optional component as necessary at a temperature equal to or higher than the melting point of the component (A).
• the aqueous phase can be prepared by mixing water and optional components as necessary.
• the addition method of (B) component, (C) component, (D), (E) component, and (F) component is not limited to the said addition method. That is, each component of (B) component, (E) component, and (F) component may manufacture a liquid softening agent composition by adding and mixing after an emulsion is obtained.
• each of the components may be added alone, or the components (B), (E) and (F) may be premixed and then added to the oil phase or emulsion.
• (E) component can also be added after an aqueous phase and an emulsion are obtained, and can also be divided and added to an oil phase and an aqueous phase.
• the component (C), the component (D), and the component (E) can be added to the aqueous phase.
• liquid softener composition of the present invention can be used in the same manner as a general liquid softener composition.
• a method of softening a washing object by dissolving the liquid softener composition of the present invention in rinse water at the stage of rinsing or water in a container such as a tub with the liquid softener composition of the present invention There is a method in which the product is dissolved, and further, an article to be cleaned is put in and immersed.
• A-1 a cationic surfactant (the compound described in Example 4 of JP-A-2003-12471).
• A-1 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R 9 is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.
• A-2 Cationic surfactant (manufactured by Stepan, trade name: Stepantex SE-88).
• A-2 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R 9 is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.
• A-3 Cationic surfactant (made by Tonan Gosei Co., Ltd., trade name: HITEX RO16E).
• A-3 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R 9 is an alkyl or alkenyl group having 15 to 17 carbon atoms) ) Is quaternized with dimethyl sulfate.
• B-1 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone.
• B-1 is a compound described in Example 4 of JP-T-2005-511710.
• B-1 is a group represented by the general formula (B-1): YSGGQ, wherein Y is Y-1 (having a double bond at positions 3 and 4), and G is carbon.
• a dodecyl group consisting of 12 atoms, a compound in which Q is a hydrogen atom.
• B-2 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone.
• B-2 was synthesized by the same method as described in Example 4 of JP-T-2005-511710 using dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) and ⁇ -nonone (manufactured by Ve Manfis Fragrance Co., Ltd.) as raw materials. did.
• B-2 is a group represented by the general formula (B-1): YSGGQ, wherein Y is Y-2 (having a double bond at positions 1 and 2), and G is carbon.
• a dodecyl group consisting of 12 atoms, a compound in which Q is a hydrogen atom.
• C-1 Trisodium methylglycine diacetate (MGDA trisodium salt) (trade name “Trilon M” manufactured by BASF AG)
• C-2 Tetrasodium ethylenediaminetetraacetate tetrahydrate (hydrate of EDTA tetrasodium salt) (Junsei Co., Ltd.)
• C-3 nitrilotriacetic acid trisodium monohydrate (NTA trisodium salt hydrate) (Tokyo Chemical Industry Co., Ltd.)
• C-4 Trisodium citrate (Wako Pure Chemical Industries, Ltd.)
• D-1 Cluster dextrin (registered trademark, Glico Nutrition Foods, Inc., weight average molecular weight: 300,000)
• E-1 Nonionic surfactant (primary isotridecyl alcohol with 60 mol of ethylene oxide adduct, obtained by adding ethylene oxide to BASF Rutensol TO3)
• [(G) component] As the component (G), calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used. The compounding quantity of the (G) component in each liquid softening agent composition was 0.3 mass% with respect to the total mass of a liquid softening agent composition.
• liquid softener composition Using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amounts of the respective components are adjusted as shown in Table 3 below.
• a liquid softener composition was prepared by the following procedure. First, (A) component, (B) component, (E) component, and (F) component were mixed and stirred to obtain an oil phase mixture. On the other hand, common component 1 was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture.
• the mass of ion-exchange water for balance corresponds to the balance obtained by subtracting the total amount of the oil phase mixture, the component (C) and the component (G) from 980 g.
• the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred.
• the split ratio of the aqueous phase mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,500 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was.
• component (C), the component (D) and the component (G) were added.
• (C) component, (D) component, and (G) component melt
• a suitable amount of hydrochloric acid (reagent 1 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) was added so that the desired softener compositions (Examples 1 to 14 and Comparative Examples 1 to 3) were obtained.
• each component of (A), (B), (C), (D), (E), (F) and (G) is the blending amount with respect to the total mass of the liquid softener composition ( Mass%).
• “(A) / (C)” indicates the mass ratio of the component (A) to the component (C).
• “(B) / (C)” indicates the mass ratio of the component (B) to the component (C).
• “(B) / (F)” indicates the mass ratio of the component (B) to the component (F).
• “initial viscosity” indicates the viscosity at 25 ° C. (measured using a B-type viscometer (manufactured by TOKIMEC)) of the liquid softener composition immediately after production.
• ⁇ Aroma evaluation of liquid softener composition 100 mL of the liquid softening agent composition was put in a lightweight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed, and the aroma was evaluated according to the following four-stage evaluation criteria. The result expressed as the average score of five professional panelists is shown in the column of “Aroma evaluation” in Table 3. In terms of product value, an average score of 2.0 or less was accepted.
• the liquid softener composition obtained in each of the above examples was added, and a softening treatment for 3 minutes (finishing agent 6.67 mL, bath ratio 20 times, using tap water at 25 ° C.) Went. After the softening treatment, dehydration was performed for 1 minute. After the treatment, the cotton towel was taken out from the two-tank washing machine, dried for 18 hours under constant temperature and humidity conditions of 20 ° C. and 40% RH, and subjected to the evaluation shown below.
• the measured viscosity is shown in the column of “Freezing / Recovering” in Table 3. The measured viscosity was classified according to the following criteria, and two or more points were determined to be acceptable in terms of commercial value.
• the present invention can be used in the field of liquid softening agents.

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