JP4757711B2 - Transparent or translucent liquid softener composition - Google Patents

Description

  The present invention relates to a transparent or translucent liquid softener composition.

  Liquid softener compositions having a transparent appearance are known, and in Patent Documents 1 to 6, addition of an organic solvent, an electrolyte, a surfactant, or the like having a specific log P is necessary for producing a transparent liquid softener composition. Techniques using agents are disclosed. Moreover, it is already known that a transparent liquid softening agent composition contains a quaternary ammonium compound having an ester group as a main base. Patent Documents 7 to 11 disclose that the composition is divided by an ester group. When a quaternary ammonium compound having a chain hydrocarbon group is used, a quaternary ammonium compound having a saturated hydrocarbon group and an unsaturated hydrocarbon group at a certain ratio is disclosed.

For example, Patent Document 7 discloses that a fiber product treated with a softener composition containing dimethyldi- (acyloxyisopropyl) -ammonium chloride (a quaternary ammonium compound) having an acyl group derived from rapeseed oil fatty acid has high hygroscopicity. It is described to show. Further, in Patent Document 8, similarly, in the quaternary ammonium salt having a long-chain alkyl ester group for the water absorption retention effect, the content of saturated alkyl and unsaturated alkyl is 2:98 to 30:70, preferably Is described as 5:95 to 15:85. Patent Document 10 describes a fabric softening technique using a quaternary ammonium ester compound, and the best softening performance can be obtained when 20 to less than 75% of the hydrocarbon substituents are unsaturated. Are listed. In order to improve the flexibility performance and the water absorption performance as described above, a technique of using a saturated group and an unsaturated group in combination as a hydrocarbon group of a raw fatty acid is known. Further, Patent Document 9 and Patent Document 11 show excellent rewetability in biodegradable fabric softener compounds, and show improved stability under long-term storage conditions at room temperature and below room temperature (precipitation, gelation, In order to recover after freezing and obtain stable viscosity characteristics, the content of the soft active ingredient having a polyunsaturated alkyl group is at least 3% by weight in the total soft active ingredient, preferably 15 It is described that such performance can be obtained by setting the weight% or more. Thus, it is disclosed that in the quaternary ammonium salt having a long-chain hydrocarbon group that is separated by an ester group, the above characteristics can be obtained by having an unsaturated group in the hydrocarbon group.
JP-T-2001-515151 JP 2001-524614 A JP-T-2001-524616 JP-T-2002-505391 Japanese Patent Laid-Open No. 2004-60079 JP 2004-232163 A JP 62-243877 A Japanese Patent No. 2956274 Japanese National Patent Publication No. 11-509277 Japanese National Patent Publication No. 11-511497 JP 2003-183981 A

  A transparent or translucent liquid softener composition is required to maintain its aesthetic appearance transparent or translucent in a wide temperature environment from high temperature to low temperature, and in particular, the appearance must be transparent or translucent. It is suitable to be filled in a transparent plastic container so that it can be visually observed, but when stored for a long time at high or low temperature, it will be separated and garbled, so it is stabilized to suppress it There was a problem that the manufacturing cost increased because a large amount of the agent had to be added.

  When a transparent or translucent liquid softener composition was prepared using a quaternary ammonium compound having an ester group based on an unsaturated fatty acid in accordance with the technique described in the above-mentioned patent document, The subject that the cloudy white and white cotton-like appearance defect were exhibited in the long-term storage occurred.

  Accordingly, the problem to be solved by the present invention is a transparent or translucent liquid softener composition containing a quaternary ammonium compound excellent in flexibility and water absorption, and at a low temperature of 0 ° C. or lower. An object of the present invention is to provide a softener composition that does not cause appearance defects (deterioration of transparency) even when stored.

  In the present invention, the term “transparent or translucent” means that when a quartz 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 30% or more. Say something.

  The inventors of the present invention have investigated the causative substances of white turbidity and white cotton-like appearance in long-term storage at a low temperature (around 0 ° C. or less). The present inventors have found that a precursor (particularly a triester precursor) having a high proportion of saturated hydrocarbon groups is the cause.

  The present inventors have found that the above-mentioned problems can be solved by controlling the ratio of the saturated hydrocarbon group and the content of the triester precursor to a specific range and using the organic solvent in combination with a specific logP. .

  The present inventors have found that the precursor of the quaternary ammonium compound in which the saturated hydrocarbon group is controlled to a low ratio can be melted even at a relatively low temperature. It was found that the reaction can be carried out. Furthermore, the present inventors have found that the quaternization in the absence of a solvent can reduce the content of a precursor (particularly, a triester precursor) and can further improve the problem of exhibiting a poor appearance.

The present invention contains the following component (a) and component (b) as means for solving the problem, the content of component (a) is 5 to 30% by mass, and the content of component (b) is 5 to 30% by mass. %, A transparent or translucent liquid softener composition is provided.
Component (a): a compound represented by the following general formula (1) and a compound represented by the general formula (2), wherein R ¹⁴ in the general formula (1) is an alkyl group having 1 to 3 carbon atoms. The ratio of the mass ratio a1 / a2 = 99/1 to 80/20 between the amount a1 and the total amount a2 of the compound represented by the general formula (2) in which R ¹⁴ in the general formula (1) is a hydrogen atom Mixture containing in.

[In General Formula (1) and General Formula (2),
R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ¹¹ , R ¹² and R ¹³ are each independently a C 14-26 saturated hydrocarbon group or an unsaturated hydrocarbon group having one or more double bonds separated by an ester group, Or it is a C1-C3 hydroxyalkyl group or a C1-C3 alkyl group. Moreover, the ratio of the saturated hydrocarbon group divided by the ester group is based on the total number of moles of the saturated hydrocarbon group divided by the ester group and the unsaturated hydrocarbon group having one or more double bonds. 0.1 to 10 mol%.
X ⁻ is an anionic group. ]
(B) component: organic solvent whose log P is -0.5 to 1.5

  The transparent or translucent liquid softening agent composition of the present invention does not cause white turbidity even during long-term storage at a low temperature (around 0 ° C. or less) and is excellent in storage stability.

[(A) component]
The component (a) of the present invention comprises a compound represented by the general formula (1) and a compound represented by the general formula (2), wherein R ^{14 in the} general formula (1) is an alkyl group having 1 to 3 carbon atoms. The mass ratio a1 / a2 of the compound a1 and the total amount a2 of the compound represented by the general formula (2) and the compound represented by the general formula (2) wherein R ^{14 in the} general formula (1) is a hydrogen atom is 99/1 to 80 It is a mixture containing at a ratio of / 20.

In the general formulas (1) and (2), R ¹¹ , R ¹² and R ¹³ have the above-mentioned meanings, but the ratio of saturated hydrocarbon groups separated by ester groups is from the viewpoint of maintaining storage stability. , 0.1 to 10 mol% based on the total number of moles of the saturated hydrocarbon group separated by the ester group and the unsaturated hydrocarbon group having one or more double bonds, and 0.3 to 7 Mol% is preferable, 0.5-6 mol% is still more preferable, 0.8-5 mol% is especially preferable, and 1-4 mol% is the most preferable.

  Moreover, the ratio of the unsaturated hydrocarbon group having one double bond separated by an ester group is the same as that of the saturated hydrocarbon group and double bond separated by an ester group from the viewpoint of maintaining storage stability. It is preferably 80 to 97 mol%, more preferably 81 to 96 mol%, particularly preferably 82 to 95 mol%, based on the total number of moles with one or more unsaturated hydrocarbon groups. And the ratio of the unsaturated hydrocarbon group which has two or more double bonds divided | segmented by ester group is the viewpoint of maintaining the storage stability, and the saturated hydrocarbon group and double bond divided | segmented by ester group are considered. 0.5 to 15 mol% is preferable, 1 to 14 mol% is more preferable, and 2 to 12 mol% is particularly preferable with respect to the total number of moles with one or more unsaturated hydrocarbon groups.

  Further, the ratio of saturated hydrocarbon groups which are derived from saturated fatty acids having 18 or more carbon atoms and which are separated by ester groups is different from saturated hydrocarbon groups which are separated by ester groups from the viewpoint of low temperature stability. 0.1-5 mol% is preferable with respect to the total number of moles with an unsaturated hydrocarbon group having one or more heavy bonds, 0.1-4 mol% is more preferable, and 0.1-3 mol% is Particularly preferred is 0.1 to 2 mol%.

In the present specification, the monoester compound is a compound in which R ^{14 in the} general formula (1) is an alkyl group having 1 to 3 carbon atoms, and one of R ¹¹ , R ^{12 and} R ¹³ A diester compound is a compound in which R ^{14 in the} general formula (1) is an alkyl group having 1 to 3 carbon atoms, and R ¹¹ , R ¹² or R ^A compound in which two of ¹³ are groups separated by an ester group; a triester compound is a compound in which R ^{14 in} the above general formula (1) is an alkyl group having 1 to 3 carbon atoms, A compound in which all (three) of R ¹¹ , R ¹² and R ¹³ are groups separated by an ester group.

In this specification, the monoester precursor is a compound in which R ^{14 in} the above general formula (1) is a hydrogen atom, or a compound represented by the above general formula (2), and R ¹¹ , R ¹² Or a compound in which one of R ¹³ is a group separated by an ester group; a diester precursor is a compound in which R ^{14 in} the above general formula (1) is a hydrogen atom, or the above general formula (2) A compound in which two of R ¹¹ , R ¹² or R ¹³ are separated by an ester group; a triester precursor refers to R in the above general formula (1) ^A compound in which ¹⁴ is a hydrogen atom, or a compound represented by the above general formula (2), wherein all (three) of R ¹¹ , R ¹² and R ¹³ are groups separated by an ester group Say.

In this specification, when a precursor is simply referred to, a compound in which R ^{14 in the} general formula (1) is a hydrogen atom, a compound represented by the general formula (2), or the monoester precursor Body, diester precursor and / or triester precursor.

  The cis / trans molar ratio of the unsaturated hydrocarbon group having one double bond is preferably 25/75 to 99.9 / 0.1 from the viewpoint of maintaining transparency and storage stability. 50-99.9 / 0.1 is still more preferable, and 60 / 40-99.9 / 0.1 is especially preferable.

In general formula (1), X ^-, as the anionic group represented a halogen ion, sulfate ion, include an alkyl sulfate ion such as 1 to 3 fatty acid or carbon atoms to 12 carbon atoms, a halogen ion, carbon A C 1-3 alkyl sulfate ion is preferred.

The compound represented by the general formula (1) of the present invention can be produced by subjecting the compound represented by the general formula (2) to a quaternization reaction using an alkylating agent. The compound represented by the general formula (2) is carbonized with a fatty acid or a fatty acid lower alkyl (alkyl group having 1 to 3 carbon atoms) ester so that R ¹¹ , R ¹² and R ¹³ have the above preferred composition. The composition of the hydrogen group is selected, and a specific number of moles of raw fatty acid or fatty acid lower alkyl (alkyl group having 1 to 3 carbon atoms) having such a composition and the corresponding alkanolamine are subjected to dehydration esterification or transesterification. It can be produced by reacting.

  Examples of the alkanolamine include a dialkylmonoalkanolamine (preferably dimethylmonoethanolamine or dimethylmonopropanolamine), a monoalkyldialkanolamine (preferably methyldiethanolamine or methyldipropanolamine), or a trialkanolamine (preferably triethanol). Amine or tripropanolamine), but is not limited thereto. A particularly preferred alkanolamine is trialkanolamine.

  In order to obtain a fatty acid or a fatty acid lower alkyl ester having the above-mentioned preferred hydrocarbon composition, a fatty acid as commonly known in fats and oils manuals is used, an isomerization reaction of an unsaturated bond, or a mixture of these fatty acids. Can be obtained.

  Further, in order to control the content of unsaturated hydrocarbon groups having two or more double bonds in the raw fatty acid or fatty acid lower alkyl ester, for example, crystallization as described in JP-A-4-306296 A method of distilling methyl ester as described in JP-A-6-41578, a selective hydrogenation reaction as described in JP-A-8-99036, and the like can be performed.

  Examples of the alkylating agent used in the quaternization reaction of the compound (precursor) represented by the general formula (2) include dialkyl sulfuric acid (alkyl group having 1 to 3 carbon atoms), alkyl halide (alkyl group having carbon number). 1-3) and the like.

  Further, the quaternization reaction using an alkylating agent can be synthesized even in the presence of a solvent (for example, ethanol, propanol, etc.). From the viewpoint of maintaining the transparency of the synthesized product and / or suppressing the generation of impurities, It is more preferable to synthesize without solvent.

  The quaternization reaction temperature is preferably about 40 to 120 ° C, more preferably about 50 to 100 ° C, and particularly preferably about 60 to reduce the precursor content and increase the degree of cationization. ~ 90 ° C.

  (A) A component can be made into the mixture containing 2 or more types of compounds selected from a monoester compound, a diester compound, and a triester compound.

In view of maintaining transparency and storage stability, the component (a) of the present invention includes an amount a1 of the compound in which R ^{14 in the} general formula (1) is an alkyl group having 1 to 3 carbon atoms, and the general formula (1). ) R ¹⁴ is a hydrogen atom and the mass ratio a1 / a2 to the total amount a2 of the compound represented by the general formula (2) is 99/1 to 80/20, preferably 95/5 to 5/5. 80/20, more preferably 95/5 to 85/15.

Such mixtures, the ratio of the fatty acid or fatty acid lower alkyl ester and alkanolamine Amin 1.2: 1.0 to 2.5: 1.0, preferably 1.5: 1.0 to 2.0 : It is obtained by reacting at a molar ratio of 1.0 to prepare a precursor, and further performing a quaternization reaction.

Furthermore, in the present invention, from the viewpoint of maintaining transparency and storage stability, a compound in which R ^{14 in the} general formula (1) is a hydrogen atom and a compound represented by the general formula (2) in the liquid softener composition The total content of is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, and particularly preferably 1.0% by mass or less.

[Component (b)]
The component (b) of the present invention is an organic solvent having a log P of -0.5 to 1.5, preferably -0.3 to 1.5. Here, logP is a coefficient indicating the affinity of an organic compound for water and 1-octanol. 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. It is common to show them in the form of their logarithm logP relative to the base 10. Log P values of many compounds are reported, and many values are listed in a database available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., and can be referred to. When there is no measured log P value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by the Hansch, Leo fragment approach together with the measured logP value, if any. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). Since this ClogP value is currently the most general and reliable estimate, it can be used in place of the actual logP value when selecting a compound. In the present invention, if there is a measured value of logP, the ClogP value calculated by the program CLOGP v4.01 is used when there is no measured value.

  Examples of the organic solvent having a log P of -0.5 to 1.5 as the component (b) of the present invention include 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethyl-1,3- Propanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-2,4-pentanediol, polyoxyethylene monobutyl ether having an average addition mole number of 1 to 3, average addition mole number of 1 to 3 One or more alcohols selected from the group consisting of polyoxypropylene monobutyl ether, polyoxypropylene monopropyl ether having an average addition mole number of 1 to 3, and polyoxyethylene monophenyl ether having an average addition mole number of 1 to 4 An organic solvent is mentioned.

  In one embodiment, the component (b) of the present invention is preferably polyoxyethylene monophenyl ether having an average addition mole number of 1 to 4 or 2-methyl-2,4-pentanediol from the viewpoint of maintaining transparency. More preferred component (b) is polyoxyethylene monophenyl ether having an average addition mole number of 1 to 4.

[Other ingredients]
The softener composition of the present invention can contain a fatty acid (hereinafter referred to as component (c)) having an iodine value of 30 to 300 and a carbon number of 12 to 26. The iodine value of the component (c) is preferably 50 to 200, more preferably 70 to 180. Moreover, 16-22 are preferable.

  Specific examples of the component (c) include Linderic acid, Tuzuic acid, Fizeteric acid, Myristoleic acid, Palmitoleic acid, Oleic acid, Elaidic acid, Linoleic acid, Linolenic acid, Petroceric acid, Vaccenoic acid, Gadelic acid, Examples thereof include unsaturated fatty acids such as gondrenic acid, cetreic acid, erucic acid, brassic acid, ceracolic acid and ximenoic acid, and these can be used alone or as a mixture of two or more thereof.

  As the component (c), a mixed fatty acid obtained by saponifying animal and vegetable oils can be used. For example, animal oil such as beef tallow, lard, fish oil, or palm oil, sunflower oil, soybean oil, rapeseed oil, safflower Mention may be made of fatty acids obtained by saponifying vegetable oils such as oil, cottonseed oil, corn oil and olive oil. The fatty acid composition derived from these animal and vegetable oils can be referred to the new edition fatty acid chemistry (edited by Jiro Hirano et al., First edition in September 1981, published by Koshobo, page 5 Table 1.1.3). In addition, in this specification, when using 2 or more types of fatty acids, the iodine value of a fatty acid means the iodine value of the said 2 or more types of mixed fatty acid.

  Component (c) is, for example, crystallization as described in JP-A-4-306296, a method of distilling methyl ester as described in JP-A-6-41578, or JP-A-8- The ratio of fatty acids containing two or more carbon-carbon unsaturated bonds can be controlled by a selective hydrogenation reaction or the like described in Japanese Patent No. 99036.

  The preferred fatty acid of component (c) of the present invention is one or more unsaturated fatty acids selected from the group consisting of oleic acid, elaidic acid and linoleic acid.

  Furthermore, the fatty acid of (c) component of this invention can use the mixed fatty acid of a saturated fatty acid and an unsaturated fatty acid. In one embodiment, the fatty acid of component (c) of the present invention is oleic acid 20 to 97% by mass, elaidic acid 0.1 to 30% by mass, linoleic acid 2 to 70% by mass, and stearic acid. A mixed fatty acid containing 0.1 to 5% by mass and 0.1 to 5% by mass of palmitic acid is suitable, and in particular, 50 to 95% by mass of oleic acid, 0.1 to 15% by mass of elaidic acid, A mixed fatty acid containing linoleic acid in an amount of 5 to 15% by mass, stearic acid in an amount of 0.1 to 3% by mass, and palmitic acid in an amount of 0.1 to 3% by mass is preferable from the viewpoint of improving the softening effect and storage stability. .

  The fatty acid of the component (c) of the present invention preferably has a cis / trans molar ratio of 25/75 to 99.9 / 0.1 from the viewpoint of storage stability, and is preferably 50/50 to 99.9. More preferred is /0.1.

  The liquid softening agent composition of the present invention contains water (hereinafter referred to as component (d)). Water from which hardness components such as calcium and magnesium present in trace amounts and heavy metals such as iron are removed is preferable, and ion-exchanged water or distilled water can be used. A small amount of chlorine may be contained for the purpose of sterilizing or sterilizing water.

  The liquid softener composition of the present invention preferably further contains a nonionic surfactant (hereinafter referred to as component (e)) from the viewpoint of improving storage stability.

  (E) As a component, the polyoxyethylene alkyl ether which has a C8-C20 alkyl group or alkenyl group is preferable, and especially the nonionic surfactant represented by following General formula (3) is favorable.

R ³¹ -E-[(R ³² O) _d -R ³³ ] _e (3)
[Wherein R ³¹ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms. R ³² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. R ³³ is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. d represents a number of 2 to 100, preferably 4 to 80, more preferably 5 to 60, and particularly preferably 6 to 40. E is -O-, -COO-, -CON <or -N <, e is 1 when E is -O- or -COO-, and e is E when -CON <or -N <. Is 2. ]
Specific examples of the compound represented by the general formula (3) include compounds represented by the following formulas (3-1) to (3-4).

R ³¹ —O— (C ₂ H ₄ O) _f —H (3-1)
[Wherein R ³¹ represents the above-mentioned meaning. f is a number of 8 to 100, preferably 10 to 60. ]
_{^{R 31 -O- (C 2 H 4}} O) g - (C 3 H 6 O) h -H (3-2)
[Wherein R ³¹ represents the above-mentioned meaning. g and h are each independently a number of 2 to 40, preferably 5 to 40, and (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]

[Wherein R ³¹ represents the above-mentioned meaning. p, q, r and s are each independently a number of 0 to 40, p + q + r + s is a number of 5 to 60, preferably 5 to 40, and (C ₂ H ₄ O) and (C ₃ H ₆ O) May be random or block adducts. R ³⁴ and R ³⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms].

The liquid softening agent composition of the present invention preferably further contains a metal sequestering agent (hereinafter referred to as component (f)) from the viewpoint of improving storage stability. Specifically, examples of the component (f) include the following compounds.
(1) Phosphate compounds such as phytic acid or salts thereof (preferably alkali metal salts or alkanolamine salts).
(2) Ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane- Phosphonic acids such as 1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid or salts thereof (preferably alkali metal salts or alkanolamine salts).
(3) Phosphonocarboxylic acid such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid or a salt thereof (preferably an alkali metal Salt or alkanolamine salt).
(4) Amino acids such as aspartic acid, glutamic acid and glycine or salts thereof (preferably alkali metal salts or alkanolamine salts).
(5) Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, alkylglycine-N, N-diacetic acid Aminopolyacetic acid such as aspartic acid-N, N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediaminesuccinic acid, or a salt thereof (preferably an alkali metal salt or an alkanolamine salt).
(6) Organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid or the like Salt (preferably an alkali metal salt or an alkanolamine salt).
(7) Aminopoly (methylenephosphonic acid) or a salt thereof (preferably an alkali metal salt or alkanolamine salt), or polyethylenepolyamine poly (methylenephosphonic acid) or a salt thereof (preferably an alkali metal salt or alkanolamine salt).

  Among these, the component (f) is preferably at least one selected from the groups (2), (5), and (6), and at least one selected from the groups (2) and (5). Species are more preferred. Particularly preferred component (f) is ethane-1-hydroxy-1,1-diphosphonic acid and / or ethylenediaminetetraacetic acid from the viewpoint of improving storage stability.

  The liquid softening agent composition of the present invention can further contain an inorganic salt (hereinafter referred to as component (g)). As the inorganic salt, sodium sulfate, sodium chloride, calcium chloride, magnesium chloride and the like are preferable from the viewpoint of storage stability. However, the liquid softening agent composition of the present invention may further contain sodium salt, potassium salt and the like contained in a surfactant such as fatty acid salts in addition to the inorganic salt.

  The liquid softener composition of the present invention further contains an ester compound (hereinafter referred to as component (h)) of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol for the purpose of improving storage stability. However, it is necessary to pay attention to the type and content in order to obtain a transparent appearance. Examples of the compound that can be blended include triglyceride, diglyceride, monoglyceride, mono-, di-, or tri-esters of pentaerythritol, sorbitan esters, and the like.

  The liquid softening agent composition of the present invention may further contain an organic solvent other than the component (b) (hereinafter referred to as component (i)). Specifically, the component (i) is an organic solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol and the like, and ethanol is particularly preferable from the point of smell. In this invention, a fragrance | flavor and dye can be suitably contained from a point of palatability as other components.

[Liquid softener composition]
The liquid softening agent composition of the present invention can be obtained by mixing the above-described components so as to have the following contents.

  Content of (a) component in a composition is 5-30 mass% from a viewpoint of improving a softness | flexibility performance, Preferably it is 10-28 mass%, More preferably, it is 15-25 mass%. (B) Content of a component is 5-30 mass% from a viewpoint of an improvement of storage stability, Preferably it is 6-25 mass%, More preferably, it is 7-23 mass%.

  Component (c) is optional, but from the viewpoint of improving the softening effect and storage stability, it is preferably 0.05 to 10% by mass, more preferably 0.3 to 7% by mass, and still more preferably 0.5 to 5%. % By mass, particularly preferably 0.5 to 4% by mass. Although the component (e) is optional, it is preferably from 0.5 to 10% by mass, more preferably from 0.8 to 8% by mass, and particularly preferably from 1 to 8% by mass from the viewpoints of storage stability improvement effect and flexibility improvement effect. 5% by mass. Although the component (f) is optional, it is preferably 50 to 2000 ppm (mass basis), more preferably 50 to 1000 ppm, and particularly preferably 50 to 500 ppm from the viewpoint of the effect of improving storage stability. The component (g) is preferably 0.01 to 5% by mass, particularly preferably 0.02 to 3% by mass.

  The component (h) and component (i) are also preferably contained from the viewpoint of storage stability, and the component (h) is preferably 0.01 to 5% by mass, particularly preferably 0.02 to 2% in the composition. It is preferable to contain 3% by mass and component (i) preferably 0.01 to 5% by mass, particularly preferably 0.02 to 3% by mass.

  Below, the synthesis example of (a) component and the comparative quaternary ammonium salt is shown.

(Synthesis Example 1)
Having the composition shown in Table 1, the dehydration condensation according to a standard method iodine value 90gI ₂ / 100g, the raw material fatty acid value of 1 201MgKOH / g and triethanolamine in a reaction molar ratio 1.85 / 1 (fatty acid / triethanolamine) Reaction was performed and the condensate was obtained. Next, 0.95 equivalent of dimethyl sulfate was used for this condensate in the absence of a solvent, and quaternization was performed by a conventional method, followed by dilution with ethanol to obtain the desired quaternary ammonium salt mixture. It was.

(Synthesis Example 2)
Synthesis Example 1 using raw material fatty acid ₂ having a composition of Table 1 and an iodine value of 90 gI 2/100 g and an acid value of 199 mg KOH / g and a reaction molar ratio of 1.95 / 1 (fatty acid / triethanolamine) The target quaternary ammonium salt mixture was obtained by the same operation as in Example 1.

(Synthesis Example 3)
Having the composition shown in Table 1, using an iodine value 92gI ₂ / 100g, a raw material fatty acid 3 and triethanolamine acid value 201MgKOH / g at a reaction molar ratio 1.85 / 1 (fatty acid / triethanolamine), Synthesis Example 1 The target quaternary ammonium salt mixture was obtained by the same operation as in Example 1.

(Synthesis Example 4)
Having the composition shown in Table 1, the dehydration condensation according to a standard method iodine value 90gI ₂ / 100g, the raw material fatty acid value of 1 201MgKOH / g and triethanolamine in a reaction molar ratio 1.95 / 1 (fatty acid / triethanolamine) Reaction was performed and the condensate was obtained. Next, in the presence of 15% by mass of ethanol with respect to the condensate, quaternization is performed by a conventional method using 0.90 equivalent of dimethyl sulfate to the condensate, thereby obtaining the desired quaternary ammonium salt A mixture was obtained.

Table 2 summarizes the acid values and iodine values of the starting fatty acids and dehydration condensates of Synthesis Examples 1 to 4, and the physical properties and compositions of the resulting quaternary ammonium salt mixtures.
Here, the contents (%) of amine, amine monomethyl sulfate, fatty acid and quaternary ammonium salt in Table 2 were determined by the following method.

<Amine content (%)>
The total amine value was calculated | required by titrating the sample melt | dissolved in the ethanol solvent using the automatic potentiometric titrator with 0.2N-HCl, and the amine content was computed using the following formula.

<Amine monomethyl sulfate and fatty acid content (%)>
A sample dissolved in an ethanol solvent was titrated with 0.1 N KOH using an automatic potentiometric titrator, and each acid value was determined. The content of amine monomethyl sulfate and fatty acid was calculated from each acid value using the following formula.

<Quaternary ammonium salt content (%)>
The content (%) of the quaternary ammonium salt was calculated using the difference between the content of amine, amine monomethyl sulfate, and fatty acid calculated by the above method and the content of the following solid content.

<Ethanol content>
The ethanol content was measured using a volatile content measuring device.

<Content of solid content>
The solid content was calculated as the difference between the quaternary ammonium salt mixture and the ethanol content.

The compounding components used in the examples are summarized below.
(A) Component (a-1): Quaternary ammonium salt mixture obtained in Synthesis Example 1 Comparative quaternary ammonium salt (a′-1): Quaternary ammonium salt mixture obtained in Synthesis Example 2 (A′-2): Quaternary ammonium salt mixture obtained in Synthesis Example 3 (a′-3): Quaternary ammonium salt mixture obtained in Synthesis Example 4 (b) Component (b-1): Phenoxyethanol (B-2): polyoxyethylene (average number of added moles 3) monophenyl ether (b-3): 2-methyl-2,4-pentanediol (b-4): 1,4-cyclohexanedimethanol (b -5): diethylene glycol monobutyl ether and other components (c-1): a mixed fatty acid having the following composition obtained by saponifying sunflower oil and performing a selective hydrogenation reaction (3.5% by mass of palmitic acid, stearic acid) 4% by mass 80 wt% oleic acid, elaidic acid 0.5 wt%, 10 wt% linoleic acid, other 2% by weight)
(C-2): Mixed fatty acid having the following composition obtained by saponifying beef tallow and performing a selective hydrogenation reaction (0.8% by mass of palmitic acid, 2.0% by mass of stearic acid, 80% by mass of oleic acid) , Elaidic acid 10 mass%, linoleic acid 2 mass%, other 5.2 mass%)
(E-1): polyoxyethylene (average addition mole number 23) monolauryl ether (e-2): polyoxyethylene (average addition mole number 8) monoalkyl (C9-10) ether (f-1): ethylenediamine 4 Acetic acid (g-1): Sodium sulfate (g-2): Magnesium chloride (h-1): Dehydration condensate of oleic acid and sorbitan. The molar ratio of oleic acid / sorbitan is 3/1.
(I-1): Ethanol Example 1
Using the components shown in Table 3, a liquid softener composition was prepared by the following method, and the stability was evaluated by the following method. The results are shown in Table 3.

<Method for Preparing Liquid Softener Composition>
A 300 mL beaker was charged with 95% of the amount of ion-exchanged water necessary for the finished mass of the softening agent composition to be 200 g, and the temperature was raised to 60 ° C. in a water bath. While stirring with a turbine-type stirring blade having three stirring blades each having a length of 2 cm (300 r / m), the required amounts of component (b) and component (e) were dissolved. Next, the mixture (40 degreeC) which mixed the required amount (a) component, (c) component, and (h) component previously was added. After stirring for 5 minutes, component (f), component (g) and component (i) were added sequentially, and after stirring for 5 minutes, the pH was adjusted to the target with 35% aqueous hydrochloric acid and 48% aqueous sodium hydroxide, An amount of ion-exchanged water at 60 ° C. necessary for the finished mass was added. Thereafter, the mixture was stirred for 10 minutes, the beaker was transferred to a water bath containing 5 ° C. water, and cooled to 20 ° C. while stirring. In addition, pH shown in Table 3 described pH after cooling (20 degreeC).

<Stability evaluation method>
The appearance of the liquid softener composition immediately after production and the appearance of the liquid softener composition after storage at 0 ° C. for 20 days were visually observed and evaluated according to the following criteria.

Evaluation criteria (appearance)
○… Transparent or translucent △… Slightly cloudy ×… Separated or cloudy

Claims (3)

By using a fatty acid or a fatty acid lower alkyl ester and an alkanolamine so that the ratio (molar ratio) is 1.2: 1.0 to 2.5: 1.0, a dehydration esterification reaction or a transesterification reaction is performed. After obtaining the compound represented by the general formula (2),
By subjecting the compound represented by the general formula (2) to a quaternization reaction using an alkylating agent in the absence of a solvent,
The compound represented by the general formula (1) and the compound represented by the general formula (2) are divided into an amount a1 of the compound in which R ¹⁴ in the general formula (1) is an alkyl group having 1 to 3 carbon atoms, and the general formula (1) R ¹⁴ is composed of a mixture containing at a mass ratio of a1 / a2 = 99 / 1~80 / 20 of the total amount a2 of the compound represented by the compounds and the general formula is a hydrogen atom (2) of ( a) After obtaining the component,
Component (a) and organic solvent (b) component log P is -0.5 to 1.5, (a) component content is 5-30 mass%, (b) component content is 5 A method for producing a transparent or translucent liquid softener composition, which is mixed so as to be ˜30% by mass.

[In General Formula (1) and General Formula (2),
R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ¹¹ , R ¹² and R ¹³ are each independently a C 14-26 saturated hydrocarbon group or an unsaturated hydrocarbon group having one or more double bonds separated by an ester group, Or it is a C1-C3 hydroxyalkyl group or a C1-C3 alkyl group. Moreover, the ratio of the saturated hydrocarbon group divided by the ester group is based on the total number of moles of the saturated hydrocarbon group divided by the ester group and the unsaturated hydrocarbon group having one or more double bonds. 0.1 to 10 mol%.
X ⁻ is an anionic group. ] In the component (a) of the liquid softener composition, the total content of the compound represented by general formula (1) wherein R ¹⁴ is a hydrogen atom and the compound represented by general formula (2) is 1.5% by mass or less. A method for producing a transparent or translucent liquid softener composition according to claim 1. (A) cis / trans of an unsaturated hydrocarbon group having one double bond separated by an ester group in R ¹¹ , R ¹² and R ¹³ of the general formula (1) and the general formula (2) of the component The manufacturing method of the transparent or translucent liquid softening agent composition of Claim 1 or 2 whose molar ratio is 25 / 75-99.9 / 0.1.