JP3914529B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a softener composition, and more particularly to a liquid softener composition for clothing comprising an imidazoline type cationic surfactant or an ester type cationic surfactant.

Commercially available household softeners are compositions mainly composed of quaternary ammonium salts having two long-chain alkyl groups in one molecule.
For example, di (cured beef tallow alkyl) dimethylammonium chloride is widely used because of its excellent flexibility and antistatic ability, but when these are used, the fiber surface becomes water repellent, The water-absorbing property was poor, and it had drawbacks such as poor sweat absorption when worn. On the other hand, dioleyldimethyl quaternary ammonium salt, which is known as one of flexible bases with excellent water absorption, has improved water absorption but insufficient flexibility. A softening composition containing a peptide obtained by hydrolyzing a protein (for example, see Patent Document 1) and a softening agent composed of a softening agent component and sericin (for example, see Patent Document 2) have been proposed.
JP-A-7-18576 JP 2001-192970 A

However, none of the conventional softening agent compositions satisfy all of the texture, flexibility, water absorption and blending stability.
It is an object of the present invention to provide a liquid softener composition for clothing that is excellent in the effect of imparting flexibility to a fabric, and has excellent water absorption and blending stability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a liquid softener composition excellent in flexibility, water absorption and blending stability by using a specific compound in combination, and have reached the present invention. did.

That is, this invention is a liquid softening agent composition containing the following (A)-(D) as an essential component.
(A): at least one cation selected from the group consisting of a cationic surfactant (A1) represented by the following general formula (1) and a cationic surfactant (A2) represented by the following general formula (2) Surfactant having at least one alkenyl group in the molecule and an iodine value of 20 to 120

In the formula, R ¹ and R ⁴ are alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, or β-hydroxyalkyl groups having 2 to 24 carbon atoms, and R ² and R ³ are 6 to 24 carbon atoms. An alkyl group, an alkenyl group having 6 to 24 carbon atoms, an alkapolyenyl group having 8 to 24 carbon atoms, or a benzyl group, two R ^{2 s} may be the same or different, and Z ¹ may be a hydrogen atom or a formula: A group represented by R ³ CO—, Q is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 2 to 24 carbon atoms, or a formula: R ³ CO—OCH ₂ A group represented by CH ₂ —, f is an integer of 1 to 5, and X ^f− is an f-valent counter ion.
(B): one or more hydrophilic solvents selected from the group consisting of glycol solvents and alcohols having 1 to 4 carbon atoms (C): water-soluble inorganic salts (D): peptides obtained by hydrolyzing natural proteins

  The liquid softener composition for apparel of the present invention has high water dispersibility and long-term blending stability, softness to fabric and antistatic properties imparting effect. The property is remarkably excellent.

In the general formulas (1) and (2) in the present invention, R ¹ and R ⁴ are linear or branched alkyl groups having 1 to 24 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. A linear or branched alkenyl group having 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, or an alkyl group having 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. It is a β-hydroxyalkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-ethylhexyl group, a pentyl group, an octyl group, an undecyl group, a tridecyl group, a pentadecyl group, and a heptadecyl group. Vinyl group, propenyl group, isopropenyl group, allyl group, methallyl group, octenyl group, undecenyl group, tridecenyl group, pentadecenyl group Such as fine heptadecenyl group, and the like. Examples of the β-hydroxyalkyl group include 2-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxylauryl group, 2-hydroxypalmityl group, 2-hydroxystearyl group and the like. . Of these, preferred are an alkyl group and a β-hydroxyalkyl group, particularly preferred are a methyl group, an ethyl group, a 2-hydroxyethyl group and a 2-hydroxypropyl group, and most preferred is a methyl group.

R ² and R ³ are linear or branched alkyl groups having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, linear or branched alkenyl groups having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, A linear or branched alkapolyenyl group having 8 to 24 carbon atoms, preferably 10 to 24 carbon atoms (an alkadienyl group such as a linoleyl group, and an alkatrienyl group) or a benzyl group. Preferred examples include alkyl groups and alkenyl groups exemplified for R ¹ as straight chain having 6 to 24 carbon atoms, and more preferred are pentadecyl group, heptadecyl group, tridecenyl group, pentadecenyl group, heptadecenyl group and mixtures thereof. .
Two R ² in the general formula (1) may be the same or different.

In the general formula (2), Z ¹ is a hydrogen atom or a formula: R ³ CO— (wherein R ³ is the same group as the above-described group R ³ , and two or more R ³ are included in one molecule. And may be the same or different, for example, octanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, and oleoyl group, preferably palmitoyl group, stearoyl group, oleoyl group. Oil bases and mixtures thereof.

Q is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 2 to 24 carbon atoms, or a formula: R ³ CO—OCH ₂ CH ₂ — (wherein R ³ is the same as that described above. It includes the same groups as exemplified as R ³ of, if in one molecule containing two or more R ³ is a group represented by may also be different) identical, preferred among these Are an alkyl group having 1 to 4 carbon atoms and a β-hydroxyalkyl group having 2 to 4 carbon atoms and a group represented by the formula: R ³ CO—OCH ₂ CH ₂ —, particularly preferably a methyl group, an ethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, and R ³ CO—, palmitoyl group, stearoyl group, oleoyl group, and a group represented by the formula: R ³ CO—OCH ₂ CH ₂ — is there.

In the general formulas (1) and (2), f is an integer of 1 to 5, preferably 1 to 3, X ^f− is an f-valent counter ion, and a halogen ion (chlor ion, fluorine ion, bromine ion) And iodine ions), OH ⁻ , inorganic acid anions (such as carbonate anions, phosphate anions and sulfate anions), and organic acid anions. Examples of the organic acid constituting the organic acid anion include monovalent or divalent to pentavalent carboxylic acids [monovalent aliphatic carboxylic acids having 1 to 18 carbon atoms (formic acid, acetic acid, butyric acid, caprylic acid, 2-ethylhexane Acid, nonanoic acid, dodecanoic acid, etc.), divalent to pentavalent aliphatic carboxylic acids (oxalic acid, adipic acid, citric acid, itaconic acid, etc.), and aromatic carboxylic acids (benzoic acid, phthalic acid, trimellitic acid, etc.) )], Sulfonic acids (sulfonic acids having an alkyl group having 1 to 18 carbon atoms, for example, alkyl-substituted aromatic sulfonic acids having an alkyl group having 1 to 18 carbon atoms such as methylsulfonic acid and ethylsulfonic acid, such as p-toluene) Sulfonic acid and dodecylbenzene sulfonic acid, naphthalene sulfonic acid and p-phenol sulfonic acid), sulfuric ester (charcoal) Sulfates having an alkyl or alkenyl group of 1 to 12, such as methyl sulfate, ethyl sulfate, octyl sulfate, 2-ethylhexyl sulfate, decyl sulfate and dodecyl sulfate, phosphoric acid esters (carbon number) Phosphates having 1 to 12 alkyl or alkenyl groups, such as octyl phosphate, 2-ethylhexyl phosphate, decyl phosphate and dodecyl phosphate, and 1 to 4 carbon atoms having 6 to 36 carbon atoms (phenol) , P-chlorophenol, β-naphthol, o- and p-nitrophenol, p-aminophenol, catechol and resorcin, and the like. Among X ^f− , preferred are chloro ion, methyl sulfate ion, ethyl sulfate ion and methyl carbonate ion, and particularly preferred are methyl sulfate ion and ethyl sulfate ion.

(A) in the present invention preferably contains one or more cationic surfactants having 1 to 3, more preferably 1 alkenyl group in the molecule.
(A1) is preferably a heptadecenyl group, in which at least a part of R ² in the general formula (1) is an alkenyl group having 8 to 24 carbon atoms, particularly a heptadecenyl group, a pentadecenyl group or a tridecenyl group. Is particularly preferred. (A2) is an alkenyl group in which at least a part of R ³ in the general formula (2) or R ³ constituting Z ¹ has 8 to 24 carbon atoms, in particular, a heptadecenyl group or a pentadecenyl group Group or a tridecenyl group is preferable, and a heptadecenyl group is particularly preferable.
(A) has an iodine value of usually 20 to 120, preferably 40 to 100, particularly preferably 50 to 90. If the iodine value is 20 or more, the water absorption is further improved, and if it is 120 or less, the flexibility is further improved.

Preferred examples of the cationic surfactant (A1) represented by the general formula (1) include R ¹ is a methyl, ethyl, butyl or β-hydroxyethyl group, R ² is pentadecyl, heptadecyl, heptadecenyl and Examples thereof include those having a 2-hydroxyoctyl group, specifically (A11) to (A15) shown below.
(A11) R ¹ = methyl, R ² = _{^{heptadecenyl, X f- = CH 3 SO 4}} -, f = 1
(A12) R ¹ = methyl group, R ² = heptadecenyl group / heptadecyl group (60/40% by mass; unless otherwise specified,% indicates% by mass), X ^f− = CH ₃ SO ₄ ⁻ , f = 1
(A13) R ¹ = β- hydroxyethyl group, R ² = pentadecyl / heptadecenyl ^{(30/70%), X f- =} CH 3 SO 4 -, f = 1
(A14) R ¹ = methyl group, R ² = pentadecyl group / heptadecyl group (40/60%), X ^f− = Cl ⁻ , f = 1
(A15) R ¹ = ethyl, R ² = pentadecyl _{^{group, X f- = C 2 H 5}} SO 4 -, f = 1
Preferred examples of the cationic surfactant (A2) represented by the general formula (2) include R ⁴ is a methyl, ethyl, butyl or β-hydroxyethyl group, R ³ is pentadecyl, heptadecyl, heptadecenyl and / or 2-hydroxyoctyl group, Z ¹ is hydrogen, myristoyl, palmitoyl, stearoyl and / or oleoyl group, and Q is a methyl, ethyl or β-hydroxyethyl group, specifically (A21) to ( A24).
(A21) R ⁴ = methyl group, R ³ = heptadecyl group / heptadecenyl group (37/63%), Z ¹ = stearoyl group / oleoyl group (37/63%), Q = β-hydroxyethyl group, X ^{f _{- = CH 3 SO 4 -,}} f = 1
(A22) R ⁴ = methyl group, R ³ = heptadecenyl group, Z ¹ = oleoyl group,
Q = β-hydroxyethyl group, X ^f− = CH ₃ SO ₄ ⁻ , f = 1
(A23) R ⁴ = ethyl group, R ³ = pentadecyl group, Z ¹ = stearoyl group,
Q = methyl group, X ^f− = C ₂ H ₅ SO ₄ ⁻ , f = 1
(A24) R ⁴ = methyl group, R ³ = pentadecyl group / heptadecyl group (40/60%), Z ¹ = palmitoyl group / stearoyl group (40/60%),
Q = β-hydroxyethyl group, X ^f− = Cl ⁻

  (A1) is, for example, amide type tertiary amine obtained by heat condensation of fatty acid having 6 to 24 carbon atoms such as palmitic acid, stearic acid, oleic acid and diethylenetriamine at 150 to 200 ° C. with hydrochloric acid, A method of neutralizing with an acid such as acetic acid, or a reaction by heating the amide type tertiary amine with an alkylating agent such as methyl chloride, benzyl chloride, dimethyl carbonate, diethyl carbonate, dimethyl sulfate, or diethyl sulfate under pressure. It is obtained by the method to do.

  (A2) is, for example, ester-type tertiary by heat-condensing a fatty acid having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms such as palmitic acid, stearic acid, or oleic acid, and triethanolamine at 150 to 200 ° C. It can be obtained by making an amine and neutralizing it with an acid such as hydrochloric acid or acetic acid, or by reacting the alkylating agent by heating under pressure.

  Among (A), preferred is (A1) or a combination of (A1) and (A2), and the preferred mass ratio of (A1) / (A2) in the combined use is 40/60 to 98/2, More preferably, it is 50 / 50-80 / 20.

The hydrophilic solvent (B) in the present invention is at least one selected from the group consisting of glycol solvents and alcohols having 1 to 4 carbon atoms.
Examples of glycol solvents include glycol solvents having a total carbon number of 2 to 10, such as glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butylene glycol and 1,3-butylene glycol, monoalkyl ethers { Such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether}, and dialkyl ethers {such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol isopropyl methyl ether} Be mentioned
Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, propanol, isopropyl alcohol, butanol and t-butyl alcohol.
Among (B), preferred are glycol solvents, more preferred are glycols, particularly ethylene glycol, propylene glycol and diethylene glycol, and particularly preferred is propylene glycol. Moreover, the ratio in the case of using 2 or more types together is not specifically limited.

The water-soluble inorganic salt (C) in the present invention includes an inorganic salt that can be dissolved in an amount of 10 g or more with respect to 100 g of water at 25 ° C., for example, an alkali metal salt [halide (sodium chloride, potassium chloride, Sodium bromide, sodium fluoride, etc.), sulfates (sodium sulfate, potassium sulfate etc.) and phosphates (sodium phosphate, potassium phosphate etc.)], alkaline earth metal salts [halides (calcium chloride, magnesium chloride) And sulfates (such as magnesium sulfate)] and ammonium salts [halides (such as ammonium chloride) and sulfates (such as ammonium sulfate)].
Of these, preferred are alkali metal salts, particularly sodium chloride or sodium sulfate.

The peptide (D) in the present invention is a peptide obtained by hydrolyzing a natural protein, and usually has two or more amino acids linked by peptide bonds. The weight average molecular weight (measured by GPC) is preferably 200 to 50,000, more preferably 400 to 10,000.
Examples of the natural protein include collagen derived from animals such as cow skin and pig skin [for example, “Collapton S” manufactured by Kawaken Fine Chemical Co., Ltd.], vegetable or soybean derived proteins [for example, “Hydrosolanam” and “Rhizosol” and the like: Croda Japan Co., Ltd.], and proteins derived from natural fibers such as silk or wool. Of these, silk-derived proteins are preferred.
Examples of proteins obtained by hydrolyzing silk include “Crossilk Liquid” manufactured by Croda Japan Co., Ltd., “Promois Silk-1000” manufactured by Seiwa Kasei Co., Ltd., and “Silkgen G Solver” Ichimaru Falcos ( Product).

  The content of (A) based on the mass of the liquid softener composition of the present invention is preferably 5 to 25%, more preferably 8 to 20%, and particularly preferably 10 to 18%. The content of (B) is preferably 1 to 15%, more preferably 2 to 12%, and particularly preferably 4 to 10%. The content of (C) is preferably 0.1 to 2%, more preferably 0.2 to 1.5%, and particularly preferably 0.4 to 1.0%. The content of (D) is preferably 0.001 to 3.0%, more preferably 0.003 to 2.0%, and particularly preferably 0.005 to 1.0%. Within this range, flexibility, water absorption and blending stability are particularly excellent.

  Moreover, the liquid softening agent composition of the present invention further includes a nonionic surfactant (E) composed of one or a mixture of two or more compounds represented by the following general formula (3) and a trivalent or higher polyvalent. The alcohol (F) is preferably contained from the viewpoint of water absorption and blending stability.

_{^{R 5 O - [(C 2}} H 4 O) m / (A 1 O) n] - (C 2 H 4 O) p-H (3)

In the formula, R ⁶ is a residue of an aliphatic alcohol, and is usually an aliphatic hydrocarbon group having 8 to 24 (preferably 12 to 18) carbon atoms [eg linear and / or branched saturated or unsaturated. A saturated aliphatic hydrocarbon group (such as an alkyl group, an alkenyl group and an alkadienyl group)] or an alicyclic hydrocarbon group [for example, a cycloalkyl group and a polycyclic hydrocarbon group].
Examples of R ⁶ include those having 8 to 24 carbon atoms among the alkyl groups and alkenyl groups mentioned above for R ¹ and R ⁴ , and examples of the alkadienyl group include a linoleyl group. Examples of the cycloalkyl group include an ethylcyclohexyl group, a propylcyclohexyl group, an octylcyclohexyl group, a nonylcyclohexyl group, and the like. Examples of the polycyclic hydrocarbon include an adamantyl group. Of these, preferred are an alkyl group and an alkenyl group, and more preferred are an alkyl group having 10 to 18 carbon atoms and an alkenyl group having 14 to 20 carbon atoms.

The aliphatic alcohol may be a natural alcohol or a synthetic alcohol (Ziegler alcohol, oxo alcohol, etc.).
The hydroxyl group of the aliphatic alcohol is preferably primary or secondary, particularly preferably primary. Further, the alkyl group portion may be linear or branched. Particularly preferred as aliphatic alcohols are dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and oleyl alcohol.

A ¹ represents an alkylene group having 3 to 8 carbon atoms or a substituted alkylene group, and an alkylene group having 3 carbon atoms is preferred. The part (A ¹ O) is formed by addition of an alkylene oxide having 3 or more carbon atoms (hereinafter abbreviated as AO). Examples of such AO include propylene oxide (hereinafter abbreviated as PO), 1,2- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, and combinations of two or more thereof. PO is preferred.

In general formula (3), m is 0 or an integer greater than or equal to 1 and having an average of 0 to 8, preferably 1 to 4. n is 0 or an integer of 1 or more with an average of 0 to 3, preferably 1 or 2. p is an integer of 0 or 1 or more whose average is usually 1 to 80, preferably 5 to 70, particularly preferably an integer of 15 to 40.
(M + n + p) is an integer having an average of usually 3 to 81, preferably 11 to 51. (M + p) / (m + n + p) is usually 0.5 or more, preferably 0.7 to 0.99. [(C ₂ H ₄ O) m / (AO) n] may be block addition [in order of (C ₂ H ₄ O) m, (AO) n] or random addition, but preferably by block addition. is there.

The weight average molecular weight (Mw) of (E) is usually 261 to 5,000, preferably 300 to 1,200. [Molecular weight is measured by gel permeation chromatograph (GPC). The same applies to the following. ]
(E) is preferably such that the ratio (Mw / Mn) between Mw and number average molecular weight (Mn) satisfies the following relational expression (4) or (5).
Mw / Mn ≦ 0.030 × Ln (v) +1.010 (4)
(Applicable when v <10)
Mw / Mn ≦ −0.026 × Ln (v) +1.139 (5)
(Applicable when v ≧ 10)
In the above formula (4) or (5), Ln (v) means the natural logarithm of v, v represents the average number of moles of AO added per mole of aliphatic alcohol, and the above general formula ( This corresponds to the average of the sum of m, n and p, which is the added mole number of each AO in 3).
When the relational expression (4) or (5) is satisfied, that is, when the molecular weight distribution is narrowed, a further sufficient surface activity can be obtained.
Mw / Mn more preferably satisfies the following relational expression (4 ′) or (5 ′).
Mw / Mn ≦ 0.030 × Ln (v) +1.000 (4 ′)
(Applicable when v <10)
Mw / Mn ≦ −0.026 × Ln (v) +1.129 (5 ′)
(Applicable when v ≧ 10)

(E) preferably satisfies the relational expression (4) or (5), and (E1) has the following distribution constant c of 2.0 or less.
c can be obtained from a relational expression (7) derived from the following Weibull distribution law expression (6).
c is more preferably 1.5 or less, particularly preferably 1.0 or less. In relational expression (7), the smaller the value of distribution constant c, that is, the smaller the content of unreacted aliphatic alcohol, the narrower the molecular weight distribution. This formula is applied when the amount of the unreacted aliphatic alcohol is not less than the detection limit (0.001% by mass), and the average number of added moles of AO can be up to 12 mol. .
_{v = c × Ln (n 00} / n 0) - (c-1) × (1-n 0 / n 00) (6)
c = (v + n ₀ / n ₀₀ -1) / [Ln (n ₀₀ / n ₀ ) + n ₀ / n ₀₀ -1] (7)
In these formulas, Ln (n ₀₀ / n ₀ ) means the natural logarithm of (n ₀₀ / n ₀ ), v is the same as above, n ₀₀ is the number of moles of the aliphatic alcohol used in the reaction, n ₀ represents the number of moles of unreacted aliphatic alcohol.

  The content of (E) is preferably 0 to 10%, more preferably 0.5 to 8%, and particularly preferably 1 to 5% based on the mass of the liquid softening agent composition. Those within this range are particularly excellent in performance (dispersibility in water, long-term storage stability).

As (F), a C3-C36 alkane polyol having a hydroxyl group of 3 to 16 (triol, such as trimethylolpropane, glycerin and hexanetriol; and the like; Pentaerythritol, sorbitol, xylitol, mannitol, etc.), intermolecular or intramolecular dehydrates (diglycerin, dipentaerythritol, sorbitan, etc.), saccharides (glucose, fructose, sucrose, etc.) and derivatives thereof (glucosides such as α -Methylglucoside) and the like. Of these, glycerin, diglycerin, sorbitan, sorbitol and glucoside are preferred, and glycerin, sorbitan and sorbitol are particularly preferred.
Further, the content of (F) is preferably 0 to 5%, more preferably 0.2 to 3%, and particularly preferably 0.5 to 2% based on the mass of the liquid softening agent composition. Those within this range are particularly excellent in performance (water absorption, long-term storage stability).

  The liquid softener composition of the present invention comprises a nonionic surfactant (G) other than (E), an anionic surfactant (H), an amphoteric surfactant (I), and a cationic surfactant other than (A). Any surfactant of (J) may be contained. Among these, (G) or (J) is preferable.

Examples of (G) include polyhydric alcohol type nonionic surfactant (G1), alkylene oxide addition type nonionic surfactant (G2), and alkylamine oxide. Of these, (G1) is preferred.
Examples of (G1) include sorbitan fatty acid ester, glycerin fatty acid ester, pentaerythritol fatty acid ester, sucrose fatty acid ester, and fatty acid alkanolamide. Of these, sorbitan fatty acid esters are preferred.
(G2) includes fatty acid AO adducts, higher alkylamine AO adducts, polyhydric alcohol (such as sorbitan) fatty acid ester ethylene oxide adducts (hereinafter, ethylene oxide is abbreviated as EO), fatty acid amide ethylene oxide adducts, etc. Is mentioned. Of these, EO adducts of sorbitan fatty acid esters are preferred.

  As (H), an ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof ((poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate, etc.), or having 8 to 24 carbon atoms. Ether sulfate ester salt having a hydrocarbon group [(poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl sulfate, etc.], sulfosuccinate ester salt having a hydrocarbon group having 8 to 24 carbon atoms [sulfosuccinic acid mono- or dialkyl Di- or mono-sodium salt of ester, sulfosuccinic acid (poly) oxyethylene (degree of polymerization = 1-100) di- or mono-sodium salt of mono- or dialkyl ester, etc.], (poly) oxyethylene (degree of polymerization = 1-100) palm Oil fatty acid sodium monoethanolamide sulfate, hydrocarbons having 8 to 24 carbon atoms Sulfonate having a group [sodium dodecylbenzenesulfonate, etc.], phosphate ester salt having a hydrocarbon group having 8 to 24 carbon atoms [sodium lauryl phosphate, (poly) oxyethylene (degree of polymerization = 1-100) lauryl Sodium ether phosphate etc.], fatty acid salt [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salt [coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N -Coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, lauroylmethyl-β-alanine sodium, etc.]. Of these, ether carboxylic acids or salts thereof, fatty acid salts and acylated amino acid salts are preferred.

  (I) includes betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, urylhydroxysulfo Betaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl phosphate, etc.], amino acid type amphoteric surfactants [sodium β-laurylaminopropionate, etc.] and the like.

  (J) includes alkyltrimethylammonium salts [cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, etc.], dialkyldimethylammonium salts [didecyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, etc.], alkylpyridinium Salts [cetylpyridinium chloride, stearamide methylpyridinium chloride, etc.]. Of these, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred.

  The total content of (G), (H), (I) and / or (J) is preferably 0-10%, more preferably 0-8%, especially based on the mass of the liquid softener composition Preferably it is 0.5 to 5%.

  In the liquid softener composition of the present invention, if necessary, an antibacterial agent (isothiazoline type, carbanide type, imidazole type, biguanide type) in an amount of 0.01 to 5% based on the mass of the liquid softener composition. , Thiazole antibacterial agents, etc.), perfumes (d-limonene, symamic aldehyde, methyl ionone, etc.), coloring agents (blue No. 1, green No. 3, red No. 1 etc.), and moisturizing ingredients other than (D) (olive oil, Avocado oil, hyaluronic acid, lecithin, alginate, lanolin, etc.) can be included if necessary.

The liquid softening agent composition of the present invention is liquid at 20 ° C. and is an emulsion or a transparent uniform liquid.
Moreover, the active ingredient density | concentration [The mass percentage of components other than water and (B) based on the mass of a liquid softening agent composition] of the liquid softening agent composition of this invention becomes like this. Preferably it is 10-60%, More preferably, it is 20 ~ 40%.
The viscosity at 25 ° C. of the liquid softener composition of the present invention is preferably 1,000 mPa · s, more preferably 10 to 500 mPa · s, and particularly preferably 10 to 300 mPa · s.

The softener composition of the present invention is particularly useful for imparting flexibility to natural fibers, synthetic fibers, and these mixed spun knitted fibers.
Examples of natural fibers include cotton, hemp, and wool. Examples of synthetic fibers include regenerated cellulose fibers such as rayon and acetate, and synthetic fibers such as polyester, polyamide fibers, acrylic, and spandex. These blended and knitted fibers include cotton, linen and other fibers (wool, polyester, polyamide, acrylic, etc.), wool and other fibers (polyester, polyamide, acrylic, etc.), polyester fibers and other fibers (rayon) , Acetate, polyamide, acrylic, spandex, etc.), polyamide fibers and other fibers (rayon, acetate, acrylic, spandex, etc.).
Examples of the fiber form include cloth, non-woven fabric, knitted fabric, and clothing.

  The liquid softener composition of the present invention is usually used at a concentration (active ingredient) in the range of 1 ppm to 0.5%.

  The bath ratio is not particularly limited, but is usually 1: 4 to 1:40, preferably 1: 6 to 1:30.

  Although the use temperature of the liquid softening agent composition of this invention can be arbitrarily selected according to the kind of fiber to apply, it is 5-80 degreeC normally, Preferably it is 20-50 degreeC.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Production Examples, but the present invention is not limited thereto. Below, a part shows a mass part.

Production Example 1
A glass pressure-resistant vessel equipped with a heating / cooling device, a stirrer, a thermometer, a nitrogen introducer, a nitrogen exhaust pipe, and a dropping funnel was charged with 600 parts of methyl oleate, 104 parts of diethylenetriamine and 1 part of hypophosphorous acid, and nitrogen was added to the liquid. The temperature is raised to 150 ° C while passing through. After sealing, the pressure was gradually reduced, and the reaction was carried out at 150 ° C. for about 5 hours while distilling off methanol and water. After cooling to 100 ° C., 243 parts of propylene glycol was charged, and 129 parts of dimethyl sulfuric acid was gradually added dropwise at 75 to 85 ° C. to prepare a solution (A11P) consisting of 75% of a cationic surfactant (A11) and 25% of propylene glycol. Got.

Production Example 2
360 parts of oleic acid, 240 parts of stearic acid, 104 parts of diethylenetriamine and 1 part of hypophosphorous acid are charged in the same pressure vessel as in Production Example 1, and the temperature is raised to 150 ° C. while introducing nitrogen into the liquid. After gradually reducing the pressure, the reaction was carried out at 150 ° C. for 5 hours while distilling off water. After cooling to 100 ° C., 243 parts of propylene glycol was added, and 129 parts of dimethyl sulfuric acid was gradually added dropwise at 75 to 85 ° C. to prepare a solution (A12P) consisting of 75% of a cationic surfactant (A12) and 25% of propylene glycol. Got.

Examples 1-14, Comparative Examples 1-4
The following components were used in the number of parts shown in Tables 1 and 2, and water was added thereto so as to be 100 parts at room temperature to prepare a liquid softener composition.
(A11P),
(A12P),
(A23P): (A23) a solution consisting of 75% and propylene glycol 25%,
(A24P): (A24) a solution comprising 75% and propylene glycol 25%,
(X1): distearyldimethylammonium chloride,
(X2): Dioleyldimethylammonium chloride
(D1): “Crossilk Liquid” manufactured by Croda Japan Co., Ltd.
(D2): “Silkgen G Solver” manufactured by Ichimaru Falcos Co., Ltd.
(D3): “Colapton S” manufactured by Kawaken Fine Chemicals Co., Ltd.
Nonionic surfactants (E1) to (E3): those listed in Table 1 below,
Propylene glycol, sodium sulfate and glycerin.

  In Table 1, (EO) ‖ (PO) indicates random addition, and-(EO) indicates block addition.

Performance test example 1
The softeners of Examples 1 to 16 and Comparative Examples 1 to 4 were allowed to stand for 1 month in a constant temperature bath at 40 ° C., and the blending stability was evaluated. The results are shown in Tables 2 and 3.
<Evaluation criteria>
Each sample was evaluated according to the following criteria.
○: Emulsified uniformly △: Slightly non-uniform layer present ×: Completely separated into two layers

  From the results of Tables 2 and 3, it can be seen that the softener composition of the present invention has excellent blending stability.

Performance test example 2
About the softening agent of Examples 1-14 and Comparative Examples 1-3, the softness | flexibility was evaluated on the following test conditions. The results are shown in Tables 2 and 3.
<Processing conditions>
The softening agent composition was diluted with water so that the concentration was 0.03% to prepare 1,000 parts of a test solution. A test cloth (cotton broad 24 × 24 cm) was put in the bath and immersed for 5 minutes (bath ratio 1:30). Next, the sample was squeezed with a centrifugal dehydrator (squeezing rate 100%) and further air-dried to prepare a sample.
<Flexibility evaluation method>
Each sample was compared with a sample cloth treated with water alone, and evaluated according to the following criteria in tactile sensation.
(Evaluation criteria)
◎: Excellent elasticity and flexibility ○: Good elasticity and flexibility △: Slightly better elasticity and flexibility than those treated with water ×: Poor elasticity and flexibility (as treated with water) Same level)

<Water absorption evaluation method>
Each sample is cut into 1 × 24 cm, hung vertically, and the height (mm) of the elevated water after 10 minutes is measured with the bottom immersed in an aqueous solution of 1 cm from the end and 25 ° C.

  From the results of Tables 2 and 3, each Example using the composition of the present invention is superior in water absorption and flexibility as compared with each Comparative Example.

  The softener composition of the present invention is extremely effective as a softener for various textile products including home use, particularly as a softener for various textile products that require water absorption such as towels and underwear.

Claims (6)

The liquid softening agent composition containing the following (A)-(D) as an essential component.
(A): at least one cation selected from the group consisting of a cationic surfactant (A1) represented by the following general formula (1) and a cationic surfactant (A2) represented by the following general formula (2) Surfactant having at least one alkenyl group in the molecule and an iodine value of 20 to 120

[Wherein, R ¹ and R ⁴ are alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, or β-hydroxyalkyl groups having 2 to 24 carbon atoms, and R ² and R ³ are 6 to 6 carbon atoms. 24 alkyl group, alkenyl group having 6 to 24 carbon atoms, alkapolyenyl group having 8 to 24 carbon atoms or benzyl group, and two R ^{2 s} may be the same or different, and Z ¹ is a hydrogen atom or A group represented by the formula: R ³ CO—, Q is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 2 to 24 carbon atoms, or a formula: R ³ CO— OCH ₂ CH ₂ -, a group represented by, f is an integer of 1 to ^{5, X f-} is f-valent counterions. ]
(B): one or more hydrophilic solvents selected from the group consisting of glycol solvents and alcohols having 1 to 4 carbon atoms (C): water-soluble inorganic salts (D): peptides obtained by hydrolyzing natural proteins (A) is 5 to 25% by mass, (B) is 1 to 15% by mass, (C) is 0.1 to 2% by mass, (D) is 0.001 to 3% by mass, and at 25 ° C. The liquid softening agent composition according to claim 1, having a viscosity of 10 to 500 mPa · s. Furthermore, the liquid softening agent composition of Claim 1 or 2 containing the nonionic surfactant (E) shown by following General formula (3).
_{^{R 5 O - [(C 2}} H 4 O) m / (A 1 O) n] - (C 2 H 4 O) p-H (3)
[Wherein R ⁵ is an aliphatic hydrocarbon group or alicyclic hydrocarbon group having 8 to 24 carbon atoms; A ¹ is an alkylene group having 3 to 8 carbon atoms; m is 0 or 1 having an average of 0 to 8; The above integer, n is an integer of 0 or 1 or more with an average of 1 to 3, p is an integer of 0 or 1 or more with an average of 1 to 80, and (m + n + p) is an integer with an average of 3 to 81 (M + p) / (m + n + p) is 0.5 or more on average. [(C ₂ H ₄ O) m / (A ¹ O) n] represents block addition or random addition when m ≠ 0 and n ≠ 0. ] The liquid according to claim 3, wherein (E) is a nonionic surfactant (E1) produced by adding alkylene oxide (b1) to aliphatic alcohol (a1) and satisfying the following (i) and (ii): Softener composition.
(I) Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn): Mw / Mn satisfies the following relational expression (4) or (5).
Mw / Mn ≦ 0.030Ln (v) +1.010 (provided that v <10) (4)
Mw / Mn ≦ −0.026Ln (v) +1.139 (provided that v ≧ 10) (5)
{However, v represents the average number of moles of alkylene oxide (b1) added per mole of aliphatic alcohol (a1). }
(Ii) The distribution constant c obtained from the following formula (6) is 2.0 or less.
_{c = (v + n 0 /} n 00 -1) / [Ln (n 00 / n 0) + n 0 / n 00 -1] (6)
{However, v is the same as in formula (4) or (5), n ₀₀ is the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ is the number of moles of the unreacted aliphatic alcohol (a1). Indicates. } (D) is a peptide obtained by hydrolyzing silk fiber, The liquid softening agent composition in any one of Claims 1-4 . Furthermore, the liquid softening agent composition in any one of Claims 1-5 containing a polyhydric alcohol (F) more than trivalence.