JP4387149B2 - Softener composition - Google Patents

Description

  The present invention relates to a softener composition and a method for treating fibers using the same.

  Conventionally, a quaternary ammonium salt or a tertiary amine acid salt having a long-chain alkyl group has been used as a softening agent. These softeners have a good softening effect on various fibers in a small amount, but have not yet been sufficiently satisfactory in softness.

On the other hand, Patent Documents 1 to 3 disclose a softener composition containing a cationic polymer in order to improve the properties of the softener. However, these compositions are still not fully satisfactory in terms of softness performance, in particular of cotton fibers.
JP-A 64-61571 Special Table 2000-503735 European Patent Application Publication No. 394133

  The subject of this invention is providing the softener composition which has a high softening effect with respect to fiber, especially cotton fiber.

  The present invention relates to a softener composition comprising a cationic group-containing monomer unit and a hydrophilic nonionic group-containing monomer unit and a partially crosslinked polymer (hereinafter referred to as component (a)). And a method for treating fibers, in which a fibrous material is immersed in the softener composition.

  The softener composition of the present invention can impart excellent flexibility and texture to fibers, particularly cotton fibers.

[(A) component]
Component (a) of the present invention includes at least one cationic group-containing vinyl monomer (hereinafter referred to as monomer (a1)) and a hydrophilic nonionic group-containing vinyl monomer (hereinafter referred to as monomer ( a2)) and at least one crosslinkable vinyl monomer having two or more vinyl groups in the molecule (hereinafter referred to as monomer (a3)) as essential constituent monomers, A copolymer obtained by radical polymerization is preferred.

  As the monomer (a1), (meth) acrylic acid ester or (meth) acrylamides having a dialkylamino group, styrenes having a dialkylamino group, vinylpyridines, N-vinyl heterocyclic compounds, amino groups Examples include acid neutralized products or quaternary ammonium salts of monomers having amino groups such as vinyl ethers; diallyl-type quaternary ammonium salts. Here, “(meth) acryl” means “acryl or methacryl”.

  Of these monomers (a1), compounds represented by the general formula (5) or (6) are preferred.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ¹³ and R ¹⁴ are the same or different and represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms, and R ¹⁵ represents a hydrogen atom or a carbon number 1 to 1 4 represents an alkyl group, X represents —O—, —NH—, —CH ₂ — or —O—CH ₂ CH (OH) —, Y represents 1 to 4 carbon atoms (where X is —CH _2). - when the represents a linear or branched alkylene group having 0-3) atoms, Z ^- denotes conjugate acid-base, halogen ions, anions of alkyl sulfate ions having 1 to 4 carbon atoms. ]

Wherein, R ¹⁶ and R ¹⁷ the same or different and each represents a hydrogen atom or a methyl group, R ¹⁸ and R ¹⁹ are identical or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z ^- Indicates the same meaning as described above. ]
When the compound represented by the general formula (5) or (6) is an acid neutralized product, preferred acids used for obtaining the acid neutralized product include hydrochloric acid, sulfuric acid, acetic acid, citric acid, succinic acid, Examples include adipic acid and sulfamic acid. Further, when the compound represented by the general formula (5) or (6) is a quaternary ammonium salt, preferable quaternizing agents for obtaining the quaternary ammonium salt include methyl chloride, methyl iodide and the like. And dialkyl sulfates such as alkyl halides, diethyl sulfate, and di-n-propyl sulfate.

  Preferable specific examples of the monomer (a1) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide as the quaternizing agent. A quaternized quaternary ammonium salt, dimethyldiallylammonium chloride, or the like can be given.

  The monomer (a2) is a hydrophilic nonionic group-containing vinyl monomer. Here, the nonionic group-containing vinyl monomer is “hydrophilic” as water at 20 ° C. and pH 3-12. It means that the solubility in is 1.0 g / L or more, preferably 5 g / L or more.

  Examples of the monomer (a2) include compounds represented by the general formula (1) or (2).

[Wherein, R ¹ has the same meaning as described above, and R ² and R ³ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. ]

[Wherein, R ¹ has the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) _n — (n represents an integer of 2 to 6). B represents —O— or —CH ₂ — group. ]
Specific examples of these compounds include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, Nt- Butyl acrylamide, N- (meth) acryloylmorpholine and the like are mentioned, N, N-dialkyl-substituted (meth) acrylamide is preferable, and N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide are further included. preferable.

  Examples of the monomer (a3) include (meth) acrylic acid esters of polyhydric alcohols or unsaturated alcohols, acrylamides, divinyl compounds, polyallyl compounds, and the like. Among these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, and the like are preferable. .

  A preferable blending ratio of the monomer (a1) and the monomer (a2) is 2/98 to 98/2, more preferably 3/97 to 60 in terms of a molar ratio of (a1) / (a2). / 40. The proportion of the monomer (a3) is preferably from 0.002 to 3% by mass, preferably from 0.002 to 0%, based on the total amount of monomers, from the viewpoint of imparting preferable softness and texture to fibers, particularly cotton fibers. .1% by mass is particularly preferred.

  The component (a) is composed of one or more of the above three types of monomers (a1), (a2) and (a3) and other vinyl monomers copolymerizable therewith. be able to. Examples of other vinyl monomers include (meth) acrylic acid derivatives such as methyl (meth) acrylate and ethyl (meth) acrylate; anionic group-containing monomers such as acrylic acid and methacrylic acid; N- (3 Examples include betaines such as -sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

  The method for producing the component (a) is preferably an aqueous solution polymerization method, a reverse phase suspension polymerization method or a precipitation polymerization method. For example, it can be produced by the method described in JP-A No. 11-71435, column 11, line 14 to column 13, line 33.

[Component (b)]
The component (b) of the present invention is a compound having at least one group selected from an amino group and a quaternary ammonium group and at least one saturated or unsaturated hydrocarbon group having 8 to 36 carbon atoms in the molecule. Although it does not specifically limit, At least 1 sort (s) chosen from the tertiary amine represented by General formula (3) or its salt, and the quaternary ammonium salt represented by General formula (4) is preferable.

[Wherein, R ⁴ and R ⁸ are each independently a linear or branched alkyl group or alkenyl group having ^{8 to} 36 carbon atoms, and R ⁵ and R ⁹ are each independently an alkylene having 1 to 6 carbon atoms. Each of D and E is independently a group selected from —COO—, —OCO—, —CONH—, and —NHCO—, and a and b are each independently a number of 0 or 1. R ⁶ and R ⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a group represented by R ⁴ — [D—R ⁵ ] _a —. R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a group represented by R ⁸ — [ER ⁹ ] _b —. R ¹² is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Z ⁻ is an anion. ]
In the compound represented by the general formula (3), R ⁴ is an alkyl group or alkenyl group having 8 to 36 carbon atoms, preferably 13 to 24 carbon atoms, preferably an alkyl group. R ⁵ is preferably an alkylene group having 1 to 4 carbon atoms. R ⁶ and R ⁷ are each independently preferably a methyl group, an ethyl group or a hydroxyethyl group, or a group represented by R ⁴ — [D—R ⁵ ] _a —, and one of R ⁶ and R ⁷ Is preferably a methyl group, an ethyl group or a hydroxyethyl group. a is preferably 1. As a particularly preferable compound among the compounds represented by the general formula (3), at least one selected from a compound represented by the following general formula (3-1) and a compound represented by the general formula (3-2) Is mentioned.

[Wherein, R ²⁰ represents an alkyl group or alkenyl group having 8 to 36 carbon atoms, preferably 13 to 24 carbon atoms, preferably an alkyl group, and c is 2 or 3. R ²¹ and R ²² are each independently a methyl group, an ethyl group or a hydroxyethyl group, or a group represented by R ²⁰ —G— (CH ₂ ) _c — (R ²⁰ and c are as defined above, Represents —COO— or —CONH—, preferably one of R ²¹ and R ²² is a methyl group or a hydroxyethyl group, and the other is a methyl group, a hydroxyethyl group or R ²⁰ —G— (CH _{2 C} ) a group represented by-. ]
The compound represented by the general formula (3-1) and the general formula (3-2) includes a fatty acid represented by R ²⁰ —COOH or an alkyl (carbon number 1 to 5) ester or acid chloride thereof, and N-amino. Alkyl-N-hydroxyalkyl-N-alkylamine, N-alkyl-N, N-dihydroxyalkylamine, N-hydroxyalkyl-N, N-dialkylamine, N-aminoalkyl-N, N-dialkylamine or N, It can be easily synthesized by reacting with N, N-trihydroxyalkylamine, and R ²⁰ may be a single alkyl chain length or a mixed alkyl chain length.

  The compound represented by the general formula (3) may be a salt neutralized with an inorganic or organic acid. Moreover, when using as a salt, before mix | blending with a softening agent composition, what neutralized the amino group of the compound represented by General formula (3) with the acid agent can also be used, and a softening agent composition is used. After blending the compound represented by the general formula (3), the amino group may be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, hydroxycarboxylic acid, citric acid, p-toluenesulfonic acid, fatty acids having 1 to 12 carbon atoms or alkyl sulfuric acids having 1 to 3 carbon atoms are preferable, In particular, hydrochloric acid, sulfuric acid, glycolic acid, citric acid, and p-toluenesulfonic acid are preferable. These acid agents used for neutralization may be used alone or in combination.

In the compound of the general formula (4), R ⁸ is an alkyl group or alkenyl group having ^{8 to} 36 carbon atoms, preferably 13 to 24 carbon atoms, preferably an alkyl group. R ⁹ is preferably an alkylene group having 1 to 4 carbon atoms. R ¹⁰ and R ¹¹ are each independently preferably a methyl group, an ethyl group, a hydroxyethyl group, or a group represented by R ⁸ — [ER ⁹ ] _b —, and one of R ¹⁰ and R ¹¹ is methyl. It is preferably a group, an ethyl group or a hydroxyethyl group. b is preferably 1. R ¹² is preferably a methyl group, an ethyl group or a hydroxyethyl group. As a particularly preferable compound among the compounds represented by the general formula (4), at least one selected from a compound represented by the following general formula (4-1) and a compound represented by the general formula (4-2) Is mentioned.

[Wherein, R ²³ is an alkyl group or alkenyl group having 8 to 36 carbon atoms, preferably 13 to 24 carbon atoms, preferably an alkyl group, and d is 2 or 3. R ²⁴ and R ²⁵ are each independently a methyl group, an ethyl group, a hydroxyethyl group or a group represented by R ²³ —G— (CH ₂ ) _d — (R ²³ , G and d have the above meanings) Is preferred. R ²⁶ is a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group or a hydroxyethyl group. Z ⁻ is substituted with an anion, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Or at least one selected from aryl sulfonate ions. ]
Compounds of general formula (4-1) and the general formula (4-2), the fatty acid or the alkyl represented by R ²³ -COOH (1 to 5 carbon atoms) ester or acid chloride, N- aminoalkyl -N -Hydroxyalkyl-N-alkylamine, N-alkyl-N, N-dihydroxyalkylamine, N-hydroxyalkyl-N, N-dialkylamine, N-aminoalkyl-N, N-dialkylamine or N, N, N It can be easily synthesized by reacting with -trihydroxyalkylamine and further quaternizing with an alkylating agent such as alkyl halide, dialkylsulfuric acid or alkylene oxide. N, N, N-trialkyl-N-hydroxyalkyl quaternary ammonium salt, N, N, N-trialkyl-N-aminoalkyl quaternary ammonium salt and fatty acid represented by R ²³ —COOH or alkyl (C1-C5) It is also possible to synthesize | combine by reaction with ester or acid chloride. R ²³ may be a single alkyl chain length or a mixed alkyl chain length.

[Softener composition]
The softening agent composition of the present invention is a composition containing the component (a), further the component (b) if necessary, and water, and the water is preferably distilled water or ion-exchanged water. The content of the component (a) in the composition is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass. The mass ratio of the component (a) and the component (b) is preferably 1/500 to 10/1, and more preferably 1/300 to 1/10. From the viewpoint of storage stability, water is preferably added to the composition in an amount of 30 to 95% by mass, more preferably 40 to 85% by mass.

  The composition of the present invention preferably has a pH at 20 ° C. of 1 to 8.5, more preferably 1 to 8 from the viewpoint of storage stability, and particularly 2 to 8 from the viewpoint of flexibility and texture. Is preferred.

  In the present invention, a nonionic surfactant can be contained as component (c) for the purpose of improving storage stability. As the nonionic surfactant, a polyoxyalkylene alkyl ether having an alkyl group or an alkenyl group having 8 to 20 carbon atoms is preferable, and a compound represented by the following general formula (7) is particularly preferable.

^{R 30 -T - [(R 31} O) j -H] k (7)
[Wherein, R ³⁰ is an alkyl group or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ³¹ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. j represents a number of 2 to 100, preferably 5 to 80, particularly preferably 10 to 60. T is —O—, —CON— or —N—. When T is —O—, k is 1, and when T is —CON— or —N—, k is 2. ]
Specific examples of the compound represented by the general formula (7) include the following compounds.

R ³⁰ —O— (C ₂ H ₄ O) _m —H
[Wherein R ³⁰ represents the above-mentioned meaning. m is a number of 8 to 100, preferably 10 to 60. ]
_{^{R 30 -O- (C 2 H 4}} O) n1 - (C 3 H 6 O) n2 -H
[Wherein R ³⁰ represents the above-mentioned meaning. n ₁ and n ₂ are each independently a number of 2 to 40, preferably 5 to 40, and ethylene oxide and propylene oxide may be random or block adducts. ]

[Wherein R ³⁰ represents the above-mentioned meaning. p ₁ , p ₂ , q ₁ and q ₂ are each independently a number of 0 to 40, preferably 5 to 40, and p ₁ + p ₂ + q ₁ + q ₂ is a number of 5 to 60, preferably 5 to 40. is there. Ethylene oxide and propylene oxide may be random or block adducts. ]
The amount of component (c) in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, and particularly preferably 0.2 to 6% by mass.

In the present invention, as the component (d) for the purpose of improving storage stability, an alkyl group or alkenyl group having 16 to 36 carbon atoms, preferably 16 to 26, an —SO ₃ M group and / or an —OSO ₃ M group [M : Counter ion] can be blended in the molecule. Specifically, alkylbenzene sulfonic acid, alkyl (or alkenyl) sulfate, polyoxyalkylene alkyl (or alkenyl) ether sulfate, olefin sulfonic acid, alkane sulfonic acid, α-sulfo having an alkyl group or alkenyl group having the above carbon number. Fatty acids, α-sulfo fatty acid esters and salts thereof are preferred. Among these, an alkyl (or alkenyl) sulfate ester having an alkyl group or alkenyl group having 16 to 26 carbon atoms, an alkyl group or alkenyl group having 16 to 26 carbon atoms, and an average addition mole number of ethylene oxide of 1 to 6, One or more selected from polyoxyethylene alkyl (or alkenyl) ether sulfates preferably 1 to 4, particularly preferably 1 to 3, and salts thereof are preferable. As the salt, sodium salt, potassium salt, ammonium salt, and alkanolamine salt are preferable.

  The amount of component (d) in the composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and particularly preferably 2 to 20% by mass.

  In this invention, the ester compound of a C8-C22 saturated or unsaturated fatty acid and a polyhydric alcohol can be mix | blended as a (e) component in order to improve storage stability. Specific examples of the ester compound include triglyceride, diglyceride, monoglyceride, and mono, di, triester, and sorbitan ester of pentaerythritol.

  The amount of component (e) in the composition of the present invention is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

  Moreover, the softening agent composition of this invention can use a solvent as (f) component. Solvents include ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, n-butanol, i-butanol, 2-butanol, n-hexanol, cyclohexanol, phenol, benzyl alcohol, phenethyl alcohol, 2-phenoxyethanol, and 2-benzyl. Oxyethanol, diethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, 2-ethylhexane-1,3-diol, hexane-1,6-diol, nonane-1,9-diol, 2-methyloctane-1,8 -Diol, 2-butoxyethanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 2- (2-methyl) propoxyethanol, diethylene Recall mono-2-methylpropyl ether, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, 2-butoxy-1-propanol, dipropylene glycol monobutyl ether, 2-t-butoxy-1-propanol, 2- Phenoxy-1-propanol, 2-ethoxypropyl-1-acetate, 2-propoxypropyl-1-acetate, 1,2-diacetoxypropane, 3-dimethyl-3-methoxy-1-propanol, 1,3-dimethylbutyl Examples include glyceryl ether, pentyl glyceryl ether, and hexyl glyceryl ether.

  Among these, ethanol, isopropanol, glycerin, ethylene glycol, and 2-phenoxyethanol are preferable, and ethanol is particularly preferable from the point of smell. 0-30 mass% is preferable, as for the compounding quantity of (f) component in the composition of this invention, 0.5-25 mass% is more preferable, 0.5-15 mass% is especially preferable, 1-10 mass % Is most preferred.

  Moreover, the softening agent composition of this invention can contain inorganic salt as (g) component. As the inorganic salt, calcium chloride, magnesium chloride and sodium chloride are preferable from the viewpoint of storage stability, and 0 to 2% by mass, preferably 10 to 10000 mg / kg is preferably added to the composition. However, although surfactants such as fatty acid salts include sodium salts and potassium salts, inorganic salts mixed into the composition by using such surfactants are not subject to the above restrictions.

  In order to improve the color and odor after storage, the softener composition of the present invention may contain a metal sequestering agent and an antioxidant that are generally known. As sequestering agents, aminocarboxylic acids represented by ethylenediaminetetraacetate, diethylenetriaminepentaacetate, etc., inorganic phosphorus compounds represented by tripolyphosphate, pyrophosphate, 1-hydroxyethane-1,1-diphosphonate And organic phosphoric acids represented by polyphosphonic acid and phytic acid, and 2,6-di-tert-butyl-4-methylphenol and 2 (3) -butyl-4-oxyanisole as antioxidants Etc. These may be blended as acids or salts. These metal sequestering agents and antioxidants are preferably blended in the softener composition of the present invention in the range of 0.1 to 1000 ppm.

  In the softener composition of the present invention, a fragrance usually blended with a fiber treatment agent (particularly preferably a combination of the fragrance components shown in components (c) and (d) described in JP-A-8-113871). Alternatively, ingredients such as pigments may be blended.

  As a manufacturing method of the softening agent composition of this invention, (c)-(f) component is dissolved in water as needed, and it heat-heats to 40-70 degreeC, Then, it is (b) as needed. Addition of component and component (g), stirring and mixing, adjusting to a predetermined pH with an acid agent, then adding component (a), cooling and then adding other components is the point of storage stability. To preferred.

  In the present invention, the fiber material can be given flexibility by immersing it in the aqueous solution of the softener composition of the present invention. When the fiber is a cotton fiber, the cotton fiber contains air. Such a soft texture can be imparted, and particularly when a softener composition of the present invention is treated on a used towel or the like, the preferred flexibility and texture can be imparted, which is particularly suitable.

Synthesis Example 1: Synthesis of Compound a-1 1.2 g of Ryoto Sugar Ester S-770 (manufactured by Mitsubishi Chemical Foods) was dissolved in 1050.0 g of cyclohexane, and N, N-dimethylacrylamide (Kojin ( 89.0 g, methacryloyloxyethyldimethylethylammonium ethyl sulfate 80% aqueous solution (MOEDES: Nitto Riken Kogyo Co., Ltd.) 38.8 g, polyethylene glycol dimethacrylate (NK-14G: Shin-Nakamura Chemical Co., Ltd.) ) 0.026 g and an aqueous solution prepared by dissolving 0.59 g of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator in 167 g of ion-exchanged water was added thereto, and a homomixer was used. The aqueous phase was dispersed until the particle size became 3 to 4 μm. This was put into a 2 L glass separable flask, heated while stirring in a nitrogen atmosphere, and polymerized and aged at 50 to 60 ° C. for 1 hour. Thereafter, the temperature was further raised to distill off 80% or more of the water in the system. Finally, cyclohexane was completely distilled off to obtain compound a-1.

Synthesis Example 2: Synthesis of Compound a-2 Compound a-1 was synthesized in the same manner as Compound a-1 except that the polyethylene glycol dimethacrylate of Compound a-1 was changed to 0.037 g.

Synthesis Example 3: Synthesis of Compound a-3 Compound a-1 was synthesized in the same manner as Compound a-1 except that the polyethylene glycol dimethacrylate of Compound a-1 was changed to 0.367 g.

Example 1
Using the following components (a) to (h), a softener composition having the composition shown in Table 1 was prepared by the following method. About the obtained softening agent composition, the softness | flexibility was evaluated by the following method. The results are shown in Table 1.

<Compounding ingredients>
(A) Component (a-1): Compound (a-2) produced in Synthesis Example 1 Compound (a-3) produced in Synthesis Example 2 Compound produced in Synthesis Example 3 (b) Component ( b-1): fatty acid / N- (3-aminopropyl) -N- (2-hydroxyethyl) -N-methylamine mixed fatty acid mixed with stearic acid / palmitic acid at 50/50 (mass ratio) N- (3-alkanoylaminopropyl) -N- (2-alkanoyloxyethyl) -N-methylamine and N- (3- A mixture of alkanoylaminopropyl) -N- (2-hydroxyethyl) -N-methylamine and unreacted fatty acid was obtained. The composition ratio was 80/15/5 (mass ratio), respectively.
(B-2): Fatty acid mixture of N- (3-aminopropyl) -N- (2-hydroxyethyl) -N-methylamine mixed with 50/50 (mass ratio) of stearic acid / palmitic acid After dehydrating and condensing by a conventional method at a molar ratio of /amine=1.9/1, this compound was alkylated with methyl chloride to give N- (3-alkanoylaminopropyl) -N- (2-alkanoyl) A mixture of (oxyethyl) -N, N-dimethylammonium chloride, N- (3-alkanoylaminopropyl) -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride and unreacted fatty acid was obtained. The composition ratio was 80/16/4 (mass ratio), respectively (note that ethanol was used as the reaction solvent during the alkylation, and the ethanol content in the synthesized product was 10% by mass).
(B-3): Fatty acid / amine = 1.9 mixed fatty acid mixed with 50/50 (mass ratio) of stearic acid / palmitic acid and N, N-bis (2-hydroxyethyl) -N-methylamine After dehydrating and condensing by a conventional method at a molar ratio of / 1, this compound is alkylated with methyl chloride, and N, N-bis (2-alkanoyloxyethyl) -N, N-dimethylammonium chloride and N A mixture of-(2-alkanoyloxyethyl) -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride and unreacted fatty acid was obtained. The composition ratio was 75/18/7 (mass ratio), respectively (note that ethanol was used as the reaction solvent during alkylation, and the ethanol content in the synthesized product was 10 mass%).
(B-4): After dehydration condensation reaction of uncured beef tallow fatty acid and triethanolamine at a molar ratio of 1.9 / 1 by a conventional method, this compound is alkylated with dimethyl sulfate, and N , N-bis (2-alkanoyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium methyl sulfate and N- (2-alkanoyloxyethyl) -N, N-bis (2-hydroxyethyl)- A mixture of N-methylammonium methylsulfate, N, N, N-tris (2-alkanoyloxyethyl) amine and unreacted fatty acid was obtained. The composition ratios were 47/29/19/5 (mass ratio), respectively (in addition, ethanol was used as the reaction solvent during alkylation, and the ethanol content in the synthesized product was 10% by mass).
(B-5): Stearic acid and N- (3-aminopropyl) -N, N-dimethylamine were subjected to a dehydration condensation reaction by a conventional method at a molar ratio of 1/1, and N- (3-alkanoyl A mixture of aminopropyl) -N, N-dimethylamine and stearic acid was obtained (composition ratio 99/1 (mass ratio)).
(B-6): A chloroacetic acid ester having 36 carbon atoms was reacted with a chloroacetic acid methyl ester having 36 carbon atoms. Next, trimethylamine was reacted to obtain a C36 gelbealkyloxycarbonylmethyl-N, N, N-trimethylammonium chloride.

(C) Component (c-1): Ethylene oxide adduct of lauryl alcohol (average EO addition mole number 20 mol)
(C-2): Isotridecyl alcohol ethylene oxide adduct (average EO addition mole number 30 mol)
(C-3): Stearylamine ethylene oxide adduct (average EO addition mole number 25 mol)
(D) Component (d-1): Sulfuric acid ester sodium salt of C24 gelve alcohol (e) Component (e-1): Stearic acid monoglyceride (f) Component (f-1): Ethylene glycol (f -2): Glycerin (f-3): 2-phenoxyethanol (f-4): ethanol (g) component (g-1): calcium chloride (g-2): magnesium chloride (h) component (h- 1): Perfume [Hexylcinnamic aldehyde (18), Neroline Yarayara (4), Tricyclodecenyl acetate (4), Benzyl acetate (10), Musk ketone (5), Anisyl acetone (2), Sandal mysol core ( 2), aldehyde C14 peach (1), linalool (18), dihydroxymyrsenol (8), borneol (4), cedrol ( ), Mugoru (5), benzyl alcohol (5), a mixture of dipropylene glycol (10): mass% in parentheses in perfumery]
<Method for preparing softener composition>
In a 300 mL beaker, 95% of the amount necessary for the final mass of the liquid treatment composition to reach 200 g, ion-exchanged water with 3 mg / kg of sodium hypochlorite added in advance, was added at 60 ° C. in a water bath. The temperature was raised to. Add the required amount of component (c) to component (f) while stirring with a turbine-type stirring blade with three blades each having a length of 2 cm at an angle of 45 ° (300 r / min). did. The components (d) and (e) can be added by premixing with the component (b) as necessary. After stirring for 5 minutes, the components (b) and (g) melted at 70 ° C. were then added. The mixture was stirred for 5 minutes. Next, the target pH was adjusted with 35% hydrochloric acid aqueous solution and 48% sodium hydroxide aqueous solution, and component (h) (fragrance component) was added as necessary. Next, the component (a) was added. Thereafter, 60 ° C. ion-exchanged water (sodium hypochlorite was added in advance at 3 mg / kg) in an amount necessary to make 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. The pH shown in Table 1 is the pH after cooling (20 ° C.).

  Moreover, the softening agent composition which does not mix | blend (a) component was prepared as a comparative product.

<Flexibility evaluation of cotton towel>
(1) Preparation method of softening towel A Washing machine using 24 commercially available cotton towels (white, 34 cm x 86 cm, 68 g / 1 sheet, 100% cotton) using a commercially available laundry detergent (Kao Corporation Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667% by mass, tap water 30L (water temperature 20 ° C.), water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. Next, 30 L of tap water (water temperature 20 ° C.) was poured, and after stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. This cycle was repeated a total of 5 times and then air-dried at room temperature. The weight of this air-dried cotton towel was measured. Next, this cotton towel was washed with a washing machine using a laundry detergent (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667 mass%, mass of air-dried cotton towel) Of water (water temperature 20 ° C.), water temperature 20 ° C., 5 minutes). Thereafter, the washing liquid was discharged, dehydrated for 3 minutes, and tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. After stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. Next, tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. Next, the softening agent composition shown in Table 1 corresponding to 0.47 mass% of the mass of the air-dried cotton towel was added and stirred for 3 minutes. Thereafter, the water was discharged, dehydrated for 3 minutes and naturally dried.

(2) Preparation method of softened towel B Washing machine using 24 commercially available cotton towels (white, 34 cm x 86 cm, 68 g / 1 sheet, 100% cotton) using a commercially available laundry detergent (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667% by mass, tap water 30L (water temperature 20 ° C.), water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, and after dehydration for 3 minutes, 30 L of tap water (water temperature 20 ° C.) was poured. After stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. Next, 30 L of tap water (water temperature 20 ° C.) was poured, and after stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. This cycle was repeated a total of 5 times and then air-dried at room temperature. The weight of this air-dried cotton towel was measured. Next, this cotton towel was washed with a washing machine using a laundry detergent (Kao Corp. Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667 mass%, mass of air-dried cotton towel) Of water (water temperature 20 ° C.), water temperature 20 ° C., 5 minutes). Thereafter, the washing liquid was discharged, dehydrated for 3 minutes, and tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. After stirring for 5 minutes, the rinsing liquid was discharged and dehydrated for 3 minutes. Next, tap water (water temperature 20 ° C.) having a mass 17 times the mass of the air-dried cotton towel was poured. Next, the softening agent composition (However, the softening agent composition remove | excluding (a) component from the composition of Table 1) corresponded to 0.47 mass% of the mass of the air-dried cotton towel was added, and it stirred for 3 minutes. Thereafter, the water was discharged, dehydrated for 3 minutes and naturally dried.

(3) Texture evaluation The texture when the above-treated cotton towel was folded in half and lightly squeezed with both hands was determined by 10 panelists (10 men in their 30s) according to the following criteria, and the average score was determined. An average score of 0.5 or more was judged as ◎, 0 or more and less than 0.5 as ○, and less than 0 as ×.
-1: Treated towel B crushed lightly compared to treated towel A 0: Feeling that treated towel A and crushed towel B were lightly crushed +1: Treated towel A was lighter than treated towel B Collapse

Claims (7)

At least one cationic group-containing vinyl monomer (a1) and at least one hydrophilic nonionic group-containing vinyl monomer (a2) represented by the following general formula (1) or (2): At least one cross-linkable vinyl monomer (a3) having two or more vinyl groups in the molecule is an essential constituent monomer, and the molar ratio of the monomer (a1) to the monomer (a2) is A monomer component in which (a1) / (a2) = 3/97 to 60/40 and the ratio of the monomer (a3) is 0.022 to 3% by mass relative to the total amount of the monomer is a radical. A softener composition containing a copolymer obtained by polymerization (hereinafter referred to as component (a)).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms. ]

[ Wherein , R ¹ represents the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) _n — (n represents an integer of 2 to 6). And B represents a —O— or —CH ₂ — group. ] Furthermore, at least one group selected from compounds having at least one group selected from an amino group and a quaternary ammonium group and at least one saturated or unsaturated hydrocarbon group having 8 to 36 carbon atoms in the molecule (hereinafter referred to as (b The softener composition according to claim 1 , wherein the softener composition comprises a component). (B) component, the general formula (3) tertiary amine or a salt thereof, and claim 1 or 2, wherein in formula at least one selected from quaternary ammonium salts represented by (4) Softener composition.

[Wherein R ⁴ and R ⁸ are each independently a linear or branched alkyl group or alkenyl group having ^{8 to} 36 carbon atoms, and R ⁵ and R ⁹ are each independently an alkylene having 1 to 6 carbon atoms. Each of D and E is independently a group selected from —COO—, —OCO—, —CONH—, and —NHCO—, and a and b are each independently a number of 0 or 1. R ⁶ and ^{R 7} each independently represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or ^R 4 - is a group represented by _{^{- [D-R 5] a}} . R ¹⁰ and ^{R 11} are independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms or ^{R 8, - [E-R} 9] b - is a group represented by. R ¹² is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Z ⁻ is an anion. ] The softening agent composition in any one of Claims 1-3 whose content of the (a) component in a composition is 0.1-10 mass%. The softener composition according to any one of claims 1 to 4 , wherein a mass ratio of the component (a) to the component (b) is (a) / (b) = 1/500 to 10/1. The softener composition according to any one of claims 1 to 5 , which is for cotton fibers. The processing method of the fiber which makes a fiber substance immersed in the softening agent composition in any one of Claims 1-6 .