JP6973884B2 - Softener composition - Google Patents

Description

The present invention relates to a softener composition.

In the past, fabric softeners used a quaternary ammonium salt or a tertiary amine compound having two long-chain alkyl groups having about 14 to 24 carbon atoms as a main base. In recent years, a long-chain alkyl group or a long-chain alkenyl group (hereinafter, "long-chain alkyl group" in the present invention is a long-chain alkenyl group for the purpose of being excellent in biodegradability and further reducing the influence on the environment. It is assumed that it is expressed including its meaning.) A flexible base material having a structure derived from a fatty acid having an ester bond or an amide bond between them has been developed and used. In particular, ester-type quaternary ammonium salts obtained by quaternizing an ester compound of triethanolamine and a long-chain fatty acid with an alkylating agent such as methyl chloride or dimethyl sulfate have become a general-purpose base material at the world level.

On the other hand, a technique of using the above-mentioned quaternary ammonium salt or tertiary amine compound having excellent biodegradability in combination with a nonionic surfactant is also known. Patent Document 1 describes the flexibility of containing an ester-type quaternary ammonium salt obtained by quaternizing an ester compound of triethanolamine and a long-chain fatty acid with an alkylating agent such as methyl chloride or dimethylsulfate, and a fatty acid ester of pentaerythritol. An excellent softening agent composition is disclosed, and Patent Document 2 suppresses the hydrolysis of the ester-type quaternary ammonium salt containing the ester-type quaternary ammonium salt and the glycerin fatty acid triester, and the storage stability is suppressed. Disclosed are excellent softener compositions. Patent Document 3 discloses a softener composition containing an ester-type quaternary ammonium salt and a sorbitan fatty acid ester, which exhibits excellent flexibility.
Further, Patent Document 4 discloses a softener composition containing an ester-type quaternary ammonium salt, a pentaerythritol fatty acid ester, and a silicone, which gives a refreshing feel. Further, Patent Document 5 discloses a softener composition having excellent rewetting properties, which contains a biodegradable cationic softener active ingredient and a small molecule silicone having a viscosity of 2 to 5,000 cSt.

Japanese Unexamined Patent Publication No. 2015-200047 Japanese Unexamined Patent Publication No. 2016-098466 Japanese Unexamined Patent Publication No. 2016-011472 Japanese Unexamined Patent Publication No. 2015-200048 Special Table No. 9-510263 Gazette

Compared with the conventional softener composition using a quaternary ammonium salt having two long-chain alkyl groups having 14 to 24 carbon atoms or a tertiary amine compound as a main base, an ester-type quaternary ammonium salt is mainly used. The base softener composition was inadequate in flexibility. As described above, a liquid softener composition having improved softening performance by combining a fatty acid ester type quaternary ammonium salt which is a soft base material and a nonionic surfactant is known. On the other hand, further improvements are required in order to reduce discomfort such as stickiness felt when wiping off moisture.

INDUSTRIAL APPLICABILITY The present invention contains a quaternary ammonium salt having a fatty acid ester structure, which can impart good flexibility to a textile product, and has the original elasticity due to a softener treatment during drying as compared with an untreated textile product. It is an object of the present invention to provide a softener composition which is not only excellent in bulkiness but also has a feeling of tightness, and further has reduced adhesiveness when wet, and can obtain a feeling of finish.
The term "adhesiveness when wet" means a state in which the surface of the textile product becomes sticky when the textile product absorbs moisture generated by sweating or the like.

In the present invention, the following component (A) is 5% by mass or more and 20% by mass or less, the following (B) component is 0.5% by mass or more and 10% by mass or less, and the following (C) component is 0.5% by mass or more and 3% by mass. % Or less, and a softener composition containing water.
<Ingredient (A)>
Represented by the following formula (1), R ⁴ is an alkyl group having 1 or more and 3 or less carbon atoms, and R ¹ is a fatty acid residue (s) obtained by removing OH from a fatty acid having 16 or more and 22 or less carbon atoms. ² and R ³ are independent hydrogen atoms or fatty acid residues (s), respectively, in a mixture of quaternary ammonium salts where ^{X − is an organic or inorganic anion.}
The ^{compound (a1) in which R 1} is the fatty acid residue (s) and R ² and R ³ are hydrogen atoms is contained in an amount of 10% by mass or more 45 in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a2) in which R 1} and R ² are the fatty acid residues (s) and R ³ is a hydrogen atom is contained in an amount of 25% by mass or more in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a3) in which R 1} , R ² and R ³ are the fatty acid residues (s) is contained in an amount of 5% by mass or more and 40% by mass or less in the total amount of the quaternary ammonium salt represented by the formula (1). Mixture of quaternary ammonium salt

<Ingredient (B)>
Ester compound of a polyhydric alcohol having 3 or more and 6 or less carbon atoms and having a trivalent or more and 6 or less valence and a fatty acid having 12 or more and 22 or less carbon atoms <(C) component>
Silicone compound with dynamic viscosity of 100-3,000 mm ^{2 / s}

According to the present invention, the treated textile product is not only superior in the original elasticity and bulkiness of the softener at the time of drying, but also has a feeling of tightness, and further when wet, as compared with the untreated textile product. Provided is a softener composition having reduced stickiness and capable of obtaining a finished feeling.

As a result of diligent studies, the present inventor has found that the softener composition contains the component (A), the component (B) and the component (C) in a specific ratio, whereby the textile product treated with the softener composition is obtained. Compared to untreated textile products, not only is it superior in the original elasticity and bulkiness of the softener when it is dried, but it also has a feeling of tightness, and the adhesiveness when it is wet is reduced, resulting in a finished feeling. I found that I could do it.

<Mixture of quaternary ammonium salt (A)>
The softener composition of the present invention contains a mixture (A) of the quaternary ammonium salt shown below (hereinafter, also referred to as "component (A)", and the component (A) also acts as a softening base material. ..
The component (A) is represented by the ^{following formula (1), R 4} is an alkyl group having 1 or more and 3 or less carbon atoms, and R ¹ is a fatty acid residue (s) obtained by removing OH from a fatty acid having 16 or more and 22 or less carbon atoms. ), Where R ² and R ³ are independent hydrogen atoms or fatty acid residues (s), respectively, in a mixture of quaternary ammonium salts where ^{X − is an organic or inorganic anion.}
The ^{compound (a1) in which R 1} is the fatty acid residue (s) and R ² and R ³ are hydrogen atoms is contained in an amount of 10% by mass or more 45 in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a2) in which R 1} and R ² are the fatty acid residues (s) and R ³ is a hydrogen atom is contained in an amount of 25% by mass or more in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a3) in which R 1} , R ² and R ³ are the fatty acid residues (s) is contained in an amount of 5% by mass or more and 40% by mass or less in the total amount of the quaternary ammonium salt represented by the formula (1). It is a mixture of quaternary ammonium salts.

When the ratio of the component (a1), the component (a2), and the component (a3) in the total amount of the quaternary ammonium salt represented by the formula (1) is within the above range, the textile product is imparted with wet conditions. The effect of reducing the adhesiveness of is improved. From such a viewpoint, the ratio of the component (a1), the component (a2), and the component (a3) to the total amount of the quaternary ammonium salt represented by the formula (1) is preferably as follows. ..

The proportion of the component (a1) in the total amount of the quaternary ammonium salt represented by the formula (1) is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass. It is 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 32% by mass or less.
The ratio of the component (a2) in the total amount of the quaternary ammonium salt represented by the formula (1) is 25% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 40% by mass. The above is more preferably 45% by mass or more, further preferably 50% by mass or more, and 70% by mass or less, preferably 65% by mass or less, and more preferably 60% by mass or less.
The proportion of the component (a3) in the total amount of the quaternary ammonium salt represented by the formula (1) is 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass. It is 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

In addition, the component (a2) and the component (a3) affect the storage stability of the softener composition containing the component (B) described later while enhancing the softening effect. Therefore, when the content of the component (a1) is within the above range, the storage stability can be improved.

In the present invention, after satisfying the ratios of the component (a1), the component (a2), and the component (a3), the component (a2) in the total mass of the quaternary ammonium salt represented by the formula (1) The content is preferably higher than that of the component (a3), and the difference between the content (% by mass) of the component (a2) and the content (% by mass) of the component (a3) is preferably 15% by mass or more. It is more preferably 20% by mass or more, further preferably 25% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more.

In the formula (1), the fatty acid residue (s) is preferably a residue obtained by removing OH (hydroxyl group) from a fatty acid having 16 or more and 22 or less carbon atoms, preferably 16 or more and 18 or less carbon atoms.
Specific examples of fatty acids include saturated fatty acids such as stearic acid and palmitic acid, unsaturated fatty acids such as oleic acid, ellagic acid, linoleic acid, and linolenic acid, palm oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids, and rapeseed oils. One or more selected from fatty acids derived from vegetable oils such as fatty acids, safflower oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, olive oil fatty acids, and hardened palm oil fatty acids, beef fatty acids, and animal oil-derived fatty acids such as hardened beef fat fatty acids. Be done. Among these, saturated fatty acids, unsaturated fatty acids and fatty acids derived from vegetable oils are preferable, fatty acids derived from vegetable oils are more preferable, and fatty acids derived from palm oil are even more preferable.

Wherein (1), R ⁴ is an alkyl group having 1 to 3 carbon atoms, a methyl group or an ethyl group is preferred.
In the formula (1), X ⁻ is an organic or inorganic anion, which is a halogen ion such as a chloro ion, an alkyl sulfate ester ion having 1 or more and 3 or less carbon atoms, a fatty acid ion having 12 or more and 18 or less carbon atoms, and carbon. Anions selected from benzenesulfonic acid ions, which may be substituted with 1 or more and 3 or less alkyl groups having a number of 1 or more and 3 or less, are preferable. In the present invention, it is more preferably an alkyl sulfate ester ion having 1 or more carbon atoms and 3 or less carbon atoms, and further preferably a methyl sulfate ester ion or an ethyl sulfate ester ion.

The component (A) used in the present invention is a method of dehydrating and transesterifying a fatty acid and triethanolamine (hereinafter referred to as "dehydration esterification method"), or a fatty acid lower alkyl ester (lower alkyl is a methyl group or an ethyl group, It can be obtained by subjecting an esterification reaction product obtained by a method of transesterifying a propyl group) and triethanolamine (hereinafter referred to as "transesterification method") to a quaternization reaction with an alkylating agent.
In order to obtain a mixture satisfying the ratio of the component (a1) to the component (a3) of the component (A) of the present invention, for example, 1.3 mol or more of a fatty acid or a fatty acid lower alkyl ester is added to 1 mol of triethanolamine. It can be obtained by quaternizing a mixture of triethanolamine fatty acid esters reacted at a ratio of preferably 1.5 mol or more and 2.0 mol or less, preferably 1.9 mol or less.

The fatty acid or the lower fatty acid alkyl ester is preferably one having a fatty acid composition obtained by saponifying fats and oils selected from beef fat, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil and olive oil. Fatty acid compositions obtained from beef fat, palm oil and sunflower oil are more preferred.
Further, since these fatty acids or fatty acid lower alkyl esters contain a large amount of alkenyl groups having two or more carbon-carbon unsaturated bonds, for example, crystallization as described in JP-A-4-306296 , A method of vacuum distillation of a methyl ester as described in JP-A-6-41578, or a selective hydrogenation reaction described in JP-A-8-99036 to form a carbon-carbon unsaturated bond. The proportion of fatty acids contained in two or more may be controlled. For example, hardened beef tallow is a fatty acid derived from beef tallow saturated by hydrogenation, and is sometimes referred to as semi-hardened as a partially hardened fatty acid. Further, those having an adjusted degree of hardening may be optionally mixed with the fatty acid which has not been cured.
When the selective hydrogenation reaction is carried out, a mixture of unsaturated bond geometric isomers is formed, but in the present invention, cis / trans is preferably 25/75 to 100/0, more preferably 50/50. ~ 95/5 (molar ratio).

In the dehydration esterification method, it is preferable that the esterification reaction temperature is 140 ° C. or higher and 230 ° C. or lower, and the reaction is carried out while removing condensed water. An ordinary esterification catalyst may be used for the purpose of accelerating the reaction. For example, an inorganic acid such as sulfuric acid or phosphoric acid, an inorganic oxide such as tin oxide or zinc oxide, or an alcoholate such as tetrapropoxytitanium can be selected. can.

The progress of the dehydration esterification reaction can be confirmed by measuring the acid value (AV) and the saponification value (SV) by the method described in JIS K0070-1992, and AV is preferably 10 mgKOH / g or less, more preferably. The esterification reaction is terminated when the content is 6 mgKOH / g or less.
The SV of the resulting mixture of ester compounds is preferably 110 mgKOH / g or more, more preferably 130 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 190 mgKOH / g or less.

In the transesterification method, the reaction temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and preferably 150 ° C. or lower, and the reaction is preferably carried out while removing the lower alcohol produced. Inorganic alkalis such as sodium hydroxide and potassium hydroxide, and alkoxy catalysts such as methylate and ethylate can also be used to promote the reaction.
For the progress of the reaction, it is preferable to directly quantify the amount of the fatty acid lower alkyl ester by using gas chromatography or the like, and the unreacted fatty acid lower alkyl ester is 10 on the gas chromatography chart with respect to the prepared fatty acid lower alkyl ester. It is preferable to terminate the reaction when the area is% or less, particularly 6 area% or less.
The SV of the resulting mixture of ester compounds is preferably 110 mgKOH / g or more, more preferably 130 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 190 mgKOH / g or less.

In order to obtain a quaternary ammonium salt, the ester compound obtained by the above method is quaternized. As the alkylating agent that can be used for quaternization, methyl chloride, dimethyl sulfate, diethyl sulfate and the like are suitable. When methyl chloride is used as the alkylating agent, it is not necessary to use a solvent in particular, but when a solvent is used, a solvent such as ethanol or isopropanol is used in an amount of 10% by mass or more and 50% by mass based on the ester compound. A solution mixed to the following extent is charged in a pressure reactor such as an autoclave made of titanium, and methyl chloride is press-fitted and reacted at a reaction temperature of 30 ° C. or higher and 120 ° C. or lower under sealing. At this time, a part of methyl chloride may be decomposed to generate hydrochloric acid. Therefore, from the viewpoint of efficiently advancing the reaction, it is preferable to add a small amount of an alkaline agent.
As for the molar ratio of the methyl chloride to the ester compound, it is preferable to use 1 equivalent or more and 1.5 equivalent or less of the methyl chloride with respect to 1 equivalent of the amino group of the ester compound.

When dimethyl sulfate or diethyl sulfate is used as the alkylating agent, a solution in which a solvent such as ethanol or isopropanol is mixed with the ester compound in an amount of about 10% by mass or more and 50% by mass or less is preferably mixed at 40 ° C. or higher and 100 ° C. or lower. It can be carried out by heating and mixing and dropping dimethyl sulfate and / or diethyl sulfate.
The molar ratio of dimethyl sulfate and / or diethyl sulfate to the ester compound is preferably 0.9 equivalent or more, more preferably 0.94 equivalent or more, based on 1 equivalent of the amino group of the ester compound. , And preferably 1.1 equivalents or less, more preferably 0.99 equivalents or less.

The softener composition of the present invention may contain a by-product produced during the production of the component (A). By-products include, for example, unreacted amines that have not been quaternized, specifically amines of fatty acid triesters and amines of fatty acid diesters. The total amount of the amine of the fatty acid triester and the amine of the fatty acid diester depends on the production method, but is usually 30 parts by mass or less with respect to 100 parts by mass of the component (A).
On the other hand, since the amine of the fatty acid monoester is easily quaternized, the content in the reaction product is usually 0.5 parts by mass or less with respect to 100 parts by mass of the component (A).
Furthermore, the total content of triethanolamine and the quaternized product of triethanolamine that have not been fatty acid esterified is usually 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the component (A). Of these, 90% by mass or more are quaternized products.
In addition to the by-products, unreacted fatty acids may be contained in the component (A).
High performance liquid chromatography (hereinafter, also referred to as “HPLC”) is used for the proportions of the compounds (a1), (a2) and (a3) and the amine compound which are the components (A), and the charge particle detector (hereinafter, also referred to as “HPLC”) is used as a detector. It was obtained using Charged Aerosol Detection (hereinafter, also referred to as "CAD"). For the measurement method using CAD, "Technology and application of charged particle detector Corona CAD" (Fukushima et al. Chromatography, Vol.32 No.3 (2011)) can be referred to. The mass ratio is ^{determined by assuming the anion (X −} ) in the formula (1) as a methyl sulfate ion.

The content of the component (A) in the softener composition of the present invention is 5% by mass or more, preferably 6% by mass or more, from the viewpoint of imparting good flexibility to the textile product and obtaining elasticity and bulkiness. , More preferably 7% by mass or more, still more preferably 8% by mass or more. Further, the content of the component (A) in the softener composition is 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably, from the viewpoint of the effect of reducing the adhesiveness at the time of wetting. Is 10% by mass or less.

<Ester compound (B)>
The softener composition of the present invention has 3 or more and 6 or less carbon atoms and a hydroxy group valence of 3 or more in order to obtain excellent elasticity, bulkiness and a feeling of tightness after drying of the textile product. It contains an ester compound (B) (hereinafter, also referred to as “component (B)”) of a polyhydric alcohol having a valence of 6 or less and a fatty acid having 12 or more and 22 or less carbon atoms.
More specifically, with polyhydric alcohols having 3 or more carbon atoms, preferably 4 or more, and 6 or less, and trivalent or more, preferably tetravalent or more, and hexavalent or less. It is an ester compound with a fatty acid having 12 or more carbon atoms, preferably 14 or more, more preferably 16 or more, and 22 or less, preferably 20 or less.

The polyhydric alcohol constituting the component (B) is selected from glycerin, trimethylolethane, trimethylolethane, 1,3,5-pentatriol, erythritol, arabitol, pentaerythritol, sorbitol, sorbitol, xylitol and mannitol1. More than one species is preferred, one or more selected from glycerin, pentaerythritol and sorbitol is more preferred, and one or more selected from pentaerythritol and sorbitol is even more preferred.

Examples of the fatty acid constituting the component (B) include saturated fatty acids such as lauric acid, myristic acid, stearic acid, and palmitic acid, unsaturated fatty acids such as oleic acid, elladic acid, linoleic acid, and linolenic acid, and palm oil fatty acids. And one or more selected from animal oil-derived fatty acids such as vegetable oil-derived fatty acids, beef fat fatty acids and hardened beef fatty acids, and one selected from saturated fatty acids, vegetable oil-derived fatty acids, and animal oil-derived fatty acids. The above is more preferable, and one or more selected from stearic acid, hardened palm oil fatty acid, and hardened beef fatty acid is further preferable.

The component (B) in the present invention includes an ester compound of pentaerythritol and a fatty acid having 16 or more and 22 or less carbon atoms (hereinafter, also referred to as “pentaerythritol fatty acid ester (b1)”), and sorbitan and a fatty acid having 16 or more and 22 or less carbon atoms. One or more selected from the ester compounds with the fatty acid of (hereinafter, also referred to as "sorbitan fatty acid ester (b2)") is preferable.

[Pentaerythritol fatty acid ester (b1)]
The pentaerythritol fatty acid ester (b1) (hereinafter, also referred to as “(b1) component”) in the present invention is a fatty acid monoester, a fatty acid diester, or a fatty acid triester obtained from pentaerythritol and a fatty acid having 16 or more and 22 or less carbon atoms. And a mixture of two or more ester compounds selected from fatty acid tetraesters.

The component (b1) in the present invention is a component composed of a plurality of ester compounds of pentaerythritol and a fatty acid having 16 or more and 22 or less carbon atoms, and more specifically, the four ester compounds having different degrees of esterification. It is a mixture of compounds. It should be noted that the mixture referred to in the present invention also means a case where it is synthesized separately and mixed in the composition of the present invention.
Among the ester compounds constituting the component (b1), the fatty acid monoester is a compound in which one of the four hydroxyl groups of pentaerythritol is an ester with a fatty acid. The fatty acid diester is a compound in which two of the four hydroxyl groups of pentaerythritol are esters with fatty acids, and the fatty acid triester is a compound in which three of the four hydroxyl groups of pentaerythritol are esters with fatty acids. Further, the fatty acid tetraester is a compound in which all four hydroxyl groups of pentaerythritol are esters with fatty acids.

The fatty acid used as a raw material for the ester compound of the component (b1) is a fatty acid having 16 or more and 22 or less carbon atoms, preferably 16 or more and 18 or less carbon atoms. Specific examples of the fatty acid used as a raw material for the ester compound of the component (b1) include saturated fatty acids such as stearic acid and palmitic acid, unsaturated fatty acids such as oleic acid, elladic acid, linoleic acid, and linolenic acid, and palm oil. One or more selected from fatty acids and fatty acids derived from animal oils such as fatty acids derived from vegetable oils of hardened palm oil fatty acids, beef fatty acids, and hardened beef fatty acids can be mentioned. Among these, one or more selected from saturated fatty acids, fatty acids derived from vegetable oils, and fatty acids derived from animal oils are preferable, and one or more selected from stearic acid, hardened palm oil fatty acids, and hardened beef fatty acids are more preferable.

The ratio of the fatty acid monoester to the total amount of the component (b1) is limited from the viewpoint of the effect of reducing the adhesiveness at the time of wetting, but is preferably 5% by mass or more from the viewpoint of improving the stability of the textile product composition. , More preferably 10% by mass or more, further preferably 12% by mass or more, still more preferably 15% by mass or more, still more preferably 18% by mass or more, still more preferably 20% by mass or more, and adhesion when wet. From the viewpoint of improving the property reducing effect, it is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, still more preferably 30% by mass or less.

In the present invention, the content ratio of ester compounds having different degrees of esterification can be measured by a gel permeation chromatogram.

In the present invention, it is preferable to limit the ratio of the fatty acid monoester in the component (b1) and increase the ratio of the fatty acid diester and the fatty acid triester because the effect of reducing the adhesiveness at the time of wetting is improved.
The total ratio of the fatty acid diester and the fatty acid triester in the total amount of the component (b1) is preferably 40% by mass or more, more preferably 45% by mass or more, from the viewpoint of improving the effect of reducing the adhesiveness at the time of wetting. It is more preferably 50% by mass or more, still more preferably 60% by mass or more, and from the viewpoint of improving the stability of the softening agent composition, it is preferably 90% by mass or less, more preferably 85% by mass or less, still more. It is preferably 80% by mass or less.

After satisfying the above total ratio, the ratio of the fatty acid diester to the total amount of the ester compound is preferably 20% by mass or more, more preferably 30% by mass or more, and more, from the viewpoint of the effect of reducing the adhesiveness at the time of wetting. It is more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less.
Further, after satisfying the above total ratio, the ratio of the fatty acid triester in the total amount of the ester compound is preferably 10% by mass or more, more preferably 15% by mass, from the viewpoint of the effect of reducing the adhesiveness at the time of wetting. The above, and preferably 40% by mass or less, more preferably 35% by mass or less.

The component (b1) may contain a fatty acid tetraester among the pentaerythritol fatty acid esters. The proportion of the fatty acid tetraester in the total amount of the ester compound is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 20 from the viewpoint of improving the stability of the softener composition. It is mass% or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 10% by mass or less.
The total amount of the fatty acid monoester, fatty acid diester and fatty acid triester in the component (b1) is preferably 80% by mass or more, preferably 85% by mass or more.

Examples of the method for obtaining a mixture of the ester compound as the component (b1) include JP-A-5-140037, JP-A-5-140038, and the like, and specifically, an ester of pentaerythritol and a fatty acid. It can be produced by a chemical reaction or a transesterification reaction between pentaerythritol and a fatty acid lower alkyl ester (lower alkyl is a methyl group, an ethyl group, or a propyl group).
In order to obtain a mixture satisfying the conditions of the component (b1), a fatty acid or a lower fatty acid alkyl ester is preferably added in an amount of 0.8 mol or more, more preferably 1.0 mol or more, more preferably, based on 1 mol of pentaerythritol. The reaction is preferably 1.2 mol or more, preferably 2.2 mol or less, more preferably 2.0 mol or less, and more preferably 1.8 mol or less.

[Sorbitan fatty acid ester (b2)]
As the sorbitan fatty acid ester (b2) (hereinafter, also referred to as “component (b2)”) in the present invention, the fatty acid is selected from saturated fatty acids such as palmitic acid and stearic acid, and unsaturated fatty acids such as oleic acid and ellagic acid. One or more sorbitan fatty acid esters are preferable, sorbitan fatty acid esters in which the fatty acid is a saturated fatty acid are more preferable, and sorbitan stearate ester is more preferable.

The component (b2) is one or more selected from sorbitan fatty acid monoester, sorbitan fatty acid diester, and sorbitan fatty acid triester, and sorbitan from the viewpoint of reducing the adhesiveness of the softener composition when wet and stability. Fatty acid monoesters are preferred, and sorbitan stearate monoesters are more preferred.
The component (b2) in the present invention may be a mixture of sorbitan fatty acid monoester, sorbitan fatty acid diester, and sorbitan fatty acid triester, and the mixture may contain a trace amount of sorbitan fatty acid tetraester. There may be. When the mixture is used, it is preferable that the content of the sorbitan fatty acid monoester is the highest in the mixture. Sorbitan fatty acid ester can be purchased from Kao Corporation under the trade name of Leodor. Further, it may be produced by a known method.

The acid value (AV) of the component (b2) is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, and preferably 12 mgKOH / g from the viewpoint of improving the effect of reducing the adhesiveness at the time of wetting. Below, it is more preferably 10 mgKOH / g or less.
Further, the saponification value (SV) of the component (b2) is preferably 130 mgKOH / g or more, more preferably 145 mgKOH / g or more, and preferably 170 mgKOH or more, from the viewpoint of improving the effect of reducing the adhesiveness at the time of wetting. It is / g or less, more preferably 160 mgKOH / g or less.
The acid value (AV) and saponification value (SV) can be measured by the method described in JIS K0070-1992.

The content of the component (B) in the softener composition of the present invention is 0.5% by mass or more, preferably 0.7, from the viewpoint of obtaining elasticity, bulkiness and a feeling of tightness after drying of the textile product. By mass or more, more preferably 0.9% by mass or more, still more preferably 1.2% by mass or more, still more preferably 1.5% by mass or more. The content of the component (B) is 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 4% by mass or less, from the viewpoint of the effect of reducing the adhesiveness at the time of wetting. More preferably, it is 3% by mass or less.

<Silicone compound (C)>
The softener composition of the present invention contains a low molecular weight silicone compound in order to suppress the wettability of the textile product after drying due to the component (B). That is, a silicone compound (C) having a dynamic viscosity of 100 to 3,000 mm ² / s (hereinafter, also referred to as “component (C)”) is used.
The dynamic viscosity is a value at 25 ° C. measured by a Ubbelohde viscometer.

As the component (C), dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methylhydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, And one or more selected from amino-modified silicones.
As the silicone compound, one or more selected from dimethyl silicone, amino-modified silicone, and polyether-modified silicone are preferable, and dimethyl silicone is more preferable, from the viewpoint of the compounding cost in the softener composition. These may be used alone or in combination of two or more.
The dimethyl silicone in the present invention refers to dimethylpolysiloxane.

The component (C) of the present invention may be oily, for example, dimethyl silicone oil may be used as it is, but it may be used as an aqueous emulsion containing a silicone compound and water.
The aqueous emulsion of the component (C) preferably uses a surfactant as an emulsifier and is dispersed in water by an emulsifier such as a homomixer, a high-pressure homogenizer, or a colloid mill.
The surfactant used in the aqueous emulsion is one or more selected from alkylbenzene sulfonic acid or a salt thereof, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate, olefin sulfonate, alkane sulfonate, and fatty acid salt. Anionic surfactant,
One or more nonionic surfactants selected from polyoxyalkylene alkyl or alkenyl ethers, polyoxyalkylene alkyl phenyl ethers, fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, and alkyl glucosides,
One or more amphoteric surfactants selected from amine oxides, sulfobetaines, and carbobetaines, and one or more cationic surfactants selected from tri-long-chain alkyl quaternary ammonium salts can be used.

As a specific example of the aqueous emulsion of the component (C), it was emulsified in water as emulsified particles having an average particle diameter of 50 nm or more and 900 nm or less by a surfactant containing a polyoxyalkylene alkyl ether type nonionic surfactant or the like. , Dimethylpolysiloxane emulsion is preferably used.
The average particle size of the emulsified particles in the dimethylpolysiloxane emulsion is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 200 nm or more, and preferably 900 nm or less, more preferably 700 nm or less, still more preferably. Is 600 nm or less, more preferably 500 nm or less.
For the preparation of the dimethylpolysiloxane emulsion, the description in JP-A-2006-2001116 can be referred to.

When the component (C) dimethylpolysiloxane is used, the dynamic viscosity of dimethylpolysiloxane at 25 ° C. is preferably 150 mm ² / s or more, more preferably 150 mm 2 / s or more, from the viewpoint of suppressing the adhesiveness of the textile product when wet. 200 mm ² / s or more, preferably 2,500 mm ² / s or less, more preferably 2,200 mm ² / s or less, ^{still more preferably 1,000 mm 2} / s or less, ^{still more preferably 500 mm 2} / s. It is as follows.

The content of the component (C) in the softener composition is preferably 0.7% by mass or more, more preferably 0.9% by mass or more, from the viewpoint of suppressing the adhesiveness of the textile product after drying when wet. And, preferably 2.5% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less. When an aqueous emulsion containing a silicone compound and water is used as the component (C), it is preferable to use the component (C) so that the amount in terms of pure content is within this range.

The mass ratio [(A) / (B)] of the component (A) to the component (B) is from the viewpoint of obtaining good flexibility of the textile product after drying and from the viewpoint of suppressing the adhesiveness at the time of wetting. Therefore, it is preferably 0.6 or more, more preferably 1.0 or more, still more preferably 1.4 or more, and preferably 19 or less, more preferably 15 or less, still more preferably 10 or less. Moreover, the mass ratio [(A) / (C)] of the component (A) to the component (C) is preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and preferably 20 or less. , More preferably 18 or less, still more preferably 15 or less.

<Fatty alcohol (D)>
The softener composition of the present invention is a fatty alcohol (D) (hereinafter, "(D) component" from the viewpoint of reducing skin stress such as clinging to the skin or sticking to the skin due to the textile product during sweating. It may also contain.). As the component (D), it is preferable to use a linear aliphatic primary saturated alcohol having 12 or more and 20 or less carbon atoms.
The component (D) in the present invention is preferably a linear aliphatic primary saturated alcohol, and it is Japanese Patent Application Laid-Open No. Inc. that the aliphatic alcohol is effective in reducing the adhesiveness of textile products when wet. Although described in Japanese Patent Laid-Open No. 2016-11471 and JP-A-2016-11470, in the present invention, the aliphatic alcohol (D) is used in combination with the component (A), the component (B) and the component (C). By doing so, it is possible to suppress skin stress such as clinging and sticking of textile products to the skin caused by sweating, and to maintain a smooth feeling.
The carbon number of the linear aliphatic primary saturated alcohol is preferably 12 or more, more preferably 14 or more, and preferably 20 or less, more preferably 18 or less, from the viewpoint of suppressing skin stress.
As a specific alcohol, it is preferable to use one or more selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol.
Among these, myristyl alcohol, cetyl alcohol and stearyl alcohol are preferable, and cetyl alcohol and stearyl alcohol are more preferable.

<Nonionic surfactant (E)>
In the present invention, a nonionic surfactant (E) (hereinafter, also referred to as “component (E)”) may be used from the viewpoint of improving the dispersion stability of the components (A) and (B). ..
The nonionic surfactant has (i) an alkyl group or an alkenyl group having 10 or more and 18 or less carbon atoms, an average addition molar number of 5 or more and 100 or less of the oxyethylene group, and an average addition of the oxyethylene group. Of the number of moles, 0 mol or more and 5 mol or less may be changed to an oxypropylene group or an oxybutylene group (however, the average number of added moles of an oxyethylene group is larger than the total number of added moles of other oxyalkylene groups. It is selected from polyoxyalkylene alkyl (alkenyl) ethers (more, preferably 5 or more), and (ii) alkyl polyglycosides having an alkyl group having 8 or more and 18 or less carbon atoms and having a sugar average condensation degree of 1 or more and 5 or less. It is preferable to use one or more.
Among these, from the viewpoint of improving the dispersion stability of the components (A) and (B), (i') has an alkyl group having 10 or more and 14 or less carbon atoms, and the average number of moles of ethylene oxide added is 10 or more and 40 or less. Polyoxyethylene alkyl ether is preferred.
The content of the component (E) in the softening agent composition is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and preferably 8.0% by mass or less, more preferably. It is 6.0% by mass or less, more preferably 4.0% by mass or less.

<Water-soluble organic solvent (F)>
In the present invention, a water-soluble organic solvent (F) (hereinafter, also referred to as “component (F)”) may be used from the viewpoint of improving the dispersion stability of the softener composition.
As a specific water-soluble organic solvent, one or more selected from volatile lower alcohols such as methanol, ethanol, propanol and isopropanol, ethylene glycol, glycerin and propylene glycol can be used.
As the water-soluble organic solvent, ethanol, propanol, ethylene glycol, propylene glycol or glycerin are preferable from the viewpoint of ease of handling.
The content of the water-soluble organic solvent (F) in the softener composition is preferably 0% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass. Below, it is more preferably 4% by mass or less.

<Water-soluble inorganic salt (G)>
In the present invention, a water-soluble inorganic salt (G) (hereinafter, also referred to as “component (G)”) may be used from the viewpoint of adjusting the viscosity of the softener composition to be suitable for use.
The water-soluble inorganic salt is preferably one or more water-soluble inorganic salts selected from sodium salt, calcium salt and magnesium salt from the viewpoint of storage stability, and is selected from sodium chloride, calcium chloride, magnesium chloride and magnesium sulfate. One or more of them are more preferable, one or more selected from calcium chloride and magnesium chloride are more preferable, and calcium chloride is even more preferable. The "water-soluble" component (G) means that 20 g or more is dissolved in 100 g of deionized water at 20 ° C.
The blending amount of the component (G) in the softener composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 1.0% by mass or less, more preferably 1.0% by mass or less. It is 0.6% by mass or less.

<Acid compound (H)>
In the present invention, the acidic compound (H) (hereinafter, also referred to as “component (H)”) is used from the viewpoint of suppressing the hydrolysis of the component (A) and the component (B) and improving the storage stability. You may.
As the acidic compound, one or more selected from inorganic acids such as hydrochloric acid and sulfuric acid and organic polybasic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid can be used. Can be used.
Of these, hydrochloric acid, sulfuric acid and citric acid are preferable. A part of the component (H) also has a function as a chelating agent. The acidic compound may be used as a pH adjuster.

<Other ingredients>
It is preferable to add the following fragrance (I), antioxidant, monocarboxylic acid, chelating agent, dye, preservative and the like to the present invention.
The softener composition of the present invention may contain a fragrance (I) (hereinafter, also referred to as "component (I)"). As the fragrance, the fragrance components described in "Practical knowledge of fragrance and fragrance" (written by Motoki Nakajima, Sangyo Tosho Co., Ltd., published on June 21, 1995) can be appropriately combined according to the fragrance and usage. Further, as long as the effect of the present invention is not impaired, the blending amount of the fragrance component or fragrance composition described in the patent documents of the softener, the paste, the styling agent or the other finishing agent known as the finishing agent may be increased. It can be used after considering including it.

From the viewpoint of fragrance quality and intensity, stability in composition, etc., for example, the following fragrance components can be mentioned.
Examples of the terpene-based fragrance component include linalool, p-cymen, α-pinen, β-pinen, β-cariophyllene, and the like, and examples of the alcohol-based fragrance component include cis-3-hexenol, trans-2-hexenol, and methyl (trimethyl). Cyclopentenyl) butenol, dihydromilsenol, l-menthol, phenylethyl alcohol, citronellol, geraniol, nerol, linalool, terpineol, tetrahydrolinalol, tetrahydrogeraniol, dimethylbenzylcarbinol, β-phenylethyl alcohol, benzyl alcohol, synamic Alcohol, anis alcohol, farnesol, nerolidol, dimethylphenylethylcarbinol, ot-butylcyclohexanol, pt-butylcyclohexanol, sandal mysol core (2-methyl-4- (2,2,3-trimethyl) -3-Cyclopentene-1-yl) -2-buten-1-ol) (manufactured by Kao Co., Ltd.), bagdanol (manufactured by IFF), Javanol (manufactured by Dibodan) and the like.

As ester-based fragrance components, benzyl acetate, dimethylbenzylcarbyl acetate, linaryl acetate, neryl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, citronellyl acetate, geranyl acetate, tetrahydrogeranyl acetate, terpenyl acetate , Isobornyl acetate, l-mentyl acetate, tricyclodecenyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, styralyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, hexyl acetate, cinnamyl acetate , Isobutyl propionate, 2-phenylethyl propionate, citronellyl propionate, benzyl propionate, tricyclodecenyl propionate, geranyl propionate, allyl propionate, geranyl butyrate, citronellyl butyrate, isoamyl butyrate, amyl butyrate, allyl butyrate , Phenoxyethyl isobutyrate, geranyl isobutyrate, geranyl isovalerate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enantate, ethyl octanate, methyl anthranylate, cis-3-hexenyl benzoate, benzyl benzoate , Amyl salicylate, Isoamyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, hexyl salicylate, 2-phenylethyl salicylate, methyldihydrojasmonate, coumarin, γ-octalactone, γ-undecalactone, γ-decalactone, γ -Nonalactone, δ-Nonalactone, δ-Decalactone, δ-Undecalactone, δ-Dodecalactone, Cyclopentadecanolide, Cyclopentadecanolide (Havanolide, manufactured by Filmenich), Cyclohexadecanolide, Ambrelid, 11 -Oxa-16-hexadecanolide (Musque R-1, manufactured by Zivodan), 10-oxa-16-hexadecanolide (oxalide, manufactured by Takasago Perfume Industry Co., Ltd.), 12-oxahexadecanolide, ethylene brush rate, ethylene dodecandio. Ate (Musk C-14) and the like can be mentioned.

Aldehyde-based fragrance components include octanal, nonanal, decanal, undecalal, 10-undecalal, dodecanal, citral, citroneral, anisaldehyde, phenylacetaldehyde, mylacaldehyde, lilial, lylar, dimethyltetrahydrobenzaldehyde, amylcinnamic aldehyde, and hexyl. Examples thereof include synamic aldehyde, cyclamenaldehyde, vanillin, ethyl vanillin, heliotropin, helional and the like, and examples of the ketones include fluorozone, l-carboxylic, menton, dihydrojasmon, methyl jasmonate, methyl dihydrojasmonate, cis jasmon and geranyl. Acenes, damascons, damasenones, α-dynascon, ionones, methylionones, β-methylnaphthylketones, isoE super, raspberry ketones, maltol, ethylmaltol, cashmerelan (manufactured by IFF), 5-cyclohexedesenone-1 -On (Musk TM-II) and the like can be mentioned.
Ethereal fragrance components include anthranil, eugenol, methyl eugenol, methyl isoeugenol, diphenyloxide, 1,8-cineol, sedrill methyl ether, and ambroxane (3α, 6,6,9α-tetramethyldodecahydronaphtho [2]. , 1-b] furan), ethoxymethylcyclododecyl ether (Boisambrenforte, manufactured by Kao Co., Ltd.), etc. Examples of the nitrogen-containing compound-based fragrance component include geranylnitrile, citronellylnitrile, indol, and acetylsedrene. , Methyl anthranilate, Methyl N-methylanthranilate, auranthial, peonyl (manufactured by Dibodan) and the like.
The fragrance component and a combination thereof may be added to the softener composition of the present invention as a composition mixed with a component called a fixative such as dipropylene glycol.
Further, the softener composition of the present invention may be used in combination with the silicic acid ester described in JP2013-231242 and JP2009-256818 as a fragrance component for the purpose of enhancing the residual fragrance of the textile product. It is possible to use a fragrance containing microcapsules that can be obtained from a specific fragrance maker or the like.

The antioxidant is, for example, an antioxidant having a phenol group in the molecule. Antioxidants having a phenolic group in the molecule are used to suppress changes in the odor of fragrances. When an antioxidant is used in combination with a fragrance, the change in odor can be suppressed, but since the antioxidant having an oxidized phenol group is colored, the discoloration of the softener composition is promoted, so that the antioxidant is prevented. The blending amount of the agent should be carefully confirmed together with the fragrance component that is easily affected by oxidation and its content before use.

From the viewpoint of availability, the antioxidants having a phenol group in the molecule include 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol. And one or more selected from butylhydroxyanisole are preferable. From the viewpoint of suppressing discoloration, one or more antioxidants selected from 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are more preferable.

A monocarboxylic acid may be used in order to enhance the softening effect of the softener composition of the present invention as long as the effect of reducing the adhesiveness at the time of wetting is not impaired. The monocarboxylic acid is contained in a small amount in the decomposition product of the component (A) and the by-product of the component (A), but the softening effect can be enhanced by further adding the monocarboxylic acid.
Specific monocarboxylic acids include saturated or unsaturated fatty acids having 12 or more and 22 or less carbon atoms such as lauric acid, myristic acid, palmitoleic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, erucic acid, and behenic acid. One or more selected from can be used. Among these, one or more selected from palmitic acid, stearic acid, oleic acid, and linoleic acid are more preferable.

The chelating agent is used to suppress discoloration of the softener composition and fading of the dye. For example, ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, L-glutamic acid-N, N-diacetic acid, N-2- One or more selected from hydroxyethyliminodiacetic acid and salts thereof are preferable. The chelating agent can also be used as the acid agent.

Dyes are used to give consumers a high degree of palatability for fabric softener compositions. For example, one or more dyes selected from a color index acidic red dye, a color index acidic yellow dye, and a color index acidic blue dye.

Specific examples of the color index acidic red dye include CIAcid Red 18, CIAcid Red 27, CIAcid Red 52, CIAcid Red 82, CIAcid Red 114, CIAcid Red 138, CIAcid Red 186 and the like.
Specific examples of the color index acidic yellow dye include CIAcid Yellow 1, CIAcid Yellow 7, CIAcid Yellow 23, CIAcid Yellow 141 and the like.
Specific examples of the color index acidic blue dye include CIAcid Blue 5, CIAcid Blue 9, and CIAcid Blue 74.
Dyes available as polymer dyes can also be used.

When the dye is used in combination with a chelating agent, it is possible to suppress discoloration of the fragrance or the softener composition containing the fragrance and the antioxidant. From the viewpoint of suppressing discoloration, one or more dyes selected from the color index acidic red dye and the color index acidic yellow dye are preferable.

Preservatives are used to impart antiseptic properties to fabric softener compositions. Also called antibacterial and antifungal agent. For example, a biguanide-based compound, an isothiazolin-based compound, an isothiazolinone-based compound and the like can be mentioned. Specific examples thereof include polyhexamethylene biguanide hydrochloride, 5-chloro-2-methyl-4-isothiazolin-3-one, and 1,2-benzisothiazolin-3-one. "Proxel IB", "Caisson CG", "Proxel BDN" and the like can also be used.

The rest of the softener composition of the present invention is water. As the water, it is preferable to use deionized water treated with hypochlorite. The softener composition of the present invention contains water, preferably 65% by mass or more, more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.

<pH of softener composition>
The pH of the softener composition of the present invention at 30 ° C. is preferably 2.5 or more, more preferably 3.0 or more, and preferably 4.5 or less, more preferably 4.0 or less. When the pH of the softener composition is within the above range, the fragrance and residual fragrance of the treated textile product are improved, and the storage stability of the softener composition is improved. The pH in the present specification is a value measured at 30 ° C. according to item 8.3 of JIS K 3362; 2008.
Examples of the method for adjusting the pH of the softener composition within the above range include a method of adjusting the pH with an alkaline agent and an acidic compound.

<Manufacturing method of softener composition>
The method for producing the softener composition of the present invention is not particularly limited, and for example, it can be produced by the following method.
First, for ion-exchanged water preferably at 40 ° C. or higher and 80 ° C. or lower, a nonionic surfactant as a component (E), a water-soluble organic solvent as a component (F), and a component (H) are required. The acidic compound is added and the aqueous solution is preferably heated to 50 ° C. or higher and 70 ° C. or lower.
Then, while stirring the obtained aqueous solution, a mixture of the quaternary ammonium salt as the component (A), the ester compound as the component (B), and if necessary, a fragrance and other components are added, preferably 50. The mixture is stirred for about 5 minutes or more and 1 hour or less while heating to 70 ° C. or higher, and further, if necessary, a water-soluble inorganic salt as a component (G) is added and stirred. When the component (A) is added to the aqueous solution, it is preferable to melt the component (A) in advance, preferably at 50 ° C. or higher and 70 ° C. or lower, from the viewpoint of uniform mixing. When the component (D) is contained, an aliphatic alcohol is added to this aqueous solution and further stirred.
Then, the aqueous solution is cooled with stirring so as to be preferably 15 ° C. or higher and 35 ° C. or lower. After cooling, the silicone compound as the component (C) and ion-exchanged water are added as necessary for the purpose of adjusting the concentration, and the mixture is preferably stirred at 15 ° C. or higher and 35 ° C. or lower for 5 minutes or longer and 1 hour or shorter. The softener composition of the present invention can be obtained.
The pH of the softener composition can be adjusted by using an aqueous hydrochloric acid solution, an aqueous solution of sodium hydroxide, or the like, if necessary.

The softener composition of the present invention is suitable for textile products. Textile products include clothing, bedding, towels and the like.
When the softener composition of the present invention is used as a softener composition for treating a textile product, a treatment method in which the softener composition of the present invention is brought into contact with the textile product using water as a medium is preferable, and specifically, drying. It is preferable that 1.0 kg of the textile product at the time is brought into contact with an aqueous solution prepared by dissolving 5 ml or more and 40 ml or less of the softener composition of the present invention. In this case, the textile product needs to be sufficiently immersed in tap water, and is preferably used as a bath ratio [textile product (kg) / treatment liquid (L)] of 5 or more and 40 or less.
The dried clothing may be dipped in an aqueous solution obtained by diluting the softener composition of the present invention, or may be added in the finishing step at the time of rinsing in the washing step. In that case, by dehydrating and drying, it is possible to obtain a textile product having flexibility and odor standing property at the time of moisture absorption.

<Synthesis Example 1: Synthesis of (A-1)>
A fatty acid having an acid value of 206.9 mgKOH / g made from palm oil and triethanolamine are subjected to a dehydration condensation reaction at a reaction molar ratio of 1.65 / 1 (fatty acid / triethanolamine) to form N, N-. A condensate containing dialkanoyloxyethyl-N-hydroxyethylamine as a main component was obtained.
Next, the amine value of this condensate was measured, and 0.95 equivalent of dimethyl sulfate was used for the condensate to perform quaternary conversion, and N, N-dialkanoyloxyethyl-N-hydroxyethyl-N- Methylammonium A quaternary ammonium salt mixture containing methyl sulfate as a main component and ethanol in an amount of 10% by mass was obtained (hereinafter referred to as (A-1)). The alkanoyl group contained in this mixture is a residue of a fatty acid derived from palm oil, and the term "alkanoyl" here also means a residue derived from an unsaturated fatty acid, for example, alkenoyl, in addition to the saturated fatty acid. It shall include. The preparation procedure and reaction conditions were carried out according to Synthesis Example 2 of JP-A-2010-209493.

In the quaternary ammonium salt of the component (A) contained in (A-1), the ratio of the component (a1) is 30% by mass, the ratio of the component (a2) is 55% by mass, and the ratio of the component (a3) is 15% by mass. %Met. (A-1) has a quaternization rate of 92% by mass, and is a tertiary amine compound having a diester structure and a triester structure in addition to the component (a1), the component (a2), the component (a3), and ethanol. , A trace amount of triethanolamine and its quaternary compound, and a trace amount of fatty acid. Here, the analysis of the component (a1), the component (a2) and the component (a3), and the other components was measured by the following conditions using HPLC.
<HPLC conditions>
Column: Inertsil NH2 5 μm (4.6 × 250 mm) Room temperature mobile phase: 0.05% TFA (trifluoroacetic acid) hexane solution: Methanol: THF (tetrahydrofuran) = 85:10: 5
Flow rate: 0.8 mL (0-10 minutes) -1.2 mL (10-55 minutes) -0.8 mL (55-60 minutes)
Injection: 20 μL
Detection: CAD

<Synthesis Example 2: Synthesis of (B-1)>
180 g of pentaerythritol, 565 g of stearic acid (1.5 mol of fatty acid for 1 mol of pentaerythritol), and 0.27 g of NaOH were placed in a four-necked flask. The four-necked flask was heated while introducing nitrogen gas, and the reaction was carried out at 235 ° C. for 5 hours while removing the water produced by the reaction. After confirming that the acid value of the reaction product was 1 mgKOH / g or less, the mixture was cooled to 70 ° C., and the precipitated unreacted pentaerythritol was removed by pressure filtration at the same temperature to obtain (B-1). rice field.
The obtained (B-1) is a mixture of pentaerythritol fatty acid esters, and the ratio of each ester compound is 29% by mass of fatty acid monoester, 43% by mass of fatty acid diester, 23% by mass of fatty acid triester, and 5 by mass of fatty acid tetraester. It was% by mass. The proportions of the fatty acid monoester, fatty acid diester, fatty acid triester, and fatty acid tetraester structure were measured under the following conditions using a high-speed GPC device HCL-8220GPC (manufactured by Tosoh Corporation).
<GPC conditions>
Column: TSKgel G1000HXL + G2000HXL (series connection)
Mobile phase: THF (tetrahydrofuran)
Flow velocity: 0.7 ml / min
Temperature: 25 ° C
Detector: RI
Sample concentration and injection volume: 1% THF solution, 20 μl

<Ingredient (A)>
(A-1): A reaction product containing the quaternary ammonium salt mixture produced in Synthesis Example 1. The numerical value of (A-1) shown in Tables 2 and 3 is the compounding amount of (A-1) as it is. The concentration of the component (A) in (A-1) is 75% by mass.

<Ingredient (B)>
(B-1): Reaction product containing the pentaerythritol fatty acid ester (b1) mixture produced in Synthesis Example 2 (B-2): Leodor SP-S10V (sorbitan monostearate, AV = 7 mgKOH / g, SV = 155 mgKOH / g, manufactured by Kao Corporation), sorbitan fatty acid ester (b2)
(B'-1): Exepearl TGO (2-ethylhexanoic acid triglyceride, AV = 0.1 mgKOH / g, ester value = 360 mgKOH / g, manufactured by Kao Corporation)

<Ingredient (C)>
(C-1): Low molecular weight silicone emulsion ^{60% by mass of dimethylpolysiloxane having a dynamic viscosity of 300 mm 2} / s at 25 ° C. and 1.5% by mass of polyoxyethylene lauryl ether having an average addition mole number of 5 mol of oxyethylene groups. , 4.5% by mass of polyoxyethylene lauryl ether with an average addition mole number of 23 mol, 0.1% by mass of sodium lauryl sulfate, and an emulsion of water residue.
(C-2): Low molecular weight silicone emulsion ^{60% by mass of dimethylpolysiloxane having a dynamic viscosity of 2,000 mm 2} / s at 25 ° C., and polyoxyethylene lauryl ether 1.5 having an average addition mole number of 5 moles of oxyethylene groups. Polyoxyethylene lauryl ether 4.5% by weight, sodium lauryl sulfate 0.1% by weight, water residue emulsion (C'-1): high molecular weight silicone emulsion dynamic at 25 ° C. 60% by mass of dimethylpolysiloxane having a viscosity of more than 100,000 mm ² / s, 1.5% by mass of polyoxyethylene lauryl ether having an average added mole of 5 mol of oxyethylene groups, and polyoxyethylene lauryl having an average added mole of 23 mol. Emulsion of 4.5% by weight ether, 0.1% by weight sodium lauryl sulfate, water residue.
The dynamic viscosity of silicone was measured at 25 ° C. using an Ubbelohde viscometer.

The above compounds (C-1), (C-2) and (C'-1) were produced by a known method or the method described in JP-A-11-229273.
The numerical value of the blending amount of the component (C) shown in Tables 2 and 3 is the net silicone concentration, and the content of the surfactant used in the emulsion is omitted in the table, but strictly speaking, the composition. It is contained in a small amount in the thing.

<(D) component>
(D-1): Cetyl alcohol <(E) component>
(E-1): Polyoxyethylene lauryl ether <(F) component> in which the average number of moles of oxyethylene groups added is 30 mol.
(F-1) Ethylene glycol <(G) component>
(G-1) Calcium chloride <(H) component>
(H-1) Citric acid

<(I) component>
(I-1): The fragrance composition shown in Table 1.
(I-2): Microcapsule fragrance synthesized in JP-A-2015-20048, Production Example 3 of Examples <Other components>
Other Additives: Proxel BDN (concentration of 83 ppm in the compositions of Examples and Comparative Examples)

Examples 1-6 and Comparative Examples 1-7
The softener composition having the composition shown in Tables 2 and 3 was prepared by the following method. The obtained softener composition was evaluated for elasticity, bulkiness, tightness, and adhesiveness when wet as described below. The results are shown in Tables 2 and 3.

<Preparation of softener composition>
In a 300 mL glass beaker (inner diameter 7 cm, height 11 cm), an amount of ion-exchanged water (65 ° C.) and (E) component corresponding to 95% of the amount required for the finished mass of the softener composition to reach 300 g. A nonionic surfactant, a water-soluble organic solvent as a component (F), and an acidic compound as a component (H) were added, and this beaker was heated in a water bath so that the content temperature became 65 ° C. ..
Next, a stirring blade (turbine type stirring blade, three blades, blade length 2 cm) mounted on a three-one motor (TYPE HEIDO 1200G manufactured by Shinto Kagaku Co., Ltd.) was installed at a height of 1 cm from the bottom surface of the beaker and rotated. A mixture of the quaternary ammonium salt as the component (A), the ester compound as the component (B), the fragrance as the component (I), and the fragrance as the component (I), which were previously melted and mixed at 65 ° C. while stirring at a frequency of 350 r / min. After adding the other components, the mixture was stirred at 350 r / min for 10 minutes under heating at 65 ° C., and further, the water-soluble inorganic salt as the component (G) was added and stirred for 10 minutes.
Then, the aliphatic alcohol as the component (D) was added, and the mixture was stirred at 350 r / min for 10 minutes under heating at 65 ° C. Then, the mixture was stirred and cooled at a rotation speed of 350 r / min until the contents reached 30 ° C. in a water bath containing ice water. After the content temperature has dropped to 30 ° C, the silicone compound as the component (C) and the amount of ion-exchanged water required for the concentration of each component to reach the values shown in Tables 2 and 3 are added, and the temperature is 30 ° C. The mixture was stirred at a rotation speed of 200 r / min for 10 minutes to obtain a softener composition.
The pH of the softener composition was adjusted to 3.5 using an aqueous hydrochloric acid solution or an aqueous sodium hydroxide solution, if necessary.

<Fiber treatment method>
Wash a commercially available cotton towel (Takei Towel Co., Ltd., # 3700) repeatedly with a commercially available liquid detergent "Attack Biogel" (Kao Corporation, registered trademark, manufactured in 2016) 5 times to remove the oil on the cloth. And dried. Inject 4.5 L of city water adjusted to 20 ° C into an electric bucket type washing machine (National, MiniMini, model number: NA-35), and add 10 g of the softener composition of Examples and Comparative Examples to 1.5 kg of cotton towel. The amount was added and the mixture was stirred for 1 minute. Then, two cotton towels were put in and stirred for another 5 minutes. A treated cloth was prepared by dehydrating in a dehydration tank of a two-tank washing machine for 5 minutes and drying in a room.

<Resilience evaluation>
The elasticity of the cotton towel treated with the softener composition having the composition shown in Tables 2 and 3 was compared with the elasticity of the cotton towel treated with Comparative Example 1 by 10 panelists. The elasticity values in Tables 2 and 3 represent the average value of 10 panelists. In this evaluation, it is preferable that the average score is 1.5 or more.
Evaluation criteria:
0: Less elastic than Comparative Example 1: Elasticity equivalent to Comparative Example 1 2: More elastic than Comparative Example 1

<Evaluation of bulkiness>
The cotton towels treated with the softener composition having the composition shown in Tables 2 and 3 were folded in eight, two sheets were stacked, and the thickness was measured. In this evaluation, the thickness is preferably 9.5 cm or more.

<Sit feeling evaluation>
The feeling of the cotton towel treated with the softener composition of the compositions shown in Tables 2 and 3 was compared with the feeling of the cotton towel treated with Comparative Example 1 by 10 panelists. The numerical values of the feeling of tightness in Tables 2 and 3 represent the average value of 10 panelists. In this evaluation, it is preferable that the average score is 1.5 or more.
Evaluation criteria:
0: No feeling of tightness compared to Comparative Example 1: 1: Same feeling of feeling as in Comparative Example 1: 2: Feeling of tightness compared to Comparative Example 1.

<Evaluation of adhesiveness when wet>
A cotton towel treated with the softener composition having the composition shown in Tables 2 and 3 was sprayed with water corresponding to 20% by mass of its own weight and acclimatized for 5 minutes to prepare a wet towel. The stickiness of the wet towel to the skin was compared with the stickiness of the cotton towel treated in Comparative Example 1 by 10 panelists. The adhesiveness values in Tables 2 and 3 represent the average value of 10 panelists. In this evaluation, it is preferable that the average score is 1.5 or more.
Evaluation criteria:
0: More adhesive than Comparative Example 1: Adhesive equivalent to Comparative Example 1: Less adhesive than Comparative Example 1

Claims (4)

The following component (A) is 5% by mass or more and 20% by mass or less, the following component (B) is 0.5% by mass or more and 10% by mass or less, the following component (C) is 0.7 % by mass or more and 3% by mass or less, and A softener composition containing water.
<Ingredient (A)>
Represented by the following formula (1), R ⁴ is an alkyl group having 1 or more and 3 or less carbon atoms, and R ¹ is a fatty acid residue (s) obtained by removing OH from a fatty acid having 16 or more and 22 or less carbon atoms. ² and R ³ are independent hydrogen atoms or fatty acid residues (s), respectively, in a mixture of quaternary ammonium salts where ^{X − is an organic or inorganic anion.}
The ^{compound (a1) in which R 1} is the fatty acid residue (s) and R ² and R ³ are hydrogen atoms is contained in an amount of 10% by mass or more 45 in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a2) in which R 1} and R ² are the fatty acid residues (s) and R ³ is a hydrogen atom is contained in an amount of 25% by mass or more in the total amount of the quaternary ammonium salt represented by the formula (1). Contains less than% by mass,
The ^{compound (a3) in which R 1} , R ² and R ³ are the fatty acid residues (s) is contained in an amount of 5% by mass or more and 40% by mass or less in the total amount of the quaternary ammonium salt represented by the formula (1). Mixture of quaternary ammonium salt

<Ingredient (B)>
Ester compound of a polyhydric alcohol having 3 or more and 6 or less carbon atoms and having a trivalent or more and 6 or less valence and a fatty acid having 12 or more and 22 or less carbon atoms <(C) component>
Silicone compounds of the dynamic viscosity of 100~ 2,200 ^mm 2 / s The softening agent composition according to claim 1, wherein the component (B) is at least one selected from a glycerin fatty acid ester, a pentaerythritol fatty acid ester, and a sorbitan fatty acid ester. The mass ratio of the component (A) to the component (B) [(A) / (B)] is 0.6 or more and 19 or less, and the mass ratio of the component (A) to the component (C) [ (A) / (C)] is 3 or more and 20 or less, according to claim 1 or 2. The softener composition according to any one of claims 1 to 3, wherein the component (C) is dimethylpolysiloxane.