KR20100065952A - Preparation method of fabric softeners - Google Patents

Abstract

PURPOSE: A manufacturing method of fabric conditioner with good conversion ratio of oil is provided to prevent production of wastewater of high concentration by applying transesterification in a manufacturing process while increasing the conversion rate of the oil. CONSTITUTION: A manufacturing method of fabric conditioner includes a step for gaining fatty acid hydroxyalkylamine ester by ester interchanging 3 class hydroxyalkylamine and vegetable or animal oil including fatty acid, and a step for gaining the fabric conditioner including ester quat of a chemical formula 1 - 3 by reacting the fatty acid hydroxyalkylamine ester with a quaternizing agent in a low molecular weight alcoholic solution. Each amount of addition of an alkali main catalyst and a sub-catalyst is 0.01-0.1% of the total weight of 3 class hydroxyalkylamine or the oil.

Description

Preparation method of fabric softener

The present invention relates to an improved method of making a fabric softener.

Fabric softener is a laundry aid used to soften the cloth after washing. It not only softens the fabric by making use of the fiber, but also helps to prevent static electricity and detergent residue by adsorbing cationic surfactant on the fiber. Do it.

Recently, as the price of fatty acid continues to rise, there is an economic problem that the manufacturing cost increases when fabricating softeners. To solve this problem, many studies have been conducted to prepare ester quart compounds through ester exchange by directly reacting oil with amine. In particular, a method of obtaining an ester quart directly by reacting an oil with an amine substituted with a hydroxy group has been mainly developed.

However, the method of preparing the cationic fiber softener directly from the oil has a high content of unconverted triglyceride oil, and the color of the fabric softener produced is not good. Strong alkali and boron hydride-based catalysts were used to prepare the compounds having improved.

Conventional techniques using the strong alkali catalyst are as follows.

In one embodiment of U.S. Patent No. 5,637,743, after partial transesterification reaction using sodium methylate as a catalyst on partially hydrogenated palm oil and triethanolamine, Quaternization with dimethylsulfate has been disclosed, and in another embodiment, hypophosphorous acid is used as a catalyst for a mixture of palm oil, dimethylaminopropylamine and triethanolamine. After the transesterification reaction, quaternization with dimethylsulfate was started.

U.S. Patent 5,869,716 discloses (1) oil and hydroxy in the presence of a catalyst selected from the group consisting of alkali metal boron hydride, alkali earth metal boron hydride and combinations thereof. Reacting a tertiary amine with functional groups; And (2) reacting the product produced in step (1) with a quaternizing agent.

In this patent, alkaline earth metal boron hydride, phosphoric acid as a catalyst to shorten the color and reaction time of the product in a method for producing ester quarts directly from natural fat or oil Or their alkaline earth metal salts, specifically, unsaturated whole or partially hydrogenated tallow or palm oil having an iodine value of 0 to 50, and diethanol methylamine, 1,2 Sodium borohydride and hypophosphorous acid as catalysts in the transesterification reaction of 1,2-dihydroxypropyl dimethylamine, triethanolamine and / or mixtures of these amines Alternatively, sodium hypophosphite was used in an amount of 0.05 wt% to 0.1 wt%, indicating a color improvement of the fabric softener.

US Patent Nos. 6,906,025 and 7,001,879 relate to softeners for use in automatic dryers and their use, in particular the softeners 20 to 80% of quaternary ammonium salts, mixtures containing glycerin and glyceryl esters 80 to 20 It is composed of%, and has a melting property at 30 ~ 65 ℃, it was disclosed that it can be used by coating on a substrate. More specifically, the softening agent was used by mixing sodium borohydride, or sodium borohydride and calcium hydroxide as a catalyst in the transesterification reaction of oil and amine in the form of triglycerides. However, since the method of the alkali / alkaline earth metal borohydride-based catalyst is a high price of 50,000 won / kg there is a problem of the cost increase in the preparation of the cationic fiber softener using the same.

In order to solve this problem, the present inventors are not only economical by combining an inexpensive alkali catalyst as a main catalyst and sodium hypophosphate as a subcatalyst instead of using an expensive boron hydride-based catalyst, and the color is improved over a conventional fabric softener. In addition, by reducing the oil content of the non-converted triglyceride form, a method of preparing a fabric softener having excellent conversion rate was developed and received a patent registration (Korea Patent No. 0861699). However, in the manufacturing method of the fabric softener, in spite of lowering the unit cost and improving the color of the fabric softener by using a low-cost catalyst, the color of the fabric softener, further improvement of the oil conversion rate in the manufacturing process, long-term There is a problem that still does not satisfy the market demand for the improvement of stability, the improvement of the fragrance of the fabric softener.

Therefore, the inventors of the present invention have been researching to develop a method for producing a fabric softener, which is not only economical but also improves the color of the fabric softener, oil conversion rate, and long-term stability. By using hypophosphorous acid or phosphorous acid instead of sodium hypophosphate, the conversion rate of oil in the form of color, unconverted triglycerides, which has been pointed out as a problem of conventional fabric softeners, can be improved more than two times, and long-term stability can be improved over one month on average. Further, the present invention was completed by finding a method of preparing a fabric softener that can greatly improve the fragrance of the fabric softener.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preparing a fabric softener having improved color, odor, long-term stability, and increased oil conversion, and a fabric softener prepared thereby.

In order to achieve the above object, the present invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and anhydrous sodium carbonate added at 0.01 to 0.1% of the sum of the weight of tertiary hydroxyalkylamine and vegetable or animal oil containing fatty acid. Vegetable or animal containing fatty acids under the main or mixed subcatalysts of hypophosphorous acid or phosphorous acid added at 0.01 to 0.1% of the sum of the weights of tertiary hydroxyalkylamines with an alkali main catalyst and Transesterifying the oil with the tertiary hydroxyalkylamine to obtain a fatty acid hydroxyalkylamine ester (step 1); And reacting the fatty acid hydroxyalkylamine ester obtained in step 1 with a quaternizing agent in a low molecular weight alcohol solvent to obtain a fibrous softener comprising an ester quart of Chemical Formulas 1 to 3 (step 2). Provided are methods for preparing an improved fabric softener.

The method of manufacturing the fabric softener according to the present invention further improves color, odor and long-term stability compared to the method of preparing the fabric softener, and further increases the conversion rate by reducing the content of unconverted triglyceride oil, as well as the manufacturing process. By applying the heavy ester exchange reaction, no reaction water is generated during the process compared to the conventional method of manufacturing the fabric softener which reacted the fatty acid and the amine, and as a result, it is possible to prevent the generation of high concentration of waste water in advance, which is very environmentally friendly. It can be usefully used for manufacturing.

In order to achieve the above object, the present invention,

Ester exchange of tertiary hydroxyalkylamines with vegetable or animal oils comprising fatty acids under a specific proportion of alkali main catalysts and hypophosphorous acid (H ₃ PO ₂ ) or phosphorous acid (H ₃ PO ₃ ) alone or in a mixed subcatalyst thereof Reacting to obtain a fatty acid hydroxyalkylamine ester (step 1); And

By using the alkali catalyst comprising the step (step 2) of reacting the fatty acid hydroxyalkylamine ester obtained in step 1 with a quaternizing agent in a low-molecular alcohol solvent to obtain a fiber softener comprising an ester quart of the formula (1) Provided are improved methods of making fabric softeners:

(In the formula 1,

R ₁ is a straight or branched chain alkyl group or alkenyl group having 6 to 22 carbon atoms, preferably 16 to 18 carbon atoms;

R ₂ and R ₃ is independently of each other hydrogen or R ₁ CO;

R ₄ is an alkyl group having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group;

m, n and p are integers from 0 to 12,

q is an integer from 1 to 12,

X represents halide, alkyl sulfate, alkyl phosphate.)

* (In Formula 2,

R ₁ , R ₂ , m, and n are as defined in Formula 1,

R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms.)

(In Chemical Formula 3,

R ₁ , R ₂ , R ₄ , m, and n are as defined in Formula 1,

R ₆ and R ₇ are each independently an alkyl group having 1 to 4 carbon atoms.)

Hereinafter, the present invention will be described in detail step by step.

First, step 1 is a step of transesterification of a tertiary hydroxyalkylamine with a vegetable or animal oil including a fatty acid under a specific ratio of an alkaline main catalyst and a hypophosphorous or phosphorous acid subcatalyst to obtain a fatty acid hydroxyalkylamine ester.

In the step 1 of the present invention, the vegetable or animal oil containing a fatty acid to be used as a raw material is a monoglyceride represented by the formula (4) or (5), a diglyceride represented by the formula (6) or (7) or a triglyceride represented by the formula (8) It consists of a mixture of forms of glycerides, mainly triglyceride forms.

The vegetable or animal oil including the fatty acid includes a fatty acid having a saturated or unsaturated hydrocarbon moiety represented by R ₈ , R ₉ , R ₁₀ , R ₁₁ , R _12, or R ₁₃ in the following Chemical Formulas _4-8 . In this case, the carbon number of the saturated or unsaturated hydrocarbon is preferably C ₆ to C ₂₂ , more preferably C ₁₆ to C ₁₈ :

(In Formula 4, R ₈ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms)

(In Formula 5, R ₈ is as defined in Formula 4)

(In Formula 6, R ₉ and R ₁₀ are independently a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms).

(In Formula 7, R ₉ and R ₁₀ are the same as defined in Formula 6)

(In Chemical Formula 8, R ₁₁ , R ₁₂ , And R ₁₃ are each independently a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms.)

At this time, the vegetable or animal oil including fatty acids used may be saturated or unsaturated bee tallow oil, palm oil, palm kernel oil, palm stearine oil, Palm olein oil, coconut oil, coconut oil, olive oil, rapeseed oil, sunflower oil, sunflower oil, cottonseed oil, soyabean oil ) And the degree of unsaturation of the vegetable or animal oil containing the fatty acid is preferably from 0 to 70. Herein, the degree of unsaturation is expressed in grams of iodine per 100 g of fatty acid, also referred to as iodine number.

The hydroxyl group of the tertiary hydroxyalkylamine used in step 1 according to the invention causes an ester exchange reaction with the fatty acids of the vegetable or animal oil. At this time, the tertiary amine used may be diethanol methylamine, 1,2-dihydroxypropyl dimethylamine, triethanolamine and the like.

In step 1 according to the present invention, the reaction molar ratio of fatty acids of vegetable or animal oils including tertiary hydroxyalkylamine and fatty acids is preferably 1: 1 to 2.7. If the reaction molar ratio of the fatty acid of the vegetable or animal oil including the tertiary hydroxyalkylamine and the fatty acid is less than 1: 1, the amount of fatty acid converted from the oil is relatively small, and as a result, the softening effect is lowered. In addition, when the reaction molar ratio exceeds 1: 2.7, the amount of triester in the fatty acid hydroxyalkylamine ester is relatively increased, resulting in a large amount of scum during emulsification.

In the present invention, the alkali catalyst is used as the main catalyst, for example, sodium hydroxide (potassium hydroxide), potassium hydroxide (calcium hydroxide), sodium carbonate anhydrous (sodium carbonate anhydrous) and the like to use Can be.

The addition amount of the alkali catalyst is preferably 0.01 to 0.1%, more preferably 0.01 to 0.05% of the sum of the weight of the vegetable or animal oil containing the fatty acid and the amine. If the amount of the alkali catalyst added is less than 0.01%, there is a problem that the content of unconverted triglyceride oil is high, and if it exceeds 0.1%, the color of the fabric softener is not good.

In addition, the subcatalyst is added to improve the color, smell and reactivity of the transesterification reaction, and the subcatalyst used herein may be used alone or in combination of the above-mentioned phosphoric acid or phosphorous acid. At this time, the amount of the subcatalyst added is preferably 0.01 to 0.1%, more preferably 0.05 to 0.1% of the sum of the weight of the vegetable or animal oil containing the fatty acid and the amine. If the added amount of the subcatalyst is less than 0.01%, there is a problem in the color of the fabric softener, if it exceeds 0.1% there is a problem of precipitation as a residue in the product and the problem of off-flavor.

The transesterification reaction of step 1 according to the present invention may be carried out preferably at 160 to 240 ℃, more preferably 160 to 220 ℃, the reaction time is preferably 1 to 12 hours, more preferably 3 It may be performed for ˜8 hours. If it is out of the above range may cause problems in the color and conversion rate of the product.

Performing step 1 according to the present invention results in the transesterification of the tertiary hydroxyalkylamine with the fatty acid moiety of the vegetable or animal oil to give a fatty acid hydroxyalkylamine ester, and the degree of performance of the transesterification reaction. Depending on this, the following residues may remain.

First, when all of the fatty acids in the oil are converted into fatty acid hydroxyalkylamine esters by tertiary hydroxyalkylamine and ester exchange reaction, glycerin of Formula 9 remains as a residue.

Next, when the fatty acid of the oil is partially converted to the fatty acid hydroxyalkylamine ester by the transesterification reaction with the tertiary hydroxyalkylamine, according to the number of fatty acids which remain unchanged in the oil, The glyceryl ester form of the compound remains as a residue.

(In Formula 10, R ₁₄ and R ₁₅ are each independently a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms.)

(In Chemical Formula 11, R ₁₄ and R ₁₅ are as defined in Chemical Formula 10.)

(In Formula 12, R ₁₆ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms independently of each other.)

(In Chemical Formula 13, R ₁₆ is as defined in Chemical Formula 12.)

Next, step 2 is a step of obtaining a fibrous softener comprising an ester quart by reacting the fatty acid hydroxyalkylamine ester obtained in step 1 with a quaternizing agent in a low molecular alcohol solvent.

The reaction molar ratio of the fatty acid hydroxyalkylamine ester and the quaternizing agent of step 2 according to the present invention is preferably 1: 0.9 to 1.0, and if the reaction molar ratio is less than 1: 0.9, the unreacted fatty acid hydroxyalkylamine ester Is relatively increased and scum occurs, and there is a problem in emulsification. If it exceeds 1: 1.0, there is a problem in that stability and color of the product are not good because the pH in the product is too low and the unreacted quaternizing agent remains.

The quaternizing agent used in step 2 according to the present invention includes alkyl halides such as methyl chloride; Dialkyl phosphates such as dimethyl sulfate and the like; It is preferable to use dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and the like.

The low molecular alcohol solvent used in step 2 according to the present invention may be used alone or mixed with isopropyl alcohol (isopropyl alcohol), ethanol (ethanol), propylene glycol (dipropylene glycol), dipropylene glycol and the like. .

The quaternization reaction of step 2 according to the present invention is preferably carried out at 50 ~ 80 ℃, more preferably 50 ~ 60 ℃, the reaction time is preferably 1 ~ 24 hours, more preferably 2 It may be performed for ˜8 hours.

Thereafter, the method may further include adding sodium chlorite and hydrogen peroxide to improve the color of the fabric softener. At this time, it is preferable that the addition amount of sodium chlorite and fruit water is 0.05 to 1.0% of the total weight. If the addition amount of the sodium chlorite and fruit tree is less than 0.05%, there is no color improving effect, and if it exceeds 1.0%, there is no further color improvement.

Finally, the preparation method according to the present invention using a specific ratio of an alkali catalyst (main catalyst), monophosphoric acid or phosphorous acid alone, or a mixture thereof (subcatalyst) is an ester quart (acyloxyalkyl of Formulas 1 to 3). Quaternary ammonium compound) 20 to 90% by weight and glycerin of Formula 9, glyceryl ester of Formula 10-13 or a mixture thereof 80 to 10% by weight can be provided.

It can be seen that the fabric softener prepared by the method according to the present invention improves the color and flavor of the fabric softener (see Tables 1 and 2) and exhibits excellent long-term stability when compared to the fabric softener prepared by the conventional method. (See Table 3).

In addition, since the catalyst used in the present invention is cheaper than the sodium borohydride catalyst conventionally used to exhibit the same color of the softener, it is very economical in terms of manufacturing cost. Therefore, the present invention can be usefully used to prepare a fabric softener.

Furthermore, the method of manufacturing the fabric softener according to the present invention does not generate any effluent during the reaction compared to the fabric softener reacting the fatty acid and the amine by applying an ester exchange reaction, thereby preventing the generation of high concentration wastewater in advance. It has the advantage of being very environmentally friendly in that it can be.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples. However, the following examples are merely to illustrate the present invention, but the content of the present invention is not limited by the following examples.

Example 1 Preparation of Fabric Softener 1

Step 1: transesterification

2,065 g of palm stearin oil in a 2-liter four-necked glass reactor equipped with a paddle type stirring device capable of controlling the rotational speed, a nitrogen supply device, a water removal cooler, and an electrothermal heating device capable of automatically controlling the temperature of the reaction system. 464.52 g of triethanolamine, 1.26 g of sodium hydroxide (0.05% of the total amount) and 2.53 g (0.1% of the total amount) of phosphoric acid were mixed and added with nitrogen microbubbles at the bottom of the reactor at a rate of 200-250 ml / min. Injected into. Thereafter, the speed of the reaction stirrer was fixed at 250 to 300 rpm, and the temperature of the reactant was raised to 120 ° C. for 1 hour to remove water included in the raw material, maintained at the temperature for 2 hours, and then heated to 190 ° C. After stirring for about 8 hours, the mixture was cooled to 65 ° C or lower to obtain a fatty acid hydroxyalkylamine ester.

Stage 2: Quaternization

130 g of isopropyl alcohol was added to 10% of the total amount of the fatty acid hydroxyalkylamine ester obtained in step 1, and the dry solid content was about 90%. Subsequently, 138.7 g of dimethyl sulfate, a quaternizing agent, was slowly dropped dropwise to prepare a fiber softener by performing a quaternization reaction at 50 to 60 ° C. for 2 hours.

Example 2 Preparation of Fabric Softener 2

Step 1: transesterification

A fatty acid hydroxyalkylamine ester was obtained in the same manner as in Step 1 of Example 1, except that 1.26 g of potassium hydroxide (0.05% of the total amount) was added to the reactor instead of sodium hydroxide.

Stage 2: Quaternization

Fabric softener was prepared in the same manner as in step 2 of Example 1.

Example 3 Preparation of Fabric Softener 3

Step 1: transesterification

A fatty acid hydroxyalkylamine ester was obtained by the same method as in step 1 of Example 1, except that 1.26 g of calcium hydroxide (0.05% of the total amount) was added to the reactor instead of sodium hydroxide.

Stage 2: Quaternization

Fabric softener was prepared in the same manner as in step 2 of Example 1.

Example 4 Preparation of Fabric Softener 4

Step 1: transesterification

A fatty acid hydroxyalkylamine ester was obtained in the same manner as in Step 1 of Example 1, except that 1.26 g of anhydrous sodium carbonate (0.05% of the total amount) was added to the reactor instead of sodium hydroxide.

Stage 2: Quaternization

Fabric softener was prepared in the same manner as in step 2 of Example 1.

Example 5 Preparation of Fabric Softener 5

Step 1: transesterification

A fatty acid hydroxyalkylamine ester was obtained in the same manner as in the step 1 of Example 1, except that 2.53 g (0.1% of the total amount) of phosphorous acid was added to the reactor.

Stage 2: Quaternization

Fabric softener was prepared in the same manner as in step 2 of Example 1.

<Comparative Example 1> Preparation of the fabric softener using subcatalysts other than the subcatalyst according to the present invention 1

A fibrous softener was prepared in the same manner as in Example 1, except that 0.1% of sodium hypophosphate was added instead of hypophosphoric acid as a subcatalyst.

Comparative Example 2 Preparation of Fabric Softener Using Subcatalysts Other Than the Subcatalyst According to the Present Invention 2

A fabric softener was prepared in the same manner as in Example 2, except that 0.1% of the total amount of sodium hypophosphate was added instead of the phosphoric acid as a subcatalyst.

<Comparative Example 3> Preparation of fabric softener using subcatalyst other than subcatalyst according to the present invention 3

A fibrous softener was prepared in the same manner as in Example 3, except that 0.1% of the total amount of sodium hypophosphate was added instead of the phosphoric acid as a subcatalyst.

<Comparative Example 4> Preparation of fabric softener using subcatalyst other than subcatalyst according to the present invention 4

A fibrous softener was prepared in the same manner as in Example 4, except that 0.1% of sodium hypophosphate was added instead of the phosphoric acid as a subcatalyst.

Comparative Example 5 Commercially Available Fabric Softener

A commercially available ester quart type softener (Ohsung Chemical Co., Ltd.) was used.

Experimental Example 1 Measurement of Color of Fabric Softener

The following experiments were performed to find out how the color of the fabric softener is improved when fabricating the fabric softener using a specific ratio of an alkali catalyst (main catalyst) and phosphoric acid or phosphorous acid (subcatalyst).

The color of the fatty acid hydroxyalkylamine ester produced after the transesterification reaction according to Examples 1 to 5 and Comparative Examples 1 to 4 was measured at 45 ° C. using a colorimeter (Lovibond Tintometer PFX195), and the color was measured. The results are shown in Table 1.

division Color Chart Example 1 1.0 Example 2 1.2 Example 3 1.1 Example 4 1.4 Example 5 1.0 Comparative Example 1 2.0 Comparative Example 2 2.1 Comparative Example 3 2.2 Comparative Example 4 2.2

As shown in Table 1, the fabric softeners of Examples 1 to 5 prepared by using a specific ratio of phosphoric acid or phosphorous acid as subcatalysts had a color of 1.0 to 1.4 Gardner. On the other hand, the fabric softeners of Comparative Examples 1 to 4 prepared by the same method as the conventional fabric softeners using sodium hypophosphate as the subcatalyst showed 2.0 to 2.2 Gardner, and thus the color of the fabric softeners of Examples 1 to 5 This is about twice as bright. In addition to the softness, the fabric softener has a bright color, so that the visual effect is very important, and the fabric softener prepared by the manufacturing method according to the present invention has an excellent effect to replace the conventional fabric softener. It can be seen.

Experimental Example 2 Measurement of Unconverted Triglyceride Oil Content

In order to determine the content of unconverted triglyceride oil in the fabrication of the fabric softener using a specific ratio of the alkali catalyst (main catalyst) and the phosphoric acid or the phosphorous acid (subcatalyst) according to the present invention, the following experiment was performed.

The unconverted triglyceride oil content after the ester exchange reaction according to Examples 1 to 5 and Comparative Examples 1 to 4 was measured using high performance liquid chromatography (HPLC, Shimadzu 20A series), and the measurement results are shown in Table 2. Indicated.

division Unconverted Triglyceride Oil Content (%) Example 1 2.0 Example 2 2.1 Example 3 2.2 Example 4 2.3 Example 5 2.2 Comparative Example 1 5.4 Comparative Example 2 5.8 Comparative Example 3 5.6 Comparative Example 4 5.6

As shown in Table 2, the fabric softeners of Examples 1 to 5 prepared by using a specific ratio of phosphoric acid or phosphorous acid as subcatalysts had an unconverted triglyceride oil content of 2.0 to 2.3%. . On the other hand, the fabric softeners of Comparative Examples 1 to 4 prepared by the same method as the conventional fabric softeners using sodium hypophosphate as the subcatalyst exhibited an unconverted oil content of 5.4 to 5.8%, and thus the fibers of Examples 1 to 5 It can be seen that the method of preparing the softening agent has improved reactivity about 50% or more compared to the conventional manufacturing method. From this it can be seen that the fabric softener produced by the production method according to the present invention is also very excellent in terms of reactivity.

Experimental Example 3 Measurement of pH, Viscosity, Odor and Long-term Stability

After preparing a fabric softener using a specific ratio of phosphoric acid or phosphorous acid as a subcatalyst, the following experiment was conducted to see how the pH, viscosity, odor and long-term stability of the emulsion were improved.

Fiber prepared according to Examples 1-5 and Comparative Examples 1-4 in a 500 ml, four-necked glass reactor equipped with a paddle type stirring device capable of controlling the rotational speed, an electrothermal heating device capable of automatically controlling the reaction system temperature 38 g of softener (7.6% of total amount), 443 g (88.6%) of water, 1 g (0.2%) of polyethyleneglycol lauryl ether, 0.1 g (0.02%) of calcium chloride and ethylene glycol 15 g (3%) of (ethylene glycol) was mixed.

At this time, the speed of the stirrer was fixed at 250-300 rpm, the temperature was raised to 50-60 ℃, and stirred for 1 hour. After stirring, the reaction solution was cooled to 30 ° C., 0.12% of dye (0.1 Soln.), 0.5% of fragrance, and a small amount of organic acid were added, followed by stirring for 30 minutes to prepare an emulsion. PH, viscosity, odor and long-term stability of the prepared emulsion were measured as follows.

(1) pH

The prepared emulsion was measured for pH using a pH meter (Orion model 310).

(2) viscosity

The viscosity of the prepared emulsion was measured at 25 ° C. using a viscometer (Brookfield LVDV II +).

(3) scent

In the prepared emulsions, Example 1, Example 5, and Comparative Example 1 were selected to have 10 panels in order to smell good, and the best of the three was scored as 3 points and the worst was 1 point. And the results are shown in Table 3 below. The higher the number, the better the smell.

division panel
One panel
2 panel
3 panel
4 panel
5 panel
6 panel
7 panel
8 panel
9 panel
10 Sum Example 1 3 3 2 2 2 3 3 3 3 3 27 Example 5 2 2 3 3 3 2 One 2 One 2 21 Comparative Example 1 One One One One One One 2 One 2 One 12

As shown in Table 3, the fabric softener prepared by mixing a specific ratio of the alkali catalyst according to the present invention with the phosphoric acid or the phosphorous acid as a subcatalyst has a better odor than the fabric softener of Comparative Example 1 using sodium hypophosphite as the subcatalyst. It can be seen that. From this, it can be seen that the method for preparing the fabric softener according to the present invention can be usefully used to prepare the fabric softener with improved odor.

(4) long-term stability

The prepared emulsion was placed in an oven at 45 ° C. and the date until separation of the emulsion occurred was measured in weeks, and the results are shown in Table 4 below.

division content(%)
pH

Viscosity
(cPs)

Long-term stability
(week) fiber
Softener Spices Calcium chloride Polyethylene Glycol Lauryl Ether dyes
(0.1% Soln.) water Example 1 7.6 0.5 0.02 0.2 0.12 88.6 2.6 126 28 Example 2 7.6 0.5 0.02 0.2 0.12 88.6 2.6 124 28 Example 3 7.6 0.5 0.02 0.2 0.12 88.6 2.5 124 28 Example 4 7.6 0.5 0.02 0.2 0.12 88.6 2.5 126 27 Example 5 7.6 0.5 0.02 0.2 0.12 88.6 2.5 126 27 Comparative Example 1 7.6 0.5 0.02 0.2 0.12 88.6 2.5 127 24 Comparative Example 2 7.6 0.5 0.02 0.2 0.12 88.6 2.4 125 25 Comparative Example 3 7.6 0.5 0.02 0.2 0.12 88.6 2.5 130 24 Comparative Example 4 7.6 0.5 0.02 0.2 0.12 88.6 2.5 126 23 Comparative Example 5 7.6 0.5 0.02 0.2 0.12 88.6 2.5 126 17

As shown in Table 4, a specific ratio of the alkaline catalyst according to the present invention and the fabric softener prepared using hypophosphorous acid or phosphorous acid as a subcatalyst showed no significant difference in terms of pH or viscosity, while long-term stability was 27 It can be seen that it shows excellent stability of ˜28 weeks. It can be seen that it is more than 10 to 11 weeks stable compared to the long-term stability (17 weeks) of Comparative Example 5 currently on the market. In addition, it can be seen that the stability was improved about 2 to 5 weeks as compared to Comparative Examples 1 to 4 using sodium hypophosphate as the subcatalyst. From this, it can be seen that the method of manufacturing the fabric softener according to the present invention can be usefully used to prepare the fabric softener having improved long-term stability.

Claims (17)

An alkali main catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and anhydrous sodium carbonate added at 0.01 to 0.1% of the sum of the weight of tertiary hydroxyalkylamine and vegetable or animal oil containing fatty acid, and containing fatty acid. Vegetable or animal oils comprising tertiary hydroxyalkylamine and tertiary hydroxyalkylamine containing fatty acids alone or in a mixed subcatalyst of phosphoric acid or phosphorous acid added at 0.01 to 0.1% of the sum of the weights of vegetable or animal oils and tertiary hydroxyalkylamines. Exchange reaction to obtain fatty acid hydroxyalkylamine ester (step 1); And By using the alkali catalyst comprising the step (step 2) of reacting the fatty acid hydroxyalkylamine ester obtained in step 1 with a quaternizing agent in a low-molecular alcohol solvent to obtain a fiber softener comprising an ester quart of the formula (1) Improved manufacturing method of fabric softener: <Formula 1>

(In the formula 1, R ₁ is a straight or branched chain alkyl group or alkenyl group having 6 to 22 carbon atoms; R ₂ and R ₃ is independently of each other hydrogen or R ₁ CO; R ₄ is an alkyl group having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group; m, n and p are integers from 0 to 12, q is an integer from 1 to 12, X represents halide, alkyl sulfate, alkyl phosphate) <Formula 2>

(In Formula 2, R ₁ , R ₂ , m and n are as defined in Formula 1, R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms) <Formula 3>

(In Chemical Formula 3, R ₁ , R ₂ , R ₄ , m and n are as defined in Formula 1, R ₆ and R ₇ are each independently an alkyl group having 1 to 4 carbon atoms). The method of claim 1, wherein R ₁ of Formula 1 is a straight or branched chain alkyl group or alkenyl group having 16 to 18 carbon atoms. According to claim 1, wherein the vegetable or animal oil comprising the fatty acid of step 1 comprises any one selected from the group consisting of mono-, di- and triglycerides represented by the formula 4 to 8 or a mixture thereof Method for producing an improved fabric softener using an alkali catalyst, characterized in that. <Formula 4>

(In Formula 4, R ₈ is a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms.) <Formula 5>

(In Chemical Formula 5, R ₈ is as defined in Chemical Formula 4.) <Formula 6>

(In Formula 6, R ₉ and R ₁₀ are independently a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms.) <Formula 7>

(In Chemical Formula 7, R ₉ and R ₁₀ are the same as defined in Chemical Formula 6.) <Formula 8>

(In Chemical Formula 8, R ₁₁ , R ₁₂ , And R ₁₃ are each independently a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms.) According to claim 3, wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ of the general formula _4-8 is independently a linear or branched alkyl or alkenyl group having 16 to 18 carbon atoms, characterized in that Method for producing an improved fabric softener using an alkali catalyst. According to claim 1, wherein the vegetable or animal oil comprising the fatty acid of step 1 is saturated or unsaturated Uji oil, palm oil, palm kernel oil, palm stearin oil, palm olein oil, coconut oil, olive oil, rapeseed oil, A process for producing an improved fibrous softener using an alkali catalyst, characterized in that any one selected from the group consisting of sunflower oil, cottonseed oil and soybean oil. The method of claim 1, wherein the tertiary hydroxyalkylamine of step 1 is any one selected from the group consisting of diethanol methylamine, 1,2-dihydroxypropyl dimethylamine and triethanolamine or a mixture thereof. An improved method for producing a fabric softener using an alkali catalyst. The method according to claim 1, wherein the reaction molar ratio of the tertiary hydroxyalkylamine of step 1 and the fatty acid of the vegetable or animal oil including fatty acids is 1: 1 to 2.7, the production of an improved fabric softener using an alkali catalyst Way. The improved fiber using an alkali catalyst according to claim 1, wherein the amount of the alkali main catalyst added in step 1 is 0.01 to 0.05% of the sum of the weights of the vegetable or animal oil including the fatty acid and the tertiary hydroxyalkylamine. Manufacturing method of softening agent. The alkali catalyst according to claim 1, wherein the addition amount of the hypophosphorous acid or phosphorous acid alone or a mixed subcatalyst thereof is 0.05-1.0% of the sum of the weight of the vegetable or animal oil including the fatty acid and the amine. Process for preparing improved fabric softeners. The method of claim 1, wherein the transesterification reaction of step 1 is carried out at 160 ~ 240 ℃ for 1 to 12 hours. The method according to claim 1, wherein the molar ratio of the fatty acid hydroxyalkylamine ester of the step 2 and the quaternizing agent is 1: 0.9 to 1.0. The method of claim 1, wherein the quaternizing agent of step 2 comprises an alkyl halide comprising methyl chloride; Dialkylsulfates, including dimethylsulfate; And a dialkyl carbonate comprising dimethyl carbonate and diethyl carbonate. The method of claim 1, wherein the low molecular alcohol is any one selected from the group consisting of isopropyl alcohol, ethanol, propylene glycol, dipropylene glycol, or a mixture thereof. . The method of claim 1, wherein the quaternization reaction of step 2 is carried out for 1 to 24 hours at 50 ~ 80 ℃. According to claim 1, wherein the improved fiber using an alkali catalyst characterized in that it further comprises the step of stirring by adding 0.05 ~ 1.0% of the total weight of the fabric softener, sodium chlorite and fruit tree to improve the color of the fabric softener Manufacturing method of softening agent. 20 to 90% by weight of the ester quarts of the formulas (1) to (3), the glycerin of the formula (9), the glyceryl ester of the formulas (10) to (13), or those prepared by the process according to any one of claims 1 to 15 Fabric softener comprising a mixture of 80 to 10% by weight. <Formula 9>

<Formula 10>

(In Formula 10, R ₁₄ and R ₁₅ are each independently a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms.) <Formula 11>

(In Chemical Formula 11, R ₁₄ and R ₁₅ are as defined in Chemical Formula 10.) <Formula 12>

(In Chemical Formula 12, R ₁₆ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms independently of each other.) <Formula 13>

(In Chemical Formula 13, R ₁₆ is as defined in Chemical Formula 12.) The fibrous softener according to claim 16, wherein R ₁₄ , R ₁₅ and R ₁₆ are each independently a linear or branched alkyl or alkenyl group having 16 to 18 carbon atoms.