KR101217737B1 - Fabric softener and preparation method thereof - Google Patents

Abstract

The present invention relates to a method for preparing a fabric softener and a fabric softener prepared by the present invention, and more particularly, a fiber containing an ester quart by transesterification of an oil and a tertiary hydroxyalkylamine under low temperature and high vacuum conditions. Method for producing a softening agent, by the manufacturing method according to the present invention can reduce the content of unconverted glycerin, glyceryl ester or mixtures thereof in the preparation of the fiber softener including the ester quart, excellent in long-term storage stability Softeners can be prepared.

Description

Fabric softener and its manufacturing method {FABRIC SOFTENER AND PREPARATION METHOD THEREOF}

The present invention relates to a method of preparing a fabric softener and a fabric softener prepared by the method, comprising the steps of preparing an ester quart by performing an ester exchange reaction and a quaternization reaction of an oil containing a fatty acid. The method of preparing the fabric softener according to the present invention has an advantage of low content of unconverted glycerin, glyceryl ester or a mixture thereof.

The fabric softener is a finishing agent for imparting flexibility to the fibers after washing, and generally provides an antistatic effect together with the effect of imparting flexibility to the fibers.

In the past, dimethyl dialkyl ammonium chloride (DDAC) was widely used as a fabric softener, but after the quaternary ammonium salt of amidoamine, imidazoline, and imidazoline esters, Fiber softeners including cationic surfactants prepared in ester quarter form by quaternizing ester compounds derived from tertiary amines are the most used worldwide.

However, since fatty acids used in the preparation of the fabric softener are expensive, recently, a method of manufacturing a fabric softener from vegetable oil by replacing expensive fatty acids for cost reduction has been developed.

As a method for preparing a fabric softener using oil, US Pat. No. 5,869,716 discloses a result of reacting a tertiary amine having a hydroxyl functional group with an oil in the presence of a catalyst such as boron hydride of an alkali metal or boron hydride of an alkaline earth metal. Disclosed is a method of preparing a fabric softener comprising reacting a product with a quaternizing agent. U.S. Pat.Nos. 6,906,025 and 7,001,879 also disclose methods for preparing fibrous softeners by transesterification of oils and amines in the form of triglycerides in the presence of sodium borohydride, or a catalyst of sodium borohydride and calcium hydroxide. However, the method of preparing the cationic fabric softener directly from the oil as in the above methods has a problem in that the oil content of the unconverted triglyceride form is high or the color of the fabric softener prepared is not good.

In this regard, a method of lowering the content of unconverted triglycerides and improving color using strong alkali and boron hydride catalysts has been proposed, but this method also has a high content of unreacted triglycerides and is poor in color and odor. There is a problem.

In addition, Patent Nos. 840499 and 861699 disclose a step of preparing an ester quart by transesterifying an oil and a tertiary amine under a high temperature nitrogen atmosphere in the presence of an alkali catalyst or a titanium alkoxide catalyst, followed by reaction with a quaternizing agent. Disclosed is a manufacturing method comprising a. However, the method has a disadvantage in that the solubility in the reactants is low, the reaction temperature is high, and the reaction time is long. In addition, since the stearic acid is added to the oil in the transesterification reaction under a high temperature nitrogen atmosphere or hydrogenated to the oil prior to the transesterification reaction, it is used in the form of a partially hydrogenated oil, and thus the color improving effect of the fabric softener is low. There is a problem that the oil content in the form of glycerin and unconverted glyceride is high. As a result, there is a problem that it is necessary to use a skin trouble and irritant bleaching agent after the reaction with the quaternizing agent to improve the color of the fabric softener.

In order to solve the problems of the prior art as described above, the present invention blocks the inflow of oxygen or air by performing a transesterification reaction under a low temperature and high vacuum, and removes glycerin to the outside of the reactor, and glycerin in the final material after the transesterification reaction and quaternization reaction And it is possible to reduce the content of glycerides, and an object of the present invention is to provide a method for producing a fiber softener comprising an ester quart, excellent in long-term storage stability.

Still another object of the present invention is to provide a fabric softener having a content of glycerin and glycerides of 5 wt% or less even by using the preparation method and without performing a separate glycerine and glyceride removal process.

The present invention, under the pressure conditions of 50mmHg or less, oil and tertiary hydroxyalkylamine containing fatty acids to perform the first ester exchange reaction at a temperature of 110 ℃ to 130 ℃, and heated up at 130 ℃ to 160 ℃ temperature Performing a second ester exchange reaction to prepare a fatty acid hydroxyalkylamine ester; And reacting the prepared fatty acid hydroxyalkylamine ester with a quaternizing agent in a solvent to prepare a fabric softener comprising an ester quart of formula (I):

[Formula 1]

In Formula 1,

A and B are each independently CH ₂ CH ₂ OH or CH ₂ CH ₂ OCR ₂ ,

R ₁ and R ₂ are each independently selected from the group consisting of C ₁₁ -C ₂₁ linear or branched alkyl groups, alkenyl groups, and combinations thereof.

The present invention also provides a fabric softener comprising the ester quart of Formula 1 prepared by the above method.

When the fabric softener including the ester quart is prepared by the production method according to the present invention, not only can the reaction time be significantly shortened by performing an ester exchange reaction using a catalyst having high solubility in the reactants at low temperature and high vacuum, It is possible to reduce the content of unconverted glycerin, glyceryl ester or a mixture thereof, and to prepare a fabric softener having excellent long-term storage stability.

Hereinafter, the present invention will be described in detail.

In general, when preparing a fiber softener comprising an ester quart, a fatty acid hydroxyalkylamine ester is produced as a result of the ester exchange reaction between the tertiary hydroxyalkylamine and the fatty acid portion of the oil, and at the same time, the ester exchange reaction is performed. Depending on the degree, by-products such as glycerin, glycerides or mixtures thereof are produced. Specifically, when the fatty acids of vegetable oils are all converted to fatty acid hydroxyalkylamine esters by transesterification with tertiary hydroxyalkylamines, some of the glycerin remains as a residue, and the fatty acids of vegetable oils are transesterified. When partially converted to the fatty acid hydroxyalkylamine ester by the reaction, depending on the number of fatty acids which are not converted and remain in the vegetable oil, compounds in the form of glyceryl ester such as triglyceride remain as residues.

In contrast, the present invention is a low-temperature high vacuum reaction during the ester exchange reaction for the preparation of ester quarts, reducing the residual of glycerin, glycerides or mixtures thereof, and excellent color improvement effect and long-term storage stability without skin trouble and irritant bleaching agent. In addition, to prepare a fabric softener that can improve the flexibility of the fiber.

The method for preparing a fabric softener according to the present invention comprises the steps of ester-exchanging an oil containing a fatty acid and a tertiary hydroxyalkylamine under low temperature and high vacuum conditions to prepare a fatty acid hydroxyalkylamine ester; And

Reacting the prepared fatty acid hydroxyalkylamine ester with a quaternizing agent in a low molecular weight alcohol solvent to prepare a fibrous softener comprising an ester quart.

In one embodiment of the present invention, the ester exchange reaction and the quaternization reaction can be performed in a closed reactor in which a vacuum pump and a glycerin storage tank are connected. For example, a closed reactor is connected to a glycerin reservoir through a pipe, a glycerin reservoir is connected to a vacuum pump, under certain conditions, the gaseous glycerin in the reactor is vented out of the reactor via a connected pipe, It is changed into a liquid phase while passing through to the connected glycerin reservoir. Under certain temperature and pressure conditions, glycerin is vaporized and discharged through a pipe connected to the reactor under low pressure. Considering the reactor temperature and pressure, it is preferable that the glycerin is discharged out of the reactor in the secondary reaction conditions during the transesterification reaction. Through this process, the content of glycerin and glyceride in the reactants is very low after the ester exchange reaction, and thus, the content of glycerin and glyceride in the final fabric softener is low, thereby obtaining an excellent fabric softener. In addition, the recovered glycerin can be used as a solvent in the quaternization reaction is more economical.

Hereinafter, the process will be described in detail for each step.

The transesterification is a step of transesterifying oil and tertiary hydroxyalkylamine to prepare a fatty acid hydroxy alkylamine ester. More specifically, under pressure conditions of 50 mmHg or less, oil and tertiary hydroxyalkylamine containing fatty acids are first transesterified at a temperature of 110 ° C. to 130 ° C., and heated to a secondary temperature at 130 ° C. to 160 ° C. The ester exchange reaction is carried out to produce fatty acid hydroxyalkylamine esters.

Preferably, the more fatty acids included in the oil can improve the flexibility of the fiber in the preparation of the ester quarter, triglycerides containing a lot of substituents in the form of fatty acids, for example palm oil, palm stearin oil, palm olein oil, Use coconut oil, olive oil or soybean oil.

In addition, as the tertiary hydroxyalkylamine that can be used in the present invention, diethanol methylamine, 1,2-dihydroxypropyl dimethylamine, triethanolamine, and the like can be used. It can be mixed and used.

The vegetable oil and the tertiary hydroxyalkylamine containing the fatty acid are preferably used in an amount such that the reaction molar ratio of the fatty acid of the vegetable oil and the tertiary hydroxyalkylamine is 1.5: 1-2.5: 1.

Moreover, as a catalyst which can be used by this invention, zinc oxide type catalysts, such as titanium oxide type catalyst zinc oxide, such as sodium alkoxide type catalyst titanium oxide, such as sodium methoxide, sodium ethoxide, sodium propoxide, or sodium butoxide; Alkali catalysts, such as silica sodium hydroxide, potassium hydroxide, calcium hydroxide, and anhydrous sodium carbonate, sodium hypophosphate, etc. can be used, Among these, it can be used individually by 1 type or in mixture of 2 or more types.

Among them, it is eco-friendly, non-toxic to human body, and excellent in reactivity, so that it can be hydrolyzed quickly by forming a small amount of water in air or solvent, and it forms a highly active photocatalyst such as titanium oxide by relatively low temperature heat drying. In addition, it is preferable to use a titanium oxide catalyst or a zinc oxide catalyst because it can add a function of the photocatalyst such as antibacterial function and odor removal to the fabric softener using the same. More preferably, the catalyst may include one or more main catalysts selected from the group consisting of sodium alkoxide-based catalysts, titanium oxide-based catalysts, zinc oxide-based catalysts, silicas, and alkali catalysts, and sodium hypophosphite subcatalysts. .

The catalyst is preferably used in an amount of 0.03-0.1 parts by weight based on a total of 100 parts by weight of the oil containing the fatty acid and the tertiary hydroxyalkylamine.

In addition, it is preferable to use an alkali catalyst and sodium hypophosphate in an amount of 0.03-0.1 parts by weight based on 100 parts by weight of a total of 100 parts by weight of the oil containing the fatty acid and the tertiary hydroxyalkylamine in the ester exchange reaction. .

The transesterification reaction may be carried out for 3 to 10 hours at a temperature range of less than 110 ℃ to 130 ℃ the first transesterification reaction, the second transesterification reaction may be carried out for 1 to 13 hours at 130 ℃ to 160 ℃ temperature have. More specifically, when the transesterification reaction proceeds without a catalyst, the first transesterification reaction is preferably performed for 6-10 hours and the second transesterification reaction for 5-13 hours, and in the case of using a catalyst The first exchange reaction can be performed for 3-7 hours and the second ester exchange reaction for 5-13 hours.

In addition, the pressure condition of the transesterification reaction is 0-50mmHg, preferably the pressure of the secondary transesterification reaction is lower than the pressure of the first transesterification reaction. If the reaction pressure of the second ester exchange reaction is lower than that of the first ester exchange reaction, the glycerin can be recovered more advantageously. For example, the pressure of the primary ester exchange reaction of the present invention is 10 to 50 mmHg, more preferably 10 to 20 mmHg, and the pressure of the secondary ester exchange reaction is 0 to 10 mmHg, more preferably 0 to 5 mmHg. If the temperature range and the vacuum pressure range is exceeded, a large amount of unconverted glycerin oil may be contained, resulting in poor color and a problem of deteriorating long-term stability.

In the first ester exchange reaction, the reaction temperature may be increased to convert the secondary ester exchange reaction to a time point at which 70% or more of the oil is converted into a reactant, and the conversion rate of the oil may be generated. It can be carried out by measuring. For example, when 70% of the oil is converted to the reactant, the content of glycerin produced may be 5-7 parts by weight based on 100 parts by weight of the first injected oil. In addition, the end point of the second ester exchange reaction may also be performed at the time when the oil is converted to a reactant of 98% or more, and the conversion of the oil may be performed by measuring the amount of glycerin produced. For example, when 98% of the oil is converted to the reactant, the amount of glycerin produced may be 0.01 to 2 parts by weight based on 100 parts by weight of the first injected oil.

The method of preparing the fabric softener according to the present invention has an advantage of low content of unconverted glycerin, glyceryl ester or a mixture thereof. Specifically, the content of one or more substances selected from the group consisting of the following glycerin according to the present invention and a glyceride represented by Formulas 2 to 6 is 0.001 to 5% by weight.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

In Formulas 2 to 6, R3 to R8 are each independently a C ₁₁ -C ₂₁ linear or branched alkyl group or alkenyl group.

The quaternization reaction is a step of obtaining a fibrous softener containing an ester quart by reacting the fatty acid hydroxyalkylamine ester obtained in the ester exchange reaction with a quaternizing agent in a low molecular alcohol solvent.

Quaternizing agents usable in the present invention include alkyl halides such as methyl chloride; Dialkyl phosphates such as dimethyl sulfate and the like; Dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and the like can be used, and among them, one kind or a mixture of two or more kinds can be used.

The fatty acid hydroxyalkylamine ester and the quaternizing agent are preferably included in a reaction molar ratio of 1: 0.9-1: 1. If the reaction molar ratio is less than 1: 0.9, the unreacted alkylamine ester may increase and the emulsifying property may be lowered. If the molar ratio is more than 1: 1, unreacted quaternizing agent may remain in the product, May occur.

Low molecular alcohol solvents usable in the present invention include lower alcohols such as ethanol (ethyl alcohol), propyl alcohol, isopropyl alcohol, ethylene glycol (ethylene glycol), diethylene glycol of 1-6 C1-C6 alkylene glycol glycerin, such as (diethylene glycol), propylene glycol, and polyethylene glycol, etc. can be used, It can be used individually by 1 type or in mixture of 2 or more types. .

The low molecular alcohol solvent is preferably used at 5-30% by weight based on the total weight of fatty acid hydroxyalkylamine.

The quaternization reaction is preferably carried out at 35-50 ° C. for 3-10 hours, preferably at 45-50 ° C. for 3-6 hours.

By the manufacturing method as described above, it is possible to prepare a fabric softener comprising an ester quart of the formula (1):

[Formula 1]

In Formula 1,

A and B are each independently CH ₂ CH ₂ OH or CH ₂ CH ₂ OCR ₂ ,

R ₁ and R ₂ are each independently selected from the group consisting of C ₁₁ -C ₂₁ linear or branched alkyl groups, alkenyl groups, and combinations thereof.

In addition, the manufacturing method according to the present invention can reduce unconverted residues such as glycerin, glyceryl ester or a mixture thereof, and recycle the recovered glycerin as a solvent in the preparation of the fabric softener, Excellent storage stability, it is easy to manufacture a fabric softener that can further improve the flexibility of the fiber.

The present invention also provides a fabric softener comprising the ester quart of Chemical Formula 1 prepared by the above method.

The fabric softener preferably contains 5-20% by weight of the ester quart of Formula 1 and 2% by weight or less of glycerin, glyceryl ester or a mixture thereof.

 If the glycerin weight is higher than this, the color stability is lowered, there is a problem that the oil layer occurs when the fabric softener.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example 1: Production of a non-catalytic fabric softener

(1) Ester exchange reaction

The reactor used in the reaction was mixed with a stirrer, a vacuum pump, a thermometer, a condenser with a condenser, a collected four-neck closed glass reactor connected to a recovered glycerin reservoir and a distillation unit, and mixed with 350 g of palm stearin oil and 110 g of triethanolamine. The speed of the stirrer was fixed at 300-400 rpm and the vacuum apparatus was operated to raise the reactor pressure to 125 ° C. under 10 mmHg to remove the water and glycerin contained in the reaction mixture and to maintain the primary for 7 hours at this temperature. An ester exchange reaction was carried out.

The glycerin content in the reactor was continuously measured at 1 hour intervals. As a result of the measurement, when the glycerin content was 5.0 parts by weight (oil conversion rate 70%), the reaction was performed for 8 hours. The reaction was terminated when the content of glycerin was 1.0 parts by weight (oil conversion rate 98%) to 100 parts by weight of the first oil injected continuously measured in the course of the reaction, and cooled to 50 ° C. or lower to 440 g of fatty acid hydroxyalkylamine ester. 44 g of glycerin were obtained in a glycerin reservoir connected to the reactor.

The glycerin content was measured by GC analysis (TE90 carbon composition analysis. 0.2 g of the sample was added to a 100 ml separative funnel, and dissolved in 1 ml of pyridine. 0.2 ml of Hexamethyldisilazane (HMDS) and Trimethylchlorosilane (TMCS) were added to the reaction. and then added to 0.1ml, shaking the case, close the cap was left, n-Hexane was added to 10ml shake politics until the sound is a 10% NaCl aqueous solution Pyridine odor 4-5 times was washed with water. Hexane layer over anhydrous Na ₂ Dehydration and filtration with SO ₄ and GC analysis were performed under the following conditions.

Column: Non-polar Column 30m

Inlet Temperature: 300 ℃

Detector temperature: 320 ° C

Oven temperature: 100 占 폚? 10 占 폚 / min? 320 占 폚 占 8 min

(2) quaternization reaction

65 g of isopropyl alcohol was added to 440 g of the fatty acid hydroxyalkylamine ester obtained in step (1) to be 10% by weight of the total weight, so that the dry solid content was about 90% by weight. Subsequently, 90 g of the quaternizing agent, dimethyl sulfate, was slowly dropped dropwise and quaternized at 45-50 ° C. for 3 hours, and 40 g of recovered glycerin was added to prepare 635 g of a fiber softener including ester quart.

<Example 2>

Except for lowering the reactor pressure in the first ester exchange reaction step of Example 1 to 50mmHg in the second ester exchange reaction, the same method as in Example 1, 635g of a fabric softener containing an ester quart Prepared.

<Example 3>

In the method of Example 1, 0.7g of sodium methoxide (0.2% by weight of the total weight), 0.4g of sodium hypophosphate (0.09% by weight of the total weight) of the mixture was added as a catalyst in step _1_ to react Proceeded.

In the same manner as in Example 1, 635 g of a fabric softener including ester quart was prepared.

<Example 4>

Except for mixing 0.7 g of sodium hydroxide (0.2% by weight of total weight) and 0.4g of sodium hypophosphate (0.09% by weight of total weight) in the second ester exchange reaction in the ester exchange step of step 1 of Example 1 Then, in the same manner as in Example 1, 635 g of ester quart was prepared.

<Example 5>

Except for mixing 0.35 g of sodium methoxide (0.1 wt% of total weight) and 0.2 g of titanium oxide (0.045 wt% of total weight) in the second transesterification reaction in the ester exchange step of step 1 of Example 1 Then, in the same manner as in Example 1, 635 g of ester quart was prepared.

<Example 6>

In the ester exchange reaction step of the step 1 of Example 1, in the second ester exchange reaction, the same method as in Example 1, ethanol was added instead of isopropyl alcohol during the quaternization reaction, to prepare 635g of ester quart It was.

Comparative Example 1 Preparation of Fabric Softener by Nitrogen Reaction

(1) Ester exchange reaction

In a four-necked glass reactor equipped with a mechanical stirrer, nitrogen supply, thermometer, condenser and distillation unit, under nitrogen atmosphere, 591 g of palm stearin oil, 170 g of triethanolamine, 0.4 g of sodium hydroxide (0.05% by weight of total weight) and sodium hypophosphate 0.4 g (0.05% by weight of the total weight) was added and mixed, and then the speed of the stirrer was fixed at 300-400 rpm, the temperature of the reaction mixture was raised to 120 ° C, nitrogen was added, and maintained at the temperature for 5 hours. Then, the mixture was heated to 170 ° C. and reacted for 3 hours, and then cooled to 50 ° C. or lower to obtain a 761 g ester of fatty acid hydroxyalkylamine.

(2) quaternization reaction

102 g of isopropyl alcohol was added to the fatty acid hydroxyalkylamine ester obtained in the step (1) to be 10% by weight of the total weight, so that the solid content was about 90% by weight. Subsequently, 135 g of dimethyl sulfate, a quaternizing agent, was slowly dropped dropwise, and a quaternization reaction was performed at 50-60 ° C. for 2 hours, thereby preparing 998 g of ester quart.

Comparative Example 2 Preparation of Fabric Softener by High Temperature Nitrogen Reaction

In the first ester exchange step of Comparative Example 1, 591 g of palm stearin oil, 170 g of triethanolamine, 0.4 g of potassium hydroxide (0.05 wt% of total weight) and 0.4 g of sodium hypophosphate (0.05 wt% of total weight) were mixed. Except for the use, the same procedure as in Comparative Example 1 was carried out to prepare 998 g of a fabric softener including ester quart.

Comparative Example 3 Preparation of Fabric Softener by High Temperature Nitrogen Reaction

In the transesterification step of Comparative Example 1, 591 g of palm stearin oil, 170 g of triethanolamine, 0.2 g of sodium methoxide (0.03 wt% of total weight) and 0.4 g of sodium phosphate (0.05 wt% of total weight) Except that the mixture was used in the same manner as in Comparative Example 1, 998 g of a fabric softener including ester quart was prepared.

&Lt; Comparative Example 4 &

In the ester exchange step of step 1 of Example 1, the reactor pressure was raised to 125 ° C. under 10 mmHg to remove water and glycerin contained in the reaction mixture, and the reaction was performed for 20 hours at the same temperature. 635 g of the fabric softener including the ester quart was prepared by the method.

Experimental Example 1 Measurement of Color of Fabric Softener

In order to determine the color improving effect of the fabric softener according to the present invention, the color was measured and compared in the following manner.

The color (Gardner) of the fatty acid hydroxyalkylamine esters produced after the ester exchange reactions according to Examples 1-6 and Comparative Examples 1-4 was measured at 45 ° C. using a colorimeter (Lovibond Tintometer PFX195) and Gardner. The results are shown in Table 1 below.

division Colorener Example 1 1.8 Example 2 2.5 Example 3 1.5 Example 4 1.9 Example 5 1.7 Example 6 1.7 Comparative Example 1 3.5 Comparative Example 2 3.6 Comparative Example 3 3.0 Comparative Example 4 3.0

As shown in Table 1, the fabric softeners of Examples 1-6 prepared by the method according to the present invention showed a color of 1.2-1.8 Gardner (Gardner), it can be seen that it is suitable for use as a fabric softener without a bleaching agent. have. In contrast, the fabric softener of Comparative Example 1-4 prepared under a high temperature nitrogen atmosphere needs to be improved in color by adding a colorant, and it is difficult to avoid skin irritation and irritation caused by the addition of a colorant.

Experimental Example 2 Measurement of Glycerin and Unconverted Glyceride Content

In order to determine the content of glycerin and unconverted glyceride in the fabric softener according to the manufacturing method of the present invention, the experiment was carried out as follows. GC analysis was performed by (TE90 carbon composition analysis).

That is, 0.2 g of the sample was put in a 100 ml separative funnel, and 1 ml of Pyridine was added to dissolve it. 0.2 ml of Hexamethyldisilazane (HMDS) and 0.1 ml of Trimethylchlorosilane (TMCS) were added to the reaction mixture, the cap was closed and shaken vigorously, and after standing still, 10 ml of n-Hexane was added thereto, followed by shaking. Water was washed 4-10 times with 10% aqueous NaCl solution until no smell of Pyridine was obtained. The Hexane layer was dehydrated with anhydrous Na ₂ SO ₄ and filtered and GC analysis was performed under the following conditions.

Column: Non-polar Column 30m

Inlet Temperature: 300 ℃

Detector temperature: 320 ° C

Oven temperature: 100 ℃ → 10 ℃ / min → 320 ℃ × 8min

Glycerin and unconverted glyceride contents after the ester exchange reaction according to Examples 1-6 and Comparative Examples 1-4 were measured using gas chromatography (GC analysis). Glycerine and glyceride content results after the first ester exchange reaction and after the completion of the second ester exchange reaction of the examples are shown in Table 2 below.

(Unit: wt%) Ester
Exchange reaction Glycerin Content Monoglyceride content Diglyceride Content Triglyceride content Total amount Example 1 Stage 1 1.2 1.1 8.8 42.2 53.3 Step 2 0.5 1.0 0.8 0.4 2.7 Example 2 Stage 1 1.2 2.1 9.8 43.2 56.6 Step 2 1.0 1.3 1.5 1.0 4.8 Example 3 Stage 1 1.2 0.7 8.0 41.2 51.1 Step 2 0.3 1.0 0.6 0.2 2.1 Example 4 Stage 1 1.2 1.5 8.8 42.6 54.1 Step 2 0.5 1.0 0.9 0.5 2.9 Example 5 Stage 1 22 1.1 8.8 43.2 55.3 Step 2 0.5 1.0 0.8 0.6 2.9 Example 6 Stage 1 1.2 1.1 8.8 42.2 53.3 Step 2 0.5 1.0 0.8 0.4 2.7 Comparative Example 1 1.5 1.5 9.0 43.5 55.5 Comparative Example 2 1.5 1.5 9.0 45.0 57.0 Comparative Example 3 1.0 1.1 8.6 41.8 52.7 Comparative Example 4 1.2 1.1 8.8 42.2 53.3

As shown in Table 2, the fabric softeners of Examples 1-6 prepared by the method according to the present invention were 2.1 to 4.8% by weight of glycerin and unconverted glycerides, compared to 52.7% to 57.0% of Comparative Example 1. It was found that the conversion rate of glyceride was high. In addition, in the comparative example, the glycerin and glyceride content is high, so the oil component is high when preparing the fabric softener, so that the stability is not good.

Experimental Example 3 Test Evaluation of Fabric Softener

Fiber softener was prepared by adding 7% by weight to the ester quarter prepared in Example 1 and Comparative Example 1. The fabric softener prepared above was requested to the Korea Apparel Testing Institute to evaluate the following items.

Test Items What performance can you see in softeners?
Tribostatic Evaluate whether the softener treatment can reduce static electricity caused by friction of textile products.
KS K 0555 B method: 2005
Lecture test
(Drapability) The degree of flexibility, which is softer by the weight of the machine, is evaluated as being more stretched down, that is, numerically evaluating how flexible the textile product, which has been stiffened by washing, has been softened by the softening agent.
KS K 0815 6.21 e) -2008
Absorbency test Softener-treated fibers are tested to absorb water well, which is a good softener, although the fibers must be soft and absorb moisture.
KS K 0851 6.27.1 b-2008

Tactile testing The evaluation of the overall sensation that a person feels when touching a garment. The panel directly touches and evaluates how soft and soft the touch of textile products coarse by synthetic detergent can have by softener.
15 panelists touch and evaluate softener-treated specimens

Metric Comparative Example 1 Example 1 Solid content (%) 6.26 6.17
Frictional high voltage (V)
Cotton friction cloth 1800 1400 Fur friction cloth 3700 2700 Average 2750 2050 Lecture (Drape modulus) 0.482 0.465
Absorbency (mm) slope 39 41 Weft 37 38 Average 38 39.5 Tactile Test Results 2.2 1.1

Claims (14)

In a reactor with a pressure of 50 mmHg or less, the oil and tertiary hydroxyalkylamine containing fatty acid were subjected to a first ester exchange reaction at a temperature of 110 ° C to 130 ° C, and the temperature was increased to a second temperature at 130 ° C to 160 ° C. Performing an ester exchange reaction to prepare a fatty acid hydroxyalkylamine ester; And
Comprising the step of reacting the fatty acid hydroxyalkylamine ester with a quaternizing agent in a solvent to perform a quaternization reaction to produce an ester quart of the formula (1) comprising the step of preparing a fabric softener comprising the ester quart Manufacturing method of fabric softeners:
[Formula 1]

In Chemical Formula 1,
A and B are each independently CH ₂ CH ₂ OH or CH ₂ CH ₂ OCR ₂ ,
R ₁ and R ₂ are each independently a C ₁₁ -C ₂₁ linear or branched alkyl group or an alkenyl group.
The method of claim 1, wherein the reactor is a closed reactor in which a pressure reducing pump and a glycerin storage tank are connected. The method of claim 2, wherein the glycerin produced in the reaction is discharged out of the reactor to move to the glycerin storage tank. The method of claim 1, wherein the secondary transesterification is carried out at a lower pressure than the primary transesterification. The method of claim 1, wherein the elevated temperature after the first ester exchange reaction is carried out at the time when at least 70% of the oil is converted to the reactant. The method of claim 1, wherein the first ester exchange reaction is performed for 3 to 10 hours, and the second ester exchange reaction is performed for 1 to 13 hours. The method according to claim 1, wherein the fibrous softener is 0.001 to 5% by weight of at least one substance selected from the group consisting of the following glycerin and a glyceride represented by Formulas 2 to 6.
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Formulas 2 to 6, R3 to R8 are each independently a C ₁₁ -C ₂₁ linear or branched alkyl group or alkenyl group. The method of claim 1,
At least one catalyst selected from the group consisting of sodium alkoxide catalyst, titanium oxide catalyst, zinc oxide catalyst, silica, alkali catalyst, sodium hypophosphate, and mixtures thereof in the step of preparing the fatty acid hydroxyalkylamine ester Method for producing a fabric softener, characterized in that further use. 9. The method according to claim 8, wherein the catalyst is used in an amount of 0.01 to 0.1% by weight based on the total amount of the vegetable oil containing fatty acid and the tertiary hydroxyalkylamine. The method of claim 1, wherein the oil is selected from the group consisting of palm oil, palm stearin oil, palm olein oil, coconut oil, olive oil, soybean oil, and mixtures thereof. The fibrous softener according to claim 1, wherein the tertiary hydroxyalkylamine is selected from the group consisting of diethanolmethylamine, 1,2-dihydroxypropyl dimethylamine, triethanolamine, and mixtures thereof. Manufacturing method. The method of claim 1, wherein the solvent is selected from the group consisting of lower alcohols having 1 to 6 carbon atoms, alkylene glycols having 1 to 6 carbon atoms, glycerin, and mixtures thereof. The method of claim 12, wherein the glycerin is glycerin recovered in the transesterification reaction. A fabric softener prepared by the method according to any one of claims 1 to 13, comprising 20-90 wt% of ester quart of formula 1 and 0.001-5 wt% of glycerin, glyceryl ester or mixtures thereof.
[Formula 1]

In Chemical Formula 1,
A and B are each independently CH ₂ CH ₂ OH or CH ₂ CH ₂ OCR ₂ ,
R ₁ and R ₂ are each independently selected from the group consisting of C ₁₁ -C ₂₁ linear or branched alkyl groups, or alkenyl groups.