CN101353862B - Method of manufacturing fiber flexibile agent for improving flexibility of fiber - Google Patents

Method of manufacturing fiber flexibile agent for improving flexibility of fiber Download PDF

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Publication number
CN101353862B
CN101353862B CN2007101489000A CN200710148900A CN101353862B CN 101353862 B CN101353862 B CN 101353862B CN 2007101489000 A CN2007101489000 A CN 2007101489000A CN 200710148900 A CN200710148900 A CN 200710148900A CN 101353862 B CN101353862 B CN 101353862B
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chemical formula
oil
softening agent
mentioned
fibres
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CN101353862A (en
Inventor
秋长佑
郑甲相
赵钒济
李晋守
河炫朱
金炯权
刘殷相
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FIVE STAR CHEMICAL INDUSTRY Co Ltd
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FIVE STAR CHEMICAL INDUSTRY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Abstract

This invention refers to a preparation method of fabric softener for improving the fiber softness, including: processing an ester exchange reaction or esterification reaction to a stearic acid, a vegetable or animal oil containing fatty acid, a tertiary amine with hydroxyalkyl so as to obtain a amine fatty acid ester with hydroxyalkyl (step 1); reacting the amine fatty acid ester with hydroxyalkyl obtained the step 1 with a four-grading agent in the low-molecular alcohol solvent to obtain the fabric softener with quaternary ammonium compound containing ester (step 2). Compared with the fabric softener prepared through the method using oil, the color tone of the fabric softener prepared by utilizing the stearic acid of this invention is remarkably improved, and the amount of the oil not reacted is reduced. The softness of the fiber is remarkably improved especially the fabric softener is used in the fiber, and the fabric softener has excellent long-period stability, therefore, the preparation method of this invention can be suitable for preparing the fabric softener.

Description

Be used to improve the manufacturing approach of softening agent for fibres of the flexibility of fiber
Technical field
The present invention relates in the vegetalitas that comprises aliphatic acid or animality oil and the ester exchange reaction (transesterification) that contains hydroxyalkyl tertiary amine (hydroxyalkylamine), add stearic acid (stearic acid) and the manufacturing approach of the softening agent for fibres that flexibility improves is reached through containing ester quaternary ammonium compound (ester quaternary ammonium salt, esterquat) softening agent for fibres of 20～90 weight % and glycerine (glycerin), glyceride (glyceryl ester) or their mixture 80～10 weight % comprising of above-mentioned manufacturing approach manufacturing.
Background technology
Softening agent for fibres is as making the soft washing accessory agent of dress material after being used to wash; Not only can make the lines of fiber in order and make dress material soft; And can make fiber absorption cation interfacial active agent and give the function that prevents static, and help not stay the washing agent residue.
Recently; Along with the price of aliphatic acid rises steadily; Produced the problem of the manufacturing cost rising of softening agent for fibres; For addressing this problem, about making the directly reaction and to contain the research of ester quaternary ammonium compound through the ester exchange reaction manufacturing also very active of oil and amine, and what developed mainly is oil and hydroxyl replacement amine to be reacted and the method that directly obtains containing the ester quaternary ammonium compound.But,, still need develop the softening agent for fibres of the flexibility that can improve fiber for satisfying the consumer.
The prior art of the manufacturing of the relevant softening agent for fibres that utilizes above-mentioned oil is following.
Following method is disclosed in an embodiment of No. the 5637743rd, U.S.'s granted patent; Promptly; After using sodium methoxide (sodium methylate) to make to carry out ester exchange reaction in partially hydrogenated palm oil (partiallyhudrogenated palm oil) and the triethanolamine (triethanolamine) as catalyst, with its technology with dimethyl suflfate (dimethylsulfate) level Fourization; In another embodiment, disclose as catalyst and use hypophosphorous acid (hypophosphorous acid) to make the mixture of palm oil (palm oil) and dimethylaminopropylamine (dimethylaminopropylamine) and triethanolamine carry out after the ester exchange reaction technology with dimethyl suflfate (dimethylsulfate) enforcement level Fourization.
In No. the 5869716th, U.S.'s granted patent; The manufacturing approach that contains the ester quaternary ammonium compound of the step that comprises following (1) and (2) is disclosed: (1) be selected from alkali metal borohydride (alkali metalboron hydride), alkaline-earth metal boron hydride (alkali earth metal boron hydride) and by the catalyst in their group that constitutes in the presence of, the step that oil and the tertiary amine with hydroxyl are reacted; (2) make the product of generation in the above-mentioned steps (1) and the step that the level Four agent is reacted.
Disclosed directly the manufacturing by natural oil (natural fat) or oil contains in the method for ester quaternary ammonium compound in above-mentioned patent; Consider the tone of goods; And in order to shorten the reaction time; Alkaline-earth metal boron hydride, hypophosphorous acid or their alkali salt (alkali earthmetal salt) have been used as catalyst; Specifically; Making iodine number as degree of unsaturation is 0～50 all or partially hydrogenated butter or palm oil and diethanol methylamine (diethanol methylamine), 1; The mixture of 2-dihydroxypropyl dimethylamine (1,2-dihydroxypropyl dimethylamine), triethanolamine and/or these amine carries out in the process of ester exchange reaction, through use the tone that has improved softening agent for fibres about sodium borohydride (sodium borohydride) and hypophosphorous acid (hypophosphorous acid) or sodium hypophosphite (sodium hypophosphite) 0.05 weight %～0.1 weight % as catalyst.
In U.S.'s granted patent No. 6906025 and No. 7001879; Disclose and be used in softener of automatic drier and uses thereof; Specifically be; Above-mentioned softener is made up of ammonium salt 20～80%, the mixture 80～20% that comprises glycerine and glyceride, has 30～65 ℃ of character of fusing down, can be coated on the matrix and use.More specifically be when making above-mentioned softener, in the ester exchange reaction of the oil of triglycerides form and amine,, to have used the mixture of sodium borohydride or sodium borohydride and calcium hydroxide (calcium hydroxide) as catalyst.
But; Above-mentioned prior art promptly, is directly made the method for cationic fiber softener by oil; Owing to there is the high perhaps bad problem of tone of the softening agent for fibres of manufacturing of content of the oil of non-switched triglycerides form; Therefore, up to now, in order to reduce the content of not changing triglyceride oil and to improve tone and used highly basic and hydroboration series catalysts.Because up to 50000 yuan/kg, therefore, when using these to make the cationic fiber softener, there is the problem of cost rising in the price of above-mentioned alkali/alkaline earth metal hydroboration series catalysts.
In view of these problems; Use alkali major catalysts such as the inventor and sodium hypophosphite co-catalyst or alkoxytitanium owner catalyst and sodium hypophosphite help catalysis and have solved the problems referred to above; And then; In order to obtain than to study with the more outstanding fiber softening effect of the softening agent for fibres of said method manufacturing; The content of oil that the result finds can to obtain excellent color tone through in oil, adding stearic acid, do not change the triglycerides form is lower, the stability of hydrolysis and absorbability is high, yellowing property is few, softening agent for fibres that the flexibility of fiber is improved, has accomplished the present invention thus.
Summary of the invention
The objective of the invention is to, be provided for improving the manufacturing approach of the softening agent for fibres of fiber softening property, wherein, stearic acid has been used in combination in the vegetalitas that comprises aliphatic acid or animality oil and the ester exchange reaction that contains the hydroxyalkyl tertiary amine.
Another object of the present invention is to, provide and utilize the softening agent for fibres that contains ester quaternary ammonium compound 20～90 weight % and glycerine, glyceride or their mixture 80～10 weight % comprising of above-mentioned manufacturing approach manufacturing.
For achieving the above object, the manufacturing approach that is used to improve the softening agent for fibres of fiber softening property of the present invention comprises:
Step 1 under the condition that catalyst exists, makes stearic acid, comprises the vegetalitas or the animality oil of aliphatic acid and contains that the hydroxyalkyl tertiary amine carries out ester exchange reaction or esterification and the step that obtains containing the hydroxyalkyl amine fatty acid ester; And
Step 2, the hydroxyalkyl amine fatty acid ester that contains that will from above-mentioned steps 1, obtain reacts with the level Four agent in low molecular alcoholic solvents, obtains comprising more than one the step of the softening agent for fibres that contains the ester quaternary ammonium compound in following Chemical formula 1～3.
[Chemical formula 1]
Figure S2007101489000D00031
(in above-mentioned Chemical formula 1,
R 1Be that carbon number is 6～22 straight or branched alkyl or alkenyl, preferred carbon number is 16～18;
R 2And R 3Separate, be hydrogen or R 1CO;
R 4Be that carbon number is 1～4 alkyl or (CH 2CH 2O) qThe H base;
M, n and p are 0～12 integers,
Q is 1～12 integer,
X representes halogen (halide), alkyl sulfate (alkyl sulfate), alkyl phosphoric acid root (alkylphosphate).)
[Chemical formula 2]
Figure S2007101489000D00041
(in above-mentioned Chemical formula 2,
R 1, R 2, m and n with in above-mentioned Chemical formula 1, define identical,
R 5And R 6Separate, be that carbon number is 1～4 alkyl.)
[chemical formula 3]
(in above-mentioned chemical formula 3,
R 1, R 2, R 4, m and n with in above-mentioned Chemical formula 1, define identical,
R 6And R 7Separate, be that carbon number is 1～4 alkyl.)
The specific embodiment
Below, specify the present invention set by step.
At first, step 1 is under the condition that catalyst exists, to make stearic acid, comprise the vegetalitas or the animality oil of aliphatic acid and contain that the hydroxyalkyl tertiary amine carries out ester exchange reaction or esterification and the step that obtains containing the hydroxyalkyl amine fatty acid ester.
In above-mentioned steps 1 of the present invention, the form that the diglyceride of monoglyceride, chemical formula 6 or 7 expressions that vegetalitas of using as raw material that comprises aliphatic acid or animality oil form chemical formula 4 or 5 expressions or the triglyceride of chemical formula 8 expressions mix.
Above-mentioned vegetalitas that comprises aliphatic acid or animality oil comprise and have R in the following chemical formula 4～8 8, R 9, R 10, R 11, R 12, or R 13The aliphatic acid at shown saturated or unsaturated hydrocarbons position.Because the aliphatic acid that is contained in the oil is many more; When containing the ester quaternary ammonium compound, manufacturing can improve the flexibility of fiber more, therefore the above-mentioned vegetalitas of aliphatic acid or the oil that animality oil is preferably the substituent triglyceride form that contains more aliphatic acid form of comprising.At this moment, the preferred C of above-mentioned carbon number saturated or unsaturated hydrocarbons 6～C 22, more preferably C 16～C 18
[chemical formula 4]
Figure S2007101489000D00051
(in above-mentioned chemical formula 4, R 8Be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
[chemical formula 5]
Figure S2007101489000D00052
(in above-mentioned chemical formula 5, R 8With in above-mentioned chemical formula 4 definition identical.)
[chemical formula 6]
Figure S2007101489000D00061
(in above-mentioned chemical formula 6, R 9And R 10Separate, be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
[chemical formula 7]
Figure S2007101489000D00062
(in above-mentioned chemical formula 7, R 9And R 10With in above-mentioned chemical formula 6 definition identical.)
[chemical formula 8]
Figure S2007101489000D00063
(in above-mentioned chemical formula 8, R 11, R 12And R 13Separate, be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
As the employed plant oil that comprises aliphatic acid at this moment; Saturated or unsaturated palm oil (palm oil), palm-kernel oil (palmkernel oil), palm stearin oil (palm stearine oil), palm oil essential oil (palm olein oil), coconut oil (coconut oil), olive oil (olive oil), rape seed oil (rapeseed oil), sunflower oil (sunflower oil), cottonseed oil (cottonseed oil), soybean oil (soyabean oil), leprosy fruit oil (Jatropha oil) etc. can be used, saturated or unsaturated butter (beeftallow oil) etc. can be used as the animality oil that comprises aliphatic acid.Above-mentioned vegetalitas or the oily degree of unsaturation of animality that comprises aliphatic acid is preferably 0～150.Here, above-mentioned degree of unsaturation is shown with the g numerical table of the iodine amount of the every 100g aliphatic acid of correspondence, is called iodine number (iodine value).
The employed hydroxyl that contains the hydroxyalkyl tertiary amine in the above-mentioned steps 1 of the present invention can carry out ester exchange reaction and esterification simultaneously with the aliphatic acid and the stearic acid of above-mentioned vegetalitas or animality oil.Can use diethanol methylamine, 1,2-dihydroxypropyl dimethylamine, triethanolamine etc. as employed tertiary amine at this moment.
In above-mentioned steps 1 of the present invention, vegetalitas or the aliphatic acid in the animality oil that comprises aliphatic acid is preferably 1: 1 with the reaction mol ratio that contains the hydroxyalkyl tertiary amine～and 2.7.If above-mentioned vegetalitas that comprises aliphatic acid or the aliphatic acid in the animality oil are lower than 1: 1 with the reaction mol ratio that contains the hydroxyalkyl tertiary amine, then the amount by the aliphatic acid of oil conversion reduces relatively, its result, and soft effect can variation.In addition, if above-mentioned reaction mol ratio is higher than 1: 2.7, then the form of three ester compounds increases relatively in containing the hydroxyalkyl amine fatty acid ester, produces the problem of a large amount of scum silica frost (scum) in the time of can causing emulsification.
As employed stearic acid in the above-mentioned steps 1 of the present invention, can use the aliphatic acid of following chemical formula 9 expressions.
[chemical formula 9]
(in above-mentioned chemical formula 9, R 17Be that carbon number is 16～17 a straight chained alkyl.)
Above-mentioned stearic acid is, to the influential C of raising of the flexibility of fiber 18One of fatty acid that composition is many, its content in softening agent for fibres is high more, can improve the flexibility of fiber more.At this moment as above-mentioned stearic acid use preferably that acid number (acid value) is 195～216, saponification number (saponification value) is 196～216, iodine number as 2max, molecular weight is 259～288 stearic acid.
With regard to above-mentioned stearic addition, preferably with respect to all fatty acid compositions in the softening agent for fibres, stearine component (C 18) be 7.5～30%.If stearine component is lower than 7.5%; Then almost do not improve the effect of flexibility; If stearine component is higher than 30%, the long-time stability of emulsion are descended and causes the resolving time to shorten, and albinism take place when making emulsion and can not present the intrinsic tone of dyestuff.In addition, in the long-time stability of emulsion are estimated, along with the prolongation of the storage time in the thermostat, can produce a large amount of scum silica frost, the dispersed low-down problem when causing dissolving.
Employed in the present invention catalyst does not have special qualification, and base catalyst, sodium hypophosphite, alkoxytitanium series catalysts etc. are used in separately preferred or mixing.
In embodiments of the present invention, can use base catalyst as above-mentioned catalyst.At this moment; Above-mentioned base catalyst uses as major catalyst; For example can use NaOH (sodiumhydroxide), potassium hydroxide (potassium hydroxide), calcium hydroxide (calciumhydroxide), natrium carbonicum calcinatum (sodium carbonate anhydrous) etc.
0.01～0.1% of the gross weight of the preferred above-mentioned vegetalitas that comprises aliphatic acid of the addition of above-mentioned base catalyst or animality oil and amine more preferably adds 0.01～0.05%.If the addition of above-mentioned base catalyst is lower than 0.01%, then there is the problem of the content increase of not changing triglyceride oil, if be higher than 0.1%, then there is the bad problem of tone of softening agent for fibres.
In addition, in embodiments of the present invention, can use the alkoxytitanium series catalysts as above-mentioned catalyst.At this moment, can use as the alkoxytitanium series catalysts
Tetraethyl titanate (tetraethyl titanate),
Metatitanic acid four n-propyls (tetra-n-propyl titanate),
Tetraisopropyl titanate (tetraisopropyl titanate),
Tetra-n-butyl titanate (tetra-n-butyl titanate),
Metatitanic acid four (2-ethylhexyl) ester (tetra-2-ethylhexyl titanate),
Metatitanic acid four different monooctyl esters (tetraisooctyl titanate),
Octylene glycol titanate (octyleneglycol titanate),
Titanium acetylacetone (titanium acetylacetonate),
Triethanolamine titanate ester (triethanolamine titanate) etc.
Because these catalyst belong to environmentally friendly; To human non-toxic; And reactive good, only use just hydrolysis rapidly of moisture seldom in air or in the solvent, form hydroxide; Therefore can form the high-activity photocatalyst titanium oxide through the heat drying of lower temperature, can give the function that antibacterial functions, deodorization functions, self-cleaning effect photochemical catalysts such as (self-cleaningeffect) are held to the softening agent for fibres that uses these catalyst.
The addition of at this moment employed alkoxytitanium series catalysts be preferably the above-mentioned vegetalitas that comprises aliphatic acid or animality oil and amine gross weight 0.01～0.1%, more preferably add 0.01～0.05%.If above-mentioned catalytic amount be lower than the above-mentioned vegetalitas that comprises aliphatic acid or animality oil and amine the weight sum 0.01%, if be higher than 0.1%, then there is the bad problem of tone in the problem that then exists the content of not changing triglyceride oil to increase.
And then, for improving the tone and the reactivity of ester exchange reaction, can use sodium hypophosphite as co-catalyst.The addition of above-mentioned co-catalyst be preferably the above-mentioned vegetalitas that comprises aliphatic acid or animality oil and amine gross weight 0.01～0.1%, more preferably 0.05～0.1%.If the addition of above-mentioned sodium hypophosphite is lower than 0.01%, then there is the tone problem of softening agent for fibres, if be higher than 0.1%, then exist in the problem and generation peculiar smell problem separated out with residue in the goods.
The ester exchange reaction of above-mentioned steps 1 of the present invention is preferably carried out under 160～240 ℃, more preferably under 160～220 ℃, carries out preferred 1～12 hour of reaction time, more preferably 3～8 hours.If exceed above-mentioned scope, then can on the tone of goods and conversion ratio, have problems.
If the above-mentioned steps of embodiment of the present invention 1; Then through the above-mentioned ester exchange reaction that contains the fatty acid part of hydroxyalkyl tertiary amine and vegetalitas or animality oil; Can obtain containing the hydroxyalkyl amine fatty acid ester, according to the difference of carrying out degree of above-mentioned ester exchange reaction, might remaining following residue.
At first, the aliphatic acid of oil all with contain the hydroxyalkyl tertiary amine and carry out ester exchange reaction and all convert under the situation that contains the hydroxyalkyl amine fatty acid ester, the glycerine of following Chemical formula 10 is remaining with residue.
[Chemical formula 1 0]
Figure S2007101489000D00091
In addition; Part converts under the situation that contains the hydroxyalkyl amine fatty acid ester with containing that the hydroxyalkyl tertiary amine carries out ester exchange reaction at the aliphatic acid of oil; According to not changing the quantity that continues to stay the aliphatic acid in the oil, the compound of glyceride form that has following Chemical formula 1 1～14 is remaining with residue.
[Chemical formula 1 1]
Figure S2007101489000D00092
(in above-mentioned Chemical formula 11, R 14And R 15Separate, be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
[Chemical formula 1 2]
Figure S2007101489000D00101
(in above-mentioned Chemical formula 12, R 14And R 15With in above-mentioned Chemical formula 11 definition identical.)
[Chemical formula 1 3]
Figure S2007101489000D00102
(in above-mentioned Chemical formula 13, R 16Separate, be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
[Chemical formula 1 4]
Figure S2007101489000D00103
(in above-mentioned Chemical formula 14, R 16With in the above-mentioned Chemical formula 13 definition identical.)
Then, step 2 is that the hydroxyalkyl amine fatty acid ester that contains that from above-mentioned steps 1, obtains is reacted with the level Four agent in low molecular alcoholic solvents, obtains comprising the step of the softening agent for fibres that contains the ester quaternary ammonium compound.
The reaction mol ratio that contains hydroxyalkyl amine fatty acid ester and level Four agent of above-mentioned steps 2 of the present invention is preferably 1: 0.9～and 1.0; If above-mentioned reaction mol ratio is lower than 1: 0.9, then unreacted contains hydroxyalkyl amine fatty acid ester increase and generation scum silica frost relatively, and the emulsibility existing problems; If greater than 1: 1.0; Then the pH in the goods is low excessively, and the agent of remained unreacted level Four, therefore has the problem of the tone decline of stability and goods.
As employed level Four agent in above-mentioned steps 2 of the present invention, preferably use chloromethane alkyl halides (alkyl halide) such as (methyl chloride); Dimethyl suflfate sulfuric acid dialkyls (dialkyl phosphate) such as (dimethyl sulfate); Dimethyl carbonate (dimethyl carbonate), diethyl carbonate dialkyl carbonates such as (diethyl carbonate) (dialkyl carbonate) etc.
Employed low molecular alcoholic solvents in above-mentioned steps 2 of the present invention can separately or be mixed and used isopropyl alcohol (isopropyl alcohol), ethanol (ethanol), propylene glycol (propylene glycol), DPG (dipropylene glycol) etc.
The level Four reaction of above-mentioned steps 2 of the present invention is preferably carried out at 50～80 ℃, more preferably under 50～60 ℃, carries out, and the reaction time is preferably 1～24 hour, more preferably carries out 2～8 hours.
Afterwards, be the tone of the softening agent for fibres that improves manufacturing, can further comprise the step of adding sodium chlorite (sodium chlorite) and hydrogen peroxide (hydrogen peroxide) and stirring.At this moment, the addition of sodium chlorite and hydrogen peroxide is preferably 0.05～1.0% of all weight.If the addition of above-mentioned sodium chlorite and hydrogen peroxide is lower than 0.05%, then there is not tone to improve effect, if be higher than 1.0%, can not further improve tone.
In sum; According in oil, adding the manufacturing approach of the present invention that stearic acid uses, the glycerine that contains ester quaternary ammonium compound (acyloxy alkyl quaternary ammonium compound) 20～90 weight % and above-mentioned Chemical formula 10 that comprises above-mentioned Chemical formula 1～3, the glyceride of Chemical formula 1 1～14 or the softening agent for fibres of their mixture 80～10 weight % can be provided.
In oil, add the softening agent for fibres of stearic acid manufacturing according to the present invention; Compare with the existing softening agent for fibres of oily manufacturing that only uses; The long-time stability of the color harmony emulsion of softening agent for fibres are in equal above (with reference to table 1, table 3), and can improve the flexibility (with reference to table 2) of fiber; Thereby the present invention goes in the manufacturing of softening agent for fibres.
Below, specify the present invention according to embodiment and Test Example.But only illustration the present invention of following embodiment, content of the present invention is not limited to following embodiment.
The manufacturing 1 of stearic softening agent for fibres is added in < embodiment 1 >
(1) ester exchange reaction
To having slurry shape agitating device, the nitrogen feedway that to control rotary speed, dewater, can controlling automatically in the four-hole glass reaction container of 2L of electric heater unit of temperature of reaction system, mix and drop into palm stearin oil 541g, triethanolamine 169g, stearic acid 49g (stearine component (C with cooler 18): 10%), NaOH 0.4g (total amount 0.05%) and sodium hypophosphite 0.8g (total amount 0.1%), inject the nitrogen micro air bubble with the speed of 200～250ml/min to the bottom of above-mentioned reaction vessel.Afterwards; The speed of reaction stirrer is fixed as 250～300rpm; After 1 hour temperature with reactant is increased to 160 ℃ and the water removing in the raw material to be comprised, under said temperature, keeps 2 hours, be warming up to 190 ℃ of reactions 8 hours; Be cooled to again below 65 ℃, thereby obtained containing the hydroxyalkyl amine fatty acid ester.
(2) level Four reaction
Add isopropyl alcohol 102g to containing in the hydroxyalkyl amine fatty acid ester of from above-mentioned (1), obtaining with 10% amount of total amount, so that the amount of drying solid composition is about 90%.Afterwards, drop by drop slowly drip dimethyl suflfate 137g, under 50～60 ℃, carry out 2 hours level Four reaction and made softening agent for fibres as the level Four agent.
The manufacturing 2 of stearic softening agent for fibres is added in < embodiment 2 >
(1) ester exchange reaction
Except in above-mentioned reaction vessel, adding palm stearin oil 442g, triethanolamine 171g, stearic acid 152g (stearine component (C 18): 20%), to have obtained containing the hydroxyalkyl amine fatty acid ester with the identical method of method of embodiment 1 (1).
(2) level Four reaction
Add isopropyl alcohol 103g to containing in the hydroxyalkyl amine fatty acid ester of from above-mentioned (1), obtaining with 10% amount of total amount, so that the amount of drying solid composition is about 90%.Afterwards, drop by drop slowly drip dimethyl suflfate 139g, under 50～60 ℃, carry out 2 hours level Four reaction and made softening agent for fibres as the level Four agent.
The manufacturing 3 of stearic softening agent for fibres is added in < embodiment 3 >
(1) ester exchange reaction
Except in above-mentioned reaction vessel, adding palm stearin oil 340g, triethanolamine 172g, stearic acid 258g (stearine component (C 18): 30%), to have obtained containing the hydroxyalkyl amine fatty acid ester with the identical method of method of embodiment 1 (1).
(2) level Four reaction
Add isopropyl alcohol 103g to containing in the hydroxyalkyl amine fatty acid ester of from above-mentioned (1), obtaining with 10% amount of total amount, so that the amount of drying solid composition is about 90%.Afterwards, drop by drop slowly drip dimethyl suflfate 140g, under 50～60 ℃, carry out 2 hours level Four reaction and made softening agent for fibres as the level Four agent.
< comparative example 1>softening agent for fibres in the past
Used the softening agent for fibres of on market, selling now that contains ester quaternary ammonium compound type (five-pointed star chemical industry (strain)).
< comparative example 2>only uses the manufacturing of the softening agent for fibres of oil
(1) ester exchange reaction
Outside the oily 591g of the palm stearin of interpolation except that stearic acid, triethanolamine 170g, obtained containing the hydroxyalkyl amine fatty acid ester with the method identical with the method for embodiment 1.
(2) level Four reaction
Add isopropyl alcohol 102g to containing in the hydroxyalkyl amine fatty acid ester of from above-mentioned (1), obtaining with 10% amount of total amount, so that the amount of drying solid composition is about 90%.Afterwards, drop by drop slowly drip dimethyl suflfate 135g, under 50～60 ℃, carry out 2 hours level Four reaction and made softening agent for fibres as the level Four agent.
< comparative example 3>adds the manufacturing 4 of stearic softening agent for fibres
(1) ester exchange reaction
Except adding palm stearin oil 235g, triethanolamine 174g, stearic acid 367g (stearine component (C 18): 40%), obtained containing the hydroxyalkyl amine fatty acid ester with the method identical with the method for embodiment 1 so that stearic stearine component exceeds outside the scope of the present invention.
(2) level Four reaction
Add isopropyl alcohol 104g to containing in the hydroxyalkyl amine fatty acid ester of from above-mentioned (1), obtaining with 10% amount of total amount, so that the amount of drying solid composition is about 90%.Afterwards, drop by drop slowly drip dimethyl suflfate 141g, under 50～60 ℃, carry out 2 hours level Four reaction and made softening agent for fibres as the level Four agent.
The tone of < Test Example 1>softening agent for fibres is measured
How many tones of softening agent for fibres improved when in oil, to add stearic acid and make softening agent for fibres as the present invention in order to investigate, and carried out following test.
Utilizing colorimeter (Lovibond Tintometer PFX195) mensuration to carry out the tone that contains the hydroxyalkyl amine fatty acid ester (Gardner) that generates after the ester exchange reaction of embodiment 1～3 and comparative example 1～2 under 45 ℃, represented the said determination result with table 1.
[table 1]
Figure 2007101489000A00800011
As shown in table 1; Because the softening agent for fibres that in oil, adds the stearic acid manufacturing of the present invention; Its tone is 1.2～1.6Gardner; Demonstrated that (tone that comparative example 1:1.0～2.0Gardner) is approximate, (comparative example 2:2.0Gardner) demonstrated brighter tone compared with the softening agent for fibres that only uses oily manufacturing, can know to be suitable as softening agent for fibres with employed softening agent for fibres in the past.
The Determination on content of < Test Example 2>non-switched triglyceride oil
For investigate as the present invention in oil, add stearic acid and when making softening agent for fibres the content of non-switched triglyceride oil, carried out following test.
(GC Shimadzu17A) measures the content of non-switched triglyceride oil after the ester exchange reaction carry out embodiment 1～3 and comparative example 2, has represented the said determination result with table 2 to utilize gas-chromatography.
[table 2]
As shown in table 2, the softening agent for fibres that in oil, adds the stearic acid manufacturing of the present invention, the content of its non-switched triglyceride oil is 2.2～2.5%, can know compared with comparative example (5.4%) conversion ratio high.Thereby combination uses stearic method to be applicable to the manufacturing of softening agent for fibres in the oil of the present invention.
The mensuration of < embodiment 3>pH, viscosity and long-time stability
Use stearic acid to make the viscosity of the emulsion behind the softening agent for fibres and the degree of long-time stability in order to investigate according to the present invention in oil combination, carried out following test.
Have slurry shape agitating device, the nitrogen feedway that can control rotary speed, dewater with cooler, can control automatically in the four-hole glass reaction container of 500mL of electric heater unit of temperature of reaction system, that has mixed softening agent for fibres and comparative example 1 through embodiment 1～3 and comparative example 2～3 manufacturings contains ester quaternary ammonium compound fiber type softener 38g (total amount 7.6%), water 443g (88.6%), polyethylene glycol lauryl ether (polyethylene lauryl ether) 1g (0.2%), calcium chloride (calcium chloride) 0.1g (0.02%) and ethylene glycol (ethylene glycol) 15g.At this moment the speed with above-mentioned mixer is fixed as 250～300rpm, after temperature rises to 50～60 ℃, stirs 1 hour.After the stirring, above-mentioned reaction solution is cooled to 30 ℃, adds dyestuff (0.1%Soln.) 0.12%, spices 0.5% and a small amount of organic acid, stirred about 30 minutes, made emulsion.PH, viscosity and the long-time stability of the emulsion of above-mentioned manufacturing are measured as follows.
(1)pH
Utilize pH acidometer (0rion model 310) to measure the pH of the emulsion of above-mentioned manufacturing.
(2) viscosity
Under 25 ℃, utilize viscosimeter (Brookfield LVDV II+) to measure the viscosity of the emulsion of above-mentioned manufacturing.
(3) (long-time stability)
The emulsion of above-mentioned manufacturing being placed in 45 ℃ the baking oven, is that unit measures the time till the separation that emulsion takes place with the week.
The mensuration result of above-mentioned (1)～(3) is represented with table 3.
[table 3]
Figure 2007101489000A00800021
As shown in table 3; Mensuration according to long-time stability can be known; Of the present invention in oil, the combination uses stearic softening agent for fibres can keep the stability in 24～25 weeks, and be therefore especially high compared with commercially available article (1,17 week of comparative example) and its stability of the stearic comparative example 3 of excessive interpolation (20 week); If do not compare with adding stearic comparative example 2 (26 week), then shown equal level.
(4) flexibility
Use the flexibility of fiber of the emulsion of above-mentioned manufacturing for mensuration, carried out following test.
Through with the towel of 100% common cotton with home-use washing machine washing after; In rinsing and dehydration; According to the standard use amount (softening agent for fibres 40mL is used with the dilution of 60L water) of home-use softening agent for fibres, the emulsion that is added in manufacturing in embodiment 1～3 and the comparative example 1～3 carries out 30 minutes soft treatment, dry afterwards above-mentioned towel; Measure the flexibility of towel by 10 testers, again it is scaled mark and has measured relative flexibility.
Also have, utilize " Drape Tester " instrumentation of JAMES H HEAL company (U.S.) to decide the degree of dangling (Drape coefficient) of the emulsion of above-mentioned manufacturing.
Represented the said determination result with table 4.At this moment, relatively flexibility is that as the relative value of benchmark, with regard to degree of dangling, its coefficient is more not little, just representes that the flexibility of fiber is good more with adding stearic the time (comparative example 2).
[table 4]
Figure 2007101489000A00800031
As shown in table 4, if more relative flexibility, the stearic softening agent for fibres (embodiment 1～3) that in oil, adds then of the present invention is than commercially available article (comparative example 1) and do not add stearic comparative example 2, and its flexibility is especially high.
As a reference; With under the situation of stearic acid interpolation 40% (comparative example 3); Though flexibility is improved; But not only produce the problem that manufacturing cost rises because of the stearic addition of high price increases, and as shown in table 3, exist the long-time stability of emulsion sharply to reduce and produce the problem of a large amount of scum silica frost.
Hence one can see that, of the present inventionly in oil, adds the manufacturing that stearic method is applicable to softening agent for fibres.
As previously discussed; The softening agent for fibres that in oil, adds the stearic acid manufacturing of the present invention; With according to the softening agent for fibres of on market, selling of in the past method manufacturing and when only using the softening agent for fibres of oily manufacturing to compare; The long-time stability of the color harmony emulsion of its softening agent for fibres are not inferior, and can improve the flexibility of fiber.Thereby the present invention goes in the manufacturing of softening agent for fibres.

Claims (20)

1. the manufacturing approach of the softening agent for fibres of a flexibility that is used to improve fiber, comprising:
Step 1 wherein, makes stearic acid, comprises the vegetalitas or the animality oil of aliphatic acid and contains the hydroxyalkyl tertiary amine and carries out ester exchange reaction or esterification and obtain containing the hydroxyalkyl amine fatty acid ester under the condition that catalyst exists;
Step 2, wherein, the hydroxyalkyl amine fatty acid ester that contains that will from above-mentioned steps 1, obtain reacts with the level Four agent in low molecular alcoholic solvents, obtains comprising the more than one softening agent for fibres that contains the ester quaternary ammonium compound in following Chemical formula 1～3,
In the step 1 stearic acid is added into respect to all fatty acid compositions in the softening agent for fibres, stearine component C 18Reach 7.5～30%,
< Chemical formula 1 >
Figure FDA00002110206800011
In above-mentioned chemical formula,
R 1Be that carbon number is 6～22 straight or branched alkyl or alkenyl,
R 2And R 3Separate, expression hydrogen or R 1CO,
R 4Be that carbon number is 1～4 alkyl or (CH 2CH 2O) qThe H base,
M, n and p are 0～12 integers,
Q is 1～12 integer,
X representes halogen, alkyl sulfate, alkyl phosphoric acid root;
< Chemical formula 2 >
In above-mentioned Chemical formula 2,
R 1, R 2, X, m and n with in above-mentioned Chemical formula 1, define identical,
R 5And R 6Separate, the expression carbon number is 1～4 alkyl;
[chemical formula 3]
Figure FDA00002110206800022
In above-mentioned chemical formula 3,
R 1, R 2, R 4, X, m and n with in above-mentioned Chemical formula 1, define identical,
R 6And R 7Separate, the expression carbon number is 1～4 alkyl.
2. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
R in the above-mentioned Chemical formula 1 1Be that carbon number is 16～18 straight or branched alkyl or alkenyl.
3. the manufacturing approach of softening agent for fibres according to claim 1; It is characterized in that; Vegetalitas that contains aliphatic acid in the step 1 or animality oil comprise the mixture of any one or they from monoglyceride, diglyceride and the triglyceride shown in the following chemical formula 4～8, selected
< chemical formula 4 >
Figure FDA00002110206800023
In above-mentioned chemical formula 4, R 8Be that carbon number is 6～22 a straight or branched alkyl or alkenyl;
< chemical formula 5 >
Figure FDA00002110206800031
In above-mentioned chemical formula 5, R 8With in above-mentioned chemical formula 4 definition identical;
< chemical formula 6 >
Figure FDA00002110206800032
In above-mentioned chemical formula 6, R 9And R 10Separate, the expression carbon number is 6～22 a straight or branched alkyl or alkenyl;
< chemical formula 7 >
Figure FDA00002110206800033
In above-mentioned chemical formula 7, R 9And R 10With in above-mentioned chemical formula 6 definition identical;
< chemical formula 8 >
Figure FDA00002110206800034
In above-mentioned chemical formula 8, R 11, R 12And R 13Separate, the expression carbon number is 6～22 a straight or branched alkyl or alkenyl.
4. the manufacturing approach of softening agent for fibres according to claim 3 is characterized in that,
R in the above-mentioned chemical formula 4～8 8, R 9, R 10, R 11, R 12And R 13Separate, the expression carbon number is 16～18 straight or branched alkyl or alkenyl.
5. the manufacturing approach of softening agent for fibres according to claim 3 is characterized in that,
Vegetalitas that contains aliphatic acid in the step 1 or animality oil are the morphogenetic oil by the triglyceride of above-mentioned chemical formula 8.
6. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Vegetalitas that contains aliphatic acid or animality oil in the step 1 are any one that from saturated or unsaturated butter, palm oil, palm-kernel oil, palm stearin oil, palm oil essential oil, coconut oil, olive oil, rape seed oil, sunflower oil, cottonseed oil, soybean oil and leprosy fruit oil, select.
7. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
The hydroxyalkyl tertiary amine that contains in the step 1 is from diethanol methylamine, 1, any one that select in 2-dihydroxypropyl dimethylamine and the triethanolamine or their mixture.
8. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Vegetalitas that contains aliphatic acid in the step 1 or the aliphatic acid in the animality oil are 1: 1～2.7 with the reaction mol ratio that contains the hydroxyalkyl tertiary amine.
9. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Stearic acid in the step 1 is the aliphatic acid shown in the following chemical formula 9,
< chemical formula 9 >
Figure FDA00002110206800041
In above-mentioned chemical formula 9, R 17Be that carbon number is 17 a straight chained alkyl.
10. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Catalyst in the step 1 is independent base catalyst or alkoxytitanium series catalysts or sodium hypophosphite or their mixture.
11. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
In the catalyst in the step 1, with base catalyst as major catalyst, with sodium hypophosphite as co-catalyst.
12. the manufacturing approach of softening agent for fibres according to claim 11 is characterized in that,
The addition of above-mentioned base catalyst be the above-mentioned vegetalitas that contains aliphatic acid or animality oil and amine gross weight 0.01～0.1%, the addition of sodium hypophosphite be above-mentioned contain the vegetalitas of aliphatic acid or animality is oily and the gross weight of amine 0.01～0.1%.
13. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
The ester exchange reaction of step 1 or esterification were carried out under 160～240 ℃ 1～12 hour.
14. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
The reaction mol ratio that contains hydroxyalkyl amine fatty acid ester and level Four agent in the step 2 is 1: 0.9～1.0.
15. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Level Four agent in the step 2 for from the alkyl halide that comprises chloromethane, the sulfuric acid dialkyl that comprises dimethyl suflfate, comprise dimethyl carbonate and diethyl carbonate dialkyl carbonate select any one.
16. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Above-mentioned low mass molecule alcohol is the mixture of any one or they from isopropyl alcohol, ethanol, propylene glycol, DPG, selected.
17. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
The level Fourization of step 2 is reflected under 50～80 ℃ carried out 1～24 hour.
18. the manufacturing approach of softening agent for fibres according to claim 1 is characterized in that,
Further be included as the tone that improves above-mentioned softening agent for fibres and sodium chlorite and hydrogen peroxide be added into 0.05～1.0% and the step that stirs of all softening agent for fibres weight.
19. a softening agent for fibres, it is to make through any described manufacturing approach in the claim 1～18, wherein comprises:
More than one ester quaternary ammonium compound 20～90 weight % that contain in the Chemical formula 1 of claim 1～3; With
The glyceride of the glycerine of following Chemical formula 10, following Chemical formula 1 1～14 or their mixture 80～10 weight %,
< Chemical formula 10 >
Figure FDA00002110206800051
< Chemical formula 11 >
Figure FDA00002110206800061
In above-mentioned Chemical formula 11, R 14And R 15Separate, the expression carbon number is 6～22 a straight or branched alkyl or alkenyl;
< Chemical formula 12 >
In above-mentioned Chemical formula 12, R 14And R 15With in above-mentioned Chemical formula 11 definition identical;
< Chemical formula 13 >
In above-mentioned Chemical formula 13, R 16The expression carbon number is 6～22 a straight or branched alkyl or alkenyl;
< Chemical formula 14 >
Figure FDA00002110206800064
In above-mentioned Chemical formula 14, R 16With in the above-mentioned Chemical formula 13 definition identical.
20. softening agent for fibres according to claim 19 is characterized in that,
Above-mentioned R 14, R 15And R 16Separate, the expression carbon number is 16～18 a straight or branched alkyl or alkenyl.
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