CN101353862A - 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
CN101353862A
CN101353862A CNA2007101489000A CN200710148900A CN101353862A CN 101353862 A CN101353862 A CN 101353862A CN A2007101489000 A CNA2007101489000 A CN A2007101489000A CN 200710148900 A CN200710148900 A CN 200710148900A CN 101353862 A CN101353862 A CN 101353862A
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chemical formula
softening agent
oil
mentioned
fibres
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CN101353862B (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
    • 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
    • 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
    • C11D1/62—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 manufacture method of softening agent for fibres of the flexibility of fiber
Technical field
The present invention relates at the vegetalitas that comprises aliphatic acid or animality oil and contain add stearic acid (stearic acid) in the ester exchange reaction (transesterification) of hydroxyalkyl tertiary amine (hydroxyalkylamine) and the manufacture method of the softening agent for fibres that flexibility improves is reached by 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 manufacture method manufacturing.
Background technology
Softening agent for fibres is as the washing accessory agent that makes the dress material softness after being used to wash, not only can make the lines of fiber in order and make the dress material softness, 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 by the ester exchange reaction manufacturing also very active of oil and amine, and what be 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 to 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 as follows.
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 the technology of its usefulness 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 manufacture method 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, make oil and have the step that the tertiary amine of hydroxyl reacts; (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, used alkaline-earth metal boron hydride as catalyst, hypophosphorous acid or their alkali salt (alkali earthmetal salt), specifically, making iodine number as degree of unsaturation is 0～50 all or partially hydrogenated butter or palm oil and diethanol methylamine (diethanol methylamine), 1,2-dihydroxypropyl dimethylamine (1,2-dihydroxypropyl dimethylamine), the mixture of triethanolamine and/or these amine carries out in the process of ester exchange reaction, by 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 of ammonium salt 20～80%, the mixture 80～20% that comprises glycerine and glyceride, have the character that melts down at 30～65 ℃, 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, directly make the method for cationic fiber softener by oil, owing to there is the bad problem of tone of the softening agent for fibres of the content height of oil of non-switched triglycerides form or manufacturing, 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, the inventor etc. use alkali major catalyst and sodium hypophosphite co-catalyst, perhaps alkoxytitanium owner catalyst and sodium hypophosphite help catalysis and have solved the problems referred to above, and then, in order to obtain than studying with the more outstanding fiber softening effect of the softening agent for fibres of said method manufacturing, found that by in oil, adding stearic acid and can obtain excellent color tone, the content of oil of not changing the triglycerides form is lower, the stability of hydrolysis and absorbability height, yellowing is few, especially make the softening agent for fibres of the flexibility raising of fiber, finished the present invention thus.
Summary of the invention
The objective of the invention is to, be provided for improving the manufacture method of the softening agent for fibres of fiber softening, wherein, at vegetalitas that comprises aliphatic acid or animality oil with contain in the ester exchange reaction of hydroxyalkyl tertiary amine and be used in combination stearic acid.
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 manufacture method manufacturing.
For achieving the above object, the manufacture method that is used to improve the softening agent for fibres of fiber softening 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 obtain from above-mentioned steps 1 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 A20071014890000101
(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 represents halogen (halide), alkyl sulfate (alkyl sulfate), alkyl phosphoric acid root (alkylphosphate).)
[Chemical formula 2]
(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]
Figure A20071014890000112
(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, describe the present invention set by step in detail.
At first, step 1 is to make stearic acid under the condition that catalyst exists, 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 diglycerides of monoglycerides, 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 or the animality oil that comprises aliphatic acid comprises and has 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 A20071014890000121
(in above-mentioned chemical formula 4, R 8Be that carbon number is 6～22 a straight or branched alkyl or alkenyl.)
[chemical formula 5]
(in above-mentioned chemical formula 5, R 8With in above-mentioned chemical formula 4 definition identical.)
[chemical formula 6]
Figure A20071014890000131
(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 A20071014890000132
(in above-mentioned chemical formula 7, R 9And R 10With in above-mentioned chemical formula 6 definition identical.)
[chemical formula 8]
Figure A20071014890000133
(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, can use 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 use saturated or unsaturated butter (beef tallow oil) etc. as the animality oil that comprises aliphatic acid.Above-mentionedly comprise the vegetalitas of aliphatic acid or the degree of unsaturation of animality oil 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, the reaction mol ratio that comprises the vegetalitas of aliphatic acid or the aliphatic acid in the animality oil and contain the hydroxyalkyl tertiary amine is preferably 1: 1～and 2.7.If above-mentioned vegetalitas that comprises aliphatic acid or the aliphatic acid in the animality oil and the reaction mol ratio that contains the hydroxyalkyl tertiary amine are lower than 1: 1, 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]
Figure A20071014890000141
(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.
There is no particular limitation for employed in the present invention catalyst, preferably is used alone or as a mixture base catalyst, sodium hypophosphite, alkoxytitanium series catalysts etc.
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, nontoxic to human body, and it is 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 by 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 of separating out with residue in the goods and produce the peculiar smell problem.
The ester exchange reaction of above-mentioned steps 1 of the present invention is preferably carried out under 160～240 ℃, more preferably carries out preferred 1～12 hour of reaction time, more preferably 3～8 hours under 160～220 ℃.If exceed above-mentioned scope, then can on the tone of goods and conversion ratio, have problems.
If implement above-mentioned steps 1 of the present invention, then by 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 be converted 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 A20071014890000161
In addition, part is converted 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]
(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 A20071014890000171
(in above-mentioned Chemical formula 12, R 14And R 15With in above-mentioned Chemical formula 11 definition identical.)
[Chemical formula 1 3]
Figure A20071014890000172
(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 A20071014890000173
(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 will obtain from above-mentioned steps 1 reacts 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 the hydroxyalkyl amine fatty acid ester increases and the generation scum silica frost relatively, and 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 be used alone or as a mixture isopropyl alcohol (isopropyl alcohol), ethanol (ethanol), propylene glycol (propylene glycol), dipropylene glycol (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 carries out under 50～60 ℃, 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 manufacture method of the present invention that stearic acid uses, can provide 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 %.
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, describe the present invention in detail 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.
＜embodiment 1〉add the manufacturing 1 of stearic softening agent for fibres
(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, be increased to 160 ℃ and the water removing in the raw material to be comprised through 1 hour temperature with reactant, after under said temperature, keeping 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.
＜embodiment 2〉add the manufacturing 2 of stearic softening agent for fibres
(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%), obtained containing the hydroxyalkyl amine fatty acid ester with the method identical with the method for 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.
＜embodiment 3〉add the manufacturing 3 of stearic softening agent for fibres
(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%), obtained containing the hydroxyalkyl amine fatty acid ester with the method identical with the method for 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〉in the past softening agent for fibres
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〉the only manufacturing of the softening agent for fibres of use oil
(1) ester exchange reaction
Outside adding palm stearin oil 591g, the triethanolamine 170g except that stearic acid, 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〉add 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.
＜test example 1〉tone of softening agent for fibres measures
How many tones of softening agent for fibres improved when to add stearic acid make softening agent for fibres in oil 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]
Distinguish Colourity (Gardner)
Embodiment 1 1.6
Embodiment 2 1.5
Embodiment 3 1.2
Comparative example 1 1.0～2.0
Comparative example 2 2.0
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 and (the tone that comparative example 1: 1.0～2.0Gardner) is approximate of employed softening agent for fibres in the past, (comparative example 2:2.0Gardner) demonstrated brighter tone compared with the softening agent for fibres that only uses oily manufacturing, is suitable as softening agent for fibres as can be known.
＜test example 2〉Determination on content of 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]
Distinguish The content of non-switched triglyceride oil (%)
Embodiment 1 2.5
Embodiment 2 2.3
Embodiment 3 2.2
Comparative example 2 5.4
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%, as can be known compared with comparative example (5.4%) conversion ratio height.Thereby, be used in combination the manufacturing that stearic method is applicable to softening agent for fibres in the oil of the present invention.
＜embodiment 3〉mensuration of pH, viscosity and long-time stability
In oil, to be used in combination stearic acid and to make the viscosity of the emulsion behind the softening agent for fibres and the degree of long-time stability in order to investigate, carried out following test according to the present invention.
Has the slurry shape agitating device that to control rotary speed, the nitrogen feedway, dewater and use 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 by embodiment 1～3 and comparative example 2～3 manufacturings and comparative example 1 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.Measure pH, viscosity and the long-time stability of the emulsion of above-mentioned manufacturing as follows.
(1)pH
Utilize pH acidometer (Orion 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 measurement result of above-mentioned (1)～(3) is represented with table 3.
[table 3]
Figure A20071014890000231
As shown in table 3, according to the mensuration of long-time stability as can be known, of the present inventionly in oil, be used in combination the stability that stearic softening agent for fibres can keep for 24～25 weeks, therefore compared with commercially available product (comparative example 1,17 weeks) and its stability of the stearic comparative example 3 of excessive interpolation (20 week) especially high, 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.
By with the towel of 100% common cotton with home-use washing machine washing after, in rinsing and dehydration, standard use amount (softening agent for fibres 40mL is used with the dilution of 60L water) according to 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 represents that the flexibility of fiber is good more with adding stearic the time (comparative example 2).
[table 4]
Figure A20071014890000241
As shown in table 4, if more relative flexibility, the stearic softening agent for fibres (embodiment 1～3) that adds in oil then of the present invention is than commercially available product (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 because of the stearic addition of high price increases the problem that not only produces the manufacturing cost rising, 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 adds the manufacturing that stearic method is applicable to softening agent for fibres in oil.
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 (21)

1. the manufacture method 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 obtain from above-mentioned steps 1 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,
＜Chemical formula 1 〉
Figure A2007101489000002C1
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 represents halogen, alkyl sulfate, alkyl phosphoric acid root;
＜Chemical formula 2 〉
Figure A2007101489000002C2
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, the expression 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, the expression carbon number is 1～4 alkyl.
2. the manufacture method 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 manufacture method of softening agent for fibres according to claim 1 is characterized in that,
Vegetalitas that contains aliphatic acid in the step 1 or animality oil comprise the mixture of any one or they selected from monoglyceride, diglyceride and the triglyceride shown in the following chemical formula 4～8,
＜chemical formula 4 〉
Figure A2007101489000003C2
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 A2007101489000003C3
In above-mentioned chemical formula 5, R 8With in above-mentioned chemical formula 4 definition identical;
＜chemical formula 6 〉
Figure A2007101489000004C1
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 〉
In above-mentioned chemical formula 7, R 9And R 10With in above-mentioned chemical formula 6 definition identical;
＜chemical formula 8 〉
Figure A2007101489000004C3
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 manufacture method 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 manufacture method of softening agent for fibres according to claim 1 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 manufacture method 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 select 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.
7. the manufacture method 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 manufacture method 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 manufacture method 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 〉
In above-mentioned chemical formula 9, R 17Be that carbon number is 16～17 a straight chained alkyl.
10. the manufacture method of softening agent for fibres according to claim 1 is characterized in that,
In the step 1 stearic acid is added into respect to all fatty acid compositions in the softening agent for fibres, stearine component (C 18) reach 7.5～30%.
11. the manufacture method 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.
12. the manufacture method 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.
13. the manufacture method of softening agent for fibres according to claim 12 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%.
14. the manufacture method of softening agent for fibres according to claim 1 is characterized in that,
The ester exchange reaction of step 1 or ester are reflected at and carried out under 160～240 ℃ 1～12 hour.
15. the manufacture method 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.
16. the manufacture method 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.
17. the manufacture method 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 selected from isopropyl alcohol, ethanol, propylene glycol, dipropylene glycol.
18. the manufacture method 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.
19. the manufacture method 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.
20. a softening agent for fibres, it is to make by any described manufacture method in the claim 1～19, 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 A2007101489000006C1
＜Chemical formula 11 〉
Figure A2007101489000007C1
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 〉
Figure A2007101489000007C2
In above-mentioned Chemical formula 12, R 14And R 15With in above-mentioned Chemical formula 11 definition identical;
＜Chemical formula 13 〉
Figure A2007101489000007C3
In above-mentioned Chemical formula 13, R 16Separate, the expression carbon number is 6～22 a straight or branched alkyl or alkenyl;
＜Chemical formula 14 〉
Figure A2007101489000007C4
In above-mentioned Chemical formula 14, R 16With in the above-mentioned Chemical formula 13 definition identical.
21. softening agent for fibres according to claim 20 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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