CN100354470C - Fibre processing agent - Google Patents
Fibre processing agent Download PDFInfo
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- CN100354470C CN100354470C CNB2005101041226A CN200510104122A CN100354470C CN 100354470 C CN100354470 C CN 100354470C CN B2005101041226 A CNB2005101041226 A CN B2005101041226A CN 200510104122 A CN200510104122 A CN 200510104122A CN 100354470 C CN100354470 C CN 100354470C
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Abstract
To provide a fiber-treating agent which can sufficiently deepen the color of polyester fibers and impart excellent anti-staticity to the polyester fibers, even when the dipping time of the polyester fibers in the fiber-treating agent is short, and has excellent stability. This fiber-treating agent is characterized by comprising polymer particles comprising a vinylic polymer AI obtained by polymerizing a vinylic monomer in the presence of a cationic surfactant and having a refractive index of <=1.50 and a glass transition temperature in a range of 110 to 150[deg.]C, polymer particles comprising a vinylic polymer AII obtained by polymerizing a vinylic monomer in the presence of a cationic surfactant and having a refractive index of <=1.50 and a glass transition temperature in a range of -20 to 20[deg.]C, a specific surfactant B and water.
Description
Technical field
The dark colorization of the polyester fiber color that the present invention relates to dye and give the fibre finish that antistatic behaviour is used to polyester fiber.
Background technology
Synthetic fiber are big because of intensity, can produce in a large number, so using in the purposes widely in recent years.Wherein polyester fiber is because the inexpensive fibre that is often used for clothes etc. replaces the natural fabric of silk etc.
In addition, the fibre of clothes etc. often requires the feeling of high class of color depth as the high added value commodity.This purposes is used usually and is dyed the polyester fiber that meets desired color.Yet,,, have the problem that color is dark, color can not be deepened so the natural fabric of the silk of the dyeing identical with use etc. is compared because polyester fiber has distinctive bright luster.Such problem for example is that the deep occasion of color such as black or dark blue is outstanding especially in the color of fiber.
The color of polyester fiber is compared the reason that can not heighten the color with the color of the natural fabric that uses identical dyeing, and for example, the refractive index (1.71) that can enumerate polyester fiber is bigger than the refractive index (1.58) of silk.Usually the many reverberation (normal reflection light) as white of light that incide in the high index of refraction fiber reflect at fiber surface.Such reverberation makes the color depth of coloured fibre original more of light color than dyestuff sometimes.
Therefore, for the color dark colorization of the polyester fiber that makes dyeing, must suppress reverberation from fiber surface.
As the catoptrical method that suppresses from fiber surface, small concavo-convex method is given on for example known surface to fiber.Particularly, have by using plasma etc. that the surface of polyester fiber is carried out etching, formed concavo-convex method at fiber surface.Yet this method is owing to the durability that makes fiber sometimes reduces, so the method that difficulty is referred to as.
In addition, also know the method for using the low resin-coated fiber surface of refractive index ratio polyester fiber as suppressing from the catoptrical method of fiber surface.If for example reported use contain refractive index below 1.5 and glass transition temperature greater than 110 ℃ polyvinyl particle and refractive index below 1.5 and glass transition temperature be lower than 20 ℃ the polyvinyl particle and the fibre finish of water, then can make the color burn (for example, with reference to Patent Document 1) of the polyester fiber of dyeing fully.
In addition, reported that also containing core and skin zone has the polyvinyl particle of core-integumentary pattern of different glass transition temperature and the fibre finish of water, also can make the color dark colorization (for example, with reference to Patent Document 2) of the polyester fiber of dyeing fully.
As using the aforementioned fibers finishing agent to form the method for tunicle on the surface of polyester fiber, for example, the method that known employing makes polyester fiber pass through in the aforementioned fibers finishing agent continuously, flood, at fiber surface adhering fibre finishing agent, then behind 80 ℃ of-120 ℃ of left and right sides heated dryings, the method that about 150 ℃-180 ℃, heats.Though the details of fiber dark colorization method and unclear considers that from the viewpoint that improves the dark colorization fibre production efficiency dip time of polyester fiber in fibre finish is very short usually as the aforementioned, most of occasions are set in about 0.5-2 about second.Even though require the very short as described above time of dip time, also can be fully attached on the fiber, can give the fibre finish of sufficient dark colorization effect again, the fibre finish that can fully satisfy this requirement is also less than discovery.
In addition, polyester fiber has the charged problem of being very easy to.When making polyester article, if polyester fiber friction etc. are charged, then dust in the atmosphere or dirt etc. stick on the fiber, destroy the quality of polyester article sometimes, as the method that addresses this problem, and the method that known use antistatic additive is handled fiber surface.As the method for using the antistatic agent treatment fiber surface, for example, have make polyester fiber continuously in containing the solution of antistatic additive by, dipping, on fiber surface, adhere to antistatic additive, carry out the method for heated drying then.
Yet, polyester fiber is implemented the operation and the aforementioned operation of giving antistatic behaviour of aforementioned dark colorization respectively individually, difficulty has been referred to as method with regard to the production efficiency of seeking to improve the polyester fiber goods.Therefore, industrial circle requires exploitation can side by side give the fibre finish of antistatic behaviour and dark colorization.
As such fibre finish, Patent Document 1 put down in writing contain refractive index below 1.50 and glass transition temperature greater than 110 ℃ polyvinyl particle, refractive index below 1.50 and glass transition temperature be lower than the fibre finish of 20 ℃ polyvinyl particle, anionic property antistatic additive and water.
Yet the dip time of polyester fiber in the aforementioned fibers finishing agent very in short-term, and be also insufficient to the antistatic behaviour that polyester fiber is given.In addition, the aforementioned fibers finishing agent, aforementioned polyvinyl and anionic property antistatic additive contained in this finishing agent condense easily, so stability is also insufficient.
In addition, also reported the polyvinyl that contains low-refraction and contain the specific alkylamino acetic acid betaine of the alkyl that has 1-4 carbon atom as the fibre finish of antistatic additive, can be with the color dark colorization of the polyester fiber of dyeing, can give good antistatic behaviour to fiber, and good stability (for example, with reference to Patent Document 3).
Yet, aforementioned specific alkylamino acetic acid betaine, since insufficient to the affinity of polyester fiber, so the dip time of polyester fiber in fibre finish is very in short-term, difficulty sticks on the fiber surface, and there is the problem that can not give sufficiently high antistatic behaviour to fiber in the result in practicality.
In addition, aforementioned specific alkylamino acetic acid betaine, because the polyvinyl that hinders low-refraction sometimes sticks on the polyester fiber, thus the aforementioned fibers finishing agent as described above dip time very in short-term, the problem of sufficiently high dark colorization effect can not be fully given in existence to fiber.
Yan Jiukaifa result so far, by setting the condition of polyester fiber sufficiently long dip time etc. in aforesaid fibre finish, the color dark colorization of polyester fiber that can make dyeing can also be given excellent antistatic behaviour to fiber to enough levels.
Yet, from now in the demand that prediction has a fiber of high additive value as the aforementioned increases, in order further to improve the production efficiency of fiber, although exploitation can be side by side and to give the fibre finish of antistatic behaviour and dark colorization very in short time essential, the present fibre finish that does not also have discovery to have this performance.
[Patent Document 1] spy opens flat 09-003774 communique
[Patent Document 2] spy opens the 2003-213580 communique
[Patent Document 3] spy opens flat 11-172576 communique
Summary of the invention
Even the problem that the present invention will solve is to provide the time that polyester fiber is flooded in fibre finish very short, also can be with the color of the polyester fiber of dyeing dark colorization and can give fibre finish sufficiently high antistatic behaviour, good stability fully to polyester fiber.
If the present inventor to aforementioned Patent Document 3 described alkylamino acetic acid betaines can improve affinity to polyester fiber, then even the dip time of polyester fiber in fibre finish is very short, the viewpoint that also can give sufficiently high antistatic behaviour or dark colorization effect to fiber in practicality is studied.
Yet, contain the described specific alkylamino acetic acid betaine that contains the alkyl that has 1-4 carbon atom of the polyvinyl particle, aforementioned documents 3 of low-refraction, and the fibre finish of water, in order to improve to the affinity of fiber and and with the fibre finish of the general various surfactants that use, can not make the color dark colorization of the polyester fiber of dyeing fully.In addition, when carrying out heated drying to being immersed in polyester fiber in the aforementioned fibers finishing agent, part sticks to aforementioned alkylamino acetic acid betaine on the fiber and is coloured to dark brownly under the influence of heat, produces the problem of destroying the fiber tone.
The present inventor is in continuing research, to the specific surfactant of antistatic behaviour function is arranged by use, the viewpoint that whether can obtain neither to hinder the dark colorization of the polyester fiber color of dyeing, can give the electrostatic fibre finish of excellent anti is again studied.
The result, discovery contains that polymerization of vinyl monomer obtains in the presence of cationic surfactant refractive index below 1.50, and the polymer particle that the polyvinyl AI that the glass transition temperature of 110 ℃ of-150 ℃ of scopes is arranged constitutes, polymerization of vinyl monomer obtains in the presence of cationic surfactant refractive index below 1.50, and the polymer particle that constitutes at the polyvinyl AII of the glass transition temperature of-20 ℃～20 ℃ of scopes, the specific alkylamino acetic acid betaine that chain alkyl is arranged, and the fibre finish of water, even the dip time of polyester fiber in this fibre finish is very short, also can give sufficiently high antistatic behaviour, can make the color dark colorization of the polyester fiber of dyeing again fully fiber.
Promptly the present invention relates to contain the polymer particle that polymerization of vinyl monomer obtains in the presence of cationic surfactant has the refractive index below 1.50 and have the polyvinyl AI of the glass transition temperature of 110 ℃ of-150 ℃ of scopes to constitute, polymerization of vinyl monomer obtains in the presence of cationic surfactant refractive index below 1.50, and the polymer particle that the polyvinyl AII that the glass transition temperature of-20 ℃～20 ℃ of scopes is arranged constitutes, the surfactant B of general formula (I) expression and the fibre finish of water.
In the general formula (I), R
1, R
2And R
3At least 1 expression the alkyl of 8-30 carbon atom is arranged, other expression independently of one another has the alkyl of 1-4 carbon atom.A represents to have the alkylidene of 1-2 carbon atom.
In addition, the present invention relates to contain the polymer particle of the core-integumentary pattern of the polyvinyl formation that the refractive index below 1.50 is arranged that polymerization of vinyl monomer obtains in the presence of cationic surfactant, the surfactant B and the water of aforementioned formula (I) expression, the polymer particle of aforementioned core-integumentary pattern has aforementioned polyvinyl AI at core, and the fibre finish of aforementioned polyvinyl AII is arranged in skin zone.
In addition, to call the technical terms of " refractive index " in the following text, be meant the value of using Abbe refractometer to measure according to JIS K7105.In addition, claim the technical terms of " glass transition temperature ", be meant the value of using differential scanning calorimeter, being measured to 150 ℃, obtaining according to JISK7121 by 20 ℃/minute of programming rates.
Even the present invention is that the dip time of polyester fiber is very short, also can make fully dyeing such as dyestuff polyester fiber the color dark colorization and can to polyester fiber give excellent anti electrostatic, in practicality extremely useful fibre finish.
Fibre finish of the present invention is the surfactant B that contains polymer particle that polymerization of vinyl monomer obtains in the presence of cationic surfactant, the refractive index below 1.5 is arranged polyvinyl constitutes, general formula (I) expression in water, and other the fibre finish of additive that adds as required.
In the general formula (I), R
1, R
2And R
3At least 1 expression the alkyl of 8-30 carbon atom is arranged, other expression independently of one another has the alkyl of 1-4 carbon atom.A represents to have the alkylidene of 1-2 carbon atom.
At first, the polymer particle that constitutes of the polyvinyl that the present invention is used describes.
The polymer particle that the polyvinyl that the present invention uses constitutes has the refractive index below 1.5.The color of polyester fiber is compared with the color of the natural fabric that uses identical dyeing and is not seemed dark, and this is because the refractive index of the natural fabric of the refractive index (about 1.71) of polyester fiber ratio silk etc. is big, wide many causes in the fiber surface reflection of incident.Therefore,, use the low polyvinyl of refractive index ratio polyester fiber, especially use the method for the polyvinyl lining fiber surface of refractive index below 1.5 to produce effect as the catoptrical method that suppresses from fiber surface.
The polymer particle that the polyvinyl AII that the polymer particle that the polyvinyl that the present invention uses constitutes is the polymer particle that has the polyvinyl AI of 110 ℃-150 ℃ glass transition temperature to constitute, have-20 ℃～20 ℃ glass transition temperature constitutes, and core have polyvinyl AI, the skin zone of 110 ℃-150 ℃ of glass transition temperatures that the polymer particle of core-integumentary pattern of the polyvinyl AII of glass transition temperature-20 ℃～20 ℃ is arranged.
The polyvinyl AI that glass transition temperature is 110 ℃-150 ℃, incomplete fusion in the heating process after on adhering to polyester fiber, and on fiber surface, form small concavo-convex.The small concavo-convex inhibition that forms is from the reverberation of fiber surface, can will use the color dark colorization of the polyester fiber of dyeing such as dyestuff.
And the polyvinyl AII of glass transition temperature-20 ℃～20 ℃, forms tunicle at fiber surface at fusion fully in the heating process after on sticking to polyester fiber.At this moment, the aforementioned polyvinyl AI of shape of particle utilizes the tunicle of aforementioned polyvinyl AII formation to load with on fiber surface owing to keep to a certain degree, so can keep the dark color effect of polyester fiber chronically.
The polymer particle that polymer particle that aforementioned polyvinyl AI constitutes and aforementioned polyvinyl AII constitute, for example, can by in the aqueous solution that contains polymerization initiator, supply with the aqueous dispersions contain vinyl monomer and cationic surfactant, stir, polymerization made in 1 hour-3 hours in 50 ℃-90 ℃ temperature range.
Among the present invention, for example can adopt preceding method to make the polymer particle of aforementioned polyvinyl AI formation and the polymer particle that aforementioned polyvinyl AII constitutes respectively individually, use the aqueous dispersions of the polymer particle of prepared polyvinyl AI formation to mix the mixing water dispersion liquid that obtains with the aqueous dispersions of the polymer particle of aforementioned polyvinyl AII formation.
Core has the polyvinyl AI of 110 ℃ of-150 ℃ of scopes of glass transition temperature, there is the polymer particle of core-integumentary pattern of the polyvinyl AII of glass transition temperature-20 ℃～20 ℃ of scopes in skin zone, for example can contain as the vinyl monomer of the raw material of the polyvinyl AII that constitutes skin zone and the aqueous dispersions of cationic surfactant by in the aqueous solution that contains polymerization initiator, supplying with, stir, 50 ℃-90 ℃ temperature range polymerizations 1 hour-3 hours, make the aqueous dispersions of the polymer particle of polyvinyl AII formation, then, supply is as the vinyl monomer of the raw material of the polyvinyl AI that constitutes core, stir, polymerization made in 1 hour-3 hours.
At this moment, as the vinyl monomer of the raw material of polyvinyl AI, must not supply with, and will supply with individually with surfactant.Therefore, can not in water, stably exist, and polymerization is carried out in the inside of the polymer particle that constitutes at already present polyvinyl AII as the vinyl monomer of the raw material of polyvinyl AI.The result makes skin zone has polyvinyl AII, core that the polymer particle of core-integumentary pattern of polyvinyl AI is arranged.
Operable vinyl monomer during as aforementioned polyvinyl AI of manufacturing and polyvinyl AII, for example can use (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) 2-EHA, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid cetyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate, (methyl) stearyl acrylate ester, (methyl) isobornyl acrylate, (methyl) acrylic acid DCPA (ジ シ Network ロ ペ Application ニ Le (メ ) ァ Network リ レ one ト), (methyl) acrylic acid 2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3,3-five fluorine propyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid perfluor cyclohexyl, (methyl) acrylate of (methyl) propenoic acid beta-(perfluoro capryl) ethyl ester etc.; The vinyl ethers of 2-ethylhexyl vinyl ethers, hexyl vinyl ethers, ethyl vinyl ether etc.; Tetrafluoroethylene, (methyl) acrylonitrile, ethene, N-vinyl pyrrolidone, vinylidene; Isoprene, chlorobutadiene, butadiene, vinyl acetate, propionate; (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, list (methyl) polyalkylene glycol acrylate ester, one (methyl) acrylic acid glyceride etc., wherein, consider preferred (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) isopropyl acrylate of using from the viewpoint that the refractive index that makes the polymer particle that obtains is adjusted to below 1.50.
Operable monomer when making aforementioned polyvinyl AI, preferred (methyl) tert-butyl acrylate that uses.The mass ratio of (methyl) tert-butyl acrylate operable vinyl monomer total amount when making aforementioned polyvinyl AI is preferably in the scope of 90 quality %-100 quality %.If the mass ratio of (methyl) tert-butyl acrylate is in the aforementioned range, then easily the glass transition temperature of the polyvinyl AI that makes is adjusted in 110 ℃-150 ℃ the scope.
Operable monomer when making aforementioned polyvinyl AII preferably uses isobutyl acrylate.The mass ratio of isobutyl acrylate total amount of operable vinyl monomer when making aforementioned polyvinyl AII is preferably in the scope of 60 quality %-80 quality %.
In addition, operable vinyl monomer during as aforementioned polyvinyl AI of manufacturing or aforementioned polyvinyl AII, the also preferred vinyl monomer that uses responding property functional group.When use has previous reaction functional group's vinyl monomer to make aforementioned polyvinyl AII, the polyvinyl AII that makes, when fiber surface forms epithelium, utilize reactive functional group and aforementioned polyvinyl AI or aforementioned polyvinyl AII bonding, form the tunicle of good endurance.As a result, the comparable dark color effect of keeping fibre finish of the present invention for long periods.
The reactive functional group that has as aforementioned vinyl monomer, can use N-methylol, glycidyl, amino, silicon atoms base etc., these, for example can utilize glycidyl and amino reaction, the reaction each other of N-methylol, the combination of silicon atoms base self-condensation reaction each other etc. is reacted.
As the vinyl monomer that the previous reaction functional group is arranged, for example can use the vinyl monomer of N-methylol, the vinyl monomer of glycidyl is arranged, amino vinyl monomer is arranged, the vinyl monomer of silicon atoms base etc. is arranged.
As the aforementioned vinyl monomer that the N-methylol is arranged, for example can use N-methylol (methyl) acrylamide etc.In addition, the N-methylol also can use etherificates such as alcohol, for example also can use N-isopropoxy methyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-isobutoxy methyl (methyl) acrylamide etc.
As the aforementioned vinyl monomer that glycidyl is arranged, for example can use (methyl) glycidyl acrylate, allyl glycidyl ether etc.
As the aforementioned vinyl monomer that amino is arranged, for example can use (methyl) acrylic acid ammonia ethyl ester, the single alkyl amino alkyl ester of (methyl) acrylic acid N-, (methyl) acrylic acid N, N-dialkylaminoalkyl ester etc.
As the aforementioned vinyl monomer that the silicon atoms base is arranged, for example can use vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (beta-methoxy-ethyoxyl) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, γ-(methyl) acryloxy propyl group three isopropoxy silane, N-β-(N-vinyl benzyl aminoethyl)-γ-An Bingjisanjiayangjiguiwan and hydrochloride thereof etc.
When using aforementioned responding property functional group's vinyl monomer to make aforementioned polyvinyl AI, aforementioned responding property functional group's vinyl monomer, the total amount of the vinyl monomer that uses when making aforementioned polyvinyl A I is preferably used in the scope of 0.1 quality %-15 quality %.
And the vinyl monomer that uses aforementioned responding property functional group is when making aforementioned polyvinyl AII, aforementioned responding property functional group's vinyl monomer, the total amount of the vinyl monomer that uses when making aforementioned polyvinyl AII is preferably used in the scope of 0.1 quality %-15 quality %.
The mass ratio of the polymer particle that the polymer particle that the aforementioned polyvinyl AI in the fibre finish of the present invention constitutes and aforementioned polyvinyl AII constitute, preferably the scope of [AI/AII]=10/90-90/10 interior, be more preferably in the scope of 5/95-30/70.
In addition, core has aforementioned polyvinyl AI, skin zone that the polymer particle of core-integumentary pattern of aforementioned polyvinyl AII is arranged, the mass ratio of aforementioned polyvinyl AI and aforementioned polyvinyl AII preferably in the scope of [AI/AII]=70/30-10/90, is more preferably in the scope of 50/50-30/70.Mass ratio by use polyvinyl AI and polyvinyl AII is the polymer particle of the core-integumentary pattern in the aforementioned range, can keep the dark color effect of the polyester fiber color of dyeing such as dyestuff for long periods.
Below, to making the polymer particle that aforementioned polyvinyl AI constitutes, the polymer particle that aforementioned polyvinyl AII constitutes, and skin zone's cationic surfactant of having aforementioned polyvinyl AII, core to have core-integumentary pattern polymer beads period of the day from 11 p.m. to 1 a.m of aforementioned polyvinyl AI to use describe.
Cationic surfactant can make polymer particle that aforementioned polyvinyl AI constitutes, polymer particle that aforementioned polyvinyl AII constitutes, and the polymer particle of aforementioned core-integumentary pattern in water, stably disperse.Cationic surfactant sticks on the surface of aforementioned polymer particle, makes the aforementioned polymer particle positively charged.
On the other hand, polyester fiber is immersed in the water, and its surface is electronegative.Positively charged aforementioned polymer particle contained in the fibre finish of the present invention sticks on the surface of electronegative polyester fiber than being easier to.
As the aforementioned male ionic surfactant, for example, can use the cationic surfactant of alkyl quaternary ammonium salts, alkyl pyridine salt, alkyl imidazoline salt, alkyl morpholine salt, primary amine salt, secondary amine salt, tertiary ammonium salt or responding property etc.
As the aforesaid alkyl quaternary ammonium salt, for example can use the compound of following general formula (II)-(V) expression.
In the general formula (II), R
4-R
7Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In the general formula (III), R
4-R
7Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In the general formula (IV), R
4-R
6Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In the general formula (V), R
4-R
6Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforesaid alkyl pyridine salt, for example can use following compound by (VI) expression.
In the general formula (VI), R
4Expression has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforesaid alkyl imidazoline salt, for example can use the compound of following general formula (VII) expression.
In the general formula (VII), R
4Expression has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforesaid alkyl morpholine salt, for example can use the compound of following general formula (VIII) expression.
In the general formula (VIII), R
4And R
5Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforementioned primary amine salt, for example can use the compound of following general formula (IX) expression.
R
4-NH
2·HX (IX)
In the general formula (IX), R
4Expression has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforementioned secondary amine salt, for example can use the compound of following general formula (X) expression.
In the general formula (X), R
4And R
5Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
As aforementioned tertiary ammonium salt, for example can use the compound of following general formula (XI) expression.
In the general formula (XI), R
4, R
5And R
6Expression independently of one another has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In addition, as the cationic surfactant that previous reaction is arranged, for example can use the compound of following general formula (XII)-(XIV) expression.
In the general formula (XII), R
4Expression has the alkyl of 1-22 carbon atom.R
8Expression hydrogen atom or methyl.R
9Expression also can have the alkylidene of 1-22 carbon atom of hydroxyl.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In the general formula (XIII), R
4Expression has the alkyl of 1-22 carbon atom.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2In any a kind functional group.
In the general formula (XIV), R
4And R
5Expression independently of one another has the alkyl of 1-22 carbon atom.R
8Expression hydrogen atom or methyl.X represents to be selected from Cl, Br, I, HCO
2And CH
3CO
2Form any a kind functional group among the group.
Cationic surfactant, preferably uses in the scope of 0.1 parts by mass-0.5 parts by mass total amount 100 parts by mass of the polymer particle that polymer particle that constitutes with respect to aforementioned polyvinyl AI and aforementioned polyvinyl AII constitute.Aforementioned male ionic surfactant's use amount is if aforementioned range, and then the aforementioned polymer particle improves the adherence of polyester fibre surface, and can give good aqueous dispersion stability to the aforementioned polymer particle.
In addition, cationic surfactant with respect to polymer particle 100 parts by mass of aforementioned core-integumentary pattern, preferably uses in 0.1 parts by mass-0.5 parts by mass scope.Aforementioned male ionic surfactant's use amount is if aforementioned range, and then the aforementioned polymer particle improves the adherence of polyester fibre surface, and can give good aqueous dispersion stability to the aforementioned polymer particle.
Make the polymer particle that aforementioned polyvinyl AI constitutes, the polymer particle that aforementioned polyvinyl AII constitutes, and aforementioned core-integumentary pattern polymer beads period of the day from 11 p.m. to 1 a.m, in order to improve the water dispersible of resulting polymers particle, except the aforementioned male ionic surfactant, in reaching the scope of the object of the invention, can also and use nonionic surfactant.
As aforementioned nonionic surfactant, for example, can use polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkanamine ether, fatty diglycollic amide, sucrose ester, polyoxyethylene lanolin alcohol ether, Wool wax alcohols,ethoxylated fatty acid ester etc.
Total amount 100 parts by mass of the polymer particle that polymer particle that constitutes with respect to aforementioned polyvinyl AI and aforementioned polyvinyl AII constitute, preferably the scope in 0.1 parts by mass-0.2 parts by mass contains aforementioned nonionic surfactant.The use amount of nonionic surfactant then can improve the aqueous dispersion stability of aforementioned polymer particle if aforementioned range.
In addition, with respect to polymer particle 100 parts by mass of aforementioned core-integumentary pattern, preferably contain nonionic surfactant in 0.1 parts by mass-0.2 parts by mass scope.The use amount of nonionic surfactant then can improve the aqueous dispersion stability of aforementioned polymer particle if aforementioned range.
In addition, as making polymer particle that aforementioned polyvinyl AI constitutes, polymer particle that aforementioned polyvinyl AII constitutes, and aforementioned core-spendable polymerization initiator of the integumentary pattern polymer beads period of the day from 11 p.m. to 1 a.m, for example can enumerate azo-compound, organic peroxide etc., wherein, preferred use 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-water-soluble azo compounds of azo two [2-(2-imidazoline-2-yl) propane] dihydrochloride etc.
Below, the surfactant B that the general formula (I) of the present invention's use is represented describes.
The surfactant B of general formula (I) expression is to contain the hydrophobicity base of the alkyl formation that has 8-30 carbon atom and the alkylamino acetic acid betaine of the hydrophily base that carbonyl constitutes.The surfactant B of general formula (I) expression, because easy and the big polyester fiber affinity of surface tension, even so the dip time of polyester fiber in fibre finish of the present invention is short, also stick to easily on the fiber surface, can give enough antistatic behaviours to fiber.
In the general formula (I), R
1, R
2And R
3At least 1 expression the alkyl of 8-30 carbon atom is arranged, other represent to have the alkyl of 1-4 carbon atom independently of one another.A represents to have the alkylidene of 1-2 carbon atom.
In addition, the R in the aforementioned formula (I)
1, R
2And R
3Be entirely have 4 following carbon atoms alkyl, for example N, N, N-trimethylglycine or R
1, R
2And R
3Be the sarcosine of hydrogen atom entirely, though the function as antistatic additive is arranged because not as the function of surfactant, so and the affinity of the big polyester fiber of surface tension insufficient.
Therefore, use N as described above, N, N-trimethylglycine etc. not as the alkylamino acetic acid betaine of surfactant function, the dip time of polyester fiber in fibre finish can not fully stick on the fiber surface very in short-term, can not give enough antistatic behaviours to fiber.
In addition, aforementioned N, N, N-trimethylglycines etc. are because the fibre finish that contains this compound reduces the affinity to polyester fiber, so during with such fibre finish, the occasion that aforementioned dip time is very short can not be given sufficient dark colorization effect to fiber.
As the surfactant B of general formula (I) expression,, preferably use the R in the aforementioned formula (I) for example from good to the affinity of polyester fiber and can give the viewpoint consideration of excellent antistatic behaviour
1, R
2And R
3At least 1 expression preferably have the alkyl of 8-20 carbon atom, the surfactant of other alkyl of representing to have 1-4 carbon atom independently of one another.More specifically preferably use lauryl dimethylamino acetic acid betaine, dodecyl dimethylamino acetic acid betaine, stearyl dimethylamino acetic acid betaine etc.
The surfactant B of general formula (I) expression, total amount 100 parts by mass of the polymer particle that polymer particle that constitutes with respect to aforementioned polyvinyl AI and aforementioned polyvinyl AII constitute are preferably used in the scope of 1 parts by mass-50 parts by mass, are more preferably used in the scope of 5 parts by mass-20 parts by mass.The use amount of aforementioned surfactants B does not then influence the dark colorization of the polyester fiber color of dyeing if aforementioned range, can give excellent antistatic behaviour to fiber.
In addition, the surfactant B of general formula (I) expression with respect to aforementioned core-integumentary pattern polymer particle 100 parts by mass, preferably acts in the scope of 1 parts by mass-50 parts by mass, more preferably uses in the scope of 5 parts by mass-20 parts by mass.The use amount of above-mentioned surfactant B does not then influence the dark colorization of the polyester fiber color of dyeing if aforementioned range, can give excellent antistatic behaviour to polyester fiber.
In addition, contained water in the fibre finish of the present invention, with respect to the total amount of aforementioned fibers finishing agent, preferably the scope at 50-99.9 quality % contains, more preferably the scope at 70-99.9 quality % contains, and the preferred again scope at 80-99.9 quality % contains.
Be the polymer particle that constitutes of the polymer particle that contained aforementioned polyvinyl AI constitutes in the fibre finish of the present invention, aforementioned polyvinyl AII, and the total amount of aforementioned surfactants B, the preferably scope of remaining 0.1-50 quality %.
More specifically, the polymer particle that the polymer particle that contained aforementioned polyvinyl AI constitutes in the fibre finish of the present invention, aforementioned polyvinyl AII constitute, the total amount that reaches aforementioned surfactants B, total amount with respect to the aforementioned fibers finishing agent is the scope of 0.1-50 quality %, and total amount 100 parts by mass of the polymer particle that polymer particle that the content of aforementioned surfactants B constitutes with respect to aforementioned polyvinyl AI and aforementioned polyvinyl AII constitute, the preferably scope of 1-50 parts by mass.
In addition, as before illustrated, polymer particle that aforementioned polyvinyl AI constitutes and the mass ratio [AI/AII] of aforementioned polyvinyl AII be the scope of 90/10-10/90 preferably.
In addition, the water that contains in the fibre finish of the present invention preferably contains in the scope of 50-99.9 quality % with respect to the total amount of aforementioned fibers finishing agent, and more preferably the scope at 70-99.9 quality % contains, preferably contains in the scope of 80-99.9 quality %.
That is the total amount of the polymer particle of the aforementioned core-integumentary pattern that contains in the fibre finish of the present invention and the aforementioned surfactants B scope of remaining 0.1-50 quality % preferably.
More specifically, the total amount of the polymer particle of aforementioned core-integumentary pattern that fibre finish of the present invention contains and aforementioned surfactants B, total amount with respect to the aforementioned fibers finishing agent is the scope of 0.1-50 quality %, and the content of aforementioned surfactants B is with respect to total amount 100 parts by mass of the polymer particle of aforementioned core-integumentary pattern, the preferably scope of 1-50 parts by mass.
In addition, as before illustrated, the aforementioned polyvinyl AI in the polymer particle of aforementioned core-integumentary pattern and the mass ratio [AI/AII] of aforementioned polyvinyl AII, the preferably scope of 70/30-10/90.
Below, the manufacture method of fibre finish of the present invention is described.
Contain polymer particle, the polymer particle that aforementioned polyvinyl AII constitutes, the surfactant B of aforementioned formula (I) expression and the fibre finish of the present invention of water that aforementioned polyvinyl AI constitutes, aqueous solution, the stirring of the aqueous dispersions of aqueous dispersions that for example can be by polymer particle that aforementioned polyvinyl AI is constituted, the polymer particle that aforementioned polyvinyl AII constitutes and the surfactant B of aforementioned formula (I) expression are made.
In addition, contain the surfactant B of polymer particle, aforementioned formula (I) expression of aforementioned core-integumentary pattern and the fibre finish of the present invention of water, for example can be by aqueous solution, the stirring of the surfactant B of the aqueous dispersions of the polymer particle of aforementioned core-integumentary pattern and aforementioned formula (I) expression are made.
Fibre finish of the present invention in order further to improve antistatic behaviour, can use the anionic property antistatic additive.
As aforementioned anionic property antistatic additive, for example, can use acid phosphoric acid ester, hydroxycarboxylic acid etc., wherein use acid phosphoric acid ester, preferred owing to the dark colorization of the polyester fiber color that does not influence dyeing such as dyestuff.
As aforementioned acid phosphoric acid ester, for example can use methyl-phosphoric acid, dimethyl phosphate, monobutyl phosphate, dibutylphosphoric acid ester or these slaine or ammonium salt etc.
As aforementioned hydroxycarboxylic acid, for example can use gluconic acid, glycollic acid, lactic acid and malic acid or these slaine etc.
Aforementioned anionic property antistatic additive, total amount 100 parts by mass of the polymer particle that polymer particle that constitutes with respect to aforementioned polyvinyl AI and aforementioned polyvinyl AII constitute are preferably used in the scope of 20 parts by mass-50 parts by mass.
In addition, aforementioned anionic property antistatic additive with respect to polymer particle 100 parts by mass of aforementioned core-integumentary pattern, preferably uses in the scope of 20 parts by mass-50 parts by mass.
Aforementioned anionic property antistatic additive, the aqueous dispersions of the polymer particle that can constitute with aforementioned polyvinyl AI, the aqueous dispersions of the polymer particle that aforementioned polyvinyl AII constitutes, the aqueous solution that reaches the surfactant B of aforementioned formula (I) expression is mixed together, and stirs.
In addition, aforementioned anionic property antistatic additive can be at the aqueous dispersions of the polymer particle of aforementioned core-integumentary pattern, and the aqueous solution of the surfactant B of aforementioned formula (I) expression mixes, use when stirring.
Fibre finish of the present invention even contact with other fiber etc. at the polyester fiber of dark colorization, the occasion of friction etc., also is difficult to destroy the dark color effect of fiber, and is with this end in view, preferred and use polysiloxane compound.It is small concavo-convex to use the surface of the polyester fiber of fibre finish of the present invention processing to form.Yet, owing to after small concavo-convex the coming off such as friction, can reduce the dark color effect of the polyester fiber of dyeing again.And fibre finish of the present invention passes through and use silicon compound, gives excellent anti-nuzzling up property to fiber, but the dark color effect of the polyester fiber of long term maintenance dyeing.
As the operable silicon compound of fibre finish of the present invention, for example, can use dimethyl silicone polymer, amino modified polysiloxane, carboxy-modified polysiloxanes, methyl alcohol modified polyorganosiloxane, epoxy-modified polysiloxane, polyether-modified polysiloxanes etc.
In addition, as aforementioned silicon compound, except aforesaid, can also use the compound that alkoxysilyl and epoxy radicals are arranged of 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.
Fibre finish of the present invention mixes aforementioned silicon compound when using, and preferred use makes aforementioned silicon compound be dispersed in aqueous dispersions in the water in advance.Operable surfactant when making aforementioned silicon compound be dispersed in the water can use known habitual surfactant.The usage ratio of aforementioned surfactants never influences the dark colorization of polyester fiber of dyeing such as dyestuff and the viewpoint that improves anti-nuzzling up property and considers that preferably the total amount with respect to silicon compound is below the 15 quality %.
Total amount 100 parts by mass of the polymer particle that polymer particle that aforementioned silicon compound constitutes with respect to aforementioned polyvinyl AI and aforementioned polymer AII constitute are preferably used 1 parts by mass～50 parts by mass.Can give anti-nuzzling up property fully to polyester fiber at the fibre finish that aforementioned range uses silicon compound to make.
In addition, aforementioned silicon compound preferably uses 1 parts by mass-50 parts by mass with respect to polymer particle 100 parts by mass of core-integumentary pattern.Can give anti-nuzzling up property fully to polyester fiber at the fibre finish that aforementioned range uses silicon compound to make.
Aforementioned silicon compound, the aqueous solution of the aqueous dispersions of the aqueous dispersions of the polymer particle that can constitute at aforementioned polyvinyl AI, the polymer particle that aforementioned polyvinyl AII constitutes and the surfactant B of aforementioned formula (I) expression mixes, use when stirring.
In addition, aforementioned silicon compound, the polymer beads period of the day from 11 p.m. to 1 a.m in the polymer particle of making aforementioned polyvinyl AI formation or aforementioned polyvinyl AII formation can be added in the water with aforementioned vinyl monomer.
In addition, aforementioned silicon compound can mix at the aqueous solution of the surfactant B of the aqueous dispersions of the polymer particle of aforementioned core-integumentary pattern and aforementioned formula (I) expression, use when stirring.
In addition, aforementioned silicon compound, the polymer beads period of the day from 11 p.m. to 1 a.m making aforementioned core-integumentary pattern can be added in the water with aforesaid vinyl monomer.
In addition,, especially use the occasion that has amino silicon compound as aforementioned silicon compound, as aforementioned polyvinyl AII, the preferred compound that hydroxyl or glycidyl are arranged that uses.Aforementioned have amino silicon compound and the base or the glycidol radical reaction that are present in the tunicle that aforementioned polyvinyl AII forms, difficultly comes off from fiber surface.The result can continue the dark color effect of fiber for a long time.
Below, the polyester fiber that the present invention is formed tunicle describes.
The present invention forms the polyester fiber of tunicle, for example, can stick to first operation on the polyester fiber by making fibre finish of the present invention, and the polyester fiber that will be stained with the aforementioned fibers finishing agent heats, second operation that forms tunicle at fiber surface is made.
As making fibre finish of the present invention stick to first operation on the polyester fiber, for example have the polyester fiber method by, dipping continuously in fibre finish that makes.
Fibre finish of the present invention even the dip time of polyester fiber is very short, the occasion of about 0.5-2 about second, also can fully stick on the polyester fiber.Polyester fiber behind the dipping preferably squeezes to press by mangle removes the excess fiber finishing agent.
As by the polyester fiber that is adhering to the aforementioned fibers finishing agent being heated, forms second operation of tunicle at fiber surface, for example have by using hot air circular drying machine under 100 ℃-120 ℃ temperature, to heat to evaporate the water in 2 minutes～3 minutes, then by heating the method that formed tunicle in 30 seconds～1 minute down at 150 ℃～160 ℃.In addition, use heating furnace to evaporate the water in 30 seconds-3 minutes in addition by heating under 80 ℃～120 ℃ temperature, then 130 ℃-180 ℃ methods that heat 30 seconds-3 minutes down,
When heating is adhering to the polyester fiber of fibre finish under temperature as the aforementioned, the partly fusion of polymer particle that the aforementioned polyvinyl AI that contains in the aforementioned fibers finishing agent constitutes, and the complete fusion of polymer particle that aforementioned polyvinyl AII constitutes, be formed with small concavo-convex tunicle at fiber surface, have this small concavo-convex tunicle to suppress reverberation from fiber surface, the color of the fiber of result's dyeing obtains dark colorization.
As the polyester fiber that can use fibre finish of the present invention processing, for example can enumerate pure polyester or and with the fabric of other materials, compile thing, nonwoven fabric, cotton, long fibered yarn, short fibre yarn etc.
The polyester fiber at fiber surface formation tunicle that uses fibre finish processing of the present invention to obtain is that dark color changes into the original dark color of dyestuff, and the electrostatic fiber of excellent anti is arranged.
The specific embodiment
Below, enumerate embodiments of the invention.
(reference example 1)
195 parts by mass metering system tert-butyl acrylates, 5 parts by mass N hydroxymethyl acrylamides, 0.7 parts by mass ァ one カ one De 16-50 (hexadecyltrimethylammonium chloride as cationic surfactant, Kao Corp's system), and 100 parts by mass ion exchange waters mix, stir, make the aqueous dispersion (a-1) of vinyl monomer.
(reference example 2)
The isobutyl acrylate of 140 parts by mass, 40 parts by mass isobutyl methacrylates, 8 parts by mass methyl methacrylates, 6 parts by mass 2-hydroxyethyl methacrylates, 4 parts by mass N hydroxymethyl acrylamides, 0.7 parts by mass ァ one カ one De 16-50 (hexadecyltrimethylammonium chloride as cationic surfactant, Kao Corp's system), and 100 parts by mass ion exchange waters mix, stir, make the aqueous dispersion (a-2) of vinyl monomer.
(reference example 3)
The isobutyl acrylate of 100 parts by mass, 28 parts by mass isobutyl methacrylates, 7 parts by mass methyl methacrylates, 5 parts by mass N hydroxymethyl acrylamides, 0.7 parts by mass ァ one カ one De 16-50 (hexadecyltrimethylammonium chloride as cationic surfactant, Kao Corp's system), and 74 parts by mass ion exchange waters mix, stir, make the aqueous dispersion (a-3) of vinyl monomer.
(synthesis example 1)
Have in 4 mouthfuls of flasks of nitrogen ingress pipe, dropping funel, backflow cooling tube, agitator at 1500ml, add the aqueous dispersion (a-1) of 450 parts by mass ion exchange waters and 60 parts by mass vinyl monomers, under nitrogen environment atmosphere, be warmed up to 75 ℃ while stirring.Add then 20 parts by mass as 2,2 of polymerization initiator '-the 1 quality % aqueous solution of azo two (2-amidine propane) dihydrochloride.
After the interpolation, respectively with aqueous dispersion (a-1) 240.7 parts by mass and 2 that dripped vinyl monomer in 120 minutes, the 1 quality % aqueous solution, 16 parts by mass of 2 '-azo two (2-amidine propane) dihydrochloride.After dripping end,, add ion exchange water, make the aqueous dispersions (non-volatile content 20 quality %) of the polyvinyl (A-1) of 120 ℃ of refractive index 1.47 and glass transition temperatures 75 ℃ of reactions 2 hours.
(synthesis example 2)
Have in the four-hole boiling flask of nitrogen ingress pipe, dropping funel, backflow cooling tube, agitator at 1500ml, add the aqueous dispersion (a-2) of 450 parts by mass ion exchange waters and 60 parts by mass vinyl monomers, under nitrogen environment atmosphere, be warmed up to 75 ℃ while stirring.Add then 20 parts by mass as 2,2 of polymerization initiator '-the 1 quality % aqueous solution of azo two (2-amidine propane) dihydrochloride.
After the interpolation, respectively with aqueous dispersion (a-2) 238.7 parts by mass and 2,2 that dripped vinyl monomer in 120 minutes '-the 1 quality % aqueous solution, 16 parts by mass of azo two (2-amidine propane) dihydrochloride.After dripping end,, add ion exchange water, make the aqueous dispersions (non-volatile content 20 quality %) of the polyvinyl (A-2) of-2 ℃ of refractive index 1.47 and glass transition temperatures 75 ℃ of reactions 2 hours.
(synthesis example 3)
Have in the four-hole boiling flask of nitrogen ingress pipe, dropping funel, backflow cooling tube, agitator at 1500ml, add the aqueous dispersion (a-3) of 450 parts by mass ion exchange waters and 60 parts by mass vinyl monomers, under nitrogen environment atmosphere, be warmed up to 75 ℃ while stirring.Then, add 20 parts by mass as 2,2 of polymerization initiator '-the 1 quality % aqueous solution of azo two (2-amidine propane) dihydrochloride.
After the interpolation, respectively with aqueous dispersion (a-3) 154.7 parts by mass and 2,2 that dripped vinyl monomer in 120 minutes '-the 1 quality % aqueous solution, 16 parts by mass of azo two (2-amidine propane) dihydrochloride.After drip finishing, kept 1 hour at 75 ℃, then respectively with 90 minutes dropping metering system tert-butyl acrylate 60 parts by mass and 2,2 '-the 1 quality % aqueous solution, 12 parts by mass of azo two (2-amidine propane) dihydrochloride.After dripping end, dripped 2 with 1 hour, 2 '-the 1 quality % aqueous solution, 2 parts by mass of azo two (2-amidine propane) dihydrochloride, reacted again 1 hour, add ion exchange water, the polyvinyl that make refractive index and be 1.47, skin zone is glass transition temperature-2 ℃, core are the aqueous dispersions (non-volatile content 20 quality %) of polyvinyl (A-3) of core-integumentary pattern of the polyvinyl of 118 ℃ of glass transition temperatures.
The refractive index and the glass transition temperature of aforementioned polyvinyl (A-1)-(A-3) use following method to make test piece, obtain according to following assay method.
The manufacture method of test piece
Aqueous dispersions 2 parts by mass of the polyvinyl that synthesis example 1-3 is made are mixed with oxolane 10 parts by mass, use 10 microns spreader to be coated on the pet film of surface smoothing (on Dongli Ltd.'s system " Le ミ ラ one ", use air drier 80 ℃ of dryings 30 minutes then, make test piece.
The assay method of refractive index
Use Abbe refractometer (KPR-30A, カ Le ニ ュ one optics industry Co., Ltd. system), measure the refractive index of the test piece that preceding method makes according to JIS K7105.
The assay method of glass transition temperature
Use differential scanning calorimeter [セ ィ コ one ィ Application ス ト Le メ Application ト Co., Ltd. system, machine name: DSC6200, parsing software: エ Network ス 1], about 10mg of the portion of the test piece that under 20 ℃/minute of programming rates preceding method is obtained is heated to 150 ℃, measures according to JIS K7121.
(embodiment 1)
The aqueous dispersions of the aqueous dispersions of the polyvinyl (A-1) that makes by 75 parts by mass synthesis examples 1, the polyvinyl (A-2) that 425 parts by mass synthesis examples 2 make, the 24 quality % aqueous solution of 42 parts by mass lauryl dimethylamino acetic acid betaines and 11958 parts by mass ion exchange waters mix, stir, and make fibre finish.The polyvinyl that contains in the fibre finish (A-1), polyvinyl (A-2), and the mass ratio of lauryl dimethylamino acetic acid betaine be shown in table 1.
(embodiment 2)
The aqueous dispersions of the polyvinyl (A-3) that 500 parts by mass synthesis examples 3 are made, the 24 quality % aqueous solution of 42 parts by mass lauryl dimethylamino acetic acid betaines, and 11958 parts by mass ion exchange waters mix, stir, make fibre finish.
(embodiment 3)
Except lauryl dimethylamino acetic acid betaine being made into decyl dimethylamino acetic acid betaine, other make fibre finish with method similarly to Example 1.
(embodiment 4)
Except lauryl dimethylamino acetic acid betaine being made into stearyl dimethylamino acetic acid betaine, other make fibre finish with method similarly to Example 1.
(embodiment 5)
The aqueous dispersions of the aqueous dispersions of the polyvinyl (A-1) that 50 weight portion synthesis examples 1 are made, the polyvinyl (A-2) that 450 weight portion synthesis examples 2 make, the 24 quality % aqueous solution of 42 weight portion lauryl dimethylamino acetic acid betaines, 150 parts by mass as the パ one マ ス ッ ト WF-18 of the anionic property antistatic additive aqueous solution, Dainippon Ink. ﹠ Chemicals Inc's system, the non-volatile content 20 quality % of dibutylphosphoric acid ester (monobutyl phosphate with), and 11908 parts by mass ion exchange waters mix, stir, make fibre finish.
(embodiment 6)
The aqueous dispersions of the polyvinyl (A-1) that 50 parts by mass synthesis examples 1 are made, the aqueous dispersions of the polyvinyl (A-2) that 450 parts by mass synthesis examples 2 make, the 24 quality % aqueous solution of 42 parts by mass lauryl dimethylamino acetic acid betaines, 150 parts by mass are as the パ one マ ス ッ ト WF-18 (aqueous solution of monobutyl phosphate and dibutylphosphoric acid ester of anionic property antistatic additive, Dainippon Ink. ﹠ Chemicals Inc's system, non-volatile content 20 quality %), (end has hydroxyl to 33 parts by mass as the デ ィ ッ Network シ リ コ Application 320 of polysiloxane compound, and amino equivalent is 20000 amino modified polysiloxane emulsion, Dainippon Ink. ﹠ Chemicals Inc's system, non-volatile part of 30 quality %), and 11875 parts by mass ion exchange waters mix, stir, make fibre finish.
(comparative example 1)
The aqueous dispersions of the aqueous dispersions of the polyvinyl (A-1) that 75 parts by mass synthesis examples 1 are made, the polyvinyl (A-2) that 425 parts by mass synthesis examples 2 make, 150 parts by mass as the パ one マ ス ッ ト WF-18 (aqueous solution of monobutyl phosphate and dibutylphosphoric acid ester, big Japanese ink chemical industrial company system, non-volatile content 20 quality %) of anionic property antistatic additive, and 11850 parts by mass ion exchange waters mix, stir, make fibre finish.
(comparative example 2)
Aqueous dispersions, the 200 parts by mass N of the aqueous dispersions of the polyvinyl (A-1) that 75 parts by mass synthesis examples 1 are made, the polyvinyl (A-2) that 425 parts by mass synthesis examples 2 make, N, the 20 quality % aqueous solution of N-trimethylglycine, and 11800 parts by mass ion exchange waters mix, stir, make fibre finish.
(comparative example 3)
The aqueous dispersions of the aqueous dispersions of the polyvinyl (A-1) that 75 parts by mass synthesis examples 1 are made, the polyvinyl (A-2) that 425 parts by mass synthesis examples 2 make, the 20 quality % aqueous solution and the 11800 parts by mass ion exchange waters of 200 parts by mass sarcosines mix, stir, and make fibre finish.
The various evaluation results of the test cloth that uses embodiment 1～6 and comparative example 1～3 described fibre finish, makes according to " preparation method of test cloth " described later are shown in table 1 and table 2.In addition, the polyester satin cloth without fibre finish processing 4 is shown in table 3 as a comparative example as the result that test cloth carries out various evaluations.In addition, the various rerum naturas of representing in the table are estimated according to the method for following expression.
" preparation method of test cloth "
The polyester satin cloth of dying black (30cm * 21cm) 2 seconds of dipping in aforesaid fibre finish, use hot air circular drying machine at 110 ℃ after predrying 3 minutes then, at 1 minute mylars of 160 ℃ of heating as test cloth.
" test cloth dark colorization Evaluation on effect method "
The polyester satin cloth of dying black of different fibre finish processing (30cm * 21cm) be converted into three foldings to make its core in the above, use beam splitting type colour difference meter (SE2000, Japanese electric look Industrial Co., Ltd system) to survey the brightness (L value) of 10 dot center part, ask its mean value.
In addition, the afore-mentioned test cloth that uses fibre finish processing is converted into three foldings makes its core in the above, use beam splitting type colour difference meter (SE2000, Japanese electric look Industrial Co., Ltd system), survey the brightness (L value) of 10 dot center part, ask its mean value.By the L value of the test cloth before the fibre finish processing with process after the degree of difference evaluation test cloth dyeingization of L value of test cloth.In addition, the difference of aforementioned L value is big more, shows all the more dark colorization of test cloth.
Zero: the difference of L value is more than 3
△: the difference of L value is more than 1～less than 3
*: the difference of L value is less than 1
" evaluation method of anti-nuzzling up property "
Use to learn vibration shape friction fastness test machine (ス ガ testing machine (strain) system), adopt the 50g loading that test cloth of the same race is nuzzled up after 100 times mutually, use aforementioned beam splitting type colour difference meter to measure the L value of nuzzling up and locating.By the L value of the test cloth before nuzzling up and the difference of the L value of the test cloth after nuzzling up estimate anti-the nuzzling up property of this test cloth.The difference of the L value before and after nuzzling up is more little, shows that anti-nuzzling up property is good more.
Zero: the difference of the L value before and after nuzzling up is less than 1.
△: the difference of the L value before and after nuzzling up is more than 1～less than 3.
*: the difference of the L value before and after nuzzling up is more than 3.
" evaluation method of antistatic behaviour "
Afore-mentioned test cloth after leaving standstill 24 hours under the environment of 20 ℃ of temperature and relative humidity 40%, (Jing Dahua grinds formula rotary static testing machine to use frictional electrification to press the mensuration machine, RST301, (strain) Xing Ya chamber of commerce), according to vertically pressing of JIS L 1094 determination test cloth with horizontal frictional electrification.The friction proof voltage of test cloth, vertically with laterally be below the 100V, use first-class in fact.
" evaluation method of thermo-color "
After filter paper (Japan filter paper Co., Ltd. system, No. 2 filter paper) is fully flooded in fibre finish, the quality of using mangle to regulate to make the fibre finish that filter paper absorbs is 100 quality % with respect to the mass ratio of filter paper, at 100 ℃ of predrying filter paper of 5 minutes as ph test paper ph.Use beam splitting type colour difference meter (SE2000, Japanese electric look Industrial Co., Ltd system) to measure the b value of afore-mentioned test paper.
Then, afore-mentioned test paper 200 ℃ of heating 10 minutes, is adopted the b value of measuring the ph test paper ph after the heating with aforementioned same method.
By the b value of the ph test paper ph before the heating with heat after b value poor of ph test paper ph, the variable color degree of evaluation test paper.The difference of b value is big more, shows that the variable color degree is big more.
In addition, comparative example 4 is except making water replacement fibre finish, and other adopt with aforementioned same method and estimate thermo-color.
Zero: the difference of b value is less than+10.
△: poor+10 of b value～less than+20.
*: the b value poor+more than 20.
" evaluation method of fibre finish stability "
The condensation product production rate that the stability of fibre finish adopts following method to ask is estimated.
1 liter of fibre finish is added in the container of transparent cylinder shape of diameter 12cm, high 20cm, use has 6 pieces of turbine impellers (diameter 4cm, wide 7mm) dispersator (the equal disperser of TK-DHL type, Tokushu Kika Kogyo K.K's system),, use 320 mesh filter screens to filter and obtain condensation product after 5 minutes according to mixing speed 800rpm stirring.Behind the condensation product that intensive drying obtains, measure the quality of condensation product.
Calculating formula (1)
Condensation product production rate (quality %)=(S/Sx) * 100
S in the calculating formula (1) represents the parts by mass of condensation product, and Sx represents the parts by mass of the polyvinyl that contains in the fibre finish.
Based on the condensation product production rate of obtaining according to aforementioned calculating formula (I), adopt following standard to estimate.
Zero: condensation product production rate 0 quality %～less than 1 quality %.
△: condensation product production rate 1 quality %～less than 30 quality %.
*: more than the condensation product production rate 30 quality %
[table 1]
| Table 1 | Mass ratio | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Polyvinyl (A-1) | 15 | 15 | 15 | 10 | 10 | |||
| Polyvinyl (A-2) | 85 | 85 | 85 | 90 | 90 | |||
| Polyvinyl (A-3) | 100 | |||||||
| Lauryl dimethylamino acetic acid betaine | 10 | 10 | 10 | 10 | ||||
| Decyl dimethylamino acetic acid betaine | 10 | |||||||
| Stearyl dimethylamino acetic acid betaine | 10 | |||||||
| N, N, N-trimethylglycine | ||||||||
| Sarcosine | ||||||||
| The mixture of monobutyl phosphate and dibutylphosphoric acid ester | 30 | 30 | ||||||
| Amino modified polysiloxane | 10 | |||||||
| The dark colorization effect | L value after the processing | 11.1 | 11.2 | 11.3 | 11.2 | 11.3 | 11.4 | |
| Estimate | ○ | ○ | ○ | ○ | ○ | ○ | ||
| Anti-nuzzling up property | L value after nuzzling up | 14.0 | 13.8 | 14.2 | 13.9 | 13.8 | 11.8 | |
| Estimate | △ | △ | △ | △ | △ | ○ | ||
| The friction proof voltage | Vertical (V) | 28 | 27 | 25 | 35 | 12 | 28 | |
| Horizontal (V) | 29 | 27 | 25 | 36 | 12 | 29 | ||
| Thermo-color | B value after the heating | 7.5 | 7.5 | 7.4 | 7.5 | 6.9 | 6.8 | |
| Estimate | ○ | ○ | ○ | ○ | ○ | ○ | ||
| The stability of fibre finish | ○ | ○ | ○ | ○ | ○ | ○ | ||
[table 2]
| Table 2 | Mass ratio | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Polyvinyl (A-1) | 15 | 15 | 15 | ||
| Polyvinyl (A-2) | 85 | 85 | 85 | ||
| Polyvinyl (A-3) | |||||
| Lauryl dimethylamino acetic acid betaine | |||||
| Decyl dimethylamino acetic acid betaine | |||||
| Stearyl dimethylamino acetic acid betaine | |||||
| N, N, N-trimethylglycine | 40 | ||||
| Sarcosine | 40 | ||||
| The mixture of monobutyl phosphate and dibutylphosphoric acid ester | 30 | ||||
| Amino modified polysiloxane | |||||
| The dark colorization effect | L value after the processing | 14.1 | 14.2 | 13.9 | |
| Estimate | × | × | × | ||
| Anti-nuzzling up property | L value after nuzzling up | 14.2 | 14.4 | 14.1 | |
| Estimate | ○ | ○ | ○ | ||
| The friction proof voltage | Vertical (V) | 4000 | 6200 | 4100 | |
| Horizontal (V) | 4300 | 6300 | 4700 | ||
| Thermo-color | B value after the heating | 1.9 | 12.2 | 28.5 | |
| Estimate | ○ | △ | × | ||
| The stability of fibre finish | × | ○ | ○ | ||
Do not implement to use the evaluation of physical property of polyester satin cloth processing, that dye black of fibre finish
| Table 3 | Comparative example 4 | |
| The L value | 14.8 | |
| Anti-nuzzling up property | 14.8 | |
| The friction proof voltage | Vertical (V) | 5700 |
| Horizontal (V) | 5400 | |
| Thermo-color | B value after the heating | 1.9 |
| Estimate | ○ | |
Claims (8)
1. fibre finish, it is characterized in that, contain: the polymer particle that polymerization of vinyl monomer obtains in the presence of cationic surfactant, the refractive index below 1.50 is arranged and have the polyvinyl AI of the glass transition temperature of 110～150 ℃ of scopes to constitute
The polymer particle that polymerization of vinyl monomer obtains in the presence of cationic surfactant, the refractive index below 1.50 is arranged and have the polyvinyl AII of the glass transition temperature of-20～20 ℃ of scopes to constitute,
The surfactant B and the water of general formula (I) expression,
In the above-mentioned general formula (I), R
1, R
2And R
3At least 1 expression the alkyl of 8-30 carbon atom is arranged, other represent to have the alkyl of 1-4 carbon atom independently of one another, A represents to have the alkylidene of 1-2 carbon atom.
2. fibre finish, it is characterized in that, the polymer particle that contains the core-integumentary pattern of the polyvinyl formation that polymerization of vinyl monomer obtains in the presence of cationic surfactant, the refractive index below 1.50 is arranged, the surfactant B and the water of general formula (I) expression
The polymer particle of aforementioned core-integumentary pattern, core have the polyvinyl AI of glass transition temperature 110-150 ℃ scope, and there is the polyvinyl AII of glass transition temperature-20～20 ℃ scope in skin zone,
In the above-mentioned general formula (I), R
1, R
2And R
3At least 1 expression the alkyl of 8-30 carbon atom is arranged, other represent to have the alkyl of 1-4 carbon atom independently of one another, A represents to have the alkylidene of 1-2 carbon atom.
3. claim 1 or 2 described fibre finishs, wherein, the R in the aforementioned formula (I)
1, R
2And R
3At least 1 be the alkyl that 8-20 carbon atom arranged, other represent to have the alkyl of 1-4 carbon atom independently of one another.
4. claim 1 or 2 described fibre finishs, wherein, the surfactant B of aforementioned formula (I) expression is at least a kind that is selected from lauryl dimethylamino acetic acid betaine, decyl dimethylamino acetic acid betaine and the stearyl dimethylamino acetic acid betaine.
5. claim 1 or 2 described fibre finishs wherein with respect to total amount 100 parts by mass of aforementioned polyvinyl AI and aforementioned polyvinyl AII, contain the surfactant B 1-50 parts by mass of aforementioned formula (I) expression.
6. claim 1 or 2 described fibre finishs wherein, also contain the anionic property antistatic additive.
7. the described fibre finish of claim 6, wherein, aforementioned anionic property antistatic additive is an acid phosphoric acid ester.
8. the polyester fiber that has tunicle, tunicle wherein sticks to claim 1 or 2 described fibre finishs on the polyester fiber, adds thermosetting then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004274907 | 2004-09-22 | ||
| JP2004274907 | 2004-09-22 |
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|---|---|
| CN1752335A CN1752335A (en) | 2006-03-29 |
| CN100354470C true CN100354470C (en) | 2007-12-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102007052968A1 (en) * | 2007-11-07 | 2009-05-14 | Bayer Materialscience Ag | Process for the preparation of polycarbonate after the melt transesterification process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH093774A (en) * | 1995-06-19 | 1997-01-07 | Dainippon Ink & Chem Inc | Color deepening agent and deepening method |
| JPH11172576A (en) * | 1997-12-04 | 1999-06-29 | Kao Corp | Antistatic agent |
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2005
- 2005-09-19 CN CNB2005101041226A patent/CN100354470C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH093774A (en) * | 1995-06-19 | 1997-01-07 | Dainippon Ink & Chem Inc | Color deepening agent and deepening method |
| JPH11172576A (en) * | 1997-12-04 | 1999-06-29 | Kao Corp | Antistatic agent |
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| CN1752335A (en) | 2006-03-29 |
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