CA2571979A1 - Disperse dyes for poly(lactic acid) based fibers - Google Patents
Disperse dyes for poly(lactic acid) based fibers Download PDFInfo
- Publication number
- CA2571979A1 CA2571979A1 CA002571979A CA2571979A CA2571979A1 CA 2571979 A1 CA2571979 A1 CA 2571979A1 CA 002571979 A CA002571979 A CA 002571979A CA 2571979 A CA2571979 A CA 2571979A CA 2571979 A1 CA2571979 A1 CA 2571979A1
- Authority
- CA
- Canada
- Prior art keywords
- poly
- lactic acid
- fibers
- dyestuffs
- yellow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- -1 poly(lactic acid) Polymers 0.000 title claims abstract description 70
- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 27
- 239000000986 disperse dye Substances 0.000 title abstract description 12
- 238000004043 dyeing Methods 0.000 claims abstract description 23
- 239000000975 dye Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 2
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002657 fibrous material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 101100294115 Caenorhabditis elegans nhr-4 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001000743 Hibana Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 235000012745 brilliant blue FCF Nutrition 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100035861 Cytosolic 5'-nucleotidase 1A Human genes 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000802744 Homo sapiens Cytosolic 5'-nucleotidase 1A Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000009980 pad dyeing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8276—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester groups
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to the use of a yellow and/or a red and/or a blue component of disperse dyes for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
Description
DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG 2004/D901 pr.My Disperse dyes for poly(lactic acid) based fibers s The present invention relates to the use of disperse dyes for dyeing poly{Iactic acid) fibers and poly(lactic ac4 based fibers comprising fiber mixtures of poly(lactic acid) fibers and other fibers, for example aromatic polyester fibers.
Poly(lactic acid) fibers are non-petroleum based fibers for which hydrocarbons of 1o vegetable origin are used as the raw material and which can be recycled in the ecological system by being degraded to water and carbon dioxide in the natural environment. Consequently, they are excellent materials in the environment where there is a shift away from petroleum depletion and the reuse of the resources is facilitated. Furthermore, when compared with other biodegradable 15 materials such as aliphatic polyesters it has a high fusion point and glass transition point and it is also as strong as general-purpose aromatic polyesters and so its widespread future use as practical fibers can be anticipated, Use as an industrial resource material, as an interior and living resource material and as fibers for clothing purposes in the form of films, sheets, span-bonded material, 2o resins and fibers has been considered, and the manufacturers are making rapid progress with developments which will extend the scope of application (for example, see Japanese Unexamined Patent Application Laid Open H8-3117$1 and Japanese Unexamined Patent Application Laid Open 2003-49374).
25 Dyes with which this material can be dyed with excellent light fastness properties will be needed if these new materials are to be widely used as fibers for automobile interior decoration and in interior applications, but as yet no dyes with which this can be achieved satisfactorily have appeared.
30 The present invention is based upon an understanding of the actual situation indicated above and is intended to provide disperse dyes with which the color fastness on poly(lactic acid) based fibers in particular is good and which have a good balance regarding light fastness among the three primary color dyestuffs, which form green and orange and also brown and grey, resembling the extents of fading of the respective dyestuffs.
The inventors have realized disperse dyes which meet the above mentioned requirements and which especially have good light fastness and dyeing properties by selecting and specifying from among the many dyestuffs which exist those dyestuffs which have comparatively good light fastness and build-up properties on poly(lactic acid) based fibers and combining these dyestuffs.
The present invention thus claims the use of a yellow component comprising at least one dyestuff of the group consisting of structural formulae (1), (2), (3), (4) and (5) ~70R
N l ~S
l NH
vw N.~ 0 t1~
wherein R' is (C1-C3} alkyl and RZ is {C4-C,f alkyl;
Br ~ ,! OH
b__ [tI0Brn (2) wherein n is 0 or 1;
as \ I
t~ S
0 (3) CI
0%2 N N~
CI N'R
Poly(lactic acid) fibers are non-petroleum based fibers for which hydrocarbons of 1o vegetable origin are used as the raw material and which can be recycled in the ecological system by being degraded to water and carbon dioxide in the natural environment. Consequently, they are excellent materials in the environment where there is a shift away from petroleum depletion and the reuse of the resources is facilitated. Furthermore, when compared with other biodegradable 15 materials such as aliphatic polyesters it has a high fusion point and glass transition point and it is also as strong as general-purpose aromatic polyesters and so its widespread future use as practical fibers can be anticipated, Use as an industrial resource material, as an interior and living resource material and as fibers for clothing purposes in the form of films, sheets, span-bonded material, 2o resins and fibers has been considered, and the manufacturers are making rapid progress with developments which will extend the scope of application (for example, see Japanese Unexamined Patent Application Laid Open H8-3117$1 and Japanese Unexamined Patent Application Laid Open 2003-49374).
25 Dyes with which this material can be dyed with excellent light fastness properties will be needed if these new materials are to be widely used as fibers for automobile interior decoration and in interior applications, but as yet no dyes with which this can be achieved satisfactorily have appeared.
30 The present invention is based upon an understanding of the actual situation indicated above and is intended to provide disperse dyes with which the color fastness on poly(lactic acid) based fibers in particular is good and which have a good balance regarding light fastness among the three primary color dyestuffs, which form green and orange and also brown and grey, resembling the extents of fading of the respective dyestuffs.
The inventors have realized disperse dyes which meet the above mentioned requirements and which especially have good light fastness and dyeing properties by selecting and specifying from among the many dyestuffs which exist those dyestuffs which have comparatively good light fastness and build-up properties on poly(lactic acid) based fibers and combining these dyestuffs.
The present invention thus claims the use of a yellow component comprising at least one dyestuff of the group consisting of structural formulae (1), (2), (3), (4) and (5) ~70R
N l ~S
l NH
vw N.~ 0 t1~
wherein R' is (C1-C3} alkyl and RZ is {C4-C,f alkyl;
Br ~ ,! OH
b__ [tI0Brn (2) wherein n is 0 or 1;
as \ I
t~ S
0 (3) CI
0%2 N N~
CI N'R
(4) wherein R3 is (C1-C.) alkyl or 2-hydroxyethyl;
s R (5) and/or a red component comprising at least one dyestuff of the group consisting of structural formulae (6) and (7) S ~ CHg N CN
R5HN N NHR4 (6) wherein one of R4 and R5 is hydrogen and the other is hydroxyethoxyethyl, hydroxy6utoxypropyl, acetoxyethoxyethyl or acetoxybutoxypropyl;
QMe 0 HHS02 &Rs (7) wherein Rfi is hydrogen or methyl;
andlor a blue component comprising at least one dyestuff of the group consisting of structural formulae (8), (9) and (10) R7 0 H(~ \
Ra 0 uH (8) wherein one of R7 and R8 is nitro and the other hydoxyl and Ro is hydrogen, chlorine or 2-hydroxyethyl;
Cl NHZ Q
cN N_R10 ~ ~
U NH2 +0 (9) 1o wherein R1O is methoxypropyl, ethoxyprapyl or methoxyethoxypropyl;
~, OS 2CH3 \ I
O HN
f~ OH (10) for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
The present invention thus provides disperse dyes and mixtures of disperse dyes with which dyeing with good light fastness can be carried out on poly(lactic acid) fibers.
In the definitions for the dyestuffs of the fflrmu9ae (1) to (10 given above s(Cl-C3) alkyl groups can be straight-chain or branched and are preferably methylf ethyl, n-propyl and iso.propyl.
(C4-C7) alkyl groups can also be straight-chain or branched and are preferably n-butyl, i-butyl, sek.-butyl, tert.-butyl, pentyl, hexyl or heptyl.
In the dyestuff of the formula (8) R9 is preferably hydrogen atom or 2-hydroxy-ethyl.
According to the present invention it is preferred to use only one of the dyestuffs of the formulae (1) to (10) for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
However, it is especially preferred to use a mixture comprising two or three of each of the yellow, the red and the blue dyestuffs.
In addition, it is also especially preferred to use a mixture comprising a yellow component comprising at least one of the dyestuffs of the formulae (1), (3) and (4), a red component comprising at least one dyestuff of the formula (6) and a 2o blue component comprising at least one dyestuff of the formula (8), It is also preferred to use one ore more dyestuffs of the formulae (1) to (10) conjointly with an ultraviolet absorber. Such ultraviolet absorbers are known to the skilled person, are described in literature and are available in the market place. Usually such ultraviolet absorbers are triazine- benzotriazole- or benzophenone-based. Examples are the products sold by Ciba Specialty Chemistry, Switzerland, under the tradename Cibafast.
The dyestuffs of the formulae (1) to (10) are insoluble or sparingly soluble in water and so for dyeing poly(lactic acid) based fibers using the dyestuff mixtures of this invention a dye bath or printing paste where they have been dispersed in the form of fine particles in an aqueous medium using a naphthalenesulfonic acid/formaldehyde condensate, higher alcohol fatty acid ester, higher alkylbenzenesulfonate or the like as a dispersant is prepared and the dyeing can then be carried out by the dip-dyeing method, the pad-dyeing method or by the dye-printing method. The dip-dyeing method in particular is preferred. If, in the case of dip-dyeing, the usual dye-treatment methods such as the high temperature dyeing method, the carrier dyeing method, the thermosof dyeing method and the like are applied then good dyeing can be achieved with poly(lactic acid) fibers or fiber mixtures in which they are included.
Poly(lactic acid) fibers are weak in respect of heat and alkaline conditions when compared io with polyester fibers and so high temperature dyeing at from 110 to 120 C
for from 15 to 30 minutes with a dye liquid pH of from 4.0 to 5.0 with the conjoint use of triazine-based, benzotriazole-based or benzophenone-based ultraviolet absorber is especially desirable.
Within the present invention the term poly(lactic acid) based fibers is understood to comprise mixtures of poly(lactic acid) fibers and other fibers. Such other fibers are preferably aromatic polyester fibers such as polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate fibers. Mixtures of propylene terephthalate fibers and poly(lactic acid),fibers are especially preferred.
The invention is described in more practical terms below by means of examples and comparative examples, but the invention is not limited by these examples.
Examples 1 to 19 The dyestuffs represented by the structural formulae (1-1), (1-2), (1-3), (2-1), (2-2), (3), (4-1), (4-2), (5), (6), (7-1), (8-1), (8-2), (8-3), (8-4), (9-1), (9-2), (9-3) and (10) indicated below were each mixed with twice the weight of naphthaJenesulphonic acid/formaldehyde condensate and disperse dyes were obtained by finely grinding and drying in the usual way. Poly(lactic acid) containing fibers (5 g) produced by the Toray Co., Japan were immersed in the dye bath which had been prepared by weighing out just the amount of disperse dye for about 112tV dyed material in the case of a single color and a total concentration of about 1/3N dyed material in the case of a compound color with respect to the standard dye concentration specified in JIS L 0808 for to 5 g of poly(lactic acid) fibers, adding the triazine based "Cibafast P" produced by the Ciba Specialty Chemical Co. as an ultraviolet absorber and dye promotor in an amount of 2% (o.w.f) and acetic acid/sodium acetate pH buffer solution (pH
4.5) to the dye bath and making up to a total of 100 ml with salt-free water, and dyeing was carried out by maintaining the bath at a temperature of 11 0 C for minutes. The dyed materials obtained were subjected to a reducing wash in 1.50 rni of water which contained 2 gfl of sodium hydrosulfiite, 2 g/l of sodium fo carbonate and 1 g/l of Hostapal LFB Conc. produced by the Clariant Co. by maintaining a temperature of 65 C for 10 minutes.
OMe N
N~
I s / NH
OnCsHi1 N1 t) (1-1) OCH
~ CH3 N~
f S
~ NH
OnC7H16 N (1-2) MeO
N
N''~
NH
diSOC4H9 !f Q
N t1-3) Br \ OH
~ O
N
~
Q
{2-1y Br \ OH
{Br)o ~
C ~
O
O
(2-2) as O
0 Ci - / ~
02N N~
N
l% CH3 .~-\ f (4-1) ~I
- ~ ~
02N N~
N N
~i l~
c2HdOH
(4-2) 5\
N NOZ
H t5S
cN f 1 .~''~ N CH3 N CN
I
R5HN N NHR4 (6) wherein R4 and R' are defined as given above OMe O NHSO2 &CH3 (7-1) NCl 0 HN O
OH 0 OH {~-1 r / ~
OH 0 HN ~' N02 O OH (8-2) ~H Q OH (8-3) ~~
NO2 0 HN ~'' x5d1 O
H 0 OH (8-4) 1'IXIII11II'IIITIN-CaH6OCH3 (9-1) 1IITI!1I1IIIIN-C3H6OC2HS
(9-2) 0 NHz O
(9-3) o Hrv / OSQ2~iH3 \ I
l f I ~
0 OH (10) The light-fastness of each dyed material was measured in accordance with the light fastness test specification of the Toyota Automobile Co. and the results obtained were as shown in Table 1.
Moreover, the light fastness test was carried out using a High Energy Xenon Fadometer produced by the Suga Testing Machine Co. for the testing apparatus under conditions of black panel temperature 73 3 C with irradiation using the to 38 cycle (1$2 hour) illumination method with 3,8 hours illumination timell hour dark time per cycle. The tests were carried out with a test cloth lined with urethane. The JIS L 0804 fading gray scale was used for assessing the grade.
Table 1 Example Structural Hue of the Dyed Light Fastness Formula Cloth (Grade) 1 (1-1} Yellow 3-4+
2 (1-2) Yellow 3-4 3 (1-3) Yellow 3-4 4 (2-1) Yellow 4+
5 (2-2) Yellow 4-5 6 (3) Yellow 4+
s R (5) and/or a red component comprising at least one dyestuff of the group consisting of structural formulae (6) and (7) S ~ CHg N CN
R5HN N NHR4 (6) wherein one of R4 and R5 is hydrogen and the other is hydroxyethoxyethyl, hydroxy6utoxypropyl, acetoxyethoxyethyl or acetoxybutoxypropyl;
QMe 0 HHS02 &Rs (7) wherein Rfi is hydrogen or methyl;
andlor a blue component comprising at least one dyestuff of the group consisting of structural formulae (8), (9) and (10) R7 0 H(~ \
Ra 0 uH (8) wherein one of R7 and R8 is nitro and the other hydoxyl and Ro is hydrogen, chlorine or 2-hydroxyethyl;
Cl NHZ Q
cN N_R10 ~ ~
U NH2 +0 (9) 1o wherein R1O is methoxypropyl, ethoxyprapyl or methoxyethoxypropyl;
~, OS 2CH3 \ I
O HN
f~ OH (10) for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
The present invention thus provides disperse dyes and mixtures of disperse dyes with which dyeing with good light fastness can be carried out on poly(lactic acid) fibers.
In the definitions for the dyestuffs of the fflrmu9ae (1) to (10 given above s(Cl-C3) alkyl groups can be straight-chain or branched and are preferably methylf ethyl, n-propyl and iso.propyl.
(C4-C7) alkyl groups can also be straight-chain or branched and are preferably n-butyl, i-butyl, sek.-butyl, tert.-butyl, pentyl, hexyl or heptyl.
In the dyestuff of the formula (8) R9 is preferably hydrogen atom or 2-hydroxy-ethyl.
According to the present invention it is preferred to use only one of the dyestuffs of the formulae (1) to (10) for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
However, it is especially preferred to use a mixture comprising two or three of each of the yellow, the red and the blue dyestuffs.
In addition, it is also especially preferred to use a mixture comprising a yellow component comprising at least one of the dyestuffs of the formulae (1), (3) and (4), a red component comprising at least one dyestuff of the formula (6) and a 2o blue component comprising at least one dyestuff of the formula (8), It is also preferred to use one ore more dyestuffs of the formulae (1) to (10) conjointly with an ultraviolet absorber. Such ultraviolet absorbers are known to the skilled person, are described in literature and are available in the market place. Usually such ultraviolet absorbers are triazine- benzotriazole- or benzophenone-based. Examples are the products sold by Ciba Specialty Chemistry, Switzerland, under the tradename Cibafast.
The dyestuffs of the formulae (1) to (10) are insoluble or sparingly soluble in water and so for dyeing poly(lactic acid) based fibers using the dyestuff mixtures of this invention a dye bath or printing paste where they have been dispersed in the form of fine particles in an aqueous medium using a naphthalenesulfonic acid/formaldehyde condensate, higher alcohol fatty acid ester, higher alkylbenzenesulfonate or the like as a dispersant is prepared and the dyeing can then be carried out by the dip-dyeing method, the pad-dyeing method or by the dye-printing method. The dip-dyeing method in particular is preferred. If, in the case of dip-dyeing, the usual dye-treatment methods such as the high temperature dyeing method, the carrier dyeing method, the thermosof dyeing method and the like are applied then good dyeing can be achieved with poly(lactic acid) fibers or fiber mixtures in which they are included.
Poly(lactic acid) fibers are weak in respect of heat and alkaline conditions when compared io with polyester fibers and so high temperature dyeing at from 110 to 120 C
for from 15 to 30 minutes with a dye liquid pH of from 4.0 to 5.0 with the conjoint use of triazine-based, benzotriazole-based or benzophenone-based ultraviolet absorber is especially desirable.
Within the present invention the term poly(lactic acid) based fibers is understood to comprise mixtures of poly(lactic acid) fibers and other fibers. Such other fibers are preferably aromatic polyester fibers such as polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate fibers. Mixtures of propylene terephthalate fibers and poly(lactic acid),fibers are especially preferred.
The invention is described in more practical terms below by means of examples and comparative examples, but the invention is not limited by these examples.
Examples 1 to 19 The dyestuffs represented by the structural formulae (1-1), (1-2), (1-3), (2-1), (2-2), (3), (4-1), (4-2), (5), (6), (7-1), (8-1), (8-2), (8-3), (8-4), (9-1), (9-2), (9-3) and (10) indicated below were each mixed with twice the weight of naphthaJenesulphonic acid/formaldehyde condensate and disperse dyes were obtained by finely grinding and drying in the usual way. Poly(lactic acid) containing fibers (5 g) produced by the Toray Co., Japan were immersed in the dye bath which had been prepared by weighing out just the amount of disperse dye for about 112tV dyed material in the case of a single color and a total concentration of about 1/3N dyed material in the case of a compound color with respect to the standard dye concentration specified in JIS L 0808 for to 5 g of poly(lactic acid) fibers, adding the triazine based "Cibafast P" produced by the Ciba Specialty Chemical Co. as an ultraviolet absorber and dye promotor in an amount of 2% (o.w.f) and acetic acid/sodium acetate pH buffer solution (pH
4.5) to the dye bath and making up to a total of 100 ml with salt-free water, and dyeing was carried out by maintaining the bath at a temperature of 11 0 C for minutes. The dyed materials obtained were subjected to a reducing wash in 1.50 rni of water which contained 2 gfl of sodium hydrosulfiite, 2 g/l of sodium fo carbonate and 1 g/l of Hostapal LFB Conc. produced by the Clariant Co. by maintaining a temperature of 65 C for 10 minutes.
OMe N
N~
I s / NH
OnCsHi1 N1 t) (1-1) OCH
~ CH3 N~
f S
~ NH
OnC7H16 N (1-2) MeO
N
N''~
NH
diSOC4H9 !f Q
N t1-3) Br \ OH
~ O
N
~
Q
{2-1y Br \ OH
{Br)o ~
C ~
O
O
(2-2) as O
0 Ci - / ~
02N N~
N
l% CH3 .~-\ f (4-1) ~I
- ~ ~
02N N~
N N
~i l~
c2HdOH
(4-2) 5\
N NOZ
H t5S
cN f 1 .~''~ N CH3 N CN
I
R5HN N NHR4 (6) wherein R4 and R' are defined as given above OMe O NHSO2 &CH3 (7-1) NCl 0 HN O
OH 0 OH {~-1 r / ~
OH 0 HN ~' N02 O OH (8-2) ~H Q OH (8-3) ~~
NO2 0 HN ~'' x5d1 O
H 0 OH (8-4) 1'IXIII11II'IIITIN-CaH6OCH3 (9-1) 1IITI!1I1IIIIN-C3H6OC2HS
(9-2) 0 NHz O
(9-3) o Hrv / OSQ2~iH3 \ I
l f I ~
0 OH (10) The light-fastness of each dyed material was measured in accordance with the light fastness test specification of the Toyota Automobile Co. and the results obtained were as shown in Table 1.
Moreover, the light fastness test was carried out using a High Energy Xenon Fadometer produced by the Suga Testing Machine Co. for the testing apparatus under conditions of black panel temperature 73 3 C with irradiation using the to 38 cycle (1$2 hour) illumination method with 3,8 hours illumination timell hour dark time per cycle. The tests were carried out with a test cloth lined with urethane. The JIS L 0804 fading gray scale was used for assessing the grade.
Table 1 Example Structural Hue of the Dyed Light Fastness Formula Cloth (Grade) 1 (1-1} Yellow 3-4+
2 (1-2) Yellow 3-4 3 (1-3) Yellow 3-4 4 (2-1) Yellow 4+
5 (2-2) Yellow 4-5 6 (3) Yellow 4+
7 (4-1) Yellow 4 Example Structural Hue of the Dyed Light Fastness Formula Cloth (Grade) 8 (4-2) Yellow 3 - 4 9 1: 1 Mixture of Yellow 3 - 4+
(3) and (4-2) (5) Yellow 3+
11 (6) Red 4-12 (7) Red 3 +
13 (8-1) Biue 3-4+
14 8 : 2 mixture of Blue 3-4 (8-1) and (8-2) (8-3) Blue 3-4 16 (8-4) Blue 3-4 17 1: 1 mixture of Blue 3-4 (9-1) and (9-2) 18 (9-3) Blue 3-4 19 (10) Blue 3-4 Comparative Examples 1 to 6 The dyeing of poly(lactic acid) based fibers was carried out in the same way as in the examples 1 to 19 using disperse dyes which had been prepared using the 5 yellow dyestuffs (A-1 ) and (A-2), the red dyestuffs (B-1 ) and (B-2) and the blue dyestuffs (C-1) and (C-2) of which the structural formulae are indicated below which have excellent light fastness on polyester fibers.
c a NHC G (A-1) iN
ci 1 ~
N
HQHdC~
(A-2) (B-1 ) is a 1:1 mixture of the two dyestuffs below CN
HC CN
rM
N ra N C2H~OC2H4OH
H-N
b CN
O2N N' N N
N H
H-N
CZH40C,H4OH
s 0 OH (B-2) OH cO2VIOH
NH2 O OH (C-1 ) ia Br NH2 0 OH (C-2) The results of the light fastness tests of these dyestuffs are given in Table Table 2 Example Structural Hue of the Dyed Light Fastness Formula Cloth (Grade) 1 (A-1 ) Yellow 2 2 (A-2) Yellow 2-3 (B-1 ) Red 1-2 4 {B-2} Red 2 + (blue modified color) 5 (C-1 ) Blue 1 - 2 6 (C-2) Blue 1 - 2 dAs becomes clear from Tables 1 and 2, the dyed materials obtained in Examples 1 to 19 were seen to have very much better light fastness when compared with the dyed materials obtained with the Comparative Examples 1 to 6.
Examples 20 to 31 Dyeing was carried out in accordance with the examples given below using mixtures of disperse dyes as indicated in Table 3, which had been prepared using the dyestuffs of the structural formulae [1-1 [, [2-2], [3]r [4-1 ], [4-2], [51, [6], [8-1 ], [8-3], [9-1 l, [9-2] and [10] as described above. However, the benzotriazole based Sunlife LP250 produced by the Hibana Chemical Co. was used for the ultraviolet absorber. The numerical values indicated as amounts compounded in the table are in units of wt%.
i5 Table 3 Formula Example (1-1) 40 16 36 (2-2) 3 5 (3) 16 25 (4-1) 50 21 23 31 39 (4-2) 24 23 23 48 (5) 23 (6) 'I 8 13 17 14 17 17 13 10 17 61 41 (8-1) 32 26 59 25 27 34 31 69 59 tD
(8-3) 54 30 54 N
1:' Mixture 5 4 ~
of (9-1) N
N
and (9-2) (10) 7 Hue of dyed Brown Brown Grey Grey Brown Grey Brown Grey Brown Green Orange Violet Cloth Light Fastness 3-4- 3 3-4 3+ 3-4 3-4 2-3 3 3-4- 3-4- 3-4- 3-4- y Comparative Examples 7 to 13 The dyeing of poly(Jactic acid) based fibers was carried out in the same way as in the examples 20 to 31, but using dyestuffs of examples 20 to 31 and dyestuffs (A-1 ), (A-2),(B-1 )f(B-2)o (C-1) and (C-2) as given in Table 4 below.
Table 4 Formula Comparative Example [1-1 I
[2-21 [3] 8 [4-11 [4-21 [5l [6] 23 12 [8-11 43 60 33 [8-31 45 1 : 7 Mixture ofi [9-111[9-2] 5 10 [10] 5 [A-1l 48 77 50 45 [A-21 63 42 [B-1l 9 4 5 17 [B-2l 22 16 [C-1l 10 15 [C-21 19 4 Hue of Dyed Brown Gray Brown Gray Brown Gray Brown Cloth Light Fastness 1- 2 2- 1 1- 2 1- 2 1- 2 1 Example 32 Dyeing was carried out in accordance with Example 20 except that the fibers used in Example 20 were replaced with a poly(Iactic acid) fiberlpolyprQpylene terephthalate fiber (50150wt /a) mixture, the dyeing conditions were changed to s 120 C x 40 minutes and the ultraviolet absorber was changed to benzophenone based Sunlife LPS855 produced by the Hibana Chemical Co. The results were such that the light fastness of the dyed material obtained was excellent at grade 4.
(3) and (4-2) (5) Yellow 3+
11 (6) Red 4-12 (7) Red 3 +
13 (8-1) Biue 3-4+
14 8 : 2 mixture of Blue 3-4 (8-1) and (8-2) (8-3) Blue 3-4 16 (8-4) Blue 3-4 17 1: 1 mixture of Blue 3-4 (9-1) and (9-2) 18 (9-3) Blue 3-4 19 (10) Blue 3-4 Comparative Examples 1 to 6 The dyeing of poly(lactic acid) based fibers was carried out in the same way as in the examples 1 to 19 using disperse dyes which had been prepared using the 5 yellow dyestuffs (A-1 ) and (A-2), the red dyestuffs (B-1 ) and (B-2) and the blue dyestuffs (C-1) and (C-2) of which the structural formulae are indicated below which have excellent light fastness on polyester fibers.
c a NHC G (A-1) iN
ci 1 ~
N
HQHdC~
(A-2) (B-1 ) is a 1:1 mixture of the two dyestuffs below CN
HC CN
rM
N ra N C2H~OC2H4OH
H-N
b CN
O2N N' N N
N H
H-N
CZH40C,H4OH
s 0 OH (B-2) OH cO2VIOH
NH2 O OH (C-1 ) ia Br NH2 0 OH (C-2) The results of the light fastness tests of these dyestuffs are given in Table Table 2 Example Structural Hue of the Dyed Light Fastness Formula Cloth (Grade) 1 (A-1 ) Yellow 2 2 (A-2) Yellow 2-3 (B-1 ) Red 1-2 4 {B-2} Red 2 + (blue modified color) 5 (C-1 ) Blue 1 - 2 6 (C-2) Blue 1 - 2 dAs becomes clear from Tables 1 and 2, the dyed materials obtained in Examples 1 to 19 were seen to have very much better light fastness when compared with the dyed materials obtained with the Comparative Examples 1 to 6.
Examples 20 to 31 Dyeing was carried out in accordance with the examples given below using mixtures of disperse dyes as indicated in Table 3, which had been prepared using the dyestuffs of the structural formulae [1-1 [, [2-2], [3]r [4-1 ], [4-2], [51, [6], [8-1 ], [8-3], [9-1 l, [9-2] and [10] as described above. However, the benzotriazole based Sunlife LP250 produced by the Hibana Chemical Co. was used for the ultraviolet absorber. The numerical values indicated as amounts compounded in the table are in units of wt%.
i5 Table 3 Formula Example (1-1) 40 16 36 (2-2) 3 5 (3) 16 25 (4-1) 50 21 23 31 39 (4-2) 24 23 23 48 (5) 23 (6) 'I 8 13 17 14 17 17 13 10 17 61 41 (8-1) 32 26 59 25 27 34 31 69 59 tD
(8-3) 54 30 54 N
1:' Mixture 5 4 ~
of (9-1) N
N
and (9-2) (10) 7 Hue of dyed Brown Brown Grey Grey Brown Grey Brown Grey Brown Green Orange Violet Cloth Light Fastness 3-4- 3 3-4 3+ 3-4 3-4 2-3 3 3-4- 3-4- 3-4- 3-4- y Comparative Examples 7 to 13 The dyeing of poly(Jactic acid) based fibers was carried out in the same way as in the examples 20 to 31, but using dyestuffs of examples 20 to 31 and dyestuffs (A-1 ), (A-2),(B-1 )f(B-2)o (C-1) and (C-2) as given in Table 4 below.
Table 4 Formula Comparative Example [1-1 I
[2-21 [3] 8 [4-11 [4-21 [5l [6] 23 12 [8-11 43 60 33 [8-31 45 1 : 7 Mixture ofi [9-111[9-2] 5 10 [10] 5 [A-1l 48 77 50 45 [A-21 63 42 [B-1l 9 4 5 17 [B-2l 22 16 [C-1l 10 15 [C-21 19 4 Hue of Dyed Brown Gray Brown Gray Brown Gray Brown Cloth Light Fastness 1- 2 2- 1 1- 2 1- 2 1- 2 1 Example 32 Dyeing was carried out in accordance with Example 20 except that the fibers used in Example 20 were replaced with a poly(Iactic acid) fiberlpolyprQpylene terephthalate fiber (50150wt /a) mixture, the dyeing conditions were changed to s 120 C x 40 minutes and the ultraviolet absorber was changed to benzophenone based Sunlife LPS855 produced by the Hibana Chemical Co. The results were such that the light fastness of the dyed material obtained was excellent at grade 4.
Claims (7)
1. Use of a yellow component comprising at least one dyestuff of the group consisting of structural formulae (1), (2), (3), (4) and (5) wherein R1 is (C1-C3) alkyl and R2 is (C4-C7) alkyl;
wherein n is 0 or 1;
wherein R3 is (C1-C3) alkyl or 2-hydroxyethyl;
and/or a red component comprising at least one dyestuff of the group consisting of structural formulae (6) and {7}
wherein one of R4 and R5 is hydrogen and the other is hydroxyethoxyethyl, hydroxybutoxypropyl, acetoxyethoxyethyl or acetoxybutoxypropyl;
wherein R6 is hydrogen or methyl;
and/or a blue component comprising at least one dyestuff of the group consisting of structural formulae (8), (9) and (10) wherein one of R7 and R8 is nitro and the other hydoxyl and R9 is hydrogen, chlorine or 2-hydroxyethyl;
wherein R10 is methoxypropyl, ethoxypropyl or methoxyethoxypropyl;
for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
wherein n is 0 or 1;
wherein R3 is (C1-C3) alkyl or 2-hydroxyethyl;
and/or a red component comprising at least one dyestuff of the group consisting of structural formulae (6) and {7}
wherein one of R4 and R5 is hydrogen and the other is hydroxyethoxyethyl, hydroxybutoxypropyl, acetoxyethoxyethyl or acetoxybutoxypropyl;
wherein R6 is hydrogen or methyl;
and/or a blue component comprising at least one dyestuff of the group consisting of structural formulae (8), (9) and (10) wherein one of R7 and R8 is nitro and the other hydoxyl and R9 is hydrogen, chlorine or 2-hydroxyethyl;
wherein R10 is methoxypropyl, ethoxypropyl or methoxyethoxypropyl;
for dyeing poly(lactic acid) fibers or poly(lactic acid) based fibers.
2. Use according to claim1, wherein one of the dyestuffs of the formulae (1) to (10) is used.
3. Use according to claim 1, wherein a mixture comprising two or three of each of the yellow, the red and the blue dyestuffs is used.
4. Use according to claim 1, wherein a mixture comprising a yellow component comprising at least one of the dyestuffs of the formulae (1), (3) and (4), a red component comprising at least one dyestuff of the formula (6) and a blue component comprising at least one dyestuff of the formula (8) is used.
5. Use according to one or more of claims 1 to 4, wherein an ultraviolet absorber is used conjointly.
6. Use according to claim 1, wherein a poly(lactic acid) based fiber is dyed which comprises a mixture of poly(lactic acid) and an aromatic polyester fiber is used.
7. Dyed poly(lactic acid) based fiber material which has been obtained by the use according to one or more of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004188921A JP2006008871A (en) | 2004-06-25 | 2004-06-25 | Disperse dye for polylactic acid fiber |
| JP2004-188921 | 2004-06-25 | ||
| PCT/EP2005/052835 WO2006003088A1 (en) | 2004-06-25 | 2005-06-17 | Disperse dyes for poly(lactic acid) based fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2571979A1 true CA2571979A1 (en) | 2006-01-12 |
Family
ID=35033668
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002571979A Abandoned CA2571979A1 (en) | 2004-06-25 | 2005-06-17 | Disperse dyes for poly(lactic acid) based fibers |
Country Status (7)
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|---|---|
| US (1) | US20070271710A1 (en) |
| JP (1) | JP2006008871A (en) |
| KR (1) | KR20070024516A (en) |
| CN (1) | CN100552130C (en) |
| CA (1) | CA2571979A1 (en) |
| TW (1) | TWI363080B (en) |
| WO (1) | WO2006003088A1 (en) |
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| US20080289156A1 (en) * | 2007-05-25 | 2008-11-27 | Mitchell Lewis | Zipper construction |
| JP2011063898A (en) * | 2009-09-16 | 2011-03-31 | Mazda Motor Corp | Skin material for vehicle interior member |
| JP5851417B2 (en) * | 2010-11-19 | 2016-02-03 | 日本化薬株式会社 | Disperse dye and method for dyeing hydrophobic fiber material using the same |
| CN103228741B (en) * | 2010-11-30 | 2015-07-08 | 日本化药株式会社 | Disperse dyes and method for dyeing hydrophobic fiber material using same |
| US8506654B2 (en) | 2011-03-29 | 2013-08-13 | Dystar L.P. | Disperse dye mixtures which have a high degree of light fastness and build-up |
| CN102604414B (en) * | 2012-01-16 | 2013-12-04 | 杭州吉华江东化工有限公司 | Azo compound containing phenylindole, preparation method and application thereof |
| CN102732056B (en) * | 2012-06-01 | 2013-09-11 | 浙江吉华集团股份有限公司 | Disperse dye mixture and application thereof |
| CN102775812B (en) * | 2012-06-13 | 2013-12-04 | 浙江吉华集团股份有限公司 | Disperse dye mixture and application thereof |
| CN103073922A (en) * | 2013-01-21 | 2013-05-01 | 江苏亚邦染料股份有限公司 | Orange disperse dye composition |
| CN109370257B (en) * | 2018-12-14 | 2020-05-19 | 苏州市吴江区绿洲染料有限公司 | Alkali-resistant disperse grey dye mixture |
| CN111535050A (en) * | 2020-05-28 | 2020-08-14 | 张家港扬子染整有限公司 | PLA wool top dyeing process |
| WO2023104610A1 (en) | 2021-12-07 | 2023-06-15 | Arapaha B.V. | Dyed substrate comprising poly(lactic acid) fibres |
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| US3826609A (en) * | 1968-03-14 | 1974-07-30 | Teijin Ltd | Method of dyeing synthetic fibers and blends |
| TW515859B (en) * | 1997-12-17 | 2003-01-01 | Ciba Sc Holding Ag | Process for ink-jet printing textile fibre materials |
| JP4493160B2 (en) * | 2000-06-02 | 2010-06-30 | 紀和化学工業株式会社 | High light fast dye composition and dyeing method using the same |
| EP1209281A3 (en) * | 2000-11-27 | 2003-08-27 | Carl Freudenberg KG | Dyed or printed nonwoven |
| JP2004168950A (en) * | 2002-11-21 | 2004-06-17 | Dystar Japan Ltd | Disperse dye mixture having high color fastness to light |
| JP4449012B2 (en) * | 2003-07-04 | 2010-04-14 | ダイスタージャパン株式会社 | Disperse dye mixture with high light fastness |
| JP4424466B2 (en) * | 2003-07-18 | 2010-03-03 | ダイスタージャパン株式会社 | Disperse dye mixture suitable for dyeing polylactic acid fiber |
-
2004
- 2004-06-25 JP JP2004188921A patent/JP2006008871A/en active Pending
-
2005
- 2005-06-17 US US11/630,496 patent/US20070271710A1/en not_active Abandoned
- 2005-06-17 WO PCT/EP2005/052835 patent/WO2006003088A1/en active Application Filing
- 2005-06-17 CN CNB2005800129473A patent/CN100552130C/en not_active Expired - Fee Related
- 2005-06-17 CA CA002571979A patent/CA2571979A1/en not_active Abandoned
- 2005-06-17 KR KR1020067021817A patent/KR20070024516A/en not_active Application Discontinuation
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| Publication number | Publication date |
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| US20070271710A1 (en) | 2007-11-29 |
| WO2006003088A1 (en) | 2006-01-12 |
| CN101040080A (en) | 2007-09-19 |
| JP2006008871A (en) | 2006-01-12 |
| KR20070024516A (en) | 2007-03-02 |
| CN100552130C (en) | 2009-10-21 |
| TWI363080B (en) | 2012-05-01 |
| TW200606220A (en) | 2006-02-16 |
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