Note: Descriptions are shown in the official language in which they were submitted.
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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
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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
0
(2)
wherein n is 0 or 1;
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as \ I
t~ S
0 (3)
CI
0%2 N N~
CI N'R
(4)
wherein R3 is (C1-C.) alkyl or 2-hydroxyethyl;
S42NH 0
N NO2
s R (5)
and/or a red component comprising at least one dyestuff of the group
consisting
of structural formulae (6) and (7)
H3C CN
CN 1
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;
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O NH2
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)
R9
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
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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
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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
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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
30
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)
/OH3
OCH
~ CH3
N~
f S
~ NH
OnC7H16
N (1-2)
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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
C1 N
l% CH3
.~-
\ f
(4-1)
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~I
- ~ ~
02N N~
N N
~i l~
c2HdOH
(4-2)
SO2NH 0
5\
N NOZ
H t5S
H3C CN
cN f 1
.~''~ N CH3
11
N CN
I
R5HN N NHR4 (6)
wherein R4 and R' are defined as given above
O NH2
OMe
O NHSO2 &CH3
(7-1)
NCl 0 HN O
OH 0 OH {~-1 r
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/ ~
OH 0 HN ~'
N02 O OH (8-2)
C2H4QH
NO2 0 HW
~H Q OH (8-3)
~~
NO2 0 HN ~''
x5d1
O
H 0 OH (8-4)
0 NH2 O
1'IXIII11II'IIITIN-CaH6OCH3
5 O NH2 0
(9-1)
O NH2 0
1IITI!1I1IIIIN-C3H6OC2HS
O NHZ 0
(9-2)
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0 NHz O
IV---C3H60C2H40CH3
O NH2 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
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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.
N 5
c
a NHC G (A-1)
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G1
O2N N
iN
ci 1 ~
N
HQHdC~
(A-2)
(B-1 ) is a 1:1 mixture of the two dyestuffs below
CN
HC CN
02N N
rM
N ra
N C2H~OC2H4OH
H-N
b
CN
M3C GN
O2N N'
N N
N H
H-N
CZH40C,H4OH
s
O NH2
0 OH (B-2)
OH cO2VIOH
NH2 O OH (C-1 )
ia
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OH 0 NH2
Br
NH2 0 OH (C-2)
The results of the light fastness tests of these dyestuffs are given in Table
2
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
20 21 22 23 24 25 26 27 28 29 30 31
(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
0
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
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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
7 8 9 10 11 12 13
[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
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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.
