U.S. patent application number 12/448034 was filed with the patent office on 2010-03-18 for dyeing quality improver for polyester-based fiber materials.
Invention is credited to Masatoshi Hayashi, Masaaki Hosoda.
Application Number | 20100064451 12/448034 |
Document ID | / |
Family ID | 40638534 |
Filed Date | 2010-03-18 |
United States Patent
Application |
20100064451 |
Kind Code |
A1 |
Hosoda; Masaaki ; et
al. |
March 18, 2010 |
DYEING QUALITY IMPROVER FOR POLYESTER-BASED FIBER MATERIALS
Abstract
The invention provides a dyeing quality improver for
polyester-based fiber materials characterized by comprising a
polyester copolymer, obtained by polycondensation of a dibasic acid
component containing a dibasic acid with a sulfonate group in an
amount of 15-65 mol % and a dihydric alcohol component containing
polyethylene glycol with a molecular weight of 900-3500, having a
molecular weight of 3000-30,000 and containing polyoxyethylene
chains in the molecule in an amount of 10-40 mass %, and at least
one compound selected from among styrenated phenolalkylene oxide
addition products and higher alcohol alkylene oxide addition
products. It is possible to solve the problem of adhesion of
polyester oligomers and the problems of dye contamination and
foreign matter contamination, during dyeing of polyester-based
fiber materials.
Inventors: |
Hosoda; Masaaki; (Fukui,
JP) ; Hayashi; Masatoshi; (Fukui, JP) |
Correspondence
Address: |
CHRISTIE, PARKER & HALE, LLP
PO BOX 7068
PASADENA
CA
91109-7068
US
|
Family ID: |
40638534 |
Appl. No.: |
12/448034 |
Filed: |
August 27, 2008 |
PCT Filed: |
August 27, 2008 |
PCT NO: |
PCT/JP2008/065797 |
371 Date: |
June 3, 2009 |
Current U.S.
Class: |
8/636 |
Current CPC
Class: |
C08L 71/02 20130101;
D06M 15/507 20130101; D06M 13/17 20130101; D06P 1/6131 20130101;
D06P 1/613 20130101; C08L 67/025 20130101; C08L 71/02 20130101;
D06M 15/53 20130101; C08L 67/025 20130101; D06P 3/52 20130101; D06P
1/5271 20130101 |
Class at
Publication: |
8/636 |
International
Class: |
D06P 1/613 20060101
D06P001/613; D06P 1/52 20060101 D06P001/52 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 2007 |
JP |
2007-293053 |
Claims
1. A dyeing quality improver for polyester-based fiber materials
characterized by comprising (A) a polyester copolymer, obtained by
polycondensation of a dibasic acid component containing a dibasic
acid with a sulfonate group in an amount of 15-65 mol % and a
dihydric alcohol component containing polyethylene glycol with a
molecular weight of 900-3500, having a molecular weight of
3000-30,000 and containing polyoxyethylene chains in the molecule
in an amount of 10-40 mass %, and (B) at least one compound
selected from among styrenated phenolalkylene oxide addition
products and higher alcohol alkylene oxide addition products.
Description
TECHNICAL FIELD
[0001] The present invention relates to a dyeing quality improver
that is suitable for polyester fiber materials and for
polyester-based fiber materials composed of composite materials
comprising polyester fiber materials and other fiber materials.
BACKGROUND ART
[0002] Dyeing of polyester fiber materials, and polyester-based
fiber materials composed of composite materials comprising them
with other fiber materials, has been associated with frequent
problems that include problems arising from the polyester
oligomers, problems of dye contamination and problems of foreign
matter contamination.
[0003] Polyester-based fiber materials are dyed under
high-temperature conditions of usually 100-140.degree. C., and this
causes the polyester oligomers to elute from the polyester-based
fiber material into the fiber surfaces or dyeing bath, adhering not
only onto the fiber surfaces but also onto the dyeing machine parts
such as the dyeing machine frame and the heat exchanger, thus
resulting in problems, including notable lowering of the quality of
the obtained fiber product and more difficult control of the
operation for raising and lowering of the temperature during the
dyeing step.
[0004] The problem of dye contamination occurs when a
polyester-based fiber material that has not been sufficiently
scoured before dyeing is introduced into the dyeing bath, and the
oil solutions, sizing agents, waxes and the like adhering to the
fiber material elute into the dyeing bath, resulting in reduced
dispersibility of the dye and formation of its aggregates, and
adhesion of the dye aggregates onto the fiber product.
Polyester-based fiber materials that have not been sufficiently
scoured are also associated with problems in terms of the level
dyeing property, such that the dyeing results in color
irregularities.
[0005] The problem of foreign matter contamination is that
treatment of functional agents such as light fastness enhancers or
flameproofing agents in the same bath as the dyeing bath produces
contamination, due to fiber surface residue of functional agents
that have not been taken up into the fiber material.
[0006] In order to solve the oligomer-related problems, methods
have been adopted that involve adding dyeing quality improvers to
the dyeing bath or to the reduction/cleaning bath after dyeing.
[0007] For example, Japanese Unexamined Patent Publication No.
2000-154466 discloses a method of preventing the trouble caused by
adhesion of oligomers, by adding to the dyeing bath an oligomer
removing agent comprising a sulfonic acid salt of polyoxyethylene
styrylphenyl ether, and a carboxyl group-containing polymer such as
an acrylic acid or methacrylic acid polymer, or a salt thereof.
[0008] Also, Japanese Unexamined Patent Publication No. 2001-159083
discloses a method of minimizing the adverse effects of polyester
decomposition products, by adding to the dyeing bath a dyeing aid
comprising as an active component one or more agents selected from
the group consisting of chelating phosphonate agents, phosphonic
acid salt-based chelating agents, polycarboxylic based chelating
agents and polycarboxylic acid salt-based chelating agents.
[0009] In addition, Japanese Unexamined Patent Publication No.
2001-295136 discloses a method of preventing elution of oligomers
by adding to the dyeing bath during the dyeing step an oligomer
preventer containing the esterified product of a polyhydric alcohol
alkylene oxide addition product and an alkyl or alkenyl fatty acid,
or an esterified product obtained by transesterification of a
polyhydric alcohol alkylene oxide addition product and a natural
animal or vegetable oil thereof comprising an alkyl or alkenyl
fatty acid. However, the polyester oligomer removing effect is low
even with addition of such oligomer removing agents or preventing
agents, and it is not possible at the current time to achieve a
satisfactory oligomer removing effect, especially with acidic
baths.
[0010] Methods of adding scouring agents to dyeing baths have also
been implemented in the prior art to counter the problem of dye
contamination. Higher alcohol alkylene oxide addition products are
generally used as scouring agents, but because their scouring
effects are minimal in acidic baths and they tend to inhibit dye
dispersibility at high temperatures, it has not been possible to
satisfactorily prevent the problem of dye contamination. For the
problem of foreign matter contamination, functional drugs are
sometimes dispersed in various anionic surfactants in an attempt to
achieve stabilization in the dyeing bath, but this has not
constituted a solution to the problem.
DISCLOSURE OF THE INVENTION
[0011] It is an object of the present invention to provide a dyeing
quality improver for polyester-based fiber materials that is able
to overcome the problems caused by deposition of polyester
oligomers and the problems of dye contamination and foreign matter
contamination that occur when they are added to the dyeing bath in
the dyeing step for a fiber material comprising a polyester fiber
material or a composite of a polyester fiber material with other
fiber materials.
[0012] As a result of much diligent research with the aim of
solving the aforementioned problems, the present inventors have
found that by combining a polyester copolymer obtained by
polycondensation of a dibasic acid component, containing a fixed
amount of a dibasic acid with a sulfonate group, and a dihydric
alcohol component, containing a fixed amount of polyethylene
glycol, with a styrenated phenolalkylene oxide addition product
and/or a higher alcohol alkylene oxide addition product, it is
possible to solve the problems of oligomer adhesion during the
dyeing step and the problems of dye contamination and foreign
matter contamination, and the present invention has been completed
based on this finding.
[0013] Specifically, the invention provides a dyeing quality
improver for polyester-based fiber materials characterized by
comprising a polyester copolymer, obtained by polycondensation of a
dibasic acid component containing a dibasic acid with a sulfonate
group in an amount of 15-65 mol % and a dihydric alcohol component
containing polyethylene glycol with a molecular weight of 900-3500,
having a molecular weight of 3000-30,000 and containing
polyoxyethylene chains in the molecule in an amount of 10-40 mass
%, and at least one compound selected from among styrenated
phenolalkylene oxide addition products and higher alcohol alkylene
oxide addition products.
[0014] Since the polyester copolymer in the dyeing quality improver
for polyester-based fiber materials according to the invention has
excellent affinity for polyester fibers, it can incorporate the
residual polyester oligomer on fiber surfaces as well as
lubricants, sizing agents and functional drugs such as light
fastness enhancers or flameproofing agents, by a synergistic
effect, to a greater extent than when using the other component (a
styrenated phenolalkylene oxide addition product or higher alcohol
alkylene oxide addition product) alone.
[0015] Moreover, because the polyester copolymer has a controlled
molecular weight it is detached easily from polyester fibers, and
therefore the polyester oligomer, as well as lubricants, sizing
agents and functional drugs such as light fastness enhancers and
flameproofing agents, can be retained in water.
[0016] In addition, since the polyester copolymer in the dyeing
quality improver of the invention contains a sulfonate group, it
does not become redeposited on the fiber material or dyeing
machine, and therefore the improver can be suitably used in dyeing
steps.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] Preferred embodiments of the invention will now be explained
in detail with the understanding that the invention is not limited
only to these embodiments, and various modifications may be
implemented that are within the spirit and scope of the
invention.
[0018] The dyeing quality improver for polyester-based fiber
materials according to the invention is characterized by comprising
(A) a polyester copolymer, obtained by polycondensation of a
dibasic acid component containing a dibasic acid with a sulfonate
group in an amount of 15-65 mol % and a dihydric alcohol component
containing polyethylene glycol with a molecular weight of 900-3500,
and (B) at least one compound selected from among styrenated
phenolalkylene oxide addition products and higher alcohol alkylene
oxide addition products.
[0019] Preferred sulfonate group-containing dibasic acids for
synthesis of polyester-based copolymers used for the invention
include metal salts of sulfoterephthalic acid, 5-sulfoisophthalic
acid and 4-sulfophthalic acid, and their ester derivatives such as
dimethyl ester, diethyl ester and diphenyl esters. As metal salts
there may be mentioned lithium salts, sodium salts, potassium salts
and magnesium salts, among which sodium and potassium salts are
preferred.
[0020] The content of the sulfonate group-containing dibasic acid
in the dibasic acid component is in the range of 15-65 mol %. The
removing power for polyester oligomers, lubricants, sizing agents
and functional agents will be impaired if the sulfonate
group-containing dibasic acid is present at less than 15 mol % in
the dibasic acid component. This is believed to be because a low
sulfonate group content lowers the dispersibility of polyester
oligomers, lubricants, sizing agents and functional agents, leading
to their redeposition in the fiber material. On the other hand, a
content exceeding 65 mol % will impede polycondensation reaction of
the polyester copolymer.
[0021] As dibasic acids other than sulfonate group-containing
dibasic acids to be included in the dibasic acid component used for
copolymerization, there may be mentioned aromatic carboxylic acids
such as terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid, diphenyldicarboxylic acid,
diphenoxyethanedicarboxylic acid, .beta.-hydroxyethoxybenzoic acid
and p-hydroxybenzoic acid or aliphatic carboxylic acids such as
adipic acid, sebacic acid, maleic acid and succinic acid, and their
acid anhydrides or ester derivatives with lower alcohols or glycols
may also be used.
[0022] The dihydric alcohol component as the other starting
material for synthesis of the polyester copolymer contains
polyethylene glycol with a molecular weight of 900-3500. A
molecular weight of less than 900 for the polyethylene glycol will
tend to lower the removing power for polyester oligomers,
lubricants, sizing agents and functional agents, while a molecular
weight of greater than 3500 will tend to impair the dispersibility
of the disperse dye. The polyester copolymer also contains 10-40
mass % polyoxyethylene chains derived from the polyethylene glycol.
A polyoxyethylene chain content of less than 10 mass % will tend to
reduce the removing power for polyester oligomers, lubricants,
sizing agents, functional agents and the like, while a
polyoxyethylene chain content of greater than 40 mass % will lead
to increased occurrence of problems such as insufficient disperse
dye dispersibility and high foamability during the dyeing
process.
[0023] Ethylene glycol is preferred as a dihydric alcohol other
than the polyethylene glycol in the dihydric alcohol component used
for synthesis of the polyester copolymer, but there may also be
used other aliphatic and aromatic diol compounds such as C3 or
greater alkylene glycols, neopentyl glycol, bisphenol A, bisphenol
S and the like.
[0024] The polyester copolymer used for the dyeing quality improver
of the invention has a molecular weight of 3000-30,000. According
to the invention, a molecular weight of less than 3000 will tend to
lower the removing power for polyester oligomers, lubricants,
sizing agents and functional agents, presumably because the
affinity of the polyester copolymer for the polyester-based fiber
material is lowered. A molecular weight of greater than 30,000 will
increase the amount of dyeing quality improver residue on the
polyester-based fiber material, thus risking an adverse effect in
the subsequent finishing step.
[0025] The dyeing quality improver of the invention comprising a
polyester copolymer, that satisfies the aforementioned content of
sulfonate group-containing dibasic acids, and the content and
molecular weight of polyoxyethylene chains derived from the
polyethylene glycol with a molecular weight of 900-3500, has
excellent removability for polyester oligomers, lubricants, sizing
agents and functional agents from polyester-based fiber materials,
and undergoes minimal redepositing onto polyester fiber materials
and dyeing machines.
[0026] The process for producing the polyester copolymer of the
invention may be any conventional process such as
transesterification or direct polymerization, without any
particular restrictions.
[0027] The molecular weight, according to the invention, refers to
the weight-average molecular weight measured by gel permeation
chromatography using an HLC-8120 apparatus (product. of Tosoh
Corp.), Column: GF310HQ (product of Shodex), and using 50% (v/v)
acetonitrile/water as the mobile phase, and using sodium
polystyrene sulfonate as the standard substance.
[0028] The dyeing quality improver of the invention contains, in
addition to the aforementioned polyester copolymer, one or more
compounds selected from the group consisting of styrenated
phenolalkylene oxide addition products and higher alcohol alkylene
oxide addition products.
[0029] According to the invention, the styrenated phenolalkylene
oxide addition product may be a polystyrenated (2-10 mol)
phenolalkylene oxide addition product such as a monostyrenated
phenolalkylene oxide addition product, distyrenated phenolalkylene
oxide addition product or tristyrenated phenolalkylene oxide
addition product. The number of moles for addition of styrene is
preferably 1-5 mol for satisfactory affinity with polyester fibers.
The higher alcohol in the higher alcohol alkylene oxide addition
product is preferably a C8-18 alcohol for more satisfactory
affinity with polyester fibers. The higher alcohol may be either
saturated or unsaturated.
[0030] For both styrenated phenolalkylene oxide addition products
and higher alcohol alkylene oxide addition products, the form of
addition is preferably simple addition of ethylene oxide or random
or block addition of ethylene oxide and propylene oxide. In the
case of addition of ethylene oxide and propylene oxide, the
proportion of ethylene oxide units among the total alkylene oxide
chains is preferably 60-100 mass %. If the proportion of ethylene
oxide units is less than 60 mass %, it will tend to be more
difficult to remove the lubricant. The number of moles for addition
of alkylene oxides is preferably 4-30 mol and more preferably 4-20
mol each. If the number of moles of addition is less than 4 mol the
removability for lubricants, sizing agents and functional agents
will tend to be impaired, while if it exceeds 30 mol the effect of
the hydrophobic groups of the alkylene oxide addition product will
be lessened, thus tending to lower the affinity for polyester
fibers and lubricants. The alkylene oxide addition products
mentioned above may be produced by processes known in the art.
[0031] According to the invention, the mass of the polyester
copolymer is preferably 0.5-10 and more preferably 1-10, with
respect to the total mass of the styrenated phenolalkylene oxide
addition product and higher alcohol alkylene oxide addition product
defined as 1, for admixture to obtain the dyeing quality improver.
Water or a mixture of water and a lower alcohol may be used as the
solvent.
[0032] Polyester-based fiber materials to which the dyeing quality
improver of the invention may be applied include polyethylene
terephthalate, polybutylene terephthalate, polypropylene
terephthalate, polytrimethylene terephthalate and polyester fiber
materials composed of copolymers comprising the same, as well as
composite fiber materials comprising these polyester fiber
materials and other synthetic fiber materials, natural fiber
materials or regenerated fiber materials, and they may be in the
form of yarns, knitted fabrics, woven fabrics, nonwoven fabrics and
the like.
[0033] A dyeing quality improver for polyester-based fiber
materials according to the invention may be added to the dyeing
bath when such polyester-based fiber materials are dyed. The amount
of dyeing quality improver used may be appropriately adjusted
depending on the type of fiber material or dye and on the desired
performance. The dyeing process may be jet dyeing or a dip dyeing
method such as cheese dyeing, beam dyeing, Obermaier dyeing,
high-pressure injection dyeing or the like, and any process may be
employed without any particular restrictions so long as it allows
the object of the invention to be achieved.
[0034] The invention will now be explained in greater detail using
examples, with the understanding that the invention is in no way
limited in scope by the examples.
Synthesis Example 1
[0035] After charging 116.4 g (0.6 mol) of dimethyl terephthalate,
118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 57 g
of ethylene glycol, 86 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate into a reactor, the
temperature was raised from 150.degree. C. to 230.degree. C. over a
period of about 3 hours while agitating under a nitrogen gas
atmosphere for transesterification, and the methanol was distilled
out of the system. Next, 0.1 g of tetrabutyl titanate was added,
the pressure was gradually reduced, and when the internal pressure
reached approximately 10 kPa, reaction was conducted at 250.degree.
C. for 2 hours to obtain 314 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 27 mass %, and the molecular weight was
12,000.
Synthesis Example 2
[0036] The same procedure was carried out as in Example 1, except
that 155.2 g (0.8 mol) of dimethyl terephthalate, 59.2 g (0.2 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 58 g of ethylene
glycol, 131 g of polyethylene glycol with a molecular weight of
2000 and 0.1 g of zinc acetate were charged into the reactor, to
obtain 340 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 38
mass %, and the molecular weight was 22,000.
Synthesis Example 3
[0037] The same procedure was carried out as in Example 1, except
that 135.8 g (0.7 mol) of dimethyl terephthalate, 88.8 g (0.3 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 54 g of ethylene
glycol, 136 g of polyethylene glycol with a molecular weight of
1000 and 0.1 g of zinc acetate were charged into the reactor, to
obtain 350 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 38
mass %, and the molecular weight was 5000.
Synthesis Example 4
[0038] The same procedure was carried out as in Example 1, except
that 97 g (0.5 mol) of dimethyl terephthalate, 148 g (0.5 mol) of
dimethyl 5-sulfoisophthalate sodium salt, 61 g of ethylene glycol,
38 g of polyethylene glycol with a molecular weight of 2000 and 0.1
g of zinc acetate were charged into the reactor, to obtain 280 g of
a polyester copolymer. The polyoxyethylene chain content of the
obtained polyester copolymer was approximately 13 mass %, and the
molecular weight was 9000.
Synthesis Example 5
[0039] The same procedure was carried out as in Example 1, except
that 77.6 g (0.4 mol) of dimethyl terephthalate, 177.6 g (0.6 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 60, g of ethylene
glycol, 39 g of polyethylene glycol with a molecular weight of 1000
and 0.1 g of zinc acetate were charged into the reactor, to obtain
290 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 13 mass %,
and the molecular weight was 3000.
Synthesis Example 6
[0040] The same procedure was carried out as in Example 1, except
that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 61 g of ethylene
glycol, 83 g of polyethylene glycol with a molecular weight of 3000
and 0.1 g of zinc acetate were charged into the reactor, to obtain
315 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 26 mass %,
and the molecular weight was 18,000.
Synthesis Example 7
[0041] The same procedure was carried out as in Example 1, except
that 129.6 g (0.6 mol) of 1,8-naphthalenedicarboxylic acid, 118.4 g
(0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 57 g of
ethylene glycol, 85 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 343 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 24 mass %, and the molecular weight was
25,000.
Synthesis Example 8
[0042] The same procedure was carried out as in Example 1, except
that 58.8 g (0.6 mol) of maleic anhydride, 118.4 g (0.4 mol) of
dimethyl 5-sulfoisophthalate sodium salt, 58 g of ethylene glycol,
68 g of polyethylene glycol with a molecular weight of 1000 and 0.1
g of zinc acetate were charged into the reactor, to obtain 267 g of
a polyester copolymer. The polyoxyethylene chain content of the
obtained polyester copolymer was approximately 25 mass %, and the
molecular weight was 7000.
Synthesis Example 9
[0043] The same procedure was carried out as in Example 1, except
that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 83 g of
1,4-butanediol, 83 g of polyethylene glycol with a molecular weight
of 1000 and 0.1 g of zinc acetate were charged into the reactor, to
obtain 337 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 24
mass %, and the molecular weight was 10,000.
Synthesis Example 10
[0044] The same procedure was carried out as in Example 1, except
that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 96 g of neopentyl
glycol, 83 g of polyethylene glycol with a molecular weight of 1000
and 0.1 g of zinc acetate were charged into the reactor, to obtain
350 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 23 mass %,
and the molecular weight was 28,000.
Synthesis Example 11
[0045] The same procedure was carried out as in Example 1, except
that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol)
of dimethyl 5-sulfoisophthalate sodium salt, 310 g of a 2 molar
ethylene oxide adduct of bisphenol S, 83 g of polyethylene glycol
with a molecular weight of 1000 and 0.1 g of zinc acetate were
charged into the reactor, to obtain 564 g of a polyester copolymer.
The polyoxyethylene chain content of the obtained polyester
copolymer was approximately 14 mass %, and the molecular weight was
30,000.
Synthesis Example 12
[0046] The same procedure was carried out as in Example 1, except
that 116.4 g (0.6 mol) of dimethyl terephthalate, 124.8 g (0.4 mol)
of dimethyl 5-sulfoisophthalate potassium salt, 57 g of ethylene
glycol, 86 g of polyethylene glycol with a molecular weight of 1000
and 0.1 g of zinc acetate were charged into the reactor, to obtain
320 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 26 mass %,
and the molecular weight was 13,000.
Synthesis Example 13
[0047] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g
(0.4 mol) of dimethyl sulfoterephthalate sodium salt, 57 g of
ethylene glycol, 86 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 314 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 27 mass %, and the molecular weight was
13,000.
Synthesis Example 14
[0048] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 124.8 g
(0.4 mol) of dimethyl sulfoterephthalate potassium salt, 57 g of
ethylene glycol, 86 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 320 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was
14,000.
Synthesis Example 15
[0049] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 129.6 g
(0.4 mol) of diethyl 4-sulfophthalate sodium salt, 57 g of ethylene
glycol, 86 g of polyethylene glycol with a molecular weight of 1000
and 0.1 g of zinc acetate were charged into the reactor, to obtain
297 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 28 mass %,
and the molecular weight was 8000.
Synthesis Example 16
[0050] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 136.0 g
(0.4 mol) of diethyl 4-sulfophthalate potassium salt, 57 g of
ethylene glycol, 86 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 303 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 27 mass %, and the molecular weight was 9000.
Comparative Synthesis Example 1
[0051] The same procedure was carried out as in Synthesis Example
1, except that 174.6 g (0.9 mol) of dimethyl terephthalate, 29.6 g
(0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 58 g of
ethylene glycol, 74 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 272 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was
20,000.
Comparative Synthesis Example 2
[0052] After charging 58.2 g (0.3 mol) of dimethyl terephthalate,
207.2 g (0.7 mol) of dimethyl 5-sulfoisophthalate sodium salt, 60 g
of ethylene glycol, 90 g of polyethylene glycol with a molecular
weight of 2000 and 0.1 g of zinc acetate into a reactor, the
temperature was raised from 150.degree. C. to 230.degree. C. over a
period of about 3 hours while agitating under a nitrogen gas
atmosphere for transesterification, and the methanol was distilled
out of the system. Next, 0.1 g of tetrabutyl titanate was added and
the pressure was gradually reduced, but stirring became impossible
when the internal pressure reached approximately 30 kPa, and the
reaction could not be continued.
Comparative Synthesis Example 3
[0053] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g
(0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 56 g of
ethylene glycol, 83 g of polyethylene glycol with a molecular
weight of 800 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 310 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was 9000.
Comparative Synthesis Example 4
[0054] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g
(0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 61 g of
ethylene glycol, 83 g of polyethylene glycol with a molecular
weight of 4000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 315 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was
12,000.
Comparative Synthesis Example 5
[0055] After charging 116.4 g (0.6 mol) of dimethyl terephthalate,
118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g
of ethylene glycol, 24 g of polyethylene glycol with a molecular
weight of 2000 and 0.1 g of zinc acetate into a reactor, the
temperature was raised from 150.degree. C. to 230.degree. C. over a
period of about 3 hours while agitating under a nitrogen gas
atmosphere for transesterification, and the methanol was distilled
out of the system. Next, 0.1 g of tetrabutyl titanate was added and
the pressure was gradually reduced, but stirring became impossible
when the internal pressure reached approximately 40 kPa, and the
reaction could not be continued.
Comparative Synthesis Example 6
[0056] The same procedure was carried out as in Synthesis Example
1, except that 116.4 g (0.6 mol) of dimethyl terephthalate, 118.4 g
(0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 49 g of
ethylene glycol, 218 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate were charged into the
reactor, to obtain 438 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 48 mass %, and the molecular weight was
16,000.
Comparative Synthesis Example 7
[0057] After charging 116.4 g (0.6 mol) of dimethyl terephthalate,
118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 57 g
of ethylene glycol, 83 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate into a reactor, the
temperature was raised from 150.degree. C. to 230.degree. C. over a
period of about 3 hours while agitating under a nitrogen gas
atmosphere for transesterification, and the methanol was distilled
out of the system. Next, 0.1 g of tetrabutyl titanate was added,
the pressure was gradually reduced, and when the internal pressure
reached approximately 30 kPa, reaction was terminated and the
mixture was cooled to obtain 312 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was 2300.
Comparative Synthesis Example 8
[0058] After charging 116.4 g (0.6 mol) of dimethyl terephthalate,
118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 57 g
of ethylene glycol, 83 g of polyethylene glycol with a molecular
weight of 1000 and 0.1 g of zinc acetate into a reactor, the
temperature was raised from 150.degree. C. to 230.degree. C. over a
period of about 3 hours while agitating under a nitrogen gas
atmosphere for transesterification, and the methanol was distilled
out of the system. Next, 0.1 g of tetrabutyl titanate was added,
the pressure was gradually reduced, and when the internal pressure
reached approximately 9 kPa, reaction was conducted at 250.degree.
C. for 5 hours to obtain 311 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 26 mass %, and the molecular weight was
34,000.
[0059] The results of synthesizing these polyester copolymers are
summarized in Table 1.
TABLE-US-00001 TABLE 1 Sulfonate group component/total Polyoxy-
dibasic acid ethylene component chain content Molecular (mol %)
(mass %) weight Synthesis Example 1 40 27 12,000 Synthesis Example
2 20 38 22,000 Synthesis Example 3 30 38 5000 Synthesis Example 4
50 13 9000 Synthesis Example 5 60 13 3000 Synthesis Example 6 40 26
18,000 Synthesis Example 7 40 24 25,000 Synthesis Example 8 40 25
7000 Synthesis Example 9 40 24 10,000 Synthesis Example 10 40 23
28,000 Synthesis Example 11 40 14 30,000 Synthesis Example 12 40 26
13,000 Synthesis Example 13 40 27 13,000 Synthesis Example 14 40 26
14,000 Synthesis Example 15 40 28 8000 Synthesis Example 16 40 27
9000 Comp. Synth. Example 1 10 26 20,000 Comp. Synth. Example 2 70
25 Reaction unsustained Comp. Synth. Example 3 40 26 9000 Comp.
Synth. Example 4 40 26 12,000 Comp. Synth. Example 5 40 9 Reacted
unsustained Comp. Synth. Example 6 40 48 16,000 Comp. Synth.
Example 7 40 26 2300 Comp. Synth. Example 8 40 26 34,000
Example 1
[0060] A dyeing quality improver was obtained by mixing 20 g of the
polyester copolymer of Synthesis Example 1, 10 g of a 10 molar
addition product of tristyrenated phenolethylene oxide and 70 g of
water.
Example 2
[0061] A dyeing quality improver was obtained by mixing 20 g of the
polyester copolymer of Synthesis Example 1, 10 g of a 20 molar
addition product of tristyrenated phenolethylene oxide and 70 g of
water.
Example 3
[0062] A dyeing quality improver was obtained by mixing 20 g of the
polyester copolymer of Synthesis Example 1, 10 g of a 7 molar
addition product of lauryl alcohol ethylene oxide and 70 g of
water.
Examples 4 and 5
[0063] A dyeing quality improver was obtained by the same procedure
as in Examples 1 and 2, except that 20 g of the polyester copolymer
of Synthesis Example 2 was used instead of 20 g of the polyester
copolymer of Synthesis Example 1.
Example 6
[0064] A dyeing quality improver was obtained by mixing 20 g of the
polyester copolymer of Synthesis Example 2, 10 g of an 8 molar
addition product of oleyl alcohol ethylene oxide and 70 g of
water.
Examples 7-20 and Comparative Examples 1-8
[0065] Dyeing quality improvers were obtained by the same procedure
as in Example 1, except that 20 g of the polyester copolymers of
Synthesis Examples 3-16 and Comparative Synthesis Examples 1-8 were
used instead of 20 g of the polyester copolymer of Synthesis
Example 1.
Comparative Example 9
[0066] An aqueous dispersion was prepared comprising 30 mass % of a
10 molar addition product of tristyrenated phenolethylene oxide,
for use as a dyeing quality improver.
Comparative Example 10
[0067] An aqueous dispersion was prepared comprising 30 mass % of a
7 molar addition product of lauryl alcohol ethylene oxide, for use
as a dyeing quality improver.
Comparative Example 11
[0068] Water was used as a dyeing quality improver.
Comparative Example 12
[0069] A mixture of 30 g of the polyester copolymer of Synthesis
Example 1 and 70 g of water was used as a dyeing quality
improver.
[0070] The obtained dyeing quality improvers were evaluated in the
following manner.
[0071] Oligomer Removability Test
[0072] For comparison of the oligomer removing effects during
dyeing, polyester satin woven fabrics containing the dyeing quality
improvers of Examples 1-20 and Comparative Examples 1, 3, 4 and
6-12 and dyed under the following conditions were subjected to
extraction using 1,4-dioxane, and the UV absorbance of the extracts
at 286 nm were measured to calculate the oligomer deposition per
gram of fabric. The results are shown in Table 2.
Dyeing Bath
TABLE-US-00002 [0073] Dye: C.I. Disperse Blue 79 1% o.w.f 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SUNSOLT 1 g/L
RM-340E (Nicca Chemical Co., Ltd.) Dyeing quality improver 1 g/L
Dyeing temperature .times. time: 130.degree. C. .times. 30 minutes
Liquor to goods ratio = 1:15
[0074] Scourability Test (Dye Contamination Resistance Test)
[0075] (1) In order to compare the scourability during dyeing,
polyester knit greiges dyed under the following conditions using
the dyeing quality improvers of Examples 1-20 or Comparative
Examples 1, 3, 4 and 6-12 were extracted using diethyl ether. The
extraction residue was dried at 105.degree. C. and allowed to stand
in a desiccator, after which the mass was measured and the oil and
fat content (mass %) was calculated with respect to the polyester
knit greige. A larger oil and fat content indicates higher
scourability.
[0076] (2) In order to compare the scourability during dyeing, two
drops (0.2 g) each of an acrylic sizing agent ("PLUSSIZE J-96" by
Goo Chemical Co., Ltd.) and wax (20 mass % aqueous dispersion of
"PARAFFIN WAX 155.degree. F." by Nippon Seiro Co., Ltd.) were
spotted on the polyester knit, and then heat setting was performed
at 160.degree. C. for 1 minute and the dyeing quality improvers of
Examples 1-20 or Comparative Examples 1, 3, 4 and 6-10 were used
for dyeing under the following conditions, after which the colored
condition at the spotted areas were visually observed and the spot
removability was evaluated as "G" (no spots), F (few spots) or P
(spots). The spotted sections are darkly colored when residue of
the acrylic sizing agent or wax remains. The evaluation results are
shown in Table 2.
Dyeing Bath
TABLE-US-00003 [0077] Dye: C.I. Disperse Red 60 0.2% o.w.f. 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SUNSOLT 1 g/L
RM-340E (Nicca Chemical Co., Ltd.) Dyeing quality improver 1 g/L
Dyeing temperature .times. time: 130.degree. C. .times. 20 minutes
Liquor to goods ratio = 1:15
[0078] Foreign Matter Contamination Resistance Test
[0079] In order to compare the foreign matter contamination
resistance effect during dyeing, a COLOR-PET (product of Nissen
Corporation) was used to wrap a scoured polyester knit onto a
holder, anchored above and below with rubber bands, and then a
dyeing quality improver of Examples 1-20 or Comparative Examples 1,
3, 4 and 6-12 was added, a light fastness enhancer or flameproofing
agent was further added as a functional agent, and the knit was
dyed under the following conditions, after which the degree of
foreign matter contamination remaining on the polyester knit was
visually observed and the extent of foreign matter contamination
was evaluated as G (no contamination), F (some contamination) or P
(notable contamination). The results are shown in Table 2.
Dyeing Bath
TABLE-US-00004 [0080] Dye: C.I. Disperse Red 167 0.1% o.w.f. 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SUNSOLT 1 g/L
RM-340E (Nicca Chemical Co., Ltd.) Functional agent Light fastness
enhancer: SANLIFE LP-240 6% o.w.f. (product of Nicca Chemical Co.,
Ltd.) or Flameproofing agent: NIKKAFINON HFT-4000 15% o.w.f. GT
(product of Nicca Chemical Co., Ltd.) Dyeing quality improver 1 g/L
Dyeing temperature .times. time: 130.degree. C. .times. 30 minutes
Liquor to goods ratio = 1:30
TABLE-US-00005 TABLE 2 Foreign matter contamination resistance
Oligomer Scourability test Light adhesion Fats and Acrylic sizing
Wax fastness Flameproof- (mg/g) oils (%) agent spots spots enhancer
ing agent Example 1 4.8 0.06 G G G G Example 2 3.2 0.06 G G G G
Example 3 7.4 0.08 G G G G Example 4 5.3 0.07 G G G G Example 5 4.5
0.07 G G G G Example 6 7.8 0.08 G G G G Example 7 6.0 0.08 G G G G
Example 8 6.1 0.07 G G G G Example 9 13.0 0.09 G G G G Example 10
10.3 0.07 G G G G Example 11 6.8 0.08 G G G G Example 12 6.1 0.08 G
G G G Example 13 6.0 0.08 G G G G Example 14 5.8 0.07 G G G G
Example 15 6.2 0.07 G G G G Example 16 5.8 0.07 G G G G Example 17
5.2 0.07 G G G G Example 18 6.8 0.08 G G G G Example 19 6.1 0.07 G
G G G Example 20 6.4 0.07 G G G G Comp. Ex. 1 24.8 0.2 F F P P
Comp. Ex. 3 25.7 0.23 P P F F Comp. Ex. 4 18.5 0.15 F G G G Comp.
Ex. 6 26.5 0.14 F G G P Comp. Ex. 7 28.0 0.17 P P P P Comp. Ex. 8
9.5 0.14 G G G G Comp. Ex. 9 28.8 0.25 P P P P Comp. Ex. 10 29.0
0.23 P P P P Comp. Ex. 11 29.0 1.41 P P P P Comp. Ex. 12 9.7 0.10 F
G G G
[0081] Dye Dispersibility Test
[0082] For comparison of the dye dispersibilities during dyeing, a
scoured polyester knit was wrapped around the holder of a CARAPET
(Nissen Corporation) and anchored above and below with rubber
bands, and this was dyed under the conditions described below using
a dyeing quality improver of Examples 1-20 or Comparative Examples
1, 3, 4 and 6-12, after which the extent of casing spots left on
the polyester knit were visually observed and the dye
dispersibility was evaluated on a 5-level scale, from 5 (no casing
spots) to 1 (numerous casing spots). The results are shown in Table
3.
Dyeing Bath
TABLE-US-00006 [0083] Dye: C.I. Disperse Red 167 2% o.w.f. 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SUNSOLT 1 g/L
RM-340E (Nicca Chemical Co., Ltd.) Dyeing quality improver 1 g/L
Dyeing temperature .times. time: 115.degree. C. .times. 1 minute
Liquor to goods ratio = 1:30
[0084] Persistence Test
[0085] For comparison of the persistences of the dyeing quality
improvers onto dyed fabrics, polyester satin woven fabrics dyed
under the same dyeing conditions as in the oligomer removability
test described above were dried at 120.degree. C..times.1 minute
and then heat treated at 180.degree. C..times.30 seconds. After
then cooling to room temperature, a single drop of water was
dropped onto the fabric and the time until complete permeation of
the water drop from the fabric surface was measured. Lower water
absorption was judged as less dyeing quality improver residue. The
results are shown in Table 3.
[0086] Processing Suitability Test
[0087] For comparison of the processing suitability for dyeing, a
high-temperature, high-pressure jet dyeing machine (MINI-JET D-100
by Texam Co., Ltd.) was used, placing a polyester pongee in a
treatment bath containing the dyeing quality improver of one of
Examples 1-20 or Comparative Examples 1, 3, 4 and 6-12, under the
conditions described below, and the condition of bubbles between
60-130.degree. C. with a heating rate of 3.degree. C/min was
compared to Comparative Example 11 wherein the dyeing quality
improver was water. The evaluation was conducted on a 3-level scale
of G (equivalent to Comparative Example 11), F (more foaming than
Comparative Example 11) and P (considerably more foaming than
Comparative Example 11), and the samples with low foaming were
judged as satisfactory. The results are shown in Table 3.
Treatment Bath
TABLE-US-00007 [0088] 80% Acetic acid 1 g/L Disperse level dyeing
agent: NICCA SUNSOLT 1 g/L RM-340E (Nicca Chemical Co., Ltd.)
Dyeing quality improver 1 g/L Liquor to goods ratio = 1:30
TABLE-US-00008 TABLE 3 Residual Dye property Processing
dispersibility (sec) suitability Example 1 5 180< G Example 2 5
180< G Example 3 5 180< G Example 4 5 180< G Example 5 5
180< G Example 6 5 180< G Example 7 5 180< G Example 8 5
180< G Example 9 5 180< G Example 10 5 180< G Example 11 5
180< G Example 12 5 180< G Example 13 5 180< G Example 14
5 180< G Example 15 5 180< G Example 16 5 180< G Example
17 5 180< G Example 18 5 180< G Example 19 5 180< G
Example 20 5 180< G Comp. Ex. 1 5 180< G Comp. Ex. 3 5
180< G Comp. Ex. 4 2 180< F Comp. Ex. 6 2 180< P Comp. Ex.
7 5 180< G Comp. Ex. 8 5 30 G Comp. Ex. 9 2 180< G Comp. Ex.
10 2 180< G Comp. Ex. 11 5 180< G Comp. Ex. 12 5 180<
G
[0089] As seen by the results in Tables 2 and 3, the dyeing quality
improvers of the examples of the invention were able to minimize
trouble caused by oligomers and problems such as dye contamination
and foreign matter contamination without affecting the dyeing
quality, and also exhibited good processing suitability evidenced
by low foaming during processing.
INDUSTRIAL APPLICABILITY
[0090] Using a dyeing quality improver according to the invention
can yield fiber products with satisfactory quality and no
processing defects arising from deposition of oligomers, dye
contamination or foreign matter contamination, while permitting
more economical dyeing of fiber products by reducing the extent of
foaming during processing, thus leading to less frequent occurrence
of troubles during processing.
* * * * *