U.S. patent application number 11/988059 was filed with the patent office on 2009-02-05 for oligomer removing agent for polyester-based fiber material.
Invention is credited to Masatoshi Hayashi, Masaaki Hosoda.
Application Number | 20090036640 11/988059 |
Document ID | / |
Family ID | 38693781 |
Filed Date | 2009-02-05 |
United States Patent
Application |
20090036640 |
Kind Code |
A1 |
Hosoda; Masaaki ; et
al. |
February 5, 2009 |
Oligomer Removing Agent for Polyester-Based Fiber Material
Abstract
An oligomer removing agent for polyester-based fiber materials
comprises a polyester copolymer which is obtained by
polycondensation of a dibasic acid component containing 15-65 mol %
of a sulfonate group-containing dibasic acid and a dihydric alcohol
component containing polyethylene glycol with a molecular weight of
900-3500, and which has a 200.degree. C. melt viscosity of
5000-23,000 mPas and has 10-40 mass % polyoxyethylene chains in the
molecule. The oligomer removing agent is able to overcome the
problems caused by deposition of polyester oligomers, when added to
the dyeing bath in a dyeing step for polyester fiber materials or
for fiber materials that are composites thereof with other 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: |
38693781 |
Appl. No.: |
11/988059 |
Filed: |
April 25, 2007 |
PCT Filed: |
April 25, 2007 |
PCT NO: |
PCT/JP2007/059407 |
371 Date: |
December 28, 2007 |
Current U.S.
Class: |
528/293 |
Current CPC
Class: |
D06P 3/52 20130101; D06P
1/5271 20130101; C08G 63/6886 20130101; C08G 63/672 20130101; D06P
3/54 20130101; D06P 5/22 20130101 |
Class at
Publication: |
528/293 |
International
Class: |
C08G 63/688 20060101
C08G063/688 |
Foreign Application Data
Date |
Code |
Application Number |
May 16, 2006 |
JP |
2006-136522 |
Claims
1. An oligomer removing agent for polyester-based fiber materials,
comprising a polyester copolymer which is obtained by
polycondensation of a dibasic acid component containing 15-65 mol %
of a sulfonate group-containing dibasic acid and a dihydric alcohol
component containing polyethylene glycol with a molecular weight of
900-3500, and which has a 200.degree. C. melt viscosity of
5000-23,000 mPas and has 10-40 mass % polyoxyethylene chain in the
molecule.
Description
TECHNICAL FIELD
[0001] The present invention relates to an oligomer removing agent
that is suitable for polyester-based fiber materials that are
polyester fiber materials and composite materials of polyester
fiber materials with other fiber materials.
BACKGROUND ART
[0002] Polyester-based fiber materials that are polyester fiber
materials and composites thereof with other fiber materials are
usually dyed under high temperature conditions of 100-140.degree.
C., but polyester oligomers cause various troubles by eluting from
the polyester-based fiber material onto the fiber surfaces or into
the dyeing bath. The serious problems that are faced are shadow
spots or calender contamination that occur when the polyester-based
fiber material is a fabric, and powder generation or winding yarn
breakage that occur when it is a yarn. In order to solve such
problems, methods have been adopted that involve adding oligomer
removing agents to the dyeing bath or to the reduction/cleaning
bath after dyeing. For example, Japanese Unexamined Patent
Publication No. 2000-154466 discloses a method for preventing
trouble resulting from oligomer deposition, by adding to the dyeing
bath an oligomer removing agent comprising a sulfonic acid salt of
polyoxyethylenestyryl phenyl ether, and a carboxyl group-containing
polymer such as an acrylic acid or methacrylic acid polymer or a
salt thereof. Also, Japanese Unexamined Patent Publication No.
2001-295136 discloses a method for preventing oligomer elution
wherein during the dyeing step there is added to the dyeing bath an
oligomer preventing agent comprising an ester of a polyhydric
alcohol-alkylene oxide addition product and an alkyl or alkenyl
fatty acid, or an ester obtained by transesterification between a
polyhydric alcohol-alkylene oxide addition product and a natural
animal or vegetable fat or oil containing 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.
DISCLOSURE OF THE INVENTION
[0003] It is an object of the present invention to provide an
oligomer removing agent for polyester-based fiber materials which
can solve the various problems caused by deposition of polyester
oligomers, by its addition to the dyeing bath in the dyeing step
for a fiber material composed of a polyester fiber material or a
composite material thereof with another fiber material.
[0004] As a result of much diligent research with the aim of
solving the aforementioned problems, the present inventors have
discovered that the problem of oligomer deposition in the dyeing
step for polyester-based fiber materials can be overcome by using
as the oligomer removing agent a polyester copolymer obtained by
polycondensation between a dibasic acid component comprising a
sulfonate group-containing dibasic acid in a specified amount and a
dihydric alcohol component containing polyethylene glycol in a
specified amount, and have completed this invention on the basis of
this discovered knowledge.
[0005] Specifically, the invention provides an oligomer removing
agent for polyester-based fiber materials, characterized by
comprising a polyester copolymer which is obtained by
polycondensation of a dibasic acid component containing 15-65 mol %
of a sulfonate group-containing dibasic acid and a dihydric alcohol
component containing polyethylene glycol with a molecular weight of
900-3500, and which has a 200.degree. C. melt viscosity of
5000-23,000 mPas and has 10-40 mass % polyoxyethylene chain in the
molecule.
[0006] Because the oligomer removing agent of the invention is
polyester copolymer-based, it has high affinity with polyester
oligomers and allows oligomers to be stably maintained in water.
Moreover, since the oligomer removing agent of the invention
contains a sulfonate group, the oligomers do not become redeposited
on the fiber material or dyeing machine, and therefore the agent
can be suitably used in dyeing steps.
BEST MODE FOR CARRYING OUT THE INVENTION
[0007] Preferred modes of the invention will now be explained with
the understanding that the invention is not limited only to these
modes, and that various modifications may be made as are within the
spirit and scope of the invention.
[0008] The oligomer removing agent of the invention comprises a
polyester copolymer obtained by polycondensation of a dibasic acid
component containing 15-65 mol % of a sulfonate group-containing
dibasic acid and a dihydric alcohol component containing
polyethylene glycol with a molecular weight of 900-3500. As
preferred sulfonate group-containing dibasic acids there may be
mentioned metal salts of sulfoterephthalic acid, 5-sulfoisophthalic
acid and 4-sulfophthalic acid, as well as their ester derivatives
such as dimethyl esters, diethyl esters 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 particularly preferred. The content of the
sulfonate group-containing dibasic acid in the dibasic acid
component is in the range of 15-65 mol %. The polyester oligomer
removing power 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 oligomer dispersibility, leading to redeposition
of the oligomer in the fiber material. On the other hand, a content
exceeding 65 mol % will impede polycondensation reaction of the
polyester copolymer. As dibasic acids other than sulfonate
group-containing dibasic acids 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 and aliphatic carboxylic acids such as
adipic acid, sebacic acid, maleic acid and succinic acid, and there
may also be used their acid anhydrides or ester derivatives thereof
with lower alcohols or glycols.
[0009] The oligomer removing agent of the invention further
contains polyethylene glycol with a molecular weight of 900-3500,
as a dihydric alcohol component, in a different starting material
for synthesis of the polyester copolymer to be used in the agent. A
molecular weight of less than 900 for the polyethylene glycol will
tend to lower the oligomer removing power, 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 % of
polyoxyethylene chains deriving from the polyethylene glycol. A
polyoxyethylene chain content of less than 10 mass % will tend to
reduce the removing power of the oligomer, while a polyoxyethylene
chain content of greater than 40 mass % will tend to increase the
frequency of problems such as insufficient disperse dye
dispersibility and high foamability during the dyeing process.
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
aliphatic or aromatic diol compounds including C3 or greater
alkylene glycols, neopentyl glycol, bisphenol A, bisphenol S and
the like.
[0010] The polyester copolymer used for the oligomer removing agent
of the invention preferably has a 200.degree. C. melt viscosity of
5000-23,000 mPas. According to the invention, the 200.degree. C.
melt viscosity may be measured using a CV-1S cone-plate viscometer
by M.S.T. Engineering, selecting a cone type and rotation rate
suitable for the melt viscosity, based on the manufacturer's
instruction manual. According to the invention, a melt viscosity of
less than 5000 mPas will tend to reduce the polyester oligomer
removing power, and may lower the affinity of the oligomer removing
agent with the polyester-based fiber material. A melt viscosity of
greater than 23,000 mPas will increase residue of the oligomer
removing agent on the polyester-based fiber material, possibly
adversely affecting the subsequent finishing step. The oligomer
removing agent of the invention, that comprises a polyester
copolymer satisfying the conditions including the sulfonate
group-containing dibasic acid content, the content of
polyoxyethylene chain from polyethylene glycol with a molecular
weight of 900-3500 and the 200.degree. C. melt viscosity, is
characterized by exhibiting an excellent ability to remove
oligomers from polyester-based fiber materials and minimizing their
redeposition onto polyester-based fiber materials and dyeing
machines. From the standpoint of handleability, the oligomer
removing agent of the invention is preferably used as an aqueous
dispersion or emulsion containing the polyester copolymer at 10-50
mass %.
[0011] The process for producing the polyester copolymer of the
invention may be any conventional process such as
transesterification or direct polymerization, without any
particularly restrictions.
[0012] As polyester-based fiber materials from which oligomers are
to be removed using the oligomer removing agent of the invention,
there may be mentioned polyester fiber materials composed of
polyethylene terephthalate, polybutylene terephthalate,
polypropylene terephthalate, polytrimethylene terephthalate and
their copolymers, or composite fiber materials composed of these
polyester fiber materials in combination with other synthetic or
natural fiber materials, while the form of the fiber material may
be a yarn, knitted fabric, woven fabric, nonwoven fabric or the
like.
[0013] The dyeing process used for dyeing of the polyester fiber
material or composite fiber material using the oligomer removing
agent of the invention may be an immersion process which may
include jet dyeing, cheese dyeing, beam dyeing, Obermaier dyeing,
high-pressure injection dyeing or the like, but any process may be
employed without any particular restrictions so long as it allows
the object of the invention to be achieved.
[0014] 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.
EXAMPLE 1
[0015] In a reactor there were charged 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, and the temperature was increased from 150.degree. C.
to 230.degree. C. over a period of 3 hours with stirring under a
nitrogen gas atmosphere for transesterification, while distilling
out the methanol from the system. Next, 0.1 g of tetrabutyl
titanate was added, the pressure was gradually reduced to an
internal pressure of approximately 10 kPa, and reaction was
conducted at 250.degree. C. for 2 hours to obtain 314 g of a
polyester copolymer. The content of polyoxyethylene chains in the
obtained polyester copolymer was approximately 27 mass %, and the
200.degree. C. melt viscosity as measured using a CV-1S cone-plate
viscometer by M.S.T. Engineering was 12,000 mPas, after selecting
the type of cone and rotation rate suitable for the melt viscosity
as according to the manufacturer's instruction manual.
EXAMPLE 2
[0016] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 340 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 38
mass %, and the 200.degree. C. melt viscosity was 20,000 mPas.
EXAMPLE 3
[0017] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 350 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 38
mass %, and the 200.degree. C. melt viscosity was 8100 mPas.
EXAMPLE 4
[0018] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 280 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 13
mass %, and the 200.degree. C. melt viscosity was 8900 mPas.
EXAMPLE 5
[0019] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 290 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 13
mass %, and the 200.degree. C. melt viscosity was 7500 mPas.
EXAMPLE 6
[0020] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 315 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 26
mass %, and the 200.degree. C. melt viscosity was 10,000 mPas.
EXAMPLE 7
[0021] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to obtain 343 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 24 mass %, and the 200.degree. C. melt viscosity
was 11,000 mPas.
EXAMPLE 8
[0022] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to obtain 267 g of a
polyester copolymer. The polyoxyethylene chain content of the
obtained polyester copolymer was approximately 25 mass %, and the
200.degree. C. melt viscosity was 10,000 mPas.
EXAMPLE 9
[0023] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 337 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 24
mass %, and the 200.degree. C. melt viscosity was 11,000 mPas.
EXAMPLE 10
[0024] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 350 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 23
mass %, and the 200.degree. C. melt viscosity was 12,000 mPas.
EXAMPLE 11
[0025] The same procedure was carried out as in Example 1, except
for charging into the reactor 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 bisphenol S-ethylene oxide 2 mol adduct, 83
g of polyethylene glycol with a molecular weight of 1000 and 10.1 g
of zinc acetate, to obtain 564 g of a polyester copolymer. The
polyoxyethylene chain content of the obtained polyester copolymer
was approximately 14 mass %, and the 200.degree. C. melt viscosity
was 12,000 mPas.
EXAMPLE 12
[0026] The same procedure was carried out as in Example 1, except
for charging into the reactor 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,
to obtain 320 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 26
mass %, and the 200.degree. C. melt viscosity was 14,000 mPas.
EXAMPLE 13
[0027] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 314 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 27
mass %, and the 200.degree. C. melt viscosity was 15,000 mPas.
EXAMPLE 14
[0028] The same procedure was carried out as in Example 1, except
for charging into the reactor 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,
to obtain 320 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 26
mass %, and the 200.degree. C. melt viscosity was 13,000 mPas.
EXAMPLE 15
[0029] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to obtain 297 g
of a polyester copolymer. The polyoxyethylene chain content of the
obtained polyester copolymer was approximately 28 mass %, and the
200.degree. C. melt viscosity was 12,000 mPas.
EXAMPLE 16
[0030] The same procedure was carried out as in Example 1, except
for charging into the reactor 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,
to obtain 303 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 27
mass %, and the 200.degree. C. melt viscosity was 12,000 mPas.
COMPARATIVE EXAMPLE 1
[0031] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 272 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 26
mass %, and the 200.degree. C. melt viscosity was 9200 mPas.
COMPARATIVE EXAMPLE 2
[0032] In a reactor there were charged 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, and the
temperature was increased from 150.degree. C. to 230.degree. C.
over a period of 3 hours with stirring under a nitrogen gas
atmosphere for transesterification, while distilling out the
methanol from 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 EXAMPLE 3
[0033] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to obtain
310 g of a polyester copolymer. The polyoxyethylene chain content
of the obtained polyester copolymer was approximately 26 mass %,
and the 200.degree. C. melt viscosity was 9700 mPas.
COMPARATIVE EXAMPLE 4
[0034] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 315 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 26
mass %, and the 200.degree. C. melt viscosity was 10,000 mPas.
COMPARATIVE EXAMPLE 5
[0035] In a reactor there were charged 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, and the temperature was increased from 150.degree. C.
to 230.degree. C. over a period of 3 hours with stirring under a
nitrogen gas atmosphere for transesterification, while distilling
out the methanol from 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 EXAMPLE 6
[0036] The same procedure was carried out as in Example 1, except
for charging into the reactor 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, to
obtain 438 g of a polyester copolymer. The polyoxyethylene chain
content of the obtained polyester copolymer was approximately 48
mass %, and the 200.degree. C. melt viscosity was 11,000 mPas.
COMPARATIVE EXAMPLE 7
[0037] In a reactor there were charged 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, and the temperature was increased from 150.degree. C.
to 230.degree. C. over a period of 3 hours with stirring under a
nitrogen gas atmosphere for transesterification, while distilling
out the methanol from the system. Next, 0.1 g of tetrabutyl
titanate was added and 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
200.degree. C. melt viscosity was 3200 mPas.
COMPARATIVE EXAMPLE 8
[0038] In a reactor there were charged 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, and the temperature was increased from 150.degree. C.
to 230.degree. C. over a period of 3 hours with stirring under a
nitrogen gas atmosphere for transesterification, while distilling
out the methanol from the system. Next, 0.1 g of tetrabutyl
titanate was added and the pressure was gradually reduced to an
internal pressure of approximately 9 kPa, and 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
200.degree. C. melt viscosity was 25,000 mPas.
[0039] The results from synthesizing these polyester copolymers are
summarized in Table 1.
TABLE-US-00001 TABLE 1 Sulfonate group/ total dibasic acid
Polyoxyethylene 200.degree. C. components chain content Melt
viscosity (mol %) (mass %) (mPa s) Example 1 40 27 12000 Example 2
20 38 20000 Example 3 30 38 8100 Example 4 50 13 8900 Example 5 60
13 7500 Example 6 40 26 10000 Example 7 40 24 11000 Example 8 40 25
10000 Example 9 40 24 11000 Example 10 40 23 12000 Example 11 40 14
12000 Example 12 40 26 14000 Example 13 40 27 15000 Example 14 40
26 13000 Example 15 40 28 12000 Example 16 40 27 12000 Comp. Ex. 1
10 26 9200 Comp. Ex. 2 70 25 reaction not continued Comp. Ex. 3 40
26 9700 Comp. Ex. 4 40 26 10000 Comp. Ex. 5 40 9 reaction not
continued Comp. Ex. 6 40 48 11000 Comp. Ex. 7 40 26 3200 Comp. Ex.
8 40 26 25000
[0040] The oligomer removing agents obtained in the examples and
comparative examples were evaluated in the following manner.
Oligomer Removing Power Test
[0041] For comparison of the oligomer removing effects during
dyeing, polyester satin woven fabrics containing the oligomer
removing agents of Examples 1-16 and Comparative Examples 1, 3, 4
6-8 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 calculated the oligomer deposition per
gram of fabric.
[0042] The results are shown in Table 2.
TABLE-US-00002 Dyeing bath Dye: C.I. Disperse Blue 79 1% o.w.f. 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SANSOLT 1 g/L
SN-558 (Nicca Chemical Co., Ltd.) Oligomer removing agent 0.3 g/L
Dyeing temperature .times. time: 130.degree. C. .times. 30 minutes
Liquor to goods ratio = 15:1
Dye Dispersibility Test
[0043] For comparison of the dye dispersibilities during dyeing, a
scoured polyester knit was wrapped around the holder of a CARAPET
(Nihon Senshoku Kikai Co.) and anchored above and below with rubber
bands, and this was dyed under the conditions described below with
addition of one of the oligomer removing agents of Examples 1-16 or
Comparative Examples 1, 3, 4 and 6-8, after which the extent of
casing spots left on the polyester knit was visually observed and
the dye dispersibility was evaluated on a 5-level scale, from 5 (no
casing spots) to 1 (numerous casing spots).
[0044] The results are shown in Table 2.
TABLE-US-00003 Dyeing bath Dye: C.I. Disperse Red 167 2% o.w.f. 80%
Acetic acid 1 g/L Disperse level dyeing agent: NICCA SANSOLT 1 g/L
SN-558 (Nicca Chemical Co., Ltd.) Oligomer removing agent 0.3 g/L
Dyeing temperature .times. time: 115.degree. C. .times. 1 minute
Liquor to goods ratio = 30:1
Persistence Test
[0045] For comparison of the persistences of the oligomer removing
agents onto dyed fabrics, polyester satin woven fabrics dyed under
the same dyeing conditions as in the oligomer removing power test
described above were dried at 120.degree. C. for 1 minute and then
heat treated at 180.degree. C. for 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. A lack of water absorption is
judged as a lack of persistence of the oligomer removing agent.
[0046] The results are shown in Table 2.
Processing Suitability Test
[0047] 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 for placement of a polyester pongee in
a treatment bath containing the oligomer removing agent of one of
Examples 1-16 or Comparative Examples 1, 3, 4 and 6-8 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 one without addition of an oligomer removing agent. The
evaluation was conducted on a 3-level scale of A (equivalent to no
addition), B (more foaming than with no addition) and C
(considerable foaming compared to no addition), and samples with
minimal foaming were judged as satisfactory.
[0048] The results of the evaluation are shown in Table 2.
TABLE-US-00004 Treatment bath 80% Acetic acid 1 g/L Disperse level
dyeing agent: NICCA SANSOLT 1 g/L SN-558 (Nicca Chemical Co., Ltd.)
Oligomer removing agent 0.3 g/L Liquor to goods ratio = 30:1
TABLE-US-00005 TABLE 2 Oligomer Oligomer removal deposition Dye
Persistence Processing agent mg/g dispersibility (sec) suitability
Example 1 9.7 5 180< A Example 2 10.4 5 180< A Example 3 10.1
5 180< A Example 4 11.7 5 180< A Example 5 11.3 5 180< A
Example 6 18.8 5 180< A Example 7 10.3 5 180< A Example 8
11.9 5 180< A Example 9 11.1 5 180< A Example 10 10.8 5
180< A Example 11 10.9 5 180< A Example 12 10.1 5 180< A
Example 13 9.9 5 180< A Example 14 10.3 5 180< A Example 15
10.7 5 180< A Example 16 10.9 5 180< A Comp. Ex. 1 25.8 5
180< A Comp. Ex. 3 26.7 5 180< A Comp. Ex. 4 18.8 2 180< B
Comp. Ex. 6 26.5 2 180< C Comp. Ex. 7 28.4 5 180< A Comp. Ex.
8 9.3 5 30 A None used 29.0 5 180< A
[0049] As seen by the results in Table 2, the oligomer removing
agents of the invention examples were able to reduce the amount of
oligomers without affecting the dyeing property, and also exhibited
good processing suitability evidenced by low foaming during
processing.
INDUSTRIAL APPLICABILITY
[0050] Using an oligomer removing agent according to the invention
can yield fiber products with satisfactory quality and no
processing defects arising from oligomer deposition, while
permitting more economical dyeing of fiber products due to reduced
foaming during processing and thus less frequent occurrence of
trouble during processing.
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