Water-dispersible block copolyesters useful as low-odor adhesive raw materials

Disclosed are linear, water-dispersible sulfopolyesters incorporating a low molecular weight polyethylene glycol and blocks of a high molecular weight polyethylene glycol. The block sulfopolyesters have improved toughness, abrasion resistance, flexibility, and adhesion. Particular utility is realized in polyester fiber sizing applications and as an adhesive.

FIELD OF THE INVENTION 
This invention relates to linear, water-dispersible sulfopolyesters 
prepared using high molecular weight polyethylene glycol blocks and low 
molecular weight polyethylene glycol. 
BACKGROUND 
Water-dispersible sulfopolyesters incorporating polyethylene glycol (PEG) 
units are known in the art. For example, U.S. Pat. Nos. 3,546,008, 
3,734,874 and 3,779,993, teach compositions useful as a size for fabrics. 
These references disclose a very large number of linear compositions that 
are limited to PEG contents of greater than 15 mol %, based on 100 mol % 
of total glycol, within a PEG molecular weight range of 106 to 898 g/mol. 
Although it is disclosed that more than one PEG could be present in a 
particular composition, there is no teaching or example of the 
advantageous use of combinations of polyethylene glycols having different 
molecular weights. 
The incorporation of high molecular weight PEGs is the subject of U.S. Pat. 
No. 4,233,196, where a molecular weight range of 106 to 22,018 g/mol was 
specified for the PEG component. Although both low and high molecular 
weight PEGs could be incorporated in a particular composition, the 
invention was limited to less than 15 mol % of total PEG based on 100 mol 
% of total glycol. 
U.S. Pat. Nos. 4,329,391, 4,483,976, 4,525,524, and 5,290,631 disclose 
additional water-dispersible sulfopolyester compositions. However, all of 
these patents are limited to PEGs having molecular weights of less than 
600 g/mol. 
Recently, European Patent Application 0 761 795 described hot melt 
adhesives based on 10-90 weight percent of a sulfonated polyester, which 
can be the condensation product of a difunctional dicarboxylic acid, a 
sulfomonomer containing at least one metallic sulfonate group, a glycol, 
and optional ingredients. There is no disclosure of using both high and 
low molecular weight PEGs. 
The utility of certain water-dispersible sulfopolyester compositions as 
adhesive raw materials is also described in detail by the teachings of 
U.S. Pat. Nos. 5,543,488; 5,552,495; 5,552,511; 5,571,876; and 5,605,764, 
and European Patent Application EP 0 761 795 A2. 
Among the many problems associated with prior art compositions utilizing 
sulfonated polyesters is the distinctive and unpleasant odor associated 
with the final product. The odor is highly undesirable, particularly when 
used, for instance, as an adhesive composition. It would be beneficial if 
a composition could be formulated having the advantageous aspects of 
sulfonated polyesters without the undesirable odor. 
The prior art disclosures relating to water-dispersible sulfopolyesters do 
not recognize the advantageous combinations of both low and high molecular 
weight PEGs and the benefits thereof. In addition, none of the examples 
given above are described as block copolyesters, indicating that the 
inventors were unaware of the structure/property advantages obtainable 
from specific architectures. 
However, it is important to recognize that a block architecture, by itself, 
will not necessarily lead to desired property improvements. In some cases 
a block architecture may actually have a deleterious effect on properties; 
for example, a high content of certain high molecular weight PEGs in the 
final polymer may lend unacceptable water-sensitivity to a particular 
article of manufacture. Therefore, it is not obvious which block 
compositions will render the key property improvements that are described 
hereinafter. 
Thus there is a need for a water-dispersible sulfopolyester composition 
that has improved properties, particularly a low odor, that can be made by 
simple selection of the proper block architecture. 
SUMMARY OF THE INVENTION 
The present invention concerns linear, water-dispersible sulfopolyesters 
that incorporate both low and high molecular weight polyethylene glycols. 
The structure of a polyethylene glycol is represented by formula (I): 
EQU H--(OCH.sub.2 CH.sub.2).sub.n --OH (I). 
The present invention more particularly concerns sulfonated polyesters 
having both low and high molecular weight polyethylene glycols, wherein 
the low molecular weight PEGs are defined by formula (II): 
EQU H--(OCH.sub.2 CH.sub.2).sub.x --OH (II) 
where x=2 to 6; and wherein the high molecular weight PEGs are defined by 
formula (III): 
EQU H--(OCH.sub.2 CH.sub.2).sub.y --OH (III) 
where y=3 to 500. The sulfonated polyesters according to the present 
invention are further characterized as having x&lt;y. 
The water-dispersible, sulfopolyester according to the present invention is 
a copolyester composition made of the reaction products of: 
(a) at least one difunctional dicarboxylic acid which does not contain a 
metal sulfonate group; 
(b) an amount sufficient to provide water-dispersibility to said polyester 
of at least one difunctional sulfomonomer containing at least one metal 
sulfonate group bonded directly to an aromatic ring, a diol containing a 
metal sulfonate group bonded directly to an aromatic ring, or a hydroxy 
acid containing a metal sulfonate group bonded directly to an aromatic 
ring, wherein the functional groups are ester, hydroxyl or carboxyl; 
(c) at least one polyethylene glycol having the structure: 
EQU H--(OCH.sub.2 CH.sub.2).sub.x --OH (II) 
where x is an integer ranging from 2 to 6; 
(d) at least one polyethylene glycol having the structure: 
EQU H--(OCH.sub.2 CH.sub.2).sub.y --OH (III) 
where y is an integer of from 3 to 500; 
and further wherein x&lt;y; 
the polymer containing substantially equal molar proportions of acid 
equivalents (100 mol %) and glycol equivalents (100 mol %) and wherein the 
inherent viscosity is at least 0.1 dL/g measured in a 60/40 parts by 
weight solution of phenol/tetrachloroethane at 25.degree. C. at a 
concentration of about 0.50 g of polymer in 100 ml of the solvent. 
The polymer can optionally comprise other monomers, such as 
hydroxycarboxylic acid, and a glycol or mixture of glycols that is (are) 
not a polyethylene glycol, such as polypropylene glycol. Such additional 
glycols that are not PEGs preferably contain two primary alcohols, i.e., 
two --CH.sub.2 --OH groups; 
Accordingly, it is an object of the present invention to describe 
elastomeric compositions that display excellent toughness and elongation 
with the retention of water-dispersibility. 
It is another object of this invention is to describe compositions having 
utility as adhesive raw materials that exhibit compatibility with a 
variety of formulation components and impart water-dispersibility to the 
finished adhesive. 
Yet another object of this invention is to set forth polyester compositions 
that do not impart odor to either the finished adhesives or the resulting 
articles of manufacture. 
Still another object of the invention is to describe a sulfopolyester-based 
adhesive able to render articles made therewith more recyclable and more 
flushable. 
These and other objects, features, and advantages of the present invention 
will become apparent as reference is made to the following detailed 
description, preferred embodiments, and specific examples.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present inventors have discovered a linear, block, water-dispersible 
polyester and compositions thereof, based on the incorporation of low and 
high molecular weight polyethylene glycol residues. 
It is to be understood that by "linear" is meant essentially linear, so 
that some minor branching is allowed for in the final polymer. It will be 
recognized by those of skill in the art in possession of the present 
disclosure that some branching may occur during polymerization. It will be 
further appreciated by the same artisan that additional branching can be 
achieved by, for instance, adding branching agents such as trimellitic 
anhydride; such polymers are not within the scope of the present 
invention. 
In general, the term "block" may be broadly defined as the incorporation of 
an oligomeric or polymeric segment, consisting of two or more repeat 
units, within a secondary, dissimilar polymer structure. This term is 
discussed in more detail below with reference to preferred embodiments of 
the invention. 
The term "water-dispersible" is often used interchangeably with other 
descriptors, such as "water dissipatable", "water-soluble", or 
"water-dispellable". In the context of this invention, all of these terms 
are to refer to the activity of water or a mixture of water and a 
water-miscible organic cosolvent on the polyesters described herein. 
Therefore, for the purposes of the present invention the term "water 
dispersable" is intended to include conditions where the polyester is 
dissolved to form a true solution or is dispersed within the aqueous 
medium to obtain a stable product. Often, due to the statistical nature of 
polyester compositions, it is possible to have soluble and dispersible 
fractions when a single polyester is acted upon by an aqueous medium. 
According to a preferred embodiment of the present invention, as described 
in the above mentioned U.S. application Ser. No. 08/651,246, which is 
hereby incorporated by reference in its entirety, and of which the present 
application is a Continuation-in-Part, a more preferred sulfopolyester 
used in a sizing composition for textile yarns made from linear polyesters 
comprises repeat units of the following monomers: 
(a) the dicarboxylic acid component is selected from the group consisting 
of aromatic dicarboxylic acids having 8 to 14 carbon atoms, saturated 
aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and 
cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms, and is 
present in the amount of 70 to 100, more preferably 85-100 mole percent, 
based on the total moles of acid; 
(b) the difunctional sulfomonomer component is selected from the group 
consisting of a dicarboxylic acid or ester thereof containing a metal 
sulfonate group bonded directly to an aromatic ring, a diol containing a 
metal sulfonate group bonded directly to an aromatic ring, and a hydroxy 
acid containing a metal sulfonate group bonded directly to an aromatic 
ring, and is present in the amount of 2.5 to 20 mole percent, more 
preferably 4 to 15 mole percent, even more preferably 5 to 12 mole 
percent, and still more preferably 5 to 10 mole percent, based on total 
moles of acid and glycol (e.g., based on 200 mol percent); 
(c) the low molecular weight polyethylene glycol component represented by 
formula (II) above, wherein x is an integer from 2 to 6, is present in the 
amount of 25 to 99.9 mole percent, more preferably 25 to 75 mole percent, 
based on total moles of glycol; and 
(d) the high molecular weight polyethylene glycol component represented by 
formula (III) above, where y is an integer from 20 to 500, is present in 
the amount of 0.1 to 20 mole percent, more preferably 0.1 to 10 mole 
percent, even more preferably 0.25 to 5 mole percent, based on total moles 
of glycol; 
wherein the linear, water-dispersible sulfopolyesters will contain 
substantially equimolar proportions of acid (100 mol %) and hydroxyl (100 
mol %) equivalents, such that the total of acid and hydroxyl equivalents 
is equal to 200 mol %. The sulfopolyester used in the preferred size 
composition is further characterized by having a Tg of -20.degree. C. to 
100.degree. C., more preferably from 30 to 50.degree. C. and an inherent 
viscosity of 0.1 to 1.1 dL/g, preferably 0.2 to 0.7 dL/g, and more 
preferably 0.3 to 0.5 dL/g, measured at 23.degree. C. using 0.50 grams of 
polymer per 100 ml of a solvent consisting of 60/40 (by weight) 
phenol/tetrachloroethane mixture. There is also a preferred proviso that 
the mole percent of the high molecular weight polyethylene glycol within 
the range of y (i.e., 20 to 500) is inversely proportional to the quantity 
of y within said range, i.e., as y increases, the molecular weight of the 
species represented by formula (III), decreases. 
When used as an adhesive or in an adhesive formulation, the sulfopolyester 
according to the present invention may be as exactly set forth above for 
the sulfopolyester used in a size composition. However, it has been found 
that the useful range of ingredients (a)-(d) above and parameters as x and 
y in formulas (II) and (III), respectively, is broader for the 
sulfopolyester used in as an adhesive, as will be described in more detail 
below. It has been found, for instance, that the useful range of y also 
includes 3-19 (thus 3.ltoreq.y.ltoreq.500), as long as x&lt;y, and the 
viscosity may range from from "water-thin" to a thick paste, depending on 
the end use. As will be appreciated by the skilled artisan in possession 
of this disclosure, the exact viscosity will be determined by the end use 
of the adhesive. 
In the sulfopolyester according to the present invention, preferred 
examples of dicarboxylic acids that may be used as (a) include aliphatic 
dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic 
acids, or mixtures of two or more of these acids. Thus, preferred 
dicarboxylic acids include, but are not limited to succinic; glutaric; 
adipic; azelaic; sebacic; fumaric; maleic; itaconic; 1,3-cyclohexane 
dicarboxylic; 1,4-cyclohexanedicarboxylic; iglycolic; 
2,5-norbornanedicarboxylic; phthalic; terephthalic; 
1,4-naphthalenedicarboxylic; 2,5-naphthalenedicarboxylic; diphenic; 
4,4'-oxydibenzoic; 4,4'-sulfonyldibenzoic; and isophthalic. More preferred 
are isophthalic and terephthalic acids. 
It is to be understood that the use of the corresponding acid anhydrides, 
esters, and acid chlorides of these acids is included in the term 
"dicarboxylic acid". Preferred diesters are dimethyl terephthalate, 
dimethyl isophthalate, and dimethyl-1,4-cyclohexanedicarboxylate. Although 
the methyl ester is the most preferred embodiment, it is also acceptable 
to include higher order alkyl esters, such as ethyl, propyl, isopropyl, 
butyl, and so forth. In addition, aromatic esters, particularly phenyl, 
may also be considered. 
The difunctional sulfomonomer component, (b), may advantageously be a 
dicarboxylic acid or ester thereof containing a metal sulfonate group 
(--SO.sub.3 M) or a glycol containing a metal sulfonate group or a hydroxy 
acid containing a metal sulfonate group. The cation of the sulfonate salt 
may be a metal ion, such as Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.++, 
Ca.sup.++, Cu.sup.++, Ni.sup.++, Fe.sup.++, Fe.sup.+++ and the like. It is 
within the scope of the present invention that the sulfonate salt is 
non-metallic and may be a nitrogenous base as described in U.S. Pat. No. 
4,304,901. A nitrogen based cation will be derived from nitrogen 
containing bases, which may be aliphatic, cycloaliphatic, or aromatic 
compounds that have ionization constants in water at 25.degree. C. of 
10.sup.-3 to 10.sup.-10, preferably 10.sup.-5 to 10.sup.-8. Examples of 
preferred nitrogen containing. bases are ammonia, pyridine, morpholine, 
and piperidine. It is known that the choice of cation will influence, 
often markedly, the water-dispersibility of the resulting polymer. 
Depending on the end-use application of the polymer, either a more or less 
easily dispersible product may be desirable. It is within the skill of the 
artisan in possession of the present disclosure to modify the 
dispersibility for the desired end use. It is possible to prepare the 
polyester using, for example, a sodium sulfonate salt and then by 
ion-exchange methods replace the sodium with a different ion, such as 
zinc, when the polymer is in the dispersed form. This type of ion-exchange 
procedure is generally superior to preparing the polymer with divalent and 
trivalent salts inasmuch as the sodium salts are usually more soluble in 
the polymer reactant melt-phase. Also, the ion-exchange procedure is 
usually necessary to obtain the nitrogenous counterions, since amine salts 
tend to be unstable at typical melt processing conditions. Advantageous 
difunctional sulfomonomers are those where the sulfonate salt group is 
attached to an aromatic acid nucleus, such as benzene, naphthalene, 
diphenyl, oxydiphenyl, sulfonyidiphenyl, or methylenediphenyl. Preferred 
results are obtained through the use of sulfophthalic acid, 
sulfoterephthalic acid, sulfoisophthalic acid, 
4-sulfonaphthalene-2,7-dicarboxylic acid, and their esters as described in 
U.S. Pat. No. 3,779,993, the disclosure of which is incorporated herein by 
reference. Particularly superior results are achieved when the 
difunctional sulfomonomer is 5-sodiosulfoisophthalic acid or esters 
thereof. It is preferred that reactant (b) be present in an amount of 5 to 
40 mol %, more preferably about 8 to 30 mol %, and most preferably about 9 
to 25 mol %, based on the total acid equivalents. 
Although not preferred for the practice of this invention, either in a size 
composition or an adhesive composition, it is possible to include from 0 
to 50 mol percent, based on total carboxyl and hydroxyl equivalents, of a 
hydroxycarboxylic acid. These hydroxycarboxylic acids may be aromatic, 
cycloaliphatic, or aliphatic and generally contain 2-20 carbon atoms, one 
--CH.sub.2 OH group and one COOH or COOR group. 
The lower molecular weight polyethylene glycol, (c), is represented by 
formula (II): 
EQU HO--(CH.sub.2 CH.sub.2 --O).sub.x --H (II) 
where x is an integer of at least 2 but less than or equal to 6. Preferred 
examples of lower molecular weight polyethylene glycols are: diethylene 
glycol, triethylene glycol, and tetraethylene glycol; diethylene and 
triethylene glycol are most preferred. 
It is important to recognize that certain glycols of (c) may be formed 
in-situ, due to side reactions that may be controlled by varying the 
process conditions. The preferred example of this is the formation of 
varying proportions of diethylene, triethylene, and tetraethylene glycols 
from ethylene glycol due to an acid-catalyzed dehydration, which occurs 
readily when a buffer is not added to raise the pH of the reaction mixture 
(i.e., render the reaction mixture less acidic). Additional compositional 
latitude is possible if the buffer is omitted from a feed containing 
various proportions of ethylene and diethylene glycols or ethylene, 
diethylene, and triethylene glycols. 
The high molecular weight polyethylene glycol component, (d), is used to 
place hydrophilic, but non-ionic blocks within the polymer backbone. In 
addition to the benefit of a secondary means to tailor the hydrophilicity 
of the sulfopolyester, a number of other advantages, for example, lower 
melt viscosity, improved adhesion, and increased abrasion resistance, may 
be realized from specific block sulfopolyester compositions. 
As mentioned above, generally the term "block" may be broadly defined as 
the incorporation of an oligomeric or polymeric segment, consisting of two 
or more repeat units, within a secondary, dissimilar polymer structure. In 
the context of this invention, the term "block" is more narrowly defined 
as a sulfopolyester containing polyethylene glycol segments ranging from 3 
to 500 repeat units. In the case of a size composition, it is preferred 
that the sulfopolyester contain polyethylene glycol segments ranging from 
20 to 500, preferably 22 to 100 repeat units. In the case of the adhesive 
composition, it has surprisingly been found that the useful range is 
larger, and here the sulfopolyester may contain polyethylene glycol 
segments ranging from 3 to 500, with the preferred proviso that these 
segments be greater than the segments in component (c). 
Thus, the definition of the term "block", as used in the present invention, 
is based on specific performance/properties of the sulfopolyester. 
Representative examples of useful high molecular weight polyethylene 
glycols of the formula (III): 
EQU HO--(CH.sub.2 CH.sub.2 --O).sub.y --H (III) 
where (3.ltoreq.y.ltoreq.500), include such commercially available products 
as "Carbowax", a product of Union Carbide. 
When used as a size or as an adhesive, it is preferred that y is 20 or 
greater. However, when used as an adhesive the useful range of y is 
greater, and may be from 3 to 500, as long as x in formula (II) is less 
than y in formula (III). In the case of 20.ltoreq.y.ltoreq.500, the 
molecular weight of (d) may range from greater than 900 to about 22,000 
g/mol. The preferred molecular weight range is from about 1000 to about 
4500. It is preferred that the molecular weight and the mol % of (d) are 
inversely proportional to each other; specifically, as the molecular 
weight is increased the mol % of (d) will be decreased. 
Although not intending to be limiting, it is illustrative of this concept 
to consider that a PEG having a molecular weight of 1000 may constitute up 
to 10 mol % of the total glycol, while a PEG having a molecular weight of 
10,000 would typically be incorporated at a level of less than one (1) 
mole percent of the total glycol. For use as a size or as an adhesive, it 
is preferred that reactant (d) is present in an amount of 0.1 to 10 mol %, 
preferably 1 to 5 mol %. based on total moles of glycol, although again 
particularly when used as an adhesive the useful range of (d) can be 
greater. 
It is to be understood that additional glycol components, different from 
(c) and (d) above, may be added. It is preferred that such glycols contain 
at least two primary alcohol groups. More preferred examples include, but 
are not limited to, aliphatic, alicyclic, and aralkyl glycols. Examples of 
these more preferred glycols include ethylene glycol; propylene glycol; 
1,3-propanediol; 2,4-dimethyl-2-ethylhexane-1,3-diol; 
2,2-dimethyl-1,3-propanediol; 2-ethyl-2-butyl-1,3-propanediol; 
2-ethyl-2-isobutyl-1,3-propanediol; 1,3-butanediol; 1,4-butanediol; 
1,5-pentanediol; 1,6-hexanediol; 2,2,4-trimethyl-1,6-hexanediol; 
thiodiethanol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 
1,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 
p-xylylenediol. 
To obtain the polymers of this invention, the difunctional sulfomonomer is 
most often added directly to the reaction mixture from which the polymer 
is made; other processes are known and may also be employed. Illustrative 
examples from the art are U.S. Pat. Nos. 3,018,272; 3,075,952; and 
3,033,822. These patents disclose interchange reactions as well as 
polymerization of build-up processes. 
Briefly, a typical procedure consists of at least two distinct stages; the 
first stage, known as ester-interchange or esterification, is conducted 
under an inert atmosphere at a temperature of 150 to 250.degree. C. for 
0.5 to 8 hours, preferably from 180 to 230.degree. C. for 1 to 4 hours. 
The glycols, depending on their reactivities and the specific experimental 
conditions employed, are commonly used in molar excesses of 1.05-2.5 moles 
per total moles of acid-functional monomers. The second stage, referred to 
as polycondensation, is conducted under reduced pressure at a temperature 
of 230 to 350.degree. C., preferably 250 to 310.degree. C., and more 
preferably 260 to 290.degree. C. for 0.1 to 6 hours, preferably 0.25 to 2 
hours. Stirring or appropriate conditions are used in both stages to 
ensure adequate heat transfer and surface renewal of the reaction mixture. 
The reactions of both stages are facilitated by appropriate catalysts, 
especially those well-known in the art, such as alkoxy titanium compounds, 
alkali metal hydroxides and alcoholates, salts of organic carboxylic 
acids, alkyl tin compounds, metal oxides, and so forth. A three-stage 
manufacturing procedure, similar to the disclosure of U.S. Pat. No. 
5,290,631, may also be used, particularly when a mixed monomer feed of 
acids and esters is employed. 
Dispersions may be obtained by adding molten or solid polymer into water 
with sufficient agitation. 
Sizing Compositions and Sized Fibrous Articles of Manufacture 
Specific examples of the sulfopolyester compositions described supra may be 
used advantageously as sizing compositions for textile yarns made from 
linear polyesters. When multifilament polyesters yarns are fabricated into 
textiles it is desirable to treat the warp yarn, before weaving, with a 
sizing composition that adheres and binds several filaments together. The 
treatment process, known as "sizing", imparts strength and abrasion 
resistance to the yarn during the weaving process. It is also critical 
that the sizing composition be completely removable from the woven fabric. 
Increased abrasion resistance will result in fewer breaks during the 
weaving process, which improves the quality of the textile product. Thus, 
one aspect of this invention is directed toward sizing compositions and 
fibrous articles of manufacture sized therewith. Although the described 
application is in reference to polyester yarns, such as poly(ethylene 
terephthalate) or poly(1,4-cyclohexanedimethylene terephthalate), the 
compositions described hereinafter may be used as sizes for a variety of 
natural and synthetic yarns. Examples of non-polyester yarns include 
rayon, acrylic, polyolefin, cotton, nylon, and cellulose acetate. Blends 
of polyester and non-polyester yarns are also within the scope of fibers 
that may be effectively sized. 
It is necessary for the size compositions to possess adequate resistance to 
blocking, which is most critically manifested when the fiber is wound on a 
warp beam or bobbin and stored for extended periods of time under ambient 
conditions. Blocking causes the sized fibers to meld together, which 
prohibits them from being unwound at the desired time. The tendency for 
blocking to occur under both normal and extreme ambient conditions of 
temperature and humidity may be directly related to the Tg of the size 
composition. Therefore, a dry Tg ranging from 30 to 60.degree. C., 
preferably 35 to 50.degree. C. is required to avoid blocking problems. 
This requirement necessitates careful selection of the acid and glycol 
components; for example too high a level of PEG will detrimentally lower 
the Tg and result in blocking. In general, as the length or molecular 
weight of a polyethylene glycol monomer is increased, at a constant molar 
percentage of incorporation, the Tg of the final polymer will be 
proportionately decreased. 
Adhesion, flexibility and, in part, desizability and water resistance are 
also related to the PEG molecular weight and content of the 
sulfopolyester. As the PEG content is increased, hydrophilicity, 
flexibility, and adhesion are also increased. If the PEG content and/or 
molecular weight is too high, then the resulting size will have a low Tg 
and marginal water resistance. The properties of desizability, water 
resistance, flexibility, and adhesion are also related to the content of 
sulfomonomer (SIP). If the SIP level is too high, the water resistance, 
flexibility, and economics of the size will be lessened, while a 
functionally low level of SIP tends to detract from the adhesion and will 
prevent adequate desizing after the weaving operation. The key property, 
as a result of this invention, is the abrasion resistance. The utility of 
the Duplan Cohesion Tester, as a measurement of abrasion resistance for a 
sized yarn, is well known to those in the art. Briefly, the Duplan test is 
performed on samples of sized yarn, under constant tension, that are 
abraded by friction plates moving back and forth over said yarn at a 
constant rate. The average number of cycles to separate the yarn filaments 
is reported as the abrasion resistance or Duplan value. Hence, higher 
Duplan values are a direct indicator of the suitability of the 
sulfopolyester as a size material. It is critical to the efficacy of this 
invention that the sulfopolyester contain blocks of high molecular weight 
PEG to obtain excellent abrasion resistance; at least 0.25 mol % and not 
greater than 5 mol %, depending on molecular weight, of a high molecular 
weight PEG will provide a sulfopolyester having excellent size properties. 
The molecular weight of the PEG will advantageously fall in the range from 
900 to 4500, preferably 1000 to 2000 grams/mol. For optimum performance, 
the overall molecular weight of the sulfopolyester is at least 0.25 dL/g, 
preferably greater than 0.3 dL/g. Molecular weights for the present 
sulfopolyester according to the present invention, as set forth in this 
disclosure, are determined by GPC and can readily be determined by one of 
ordinary skill in the art. 
In summary, this particular preferred embodiment of the invention, which is 
related to a size material and the fibrous articles of manufacture sized 
therewith, may be described in a preferred embodiment as a linear, 
water-dispersible sulfopolyester useful as a size on fabrics of all types, 
including woven and non-woven fabrics. 
Adhesive Raw Material Compositions, Formulated Adhesives, and Articles of 
Manufacture 
In another preferred embodiment of the present invention, the 
sulfopolyester according to the present invention is also useful as an 
adhesive raw material and specific examples of the sulfopolyester 
compositions may be used, in even more preferred embodiments, for both 
hot-melt and liquid adhesive formulations, for pressure sensitive 
adhesives (PSAs), and hot-melt PSAs. Furthermore, it is within the scope 
of this invention to include a process of applying the adhesive 
formulations described hereinafter on a single substrate or between two 
substrates to form a laminate. One of the more surprising discoveries of 
the present inventors is that a composition according to the present 
invention is useful as an adhesive on a variety of substrates including, 
but not limited to, plastics, metals, fabrics, wood, and wood-derived 
products such as paper. By "paper" is meant a material containing wood 
pulp, which may contain a variety of other additives and may be coated or 
uncoated. 
In another particularly advantageous aspect of the present invention, the 
adhesive comprising the sulfopolyester can be separated from the 
substrates, after use, in a recycling process comprised of repulping a 
repulpable article. Separation is accomplished by repulping the entire 
laminate structure. Repulping per se is within the skill of the artisan. 
Thus, this invention also concerns, in a more preferred embodiment, 
applying the water-dispersible adhesive compositions, described more fully 
below, in liquid form to a surface of a substrate and, while the adhesive 
composition remains in liquid form, applying a second surface of a 
substrate to the water-dispersible adhesive composition thereby forming an 
article of manufacture that comprises the water-dispersible adhesive 
composition laminated between two substrates or two surfaces of a 
substrate. It will be recognized by one of skill in the art in possession 
of the present disclosure that the water-dispersibility of the adhesive 
composition according to the present invention allows for a more 
environmentally-friendly product which will more readily disperse in an 
aqueous environment, i.e., municipal water/sewage systems, thus rendering 
such a product more amenable to being flushed down a toilet. Such products 
include, but are not limited to, personal hygiene products. 
Yet another aspect of this invention comprises bonded articles of 
manufacture having the adhesive composition between two substrates such as 
in carton sealings, corrugated board, bookbinding, sanitary napkins and 
diaper constructions. 
As previously mentioned, the utility of certain water-dispersible 
sulfopolyester compositions as adhesive raw materials is described in 
detail by the teachings of U.S. Pat. Nos. 5,543,488; 5,552,495; 5,552,511; 
5,571,876; and 5,605,764, and European Patent Applications EP 0 761 795 A2 
and EP 0 781 538 A2. The sulfopolyester according to the present invention 
can be used in any of the applications recited in these references. 
The molecular weight of the water-dispersible polyesters is an important 
consideration to the formulation and application of the finished 
adhesives. Normally, it is desirable to achieve as high a molecular weight 
as possible to maximize physical properties, such as tensile strength, 
peel strength, resistance to cold flow, and the like. Specification of a 
molecular weight range is particularly relevant to hot-melt adhesives, 
where too high of a molecular weight will result in melt viscosities that 
exceed the capabilities of application methods that are known in the art. 
At the other extreme, very low molecular weights are also unsuitable as 
they will lack cohesive strength. As known to the skilled artisan, 
molecular weight for adhesive purposes is generally expressed in terms of 
inherent viscosity. It is preferred that the water-dispersible polyesters 
of the present invention when used in the aforementioned adhesive 
applications have an inherent viscosity (IV) of at least 0.1 dL/g, more 
preferably about 0.1 to 0.8 dL/g, still more preferably 0.2 to 0.8 dL/g, 
measured in a 60/40 parts by weight solution of phenol/tetrachloroethylene 
at 25.degree. C., and at a concentration of about 0.50 g of polymer in 100 
mL of solvent. 
Glass transition temperature (Tg) is another critical parameter related to 
adhesive performance and it is preferred that the Tg is advantageously 
less than ambient temperatures (20.degree. C.) to insure flexibility. It 
is generally preferred that the Tg should be as low as possible to ensure 
a flexible product that will not crack or shatter at more extreme use 
temperatures. However, lowering the Tg of amorphous sulfopolyesters 
generally results in a lowering of the Ring and Ball Softening Point 
(RBSP). The RBSP is commonly used in the specification of adhesives as 
described in ASTM E 28 and it is generally desirable to have as high a 
RBSP as high as possible to provide heat resistance to the adhesive. 
Although Tg and RBSP are generally inversely related, it is possible to 
maximize the difference between them to achieve optimum performance. It is 
particularly advantageous that the Tg be from -50 to 20.degree. C., more 
preferably below 20.degree. C., still more preferably less than 0.degree. 
C., and even more preferably less than -10.degree. C., while the RBSP is 
preferably at least 80.degree. C., more preferably at least 100.degree. C. 
Futhermore, it is preferred to have the difference between the Tg and RBSP 
be at least 90.degree. C., more preferably 100.degree. C. Crystalline 
compositions are also within the scope of this invention and represent one 
avenue to low Tg and high RBSP polyester compositions as crystalline 
melting points (Tm) are usually far above the Tg. 
The adhesive compositions according to the present invention are 
particularly useful due to their good combination of properties and are 
suitable for use as adhesives for many substrates including non-woven 
assemblies, paper, wood, plastic, and metal. In the case of paper and wood 
pulp derived substrates, improved repulpability/recyclability result. 
In the case of a laminated structure, according to one embodiment of the 
invention the adhesive composition is applied to one substrate with a 
second substrate being placed on top of the adhesive, thus forming an 
article having the adhesive laminated between two substrates. Depending on 
the end-use, it is possible for the substrates to be dissimilar materials, 
i.e., paper can be laminated to plastic. 
It is within the scope of this invention to also apply the polyester 
composition in a liquid vehicle that includes water, organic solvents, and 
combinations thereof. Preferred organic solvents are aromatic and polar 
solvent, such as ketones (i.e., methy ethyl ketones), toluene, glycol 
ethers, glycol esters, and alcohols. Depending on the specific 
application/end-use requirements, typical solution concentrations may 
range from about 5 to about 80% polyester based on total weight of 
solution. Elevated application temperatures may be advantageously 
employed, especially at higher concentrations of polyester. Additives 
known in the liquid formulation art, such as surfactants, thickeners, 
biocides, defoamers, and the like, may also be present. When applied as a 
solution, the adhesive compositions are most often applied by conventional 
processes, such as spray coating, roll coating, brush coating, dip 
coating, and the like. 
It is a preferred embodiment to use the polyester compositions of this 
invention as hot melt adhesive raw materials. The hot melt adhesive is 
typically applied at a temperature of about 125.degree. C. to about 
250.degree. C., preferably 150.degree. C. to 200.degree. C., to a surface 
of a substrate, and while remaining molten and pliable, applying a second 
surface of a substrate to the water-dispersible hot melt adhesive 
composition that has been laminated between two substrates or two surfaces 
of a substrate. 
In another preferred embodiment, the sulfopolyesters according to the 
present invention may be used in pressure sensitive adhesive formulations 
(PSAs), and the PSAs may be hot-melt PSAs. As is known to the skilled 
artisan, the various formulations, whether as hot melt adhesives, PSAs, or 
hot-melt PSAs can be made principally by varying additives, and more 
particularly, principally by varying the amount of tackifiers and/or 
plasticizers. 
The polyesters have functional end groups, which are predominately hydroxyl 
in the case of the present invention, and may be crosslinked with 
melamines, polyepoxides, diisocyanates and other suitable compounds known 
in the art. Although crosslinking is not preferred because it would 
prevent or at least decrease water dispersibility or repulpability, it is 
within the scope of this invention to include crosslinking since it would 
improve tensile properties. However, non-crosslinked sulfopolyesters are 
preferred. 
The presence of reactive end groups also allows for reactive blending by 
transesterifying with other polyesters. Such reactive blending is within 
the scope of the invention. Reactive blending by transesterification is 
within the skill of the artisan in possession of the present disclosure. 
In a preferred embodiment, the sulfopolyesters according to the present 
invention are reactively blended with biodegradable polyesters, such as 
those described in U.S. Pat. Nos. 5,446,079, 5,580,911, and 5,599,858. 
While adhesives consisting of the neat sulfopolyester are not excluded, 
most often it is intended for the polyesters to serve as one of the 
components in an adhesive formulation. The other constituents may be 
incorporated to tailor the properties of the final adhesive to a variety 
of applications. Often it is preferred that the formulation components 
have sufficient polarity to render a compatible formulation with the 
polyester. Thus, suitable formulation components include tackifiers, 
plasticizers, elastomers, amorphous and crystalline thermoplastic resins, 
waxes, oils, diluents, and other additives. 
Additives may be present in the solid polymer as needed. Additives include, 
but are not limited to: oxidative stabilizers, UV absorbers, colorants, 
pigments, fillers, nucleating agents, catalysts, and fragrances, all of 
which are known per se. 
Oxidative stabilizers are typically added as packages where primary and 
secondary components combine to provide an optimum of increased pot-life, 
shelf-life, resistance to skinning, and minimization of discoloration, 
especially at elevated temperatures. Stabilizers are typically added at 
levels between 0.05 and 1 weight percent, more preferably 0.1 to 0.5 
weight percent, based on the weight of total formulation (including 
solvent, if present). Suitable stabilizers include the antioxidant type 
and generally consist of hindered phenols, thio-compounds, and 
phosphorous-containing compounds. Especially useful due to its efficacy 
and easily to handle powder form is Irganox 1010 (Ciba-Geigy, Hawthorne, 
N.Y.), which is a pentaerythritol tetrakis-3(3,5-di-tertiary 
butyl-4-hydroxyphenyl)propionate. 
Fillers, such as silicas (e.g., fumed silica known as Cabosil from Cabot 
Corp.), silicates, aluminum oxides, carbon black, calcium carbonate, talc, 
barium sulfate, gypsum, are often useful as a low cost means to increase 
the RBSP and reduce the cold flow of the adhesive formulation. It is 
preferred that fillers, if added, be present in the adhesive composition 
in the amount of no more than 65 percent by weight. More preferably, 
fillers are present in the amount of from 1 to 40 percent by weight, based 
on the total weight of the composition (including solvent, if any). 
Plasticizers are added to lower the Tg and typical examples are found in 
phthalate esters, adipate esters, glycols, glycol dibenzoates, and 
phenols. Preferred examples of esters are di-octyl phthalate and di-octyl 
adipate. Polymeric plasticizers are also useful and represent a preferred 
embodiment of the present invention. Polymeric plasticizers may be 
crystalline or amorphous, and are typically lower molecular weight 
polymers possessing a low Tg, preferably less than 0.degree. C., and more 
preferably less than -20.degree. C. Examples of suitable polymeric 
plasticizers include: polyethylene glycol, polypropylene glycol, 
polytetramethylene glycol, and polyester resins. Polyethylene glycol is 
preferred due to its inherent water solubility. Plasticizers, if added, 
may be present in the adhesive compsition in the amount of up to 65 
percent by weight, more preferably from 1 to 40 percent by weight, based 
on the total weight of the composition (including solvent, if any). 
Elastomers are generally block copolymers of styrene and 1,3-dienes, such 
as those marketed by Shell Chemical under the KRATON.TM. tradename. 
Another elastomer type is a polyolefin synthesized using metallocene 
catalysts to obtain polymer architectures having alternating sequences of 
crystalline and amorphous character. The crystalline regions serve as 
crosslinks to provide the elastomeric properties. Elastomeric properties 
are usually enhanced by the absence of substantial amounts of 
crystallinity. Additional examples of elastomers may be found in copolymer 
of ethylene with functional comonomers such as vinyl acetate or acrylic 
acid. In general, the compatibility of elastomers will be enhanced by the 
incorporation of polar comonomers. Elastomers, if added, are present in 
the adhesive composition in the amount of up to 65 weight percent, more 
preferably 1 to 40 weight percent, based on the total weight of the 
composition (including solvent, if any). 
Tackifiers may be added to the polyester composition to increase the 
softening point, reduce cold flow, and improve the adhesion. Tackifiers 
are typically selected from at least one of the groups consisting of 
hydrocarbon resins, synthetic polyterpenes, functional copolymers and 
rosin esters. Hydrocarbon resins are disclosed in U.S. Pat. No. 3,850,858 
and functional copolymers, such as styrene-co-maleic anhydride are known 
in the art. Hydrocarbon resins, prepared according to U.S. Pat. No. 
3,701,760, polyterpenes, and rosin esters can be used alone or in 
combinations. These tackifying resins, preferably have softening points of 
at least 100.degree. C., more preferably at least 120.degree. C., and may 
comprise 10 to 70% by weight of the adhesive formulation, preferably 20 to 
50% by weight. Suitable resins and rosin esters are the terpene polymers 
having a sufficiently high RBSP as discussed supra, specifically, resinous 
materials including dimers as well as higher polymers obtained by 
polymerization and/or copolymerization of terpene hydrocarbons such as the 
alicyclic, monocyclic, and bicyclic monoterpenes and their mixtures, 
including alloocimene,carene, isomerized pinene, pinene, dipentene, 
terpinene, terpinolene, limonene, turpentine, a terpene cut of fraction, 
and various other terpenes. Commercially available resins of the terpene 
type include the Zonarez terpene B-series and the 7000 series from Arizona 
Chemical. Also included are the rosin esters with acid numbers above 5, 
such as the Zonatac resins from Arizona Chemical. Particularly useful 
materials are terpene mixtures containing sulfate terpene and at least 20% 
of at least one other terpene selected from the group consisting of 
pinene, limonene, or dipentene. Tackifiers, when present, are added to the 
adhesive composition in the amount of no more than 65 weight percent, more 
preferably from 1 to 40 weight percent, based on the total weight of the 
composition (including solvent, if any). 
In a preferred embodiment, at least one additive selected from crystalline 
thermoplastic polymers and crystalline waxes is included in the 
composition according to the present invention. By "crystalline" is meant 
that the polymer or wax has a defined melting point. It is preferred that 
the crystalline thermoplastic polymers not be crosslinked. The crystalline 
thermoplastic polymers and/or crystalline waxes, when present, are added 
in the amount of no more than 65 weight percent, more preferably 1 to 40 
weight percent, based on the total weight of the composition (including 
solvent, if any). 
Crystalline thermoplastic polymers may also be incorporated to reduce cold 
flow, improve tensile properties, and raise the softening point. 
Particularly useful for this purpose are copolymers of ethylene with vinyl 
acetate, acrylic acid, methacrylic acid (e.g., SURLYN a DuPont tradename), 
glycidyl methacrylate, hydroxyethyl methacrylate, alkyl acrylates, alkyl 
methacrylates, and maleated polyolefins. Also included are crystalline 
polyesters, polyamides, polyester-ethers, polyester-amides, and high 
molecular weight polyethylene oxides. As discussed previously, the 
compatibility of the polyester is enhanced by the presence of sufficient 
polarity within the ethylene copolymer. 
Lower molecular weight crystalline waxes are also useful for certain 
applications, particularly the functional varieties, such as stearamides, 
preferably hydroxy stearamide; low molecular weight maleated polyolefins 
may also be useful waxes. 
The present copolyester composition can be modified with random or 
alternating styrenic copolymers that are prepared by any of the several 
methods available for their synthesis. For example, the copolymers may be 
obtained by solution copolymerization directly from the respective 
monomers by incremental additions of the more reactive monomer as taught 
by U.S. Pat. No. 2,971,939 or by a continuous recycle polymerization 
process in U.S. Pat. Nos. 2,769,804 and 2,989,517. Commercially available 
random or alternating copolymers include the "Dylark" styrene/maleic 
anhydride copolymers. 
In a preferred process according to the present invention, the adhesive 
compositions may be prepared using one or more or the above recited 
additives by blending with the block copolyester at melt temperatures of 
about 150-250.degree. C. and mixing until a homogeneous mixture is 
obtained. A cowles stirrer or sigma blade mixer provides effective mixing 
for these preparations. 
Other polyesters may be physically blended or reactively blended with the 
above recited sulfopolyester. Particularly useful polyesters to be 
blended, whether as a physical mixture or by reactively blended, include 
biodegradable polyesters such as those disclosed above. More preferably, 
polyesters based on 1,4-butanediol/adipic acid polyesters are useful to 
reduce cold flow, lower Tg, and increase tensile strength. 
In the more preferred embodiment of the adhesive formulation according to 
the present invention, including the laminated articles of manufacture 
adhered therewith, the adhesive formulation includes a linear, 
water-dispersible sulfopolyester, having a dry Tg ranging from -50 to 
20.degree. C., comprised of the reaction products of: 
(i) a dicarboxylic acid that is not a sulfomonomer, preferably in the 
amount of 70 to 100 mol percent, based on total moles of acid equivalents. 
The dicarboxylic acid component is preferably selected from the group 
consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, 
saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and 
cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms; 
(ii) at least one difunctional sulfomonomer containing at least one metal 
sulfonate group bonded to an aromatic ring wherein the functional groups 
are ester, hydroxyl, or carboxyl, preferably in the amount of 2 to 20, 
more preferably 2.5 to 15 mol percent, based on total moles of acid and 
glycol equivalents. The difunctional sulfomonomer is preferably selected 
from dicarboxylic acids or esters thereof containing at least one metal 
sulfonate group bonded to an aromatic ring, a diol containing a metal 
sulfonate group bonded directly to an aromatic ring, and a hydroxy acid 
containing a metal sulfonate group bonded directly to an aromatic ring; 
(iii) from about 25 to 99.9 mol %, based on total mol % of hydroxyl 
equivalents, of the polyethylene glycol having the structure: 
EQU H--(OCH.sub.2 CH.sub.2).sub.x --OH (II) 
where n is an integar from 2 to 6, most preferably 2; 
(iv) at least one polyethylene glycol having the structure: 
EQU H--(OCH.sub.2 CH.sub.2).sub.y --OH (III) 
where y is 3 to about 500, more preferably y is 20 to 500, and even more 
preferably y is 21 to 100, where the species represented by (III) is 
preferably present in the amount of 0.1 to 20 mol percent, more preferably 
in the amount of 0.1 to 10 mol percent, based on total moles of hydroxyl 
equivalents, and with the preferred proviso that the mol percent of said 
polyethylene glycol is inversely proportional to the quantity n within 
said range; 
x&lt;y; 
the polymer containing substantially equal molar proportions of acid 
equivalents (100 mol %) and glycol equivalents (100 mol %) wherein the 
inherent viscosity is at least 0.1 dL/g, more preferably 0.1 to 0.8 dL/g, 
even more preferably about 0.25 dL/g, as measured in a 60/40 parts by 
weight solution of phenol/tetrachloroethane at 25.degree. C. at a 
concentration of about 0.50 g of polymer in 100 ml of the solvent. 
The actual viscosity of the final adhesive formulation depends on the 
application, and can range, for example, from a "water-thin" formulation 
to a thick paste formulation. 
EXAMPLES 
The following examples are intended to illustrate the present invention. 
Numerous modifications and variations are possible, and it is to be 
understood that within the scope of the appended claims, the invention may 
be practiced otherwise than as specifically described herein. 
Example 1 
Preparation of Water-Dispersible Block Polyester Containing 12 Mole % 
5-Sodiosulfoisophthalate and 5 Mole % PEG1000 
A 500 mL round bottom flask equipped with a ground-glass head, agitator 
shaft, nitrogen inlet, and a sidearm to allow for removal of volatile 
materials was charged with 85.6 grams (0.44 mol) dimethyl terephthalate, 
17.8 grams (0.06 mol) dimethyl-5-sodiosulfoisophthalate, 42.2 grams (0.68 
mol) ethylene glycol, 31.3 grams (0.30 mol) diethylene glycol, 25.0 grams 
(0.025 mol) Carbowax.RTM. polyethylene glycol 1000, 0.49 grams (0.006 mol) 
anhydrous sodium acetate, and 0.5 mL of a 1.46% (w/v) solution of titanium 
isopropoxide in n-butanol. The flask was purged with nitrogen and immersed 
in a Belmont metal bath at 200.degree. C. for 90 minutes and 210.degree. 
C. for an additional 90 minutes under a slow nitrogen sweep with 
sufficient agitation. After elevating the temperature to 280.degree. C. a 
vacuum &lt;=0.5 mm was attained and held for 30 minutes to perform the 
polycondensation. The vacuum was then displaced with a nitrogen atmosphere 
and the clear, slightly yellow polymer was allowed to cool before removal 
from the flask. An inherent viscosity of 0.52 dL/g was determined for the 
recovered polymer according to ASTM D3835-79. NMR analysis indicated that 
the actual glycol composition was 60 mol % EG, 35 mol % DEG, and 5 mol % 
Carbowax.RTM. polyethylene glycol 1000. A glass transition temperature 
(Tg) of 28.degree. C. was obtained for the polymer from thermal analysis 
by DSC. Tensile properties were obtained in the manner set forth by 
ASTM-D638. A tough, elastomeric material was observed as the yield stress 
and yield elongation were 15 MPa and 7%, respectively, while the break 
stress and elongation at break were 9 MPa and 175%, respectively. 
Example 2 
Preparation of Water-Dispersible Block Polyester Containing 12 Mole % 
5-Sodiosulfoisophthalate and 0.5 Mole % PEG10,000 
The apparatus and general procedure described in EXAMPLE 1 was used with 
the exception that polycondensation time was changed. The amounts 
initially charged to the flask were: 85.4 grams (0.44 mol) dimethyl 
terephthalate, 17.8 grams (0.06 mol) dimethyl-5-sodiosulfoisophthalate, 
42.2 grams (0.68 mol) ethylene glycol, 31.8 grams (0.30 mol) diethylene 
glycol, 25.0 grams (0.0025 mol) polyethylene glycol (Mn=10,000 g/mol), 
0.49 grams (0.006 mol) sodium acetate, and 0.5 mL of a 1.46% (w/v) 
solution of titanium(IV)isopropoxide in n-butanol. The polycondensaton was 
performed at 280.degree. C. for 17 minutes at a pressure 0.35 mm of Hg. 
The recovered polymer had an inherent viscosity of 0.63 (ASTM D3835-79) 
and a Tg, as measured by DSC, of 19.degree. C. Analysis by NMR indicated 
that the actual glycol composition was 58 mol % EG, 41.5 mol % DEG, and 
0.5 mol % PEG10,000. 
Example 3 
Preparation of Water-Dispersible Block Polyester Containing 11 Mole % 
5-Sodiosulfoisophthalate and 2 Mole % PEG1000 
The apparatus and general procedure described in EXAMPLE 1 was used with 
the exception that the transesterification and polycondensation times were 
changed. The initial reactant charge consisted of: 67.9 grams (0.35 mol) 
dimethyl terephthalate, 19.4 grams (0.10 mol) dimethyl isophthalate, 14.8 
grams (0.05 mol) dimethyl-5-sodiosulfoisophthalate, 24.2 grams (0.39 mol) 
ethylene glycol, 31.8 grams (0.30 mol) diethylene glycol, 7.5 grams (0.008 
mol) Carbowax.RTM. polyethylene glycol 1000, 0.4 grams (0.005 mol) sodium 
acetate, and 0.35 mL of a 1.46% (w/v) solution of titanium(IV)isopropoxide 
in n-butanol. The polyesterification was conducted at 200.degree. C. for 
60 minutes and 225.degree. C. for 90 minutes, followed by a 
polycondensation stage at 280.degree. C. and 0.4 mm Hg for 37 minutes. 
Inherent viscosity and Tg values of 0.40 and 45.degree. C., respectively, 
were obtained in the same manner as described previously. NMR analysis 
indicated the polymer acid composition was consistent with 69 mol % 
terephthalate, 20 mol % isophthalate, and 11 mol % 
5-sodiosulfoisophthalate units, while the glycol portion consisted of 57 
mol % EG, 41 mol % DEG, and 2.0 mol % Carbowax.RTM. polyethylene glycol 
1000. 
Example 4 
Preparation of Water-Dispersible Block Copolyester Containing 11 Mole % 
5-Sodiosulfoisophthalate and 6 Mole % PEG300 
(Comparative) 
The apparatus and procedure used were the same as EXAMPLE 1 with the 
exception that the transesterification was conducted at 200.degree. C. for 
60 minutes and 230.degree. C. for 90 minutes, while the polycondensation 
was performed at 280.degree. C. and 0.3 mm for 34 minutes. The reactants 
and their respective amounts were: 67.9 grams (0.35 mol) dimethyl 
terephthalate, 19.4 grams (0.10 mol) dimethyl isophthalate, 14.8 grams 
(0.05 mol) dimethyl-5-sodiosulfoisophthalate, 27.3 grams (0.44 mol) 
ethylene glycol, 21.2 grams (0.20 mol) diethylene glycol, 7.5 grams (0.025 
mol) Carbowax.RTM. polyethylene glycol 300 (Mn=300 g/mol), 0.41 grams 
(0.005 mol) sodium acetate, and 0.32 mL of a 1.46% (w/v) solution of 
titanium(IV)isopropoxide in n-butanol. The recovered polymer was analyzed 
in the same manner as described previously and an inherent viscosity of 
0.35 dL/g and a Tg of 40.degree. C. were obtained. NMR analysis determined 
that the polymer structure (total mol %=200 containing equal amounts of 
acid and glycol units) was comprised of 70 mol % terephthalate, 19 mol % 
isophthalate, 11 mol % 5-sodiosulfoisophthalate, 58 mol % EG, 36 mol % 
DEG, and 5.9 mol % Carbowax.RTM. polyethylene glycol 300. 
Example 5 
Preparation of Water-Dispersible Polyester Containing 10 Mole % 
5-Sodiosulfoisophthlate and 3.2 Mole % PEG600 
(Comparative) 
The apparatus described in EXAMPLE1 and the procedure followed in EXAMPLE 4 
were used with the exception that the time of polycondensation was changed 
to 50 minutes. The initial reactant charge consisted of: 67.9 grams (0.35 
mol) dimethyl terephthalate, 19.4 grams (0.10 mol) dimethylisophthalate, 
14.8 grams (0.05 mol) dimethyl-5-sidiosulfoisophthalate, 27.3 grams (0.44 
mol) ethylene glycol, 21.2 grams (0.20 mol) diethylene glycol, 9.0 grams 
(0.015 mol) Carbowax.RTM. polyethylene glycol 600 (Mn=570-630 g/mol), 0.4 
grams (0.005 mol) sodium acetate, and 0.33 mL of a 1.46% (w/v) solution of 
titanium(IV)isopropoxide in n-butanol. Inherent viscosity and Tg values of 
0.35 and 46.degree. C., respectively were obtained as before. NMR analysis 
indicated the polymer composition was consistent with 69 mol % 
terephthalate, 21 mol % isophthalate, 10 mol % 5-sodiosulfoisophthalate, 
63 mol % EG, 34 mol % DEG, and 3.2 mol % PEG600 structural units. 
Example 6 
Preparation of Water-Dispersible Polyester Containing 11 Mole % 
5-Sodiosulfoisophthalate 
(Comparative) 
The same apparatus was used as described in EXAMPLE 1. Initial reactant 
charges were: 77.6 grams (0.40 mol) dimethyl terephthalate, 19.4 grams 
(0.10 mol) dimethyl isophthalate, 16.28 grams (0.055 mol) 
dimethyl-5-sodiosulfoisophthalate, 62.0 grams (1.00 mol) ethylene glycol, 
and 0.38 mL of a 1.46% (w/v) solution of titanium(IV)isopropoxide in 
n-butanol. After purging the reactants with nitrogen, the flask was 
immersed in a Belmont metal bath at 200.degree. C. for 60 minutes and 
230.degree. C. for an additional 120 minutes under a nitrogen sweep with 
sufficient agitation to complete the transesterification. After elevating 
the temperature to 280.degree. C., a vacuum of &lt;0.5 mm Hg was instituted 
and maintained for 93 minutes to accomplish the polycondensation stage. 
Inherent viscosity and Tg measurements were performed as described supra 
with the respective values, 0.42 dL/g and 55.degree. C., noted for each. 
The actual composition, as determined by NMR and GC analyses, was 
consistent with 64 mol % terephthalate, 25 mol % isophthalate, 11 mol % 
5-sodiosulfoisophthalate, 67 mol % EG, 26 mol % DEG, and 7 mole % 
triethylene glycolate (TEG) units. 
Comparison of Film and Fiber Sizing Properties 
Table 1, below, shows the comparative fiber sizing and film properties of 
polymers synthesized in the previous EXAMPLES. 
All of the polymers were dispersed in deionized water at a solids level of 
30 weight % and diluted appropriately for slashing. Film tests were 
obtained by casting and drying circular film dots on a sheet of mylar. 
Fiber testing was accomplished by passing (i.e., slashing) a 40 
filament/150 denier warp drawn polyester yarn through an aqueous 
dispersion of the size composition and drying. 
In the table below, T represents the amount of terephthalate, I the amount 
of isophthalate, SIP the amount of the sulfomonomer, EG, DEG, and PEG 
representing, respectively, the amount of ethylene glycol, diethylene 
glycol, and polyethylene glycol in the sulfopolyester. 
TABLE 1 
______________________________________ 
Comparative Data for Film and Fiber Properties 
EXAMPLE Composition % Flexi- 
Abrasion 
Number (Mole %) Pickup Adhesion 
bility 
Cycles 
______________________________________ 
3 T = 69, I = 20, 
4.5 PASS PASS 100 
SIP = 11, EG = 
57, 
DEG = 41, 
PEG 1000 = 2.0 
4 T = 70, I = 19, 
4.8 PASS FAIL 30 
SIP = 11, EG = 
58 
DEG = 36, 
PEG 300 = 5.9 
5 T = 69, I = 21, 
4.3 PASS FAIL 40 
SIP = 10, EG = 
63, 
DEG = 34, 
PEG 600 = 3.2 
6 T = 64, I = 25, 
4.2 FAIL FAIL 65 
SIP = 11, EG = 
67, 
DEG = 26, 
TEG = 7 
______________________________________ 
*Total acid and glycol = 200 mole % 
The results in Table 1 clearly demonstrate the efficacy of the present 
invention as a textile size; EXAMPLES 4, 5, and 6 are outside the scope 
and teachings of this invention and are included for the sole purpose of 
distinguishing these non-obvious teachings from the prior art, while 
EXAMPLE 3 is a preferred embodiment of the present invention. Pickup level 
or the amount of dry size applied to the fiber was essentially constant 
for all of the EXAMPLES, which had nearly the same ratios of T: I: SIP in 
each case. The polyester that did not contain any PEG (EXAMPLE 6) failed 
both the adhesion and flexibility tests and had only 65% of the abrasion 
resistance that was shown by EXAMPLE 3. The samples containing the lower 
molecular weight polyethylene glycols (EXAMPLES 4 and 5) both failed the 
flexibility test and exhibited greatly inferior abrasion resistance in 
comparison to EXAMPLE 3. It is to be noted that the level of polyethylene 
glycol was chosen for EXAMPLES 3, 4, and 5 to yield a constant weight 
percent of polyethylene glycol, thus further demonstrating the uniqueness 
of sulfopolyesters containing blocks of high molecular weight polyethylene 
glycol. 
Adhesive Tests 
In the examples set forth below, the T-peel adhesion test was run according 
to ASTM D1876. There is no detectable odor observed for any of the 
adhesive compositions set forth below. Odor detection was made by a human 
observer. 
Example 7 
Adhesive Properties of Neat Polyester Containing 11 Mole % 
5-Sodiosulfoisophthalate and 5 Mole % PEG1000 
A copolyester was synthesized using the apparatus and general procedure 
described in EXAMPLE 1. The composition contained only isopthalate, 
diethylene glycolate, 5-sodiosulfoisophthalate, and polyethylene glycolate 
units and was determined to have an IV of 0.40 and a Tg of 10.degree. C. 
The RBSP was 102.degree. C. and a melt viscosity of 144,900 cp at 
177.degree. C. A T-peel adhesion test was run and a value of 51 g/mm was 
recorded for adhesion to a polyethylene (PE) substrate. 
Example 8 
Adhesive Formulation Based on a Polyester Containing 11 Mole % 
5-Sodiosulfoisophthalate and 5 Mole % PEG1000 
The copolyester synthesized in EXAMPLE 7 was formulated in the following 
ratios: 60-parts copolyester, 10 parts of Benzoflex 9-88 plasticizer (a 
product of Velsicol), and 30 parts of Staybelite wood rosin (a product of 
Hercules). The formulation had a melt viscosity of 1800 cp at 177.degree. 
C. and was completely dispersible in tap water. T-peel results of 10.7 
g/mm and 21 g/mm were measured for mylar and PE to stainless steel 
substrates, respectively. 
Example 9 
Adhesive Properties of a Neat Polyester containing 11 Mole % 
5-Sodiosulfoisophthalic acid and 10 Mole % PEG1000 
A copolyester was synthesized using the apparatus and procedure described 
in EXAMPLE 1 and was determined to have the same monomer components as 
EXAMPLE 7. The copolyester had a Tg of 4.degree. C., RBSP of 86.degree. C. 
and a melt viscosity of 37,500 cp at 177.degree. C. A 77.9 g/mm T-Peel 
adhesion was recorded for PE substrates and the sample exhibited cohesive 
failure after an elongation of 1324% was obtained. Complete dispersibility 
was noted in tap water after &lt;4 hours at room temperature. 
Example 10 
Adhesive Formulation Based on a Polyester Containing 11 Mole % 
5-Sodiosulfoisophthalate and 10 Mole % PEG1000 
The copolyester synthesized in EXAMPLE 9 was formulated in the exact same 
manner as EXAMPLE 8. A melt viscosity of 1200 cp at 177.degree. C. was 
obtained for the formulation, which exhibited a T-Peel adhesion of 4.5 
g/mm to PE substrates. 
Example 11 
Adhesive Properties of a Neat Polyester Containing 12 Mole % 
5-Sodiosulfoisophthalate and 45 Mole % Triethylene Glycol (TEG) 
The same general apparatus configuration was used as described in EXAMPLE 1 
except a 1000 mL flask was employed to increase the scale of the 
synthesis. An initial charge consisting of: 148 g (0.89 mole) isophthalic 
acid, 32.6 g (0.11 mole) dimethyl-5-sodiosulfoisophthalate, 106 g (1.0 
mole) diethylene glycol, 75 g (0.5 mole) TEG, 0.9 g (0.01 mole) sodium 
acetate, and 100 ppm of Ti that was added as titanium(IV)tetrisopropoxide 
was added to the flask before purging with nitrogen. The flask was then 
immersed in the Belmont metal bath at 200 C for 60 minutes and 210.degree. 
C. for 2 hours under a slow sweep of nitrogen with sufficient agitation. 
After elevating the temperature to 250.degree. C. a vacuum of 0.2 mm Hg 
was attained and held for 135 minutes to perform the polycondensation. The 
vacuum was displaced with nitrogen and the hazy, amber polymer melt was 
allowed to cool before removal from the flask. An inherent viscosity of 
0.32 was determined for the polymer and NMR analysis indicated that the 
glycol composition was 55 mole % DEG and 45 mole % TEG. A Tg of 17.degree. 
C., RBSP of 114.degree. C., and melt viscosity of 273,000 cp at 
177.degree. C. were recorded for the polymer. The T-peel adhesion was 57 
g/mm when bonded to PE substrates. 
Example 12 
Onto a 4.times.6 inch corona-treated polyethylene substrate was placed a 1 
ml thick layer of a sulfopolyester adhesive composition according to the 
present invention. The thus-treated substrate was place in a plastic bag. 
the bag was sealed and placed into an oven at 110.degree. F. 
(43.30.degree. C. ) for 1 week. The bag was then opened and there was no 
detectable odor. 
Examples 7-11 demonstrate that the sulfopolyester according to the present 
invention is useful in bonding to various substrates, including plastic 
and metal substrates, and that the adhesive material is water dispersible. 
Examples 7-12 demonstrate that there is no detectable odor to humans, with 
Example 12 particularly showing that even under moderate heating the 
sulfopolyester does not have an objectionable odor, which is highly 
surprising. 
Accordingly, the present inventors have shown the utility of a linear, 
block sulfopolyester having at least two different polyethylene glycol 
units. The sulfopolyester according to the present invention is water 
dispersible and has excellent adhesive properties to a wide variety of 
substrates, from plastics, including but not limited to polyolefins and 
polyesters, to fabrics, including but not limited to natural and synthetic 
fabrics, and woven and non-woven fabrics, to metals, including but not 
limited to metal foils, and to wood and wood-derived products, including 
but not limited to paper. It will be recognized by those of skill in the 
art that variations and modifications other than as specifically described 
herein can be effected within the spirit and scope of the appended claims. 
Moreover, all patents, patent applications, and literature references 
noted above are incorporated herein by reference for any disclosure 
pertinent to the practice of this invention.