Europäisches Patentamt

(19) European Patent Office *EP000960021B1*

Office européen des brevets (11) EP 0 960 021 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: B32B 19/00, C08F 283/02,
of the grant of the patent: C08G 63/91, C09D 167/00
18.06.2003 Bulletin 2003/25
(86) International application number:
(21) Application number: 98904606.5 PCT/US98/01075

(22) Date of filing: 27.01.1998 (87) International publication number:

WO 98/033646 (06.08.1998 Gazette 1998/31)

(54) WATER DISPERSIBLE/REDISPERSIBLE HYDROPHOBIC POLYESTER RESINS AND THEIR

APPLICATION IN COATINGS
WASSERDISPERZIERBARE/WIEDERDISPERGIERBARE HYDROPHOBE POLYESTERHÄRZE
UND IHRE BESCHICHTUNGEN
RESINES POLYESTERS HYDROPHOBES DISPERSABLES/REDISPERSABLES DANS L’EAU ET
LEUR UTILISATION DANS DES REVETEMENTS

(84) Designated Contracting States: (72) Inventor: SALSMAN, Robert, Keith

AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC Hoschton, GA 30548 (US)
NL PT SE
(74) Representative:
(30) Priority: 31.01.1997 US 792635 Neubauer, Hans-Jürgen, Dipl.-Phys.
Neubauer Liebl,
(43) Date of publication of application: Fauststr. 30
01.12.1999 Bulletin 1999/48 85051 Ingolstadt (DE)

(73) Proprietor: Seydel Research, Inc. (56) References cited:

N.W. Atlanta, GA 30327 (US) EP-A- 0 406 671 US-A- 5 252 615
EP 0 960 021 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 0 960 021 B1

Description

FIELD OF THE INVENTION

5 [0001] This invention relates to the synthesis from polyethylene terephthalate (PET) such as virgin PET, recycled
PET, post consumer PET, or precursor raw materials of novel water dispersible or water emulsifiable polyester resins
having improved hydrophobicity or non-polar characteristics. The present invention also relates to resins having ex-
cellent hydrophobic character, also good ability to orient the hydrophobic groups away from substrates to which they
are applied and high water drop contact angles of the coated surface. The above characteristics give the applied film
10 of these dispersions or emulsions much improved water repellency while at the same time retaining their redispersible
or reemulsifiable properties. Such resins can be used for many applications in the paper, textile, coatings, paint, con-
struction, and other industries.

BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE PRIOR ART

15
[0002] Several patents have been written relating to the synthesis of water soluble, dispersible, or emulsifiable pol-
yester resins. For example, Altenberg, in U.S. Pat. No. 4,604,410, has proposed making etherified aromatic polyols
by digesting scrap polyalkylene terephthalate with a low molecular weight polyhydroxy compound, containing 3-8 hy-
droxyl groups. A resulting intermediate is alkoxylated with 1-4 moles of ethylene oxide and/or propylene oxide. The
20 final product is useful in making polyurcthane and polyisocyanurate foams.
[0003] Sperenza et al. U.S. Pat. No. 4,485,196 have recited reacting recycled polyethylene terephthalate scrap with
an alkylene oxide, such as propylene oxide. The product can be used in making rigid foams.
[0004] Other methods of reacting scrap polyalkylene terephthalate with glycols or polyols are proposed by Svoboda
et al. in U.S. Pat. No. 4,048,104; and Altenberg et al. U.S. Pat. No. 4,701,477. In applicant's previous invention (U.S.
25 Pat. No. 4,977,191 to Salsman) there is disclosed a water-soluble or water-dispersible polyester resin suitable for
textile sizing applications. The polyester resin comprises a reaction product of 20-50% by weight of waste terephthalate
polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one oxyalkylated polyol. Preferred
compositions also comprise 20-50% by weight of isophthalic acid. A further water-soluble or water-dispersible resin
comprises a reaction product of 20-50% by weight of waste terephthalate polymer, 10-50% by weight of at least one
30 glycol and 20-50% by weight of isophthalic acid.
[0005] U.S. 5,252,615 to Rao et al teaches coating compositions derived from alcoholysis of polyethylene tereph-
thalate (PET). Most preferably, the PET is recycled or reclaimed from plastic articles.
[0006] Dale et al., in U.S. Pat. No. 4,104,222, have proposed making a dispersion of linear polyester resins by mixing
linear polyester resin with a higher alcohol/ethylene oxide addition-type surface-active agent, melting the mixture and
35 dispersing the resulting melt in an aqueous alkali solution. The products are used as coating and impregnating agents.
[0007] References proposing the use of copolymers containing terephthalic units and units derived from alkylene
and polyoxyalkylene glycols for fiber or fabric treatment include Hayes (U.S. Pat. No. 3,939,230), Nicol et al. (U.S. Pat.
No, 3,962,152), Wada et al. (U.S. Pat. No. 4,027,346), Nicol (U.S. Pat. No. 4,125,370) and Bauer (U.S. Pat. No.
4,370,143).
40 [0008] Marshall et al., in U.S. pat. No. 3,814,627, have proposed applying an ester, based on polyethylene glycol,
to polyester yarn.
[0009] In our other patent U.S. 5,281,630 (Salsman), we disclose sulfonated water-soluble or water-dispersible pol-
yester resin compositions made by treating a polyester glycolysis product with an alpha, beta-ethylenically unsaturated
dicarboxylic acid and then with a sulfite.
45 [0010] The following U.S. patents describe polyester resins containing fatty acid moieties: 4,080,316; 4,179,420;
4,181,638; 4,413,116; 4,497,933; 4,517,334; 4,540,751; 4,555,564; 4,686,275; 5,075,417 and 5,530,059. None of the
above patents disclose the resins of the present invention which have excellent hydrophobic and high contact angles
when a drop of water is applied to surfaces coated with such resins.
[0011] The resins described in the above prior art have found applications in textiles, coatings, and adhesive. All of
50 these resins however have a fairly polar nature which limits their use to adhesion promoters or coating applications
where water resistance is not a major factor or where the water resistance is being supplied by other additives. No
mention of water repellent properties has been associated with these polyester resins.
[0012] In some instances larger amounts of oils are fatty acids are used to supply cross-linking and thermosetting
properties to the polyester resins. This chemistry has been labeled "alkyd" chemistry. During the drying phase cross-
55 linking occurs between chains, and the applied coating becomes insoluble.
[0013] To this date the inventor has no knowledge of prior polyester art where the water dispersible or emulsifiable
polyester resins of said art has incorporated enough non-polar groups to supply hydrophobic character or properties
to the substrate on which these dispersions are applied and/or at the same time retain water redispersibility.

2
 EP 0 960 021 B1

[0014] The main problem with most non-polar materials that have reactive condensation sites is that these materials
have only one reactive site. ( For example stearic acid, oleic acid, palmitic acid, behenic acid, etc. These are most
likely isolated from naturally occurring triglycerides such as vegetable and animal fats and oils.) This means that in the
polyester condensation reaction they become chain terminators and the amounts that can be used are severely limited
5 because the greater the amount the less the molecular weight of the resin. In alkyd chemistry advantage is taken from
the unsaturation in oils and cross linking reactions can be used. However reaction through unsaturation does not
exposed sufficient areas of the oil modified chain to provide hydrophobic and water repellent properties to the coatings
produced from this chemistry.
[0015] The resins described in this invention have overcome the problem of chain termination by using a highly
10 modified polyester backbone. In this way polyester resins can be made containing 30 percent or more of monofunctional
monomers, such as stearic acid, to provide a much improved non-polar nature. Then, using reactions cited in our
previous patents, these resins can be made into water dispersions or emulsions. Because of the large amount of
hydrophobic or non-polar functionality these resins cannot be considered water soluble as some previous sulfonated
resins have been. When these dispersions or emulsions are applied to most substrates and dried, orientation of the
15 hydrophobic areas of the chain occurs and the surface of the substrate becomes water repellent, with the degree of
water repellency corresponding to the thickness and concentration of the initial coating. This water repellency is obvious
from the high contact angle of a drop of distilled water placed on the substrate. This high contact angle is not evident
in previous water dispersible resins.
[0016] The prior art is silent regarding the new water dispersible and polyester resins of the present invention which
20 are derived from polyethylene terephthalate and which exhibits high water repellency as evidenced by high contact
angles.

OBJECTS OF THE INVENTION

25 [0017] It is a primary object of the invention to provide water-soluble or water-dispersible polyester resin compositions
having improved hydrophobicity.
[0018] It is a further object of the invention to provide water-soluble or water-dispersible polyester resin compositions
having improved hydrophobicity and non-polar characteristics.
[0019] It is an additional object of the invention to provide water-soluble or water-dispersible polyester resin compo-
30 sitions having improved water repellency.
[0020] It is yet another object of the invention to provide water-soluble or water-dispersible polyester resin compo-
sitions having improved oil and water-repellency.
[0021] An additional object of the invention is to utilize waste polyester material in the production of polyester resins
having improved hydrophobicity and non-polar characteristics.
35 [0022] It is still another object of the invention to use the water-dispersible polyester compositions as coatings for
fiber, paper or fabric.
[0023] It is yet a further object of the invention to produce water-soluble or water-dispersible polyester coating com-
positions having improved oil and water-repellency.

40 SUMMARY OF THE INVENTION

[0024] Briefly, the present invention relates to water dispersible/and redispersible hydrophobic polyester resins de-
rived typically from PET, especially recycled PET having improved hydrophobicity or non-polar characteristics. The
present invention is directed to polyester resins having the following general formula:
45

I n -P-A m

wherein I is the ionic group; n is an integer in the range of 1-3 and defines the number of ionic groups; P is a polyester
50 backbone; A is an aliphatic group; and m is an integer in the range of 3-8 and defines the number of aliphatic groups.
[0025] The ionic groups I which are required for water-dispersibility are typically derived from a carboxylic acid group
which is introduced into the resin by polyacid monomers The weight percent of ionic monomers in the resin is from 1%
to 20% percent, with 5 to 10% of ionic monomer being preferred.
[0026] The backbone P of the polymer is composed of polyester groups. It can be any linear or branched polyester
55 made using polyacids and polyalcohols. The preferred method is to generate the backbone using polyester from re-
cycled sources. The weight percent of the polyester backbone ingredients range from 30-80% of the whole resin, with
the most preferred being 50-60% by weight.
[0027] The aliphatic groups A consist of stright or branched 6-24 carbon chain fatty acids or triglycerides thereof.

3
 EP 0 960 021 B1

The weight percent of the aliphatic moiety can be 10-60% with 20-40% by weight being the preferred amount.
[0028] The water dispersible and hydrophobic polyester resins of the present invention have excellent water repellent
properties as evidenced by their contact angle measurements when used as coatings. The contact angles achieved
when the resins are coated on paper are of the order of 98 or higher.
5 [0029] The present invention is also directed to a water dispersible and hydrophobic polyester resin, comprising a
reaction product of 30-70% by weight of a terephthalate polymer; 5-40% by weight of a hydroxy functional compound
having at least two hydroxyl groups; 1-20% by weight of a carboxy functional compound having at least two carboxyl
groups and 10 - 60% by weight of a compound selected from the group of C6-C24 straight chain or branched fatty acid
or triglycerides thereof said resin being further characterized in that the hydroxy functional compound is present at 1-3
10 times the equivalents of the hydrophobic moiety.
[0030] The instant invention is also directed to substrates such as paper, paperboard, food packaging, textiles, con-
crete and the like coated with a polyester resin comprising a reaction product of 30-70% by weight of a terephthalate
polymer; 5-40% by weight of a hydroxy functional compound having at least two hydroxyl groups; 1-20% by weight of
a carboxy functional compound having at least two carboxyl groups and 10 - 60% by weight of a hydrophobic compound
15 selected from the group consisting of C6-C24 straight chain or branched fatty acid or triglycerides thereof.
[0031] The present invention is also directed to an article of manufacture comprising a substrate coated with a water
dispersible and hydrophobic polyester coating composition comprising a reaction product of 40-60% by weight of pol-
yethylene terephthalate polymer; 1-10% by weight of neopentylglycol; 5-10% pentaerythritol; 3 to 15% by weight of
trimellitic acid or trimellitic anhydride; and 10-45% by weight of stearic acid.
20 [0032] The invention also features a water repellent polyester coating composition, comprising a reaction product of
30-70% by weight of a terephthalate polymer; 5-40% by weight of a hydroxy functional compound having at least two
hydroxyl groups; 1-20% by weight of a carboxy functional compound having at least two carboxyl groups and 10 - 60%
by weight of a hydrophobic compound selected from the group consisting of C6-C24 straight chain or branched fatty
acid or triglycerides thereof.
25 [0033] Another novel aspect of the invention is a water repellent polyester coating composition, comprising a reaction
product of 40-60% by weight of polyethylene terephthalate polymer; 1-10% by weight of neopentylglycol; 5-10% pen-
taerythritol; 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and 10-45% by weight of stearic acid.
[0034] The invention is also directed to a method for imparting water repellency to substrates selected from the group
consisting of fibrous substrates and leather comprising applying to such susbtrates a composition comprising the re-
30 action product of 30-70% by weight of a terephthalate polymer; 5-40% by weight of a hydroxy functional compound
having at least two hydroxyl groups; 1-20% by weight of a carboxy functional compound having at least two carboxyl
groups and 10 - 60% by weight of a hydrophobic compound selected from the group consisting of C6-C24 straight chain
or branched fatty acid or triglycerides thereof.
[0035] The invention also describes polyester resins which can be made containing 30 percent or more of mono-
35 functional monomers, such as stearic acid, to provide a much improved non-polar nature.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] The objects of the present invention and many of the expected advantages of the present invention will be
40 readily appreciated as the same becomes better understood by reference to the following detailed description.
[0037] The novel water dispersible resins of the present invention can be represented as shown by the following
structure:

I n -P-A m
45

where I is the ionic group; n=1-3 defines the number of the ionic groups; P is polyester; A is an aliphatic group; and
m=3-8 represents the aliphatic group number.
[0038] There are four necessary requirements for the polyester chemistry of the present invention:
50
1. A polyester backbone.
2. A multifunctional glycol in the backbone providing additional hydroxyl functionality present at 1-3 times the
equivalents of group 3.
3. A hydrophobic moiety, such as but not limited to, a saturated fatty acid. This moiety is present at one third to
55 two thirds the equivalents of the number 2 component and must be present in total formula at 10 to 50 weight
percent, the preferred level being 15-40 weight percent depending on the needed degree of water repellency.
4. An ionic moiety, either in the backbone or terminally located, present at 5-20 weight percent, the preferred
quantity being 10-15 weight percent. This moiety can be neutralized with base if necessary to supply dispersibility

4
 EP 0 960 021 B1

in water.

[0039] There physical properties that make the resins of the present invention unique are:

5 1. Hydrophobic character.
2. Ability of these resins to orient the hydrophobic groups away from substrates to which they are applied.
3. Evidence of hydrophobic orientation as characterized by high water drop contact angles of the coated surface.

[0040] The water dispersible and hydrophobic polyester compositions of this invention imparts desirable water and
10 oil repellency to susbtrates treated therewith without adversely affecting other desirable properties of the substrate,
such as soft hand (or feeling). The composition of the present invention can be used for providing water and oil repel-
lency to fibrous substrates such as textiles, papers, non-woven articles or leather or to other susbtrates such as plastic ,
wood, metals, glass, stone and concrete.
[0041] The water-dispersible resins of the present invention are synthesized by condensation polymerization with
15 original or recycled PET or polyacid-polyalcohol [mutifunctional acids or alcohols] used to make polyesters along with
aliphatic acids or hydrogenated or unhydrogenated animal or vegetable triglycerides.
[0042] The water-soluble or water-dispersible resins are made from waste terephthalate polymers, including bottles,
sheet material, textile wastes and the like. The waste terephthalate plastics may be bought from recyclers and include,
but are not limited to, material identified as "PET rock". The waste terephthalate can be characterized by the unit formula
20

25

wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons of or oxygenated glycol of the formula

30
HO(C x H 2x O) n C x H 2x OH (2)

wherein x is an integer from 2-4 and n is 1-10.

[0043] Preferably the waste terephthalate polymer is a polyalkylene terephthalates such as polyethylene terephtha-
late and polybutylene terephthalate, polycyclohexanedimethanol terephthalate or a mixture thereof. Other suitable
35 polyester polymers which can be used in the practice of the present invention include poly1,2 and poly1,3 propylene
terephthalate and polyethylene naphthanate. It will be understood that, for reasons of economy, the use of waste
terephthalates is preferred. However, the use of virgin terephthalate resins is to be included within the scope of the
disclosure and appended claims.
[0044] The ionic group In needed for water-dispersibility can be a carboxylic acid which is introduced into the resin
40 by polyacid monomers such as Trimellitic anhydride, Trimellitic acid, or Maleic Anhydride or sulfonate groups which
come from monomers such as dimethyl 5-sulfoisophthalate (DMSIP or dimethyl 5-sulfo, 1,3-benzenedicarboxylate),
sulfoisophthalate ethylene glycol (SIPEG or dihydroxyethyl 5-sulfol,3-benzenedicarboxylate, or from sulfonated alken-
ically unsaturated end groups as described in Salsman Patent No. 5,281,630. The polyacid is preferably selected from
the group consisting of isophthalic acid, terephthalic acid, phthalic anhydride (acid), adipic acid and etc. Other preferred
45 polyacids but not limited to are phthalic anhydride (acid), isophthalic and terephthalic acids, adipic acid, fumaric acid,
2,6 naphthalene dicarboxylic acid and glutaric acid. Mixtures of the above acids and anhydrides can be used in the
practice of the present invention. The weight percent of ionic monomers in the resin is from 1% to 20% percent, but 5
to 10% is preferred.
[0045] The backbone of the polymer is composed of polyester groups. It can be any linear or branched polyester
50 made using polyacids and polyalcohols. The preferred method is to generate the backbone using polyester from re-
cycled sources. The weight percent of the polyester backbone ingredients range from 30-80% of the whole resin, with
the most preferred being 50-60%. Such backbone is typically derived by reacting PET such as waste PET with a
hydroxy functional compound containing at least two hydroxyl groups. The hydroxy functional compound having at
least two hydroxy groups is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol,
55 cyclohexanedimethanol, propylene glycol, 1,2-propylene glycol, 1,3-propane diol, 1,2-butylene glycol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, pen-
taerythritol, erythritol or a monosaccharide. In another embodiment, other hydroxy compounds having at least two

5
 EP 0 960 021 B1

hydroxyl groups include derivatives of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or a

monosaccharide oxyalkylated with 5-30 moles of ethylene oxide, propylene oxide or a mixture thereof, per hydroxyl of
the hydroxy functional compound.
[0046] The aliphatic groups consist of 6-24 carbon chain fatty acids or triglycerides thereof such as stearic, oleic,
5 palmitic, lauric, linoleic, linolenic, behenic acid or their mixtures. These can come from hydrogenated or unhydrogenated
animal or vegetable oil, such as beef tallow, lard, corn oil, soy bean oil, etc., etc. If highly unsaturated fatty acids or
triglycerides are used care must be taken to prevent cross-linking through the unsaturated group. The weight percent
of the aliphatic moiety can be 10-60% with 20- 40% the preferred amount.
There are two basic routes to the manufacture of these resins. These routes are outlined below:
10
Route 1

[0047]

15 (1) Aliphatic Acids or Esters + Multifunctional Glycol → Esterification or transesterification = Hydrophobic Glycol
(2) Hydrophobic Glycol + PET (or Diacid with Dialcohol) → esterification or transesterification = Hydrophobic Pol-
yester
(3) Hydrophobic Polyester + Ionic monomer → esterification or transesterifcation = Water Dispersible and Hydro-
phobic Polyester Resin
20
Route 2

[0048]

25 (1) Diacid or PET + Multifunctional Glycol → esterification or tranesterification = grafting polyester with hydroxyl
groups throughout chain and/or as end groups
(2) Grafting polyester + Aliphatic Acids or Esters → esterification or tranesterification = Hydrophobic Polyester
Resin
(3) Hydrophobic Polyester + ionic monomer → esterification or transesterification = Water Dispersible and Hydro-
30 phobic Polyester Resin

[0049] The following steps are used in the process to produce the resin of the present invention:

1. Incorporation of a non-polar group or groups which can be chosen from the following: fatty acids of the type
35 stearic acid, behenic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, etc.; triglycerides from animal or veg-
etable sources of the type beef tallow, corn oil, soybean oil, peanut oil, safflower oil, hydrogenated versions of
these, etc.; reactive silicones, blown paraffins or mineral oils, hydrophobic urethanes, etc. This group must be
present at 10-50 weight percent.
2. Incorporation by esterification or transesterification of a multifunctional hydroxyl component or components such
40 as pentaerythritol, sorbitol, glycerol, etc. at levels consistent with but not limited to 1 to 3 times the reactive equiv-
alent of components from group 1.
3. Esterification or transesterification of ingredients typical of those used to make polyester polymers. These in-
gredients can be chosen from Polyethylene Terephthalate or similar terephthalates and/or difunctional acids such
as terephthalic acid, isophthalic acid, phthalic acid or anhydride combined with difunctional alcohols such as eth-
45 ylene glycol, diethylene glycol, neopentyl glycol, propylene glycol, etc.
4. Incorporation of a ionic group or groups needed for dispersing the resin in water. Examples of these groups are
trimellitic anhydride, maleic anhydride, sulfo succinate, sulfonated isophthalic acid or its esters, etc.
5. Dispersing the resin in water containing an amount of base, if needed, to neutralize the pendant acid groups.

50 [0050] In practicing the process of the present invention, steps 1-3 can be done in any order but the preferred process
embodiment order is as listed above.
[0051] The polyester resins are usually and preferably made using an ester-interchange catalyst. These catalysts
are metal carboxylates and well known organometallic compounds, particularly compounds of tin or titanium. Preferred
catalysts include manganese acetate, sodium acetate, zinc acetate, cobalt acetate or calcium acetate, tetraalkyl titan-
55 ates, in which the alkyl is of up to 8 carbon atoms, as well as alkyl stannoic acid or dialkyl tin oxides, such as monobutyl
stannoic acid or dialkyl tin oxide. Preferred catalysts include monobutyl stannoic acid and tetrapropyl or tetrabutyl
titanate, or a mixture thereof.
[0052] The resulting resinous products obtained are generally taken up in relatively concentrated aqueous solutions

6
 EP 0 960 021 B1

of alkali metal or ammonium hydroxides or carbonates. The concentration employed can be determined by routine
experimentation. However, if shipping of the concentrated aqueous solutions to a point of use is contemplated, it is
preferred to produce highly concentrated solutions. It is within the scope of this invention to produce initial solutions
or dispersions, containing 20-30% or more of resin solids.
5 [0053] The resins of the present invention typically have average molecular weights in the range of 3000 to as high
as 50,000. Preferred resins typically have a molecular weight of about 4000 to about 8000. Of course the intended end
use will determine which molecular weight will be optimum. The average molecular weight of the resins is typically
determined by GPC or by viscosity measurements or other methods well known in the art of polymer chemistry.

10 EXAMPLES

[0054] The following examples are set forth for the purpose of illustrating the invention in more detail. The examples
are intended to be illustrative and should not be construed as limiting the invention in any way. All parts, ratios, per-
centage, etc. in the examples and the rest of the specification, are by weight unless otherwise noted.
15 [0055] Throughout all the Examples described below, a1000 mL four-neck flask reactor suitable for high temperature
cooking is used for the reactions. The flask is equipped with a condenser, a nitrogen inlet, a thermometer, and a stirrer.
The chemicals and their ratio are listed as shown in the following examples:

EXAMPLE 1
20
[0056]

Ingredients Wt% Grams

25
Recycled PET 56.29 598.8
Pentaerythritol 6.71 71.4
Neopentyl Glycol 2.6 27.7
Tetra Propyl 0.08 0.8
30 Titanate(TPT)
Stearic Acid 28.24 300.4
Monobutyl Stannic Acid 0.08 0.9
Trimellitic Anhydride 6 63.8
35

The PET, pentaerythritol, neopentyl glycol, and the TPT are added into reactor and heated to 200-270 °C under a
nitrogen blanket. The transesterification reaction takes 30 to 180 minutes and is monitored by the presence of a clear
pill. Then stearic acid and monobutyl stannoic acid are added and reacted until the acid value is less than 10. Then
Trimellitic Anhydride is added and reacted in at 160-180 degrees Centigrade for thirty minutes. The whole reaction will
40
last for 5 to 12 hours. The obtained resin is dispersed in dilute ammonium solution. The amount of the ammonium
hydroxide used depends on the final dispersed resin pH. Using this method a white dispersion or emulsion of the resin
is obtained.
[0057] Using this solution with or without clay and with or without dye to coat paper or paperboard, a glossy and
water repelling surface finish on the paper or paperboard is obtained. The strength of the coated paper or paperboard
45
is increased as well. When the coated paper or paperboard is pulped (stirred vigorously) in a dilute sodium hydroxide
solution at room temperature or higher, the resin is removed and redispersed and the paper is repulped nicely.

EXAMPLE 2
50
[0058]

Ingredients Wt% Grams

Recycled PET 56.29 598.8
55
Pentaerythritol 6.71 71.4
Neopentyl Glycol 2.6 27.7

7
 EP 0 960 021 B1

(continued)

Ingredients Wt% Grams

Tetra Propyl 0.08 0.8
5
Titanate(TPT)
Oleic Acid/stearic acid 28.24 300.4
Monobutyl Stannic Acid 0.08 0.9

10 Maleic anhydride 6.00 63.83

The PET, pentaerythritol, neopentyl glycol, and the TPT are added into reactor and heated to 200-270 °C under a
nitrogen blanket. The reaction takes 30 to 180 minutes and is monitored by the presence of a clear pill. Then stearic
acid and monobutyl stannoic acid are added and the whole is esterified until the acid value is less than 10. Maleic
15 anhydride is added and reacted at 150-180 degrees Centigrade for 15 minutes. The whole reaction will take 5 to 12
hours. The final resin is poured into a sodium sulfite solution in which the amount of sodium sulfite is at same mole
ratio, or slightly less than the maleic anhydride. Using this method a white dispersion or emulsion of the resin is obtained.
The water-dispersed resin is coated on the paper and paperboard, which leads to the same results as example 1.

20 EXAMPLE 3

[0059] A recipe containing a triglyceride is shown as follows:

Ingredients Weight Grams

25
%
Recycled PET 48.80 480
Pentaerythritol 6.83 67.17

30
Neopentyl Glycol(NPG) 2.65 26.04
Tetra Propyl Titanate(TPT) 0.08 0.8
Hydrogenated Tallow 24.98 245.7
Monobutyl Stannic Acid 0.08 0.8
35
Trimellitic Anhydride or 9.83 96.67
Maleic Anhydride
Isophthalic acid 6.76 66.45

40 The hydrogenated tallow triglycerides are first reacted with pentaerythritol at 180 to 270 degrees Centigrade, then PET,
NPG, and TPT are added to the reactor and transesterified with the alcoholized triglyceride. Isophthalic Acid or Phthalic
Acid is then added to increase the resin molecular weight. Finally Trimellitic Anhydride or Maleic Anhydride is reacted
in to provide a neutralizable end group. With this formula other polyalcohols and polyacids can be used as well. The
final resin is diluted in ammonium or sodium sulfite solution at 50 to 90 degrees Centigrade. The final water-dispersed
45 resin is a stable emulsion. The coated paper or paperboard's surface exhibits the same water repellant properties as
the previous examples. The board is easily repulped and the coated paper's printing holdout, strength, gloss, and other
properties are much improved.

EXAMPLE 4
50
[0060] In this example the same formula is used as in example 3 except the hydrogenated tallow triglycerides are
substituted with corn oil or soy-bean oil. Care must be taken to prevent cross-linking reactions from occurring. The
resin properties are similar to those of example 3 except that the presence of unsaturated groups in the oil makes the
resin less firm. The coating on paper or paperboard has a slightly higher gloss than those produced with hydrogenated
55 triglycerides.

8
 EP 0 960 021 B1

EXAMPLE 5

[0061] The formula is shown as follows:

5 Ingredients Weight% Grams

Pentaerythritol(PE) 7.07 67.7
Neopentyl Glycol 19.18 182.26
Diethylene Glycol 3.35 31.84
10
Stearic Acid 24.98 245.7
Monobutyl Stannic Acid 0.1 0.96
Trimellitic 10.17 96.67
15 Anhydride(TMA) or Maleic Anhydride(MA)
Isophthalic acid 34.27 325.64

The Stearic acid, the Monobutyl Stannoic Acid, and the Pentaerythritol are added to the vessel and reacted at 160 to
270 degree C until the acid value is less than 100. The Isophthalic acid, the Neopentyl Glycol, and the Diethylene
20
Glycol are added to reactor and the polymerization is continued until the acid value is below 10. Finally the TMA or
MA is added at a reduced temperature to ensure control. The final resin is dispersed in ammonium or sodium sulfite
solution as in previous examples. The resin dispersion has the appearance of a stable emulsion. The coated paper or
paperboard shows great water repelling properties. The gloss also is increased for coated papers.
25
EXAMPLE 6

[0062] The same formula is used as in example 5 except the Isophthalic acid is replaced with Terephthalic acid with
the same results.
30
EXAMPLE 7

[0063] The same formula is used as in example 5 except the Isophthalic is replaced with Phthalic acid with similar
results.
35
EXAMPLE 8

[0064] The formula is shown as follows:

40 Ingredients Weight% Grams

Pentaerythritol(PE) 7.07 67.7
Neopentyl Glycol 19.18 182.26
Diethylene Glycol 3.35 31.84
45
Stearic Acid 24.98 245.7
Monobutyl Stannic Acid 0.1 0.96
Trimellitic 10.17 96.67
Anhydride(TMA) or Maleic Anhydride(MA)
50
Phthalic acid 34.27 325.64

The Stearic acid, the Monobutyl Stannoic Acid, and the Pentaerythritol are added to the vessel and reacted at 160 to
270 degree C until the acid value is less than 100. The Phthalic acid, the Neopentyl Glycol, and the Diethylene Glycol
55 are added to reactor and the polymerization is continued until the acid value is below 10. Finally the TMA or MA is
added at a reduced temperature to ensure control. The final resin is dispersed in ammonium or sodium sulfite solution
as in previous examples. The resin dispersion has the appearance of a stable emulsion. The coated paper or paper-
board shows great water repelling properties. The gloss also is increased for coated papers.

9
 EP 0 960 021 B1

EXAMPLE 9

[0065] The same formula is use as in example 5 except the TMA or MA is replaced with DMSIP or SIPEG and reacted
as a polyacid or polyalcohol. A good water-dispersible resin is obtained and the resin shows similar properties as
5 described above.
[0066] The novel water dispersible and hydrophobic polyester resins of the present invention can be used to coat
substrates such as cellulosic or synthetic substrates such as paper. More in particular, the polyester resins find use as
coatings in the following industrial applications:

10 I. PAPER

[0067] Because these resins contain a high concentration of hydrophobic groups and have a much improved ability
to orient those hydrophobic groups away from the paper or paperboard, the surface of paper or paperboard coated
with these resins shows an amazing water repelling effect. This water repelling effect produces surfaces that have
15 higher water drop contact angles than other currently used resins. Therefore these resins can effectively make the
paper or paperboard surface waterproof or water repellent at much lower concentrations than other commonly used
resins. In addition the resins described here can be easily removed from the paper, paperboard, or other substrate by
washing with water that has been made basic by the addition of ammonium hydroxide, sodium hydroxide, or other
commonly used basic additives. The advantages for using these resins in the paper and paperboard industry are
20 threefold. One advantage is in the use of lesser amounts of materials on the paper of paperboard, a second advantage
is the recycling of waste PET (possibly from bottle sources) back into packaging materials, and the third advantage is
that all materials coated in this manner can be easily repulped and therefore recycled. In connection with paper coating
applications, the following are particularly preferred:

25 A. Paper or paperboard for food packaging

[0068] Some food packages (fresh produce, frozen goods, dry food, dairy products, etc.) need high hydrophobic
properties of the package box surface to ensure package shelf-life under high moisture conditions. In addition to plastic
packages, coated paper or paperboard is commonly used. The coating on this paper or paperboard is generally very
30 hydrophobic. The resins most widely used in paper or paperboard coatings are the mixture of polyethylene vinyl acetate
copolymers (usually referred to as EVA for ethylene vinyl acetate) in combination with paraffin wax. This type of coating
system produces hydrophobic coatings which are water insoluble and therefore very difficult to remove from the paper
or paperboard during repulping. This difficulty in repulping inhibits easy recycling of these paper products. The resins
described in this invention are easily repulped using basic additives as described above.
35 [0069] The resins described in this invention are composed of raw materials that have a reputation of being generally
regarded as safe and non-toxic. This fact along with the great need for water repellent coatings in the paper industry
for food packaging etc., and the inexpensive nature of these resins which may be produced from recycled PET, make
these resins highly desirable for coating paper or paperboard intended for food packaging.
[0070] In the Frozen Food Industry paper containers are used to store food for use in instant cooking, microwave
40 ovens. These containers must be moisture resistant to handle the freezing and thawing conditions they are subjected
to. The disclosed resins, because of their FDA status for food contact, would be ideal candidates for the protection of
these paper containers.

B. Printing Paper
45
[0071] Paper intended for printing or magazine paper has a coating that consists of Styrene Butadiene Rubber latex
(SBR), polyvinyl acetate latex, rosin and/or other materials such as clay and starch. The coating is used to impart
properties such as surface smoothness, strength, gloss, ink holdout, and water resistance. The new resins disclosed
in this patent can also be used to impart these properties at lower coating weights. For example printing paper coated
50 with these resins alone have excellent water repellency and ink holdout as well as increased strength and gloss.

C. Paper or paperboard for storage or transport

[0072] Paper Bags for carrying consumer purchases, etc. have a problem in that if they get wet they lose their strength
55 and tear easily. Making these bags water repellent or just water resistant would help solve this problem. Letters, en-
velopes, and courier packages need waterproofing to keep the contents dry during mailing or shipping. Envelopes or
packaging board coated with these disclosed resins provide sufficient protection.

10
 EP 0 960 021 B1

D. Release Paper

[0073] Release coatings are used where an adhesive material needs to hold to a surface but not so much that it
tears the surface when pulled from it. Currently silicones are used for this purpose. The resins described here can be
5 used for this purpose as well since the hydrophobic properties make them ideally suited as adhesive release agents.

E. Miscellaneous Paper Items

[0074] Other paper products which could benefit from an inexpensive waterproofing system would be fiber drums,
10 book and notebook covers, popcorn bags, paper plates, paper cups, paper rainwear such as disposable clothing, paper
construction materials (wallpaper, dry wall, sound board, or concrete construction forms), and any other outdoor use
paper product that could be damaged by rain, rainwater, or high moisture conditions.

II. TEXTILES
15
[0075] In the textile industry there are several needs for waterproofing or water resistant finishes. The currently used
resins can be expensive and difficult to apply. The resins described here can find applications in a number of areas in
the textile industry. Some of these areas of application include: Fiber or Thread Finishes, clothing or apparel in general,
tarps, rainwear, non-wovens, nylon microdenier fabrics, bedding, mail bags, reapplication of waterproofing agents and
20 footwear.

III. WOOD

[0076] Wood products especially those used in outdoor applications, need to be protected from rain and weather.
25 The resins described here can be used to waterproof wood products. Some examples of wood products where the
described resins could be applied are: Furniture, wood decks, construction lumber, plywood, wood for concrete molds,
siding for houses, telephone poles, roofing tiles, paneling for interior walls, wooden crates and boxes for shipping and
storing, and wooden boats or boat parts.

30 IV. CONCRETE

[0077] It is desirable in some concrete applications for there to be a sealer or water resistant finish applied to the
concrete after it has set. This finish provides increased durability and longer life of the concrete surface as well as
allowing rain water to run off more effectively. The products described in this invention can be used for this purpose.
35 Some examples are: Overpasses and bridges on roads, high traffic areas such as stadium decks, Etc., outdoor stadium
seats, driveways, roadways and concrete housing.

V. PAINT

40 [0078] In some instances it is desirable for a paint (or protective coating) to exhibit a certain amount of water repel-
lency. Some examples are: Traffic Paint- to replace currently used solvent based alkyd resins and general purpose
Latex. In the case of the latex, the inventive resins can be used as additives

VI. LEATHER
45
[0079] Leather products can be treated for water repellency. Here the added gloss would also be desirable. Typical
leather products include shoes, handbags, coats and gloves.

VII INKS
50
[0080] In the ink market resins are used to adhere the ink to some substrate. Once dry they must be moisture and
abrasion resistant. Many currently used resins are water based. The described resins here would make ideal candidates
as ink resins or additives since the resins are very adhesive, especially to cellulosics, and once dry would be very
water resistant.
55
VIII. GLASS

[0081] Fiberglass is used as the structural material for a great deal of commonly used items such as shower stalls,

11
 EP 0 960 021 B1

boats, kitchen and bathroom sinks. The described resin could be used as part of the formulation to make these products
repel water more effectively. The dispersions of this invention could also be used to treat the glass fibers themselves,
as in sizing, for greater water repellency or greater resin solubility.

5 IX. METAL COATINGS

[0082] Metal coils are commonly coated with a resin to prevent rust or oxidation caused by moisture in the air. The
currently used products are generally resins dissolved in some solvent. The resins described here could be used as
replacements for these coatings. Cars, gutters and appliances may be coated with the resins of the present invention.
10 [0083] The amount of the composition applied to a substrate in accordance with the present invention is chosen so
that sufficiently high or desirable water and oil repellencies are imparted to the substrate surface, said amount usually
being such that 0.01% to 10% by weight, preferably 0.05 to 5% by weight, based on the weight of the substrate, of
polyester is present on the treated susbtrate. The amount which is sufficient to impart desired repellency can be de-
termined empirically and can be increased as necessary or desired.
15 [0084] The treatment of fibrous substrates using the water and oil repellency imparting composition of the present
invention is carried out by using well-known methods including dipping, spraying, padding, knife coating, and roll coat-
ing. Drying of the substrate is done at 120° C. or below, including room temperature, e.g., about 20° C. with optionally
heat-treating the textile products in the same manner as in conventional textile processing methods.
[0085] The effectiveness of the coatings resulting from the resins of the present invention is illustrated in Example 10.
20
EXAMPLE 10

Contact Angle Comparisons

25 [0086] The following example illustrates the effectiveness of applicant's polyester resins as water repellent coatings
for paper or paperboard. The test was performed using a Kernco Model G-I Contact Angle Goniometer used to measure
the contact
angles between the surface of a piece of paper or paperboard and a drop of distilled water placed on the paper.

30 PROCEDURE

[0087] A 0.1ml sample of distilled water was place on the surface of a piece of uncoated(control) and coated paper-
board using a micro syringe. The initial angle of the drop to the paperboard surface was taken. A time of 5 minutes
was allowed to elapse and a second contact angle was taken. The test was performed ten times and the average
35 values calculated. The difference between the two average values was calculated as the Lose of Angle.

RESULTS

[0088] The following chart reflects the results using uncoated paper and various coating formulas.
40

TEST SAMPLE Initial Angle 5 min. Angle Lose of Angle

Control: No coating 78.2 64.3 13.9
Graphsize: polyurethane size 91.3 84.4 6.9
45
PE-230: Hydrophilic polyester size 68.5 52.7 15.8
LB-100(30%): Eastman polyester 68.0 53.3 14.7
Styrene Maleic Polymer 95.0 77.7 17.3

50 2161: XWP with 43.17% Fatty acid 110.3 N/D N/D

2160: XWP with 37.94% Fatty acid 112.0 103.8 8.2
2148: XWP with 28.82% Fatty acid 107.5 N/D N/D
2141: XWP with 25.86% Fatty acid 104.3 96.6 7.7
55
2180: XWP with 20.00% Fatty acid 102.0 94.3 7.7
2086: XWP with 15.00% Fatty acid 98.8 81.0 17.8

12
 EP 0 960 021 B1

[0089] In the table above, the resin compositions of the invention are defined as follows:

Resin 2161: This resin is the reaction product of: 38.57 wt% PET, 43.17 wt% fatty acid (6.50 wt% stearic; 10.22
wt% oleic and 26.45 wt% hydrogenated tallow glyceride), 8.10 wt% pentaerythritol and 10 wt% trimellitic anhydride.
5 Resin 2160: This resin is the reaction product of: 42.84 wt% PET, 37.94 wt% fatty acid (18.97 wt% stearic and
18.97 wt% hydrogenated tallow glyceride), 9.08 wt% pentaerythritol and 9.96 wt% trimellitic anhydride.
Resin 2148: This resin is the reaction product of: 48.08 wt% PET, 28.82 wt% fatty acid (14.41 wt% stearic acid
and 14.41 wt% soybean oil), 6.89 wt% pentaerythritol, 2.58 wt% neopentylglycol, 9.96 wt% trimellitic anhydride
and 3.68 wt% isophthalic acid.
10 Resin 2141: This resin is the reaction product of: 34.27 wt% isophthalic acid, 25.86 wt% stearic acid, 7.07 wt%
pentaerythritol, 19.18 wt% neopentylglycol, 3.35 wt% diethyelenglycol and 10.17 wt% trimellitic anhydride.
Resin 2180: This resin is the reaction product of: 61.72 wt% PET, 20.00 wt% stearic acid, 4.75 wt% pentaerythritol,
2.46 wt% neopentylglycol, 0.91 wt% diethyleneglycol, 10.00 wt% trimellitic anhydride.
Resin 2086: This resin is the reaction product of: 74.90 wt% PET, 15.00 wt% stearic acid, 4.50 wt% pentaerythritol,
15 3.47 wt% neopentylglycol, 1.96 wt% diethyleneglycol.

The physical properties that make this resin unique are:

1. Hydrophobic character.
20 2. Ability of these resins to orient the hydrophobic groups away from substrates to which they are applied.
3. Evidence of hydrophobic orientation as characterized by high water drop contact angles of the coated surface.

[0090] It will be apparent from the foregoing that many other variations and modifications may be made regarding
the hydrophobic polyester resins described herein, without departing substantially from the essential features and
25 concepts of the present invention. Accordingly, it should be clearly understood that the forms of the inventions described
herein are exemplary only and are not intended as limitations on the scope of the present invention as defined in the
appended claims.

30 Claims

1. A water dispersible and hydrophobic polyester resin having the formula:

I n -P-A m
35

wherein I is an ionic group; n=1-3 is the number of ionic groups; P is a polyester backbone; A is a fatty aliphatic
group; m=3-8 is the number of fatty aliphatic groups and wherein I is present in amount of from about 1% to 20%
by weight; the polyester backbone is present in an amount of from about 30% to 80% by weight and the fatty
40 aliphatic group is present in an amount of about 10% to 60% by weight; said polyester resins exhibiting high water
repellency as shown by an initial contact angle of at least 98 when a drop of water is applied to the surface of a
cellulosic substrate which has been coated with said resin.

2. The water dispersible and hydrophobic polyester resin of claim 1

45 wherein I is present in an amount ranging from 5% to 10% by weight.

3. The water dispersible and hydrophobic polyester resin of claim 1

wherein the polyester backbone P is present in an amount ranging from 50% to 60% by weight.

50 4. The water dispersible and hydrophobic polyester resin of claim 1

wherein the fatty acid group A is present in an amount ranging from 20% to 40% by weight.

5. The water dispersible and hydrophobic polyester resin of claim 1

wherein I is derived from polycarboxylic acid or anhydrides selected from the group consisting of trimellitic anhy-
55 dride, trimellitic acid and maleic anhydride.

6. The water dispersible and hydrophobic polyester resin of claim 1

wherein the polyester backbone P is a polyalkylene terephthalate selected from the group consisting of polyeth-

13
 EP 0 960 021 B1

ylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.

7. The water dispersible and hydrophobic polyester resin of claim 1

wherein the fatty acid group A is selected from the group consisting of stearic acid, behenic acid, palmitic acid,
5 lauric acid, oleic acid and linoleic acid.

8. A water dispersible and hydrophobic polyester resin, comprising a reaction product of 30-70% by weight of a
terephthalate polymer; 5-40% by weight of a hydroxy functional compound having at least two hydroxyl groups;
1-20% by weight of a carboxy functional compound having at least two carboxyl groups and 10 - 60% by weight
10 of a hydrophobic compound selected from the group consisting of C6-C24 straight chain or branched fatty acid or
triglycerides thereof; said resin being further characterized in that the hydroxy functional compound is present
at 1-3 times the equivalents of the hydrophobic moiety.

9. The water dispersible and hydrophobic polyester resin of claim 8, comprising the reaction product of waste tereph-
15 thalate of the unit formula

20

wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons of or oxygenated glycol of the formula

25
HO(C x H 2x O) n C x H 2x OH (2)

wherein x is an integer from 2-4 and n is 1-10.

30 10. The water dispersible and hydrophobic polyester resin of claim 8, wherein the waste terephthalate polymer is
polyethylene terephthalate, poly 1,2 propylene terephthalate, poly1,3 propylene terephthalate, polybutylene
terephthalate, poly(cyclohexanedimethanol terephthalate) or a mixture thereof.

11. The water dispersible and hydrophobic polyester resin of claim 8, wherein said hydroxy functional compound having
35 at least two hydroxyl groups is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene
glycol, cyclohexanedimethanol, propylene glycol, 1,2-propylene glycol, 1,3-propane diol, 1,2-butylene glycol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, tri-
methylolethane, pentaerythritol, erythritol or a monosaccharide.

40 12. The water dispersible and hydrophobic polyester resin of claim 8, wherein said hydroxy functional compound having
at least two hydroxyl groups is selected from the group consisting of derivatives of glycerol, trimethylolpropane,
trimethylolethane, pentaerythritol, erythritol or a monosaccharide oxyaikylated with 5-30 moles of ethylene oxide,
propylene oxide or a mixture thereof, per hydroxyl of the hydroxy functional compound.

45 13. The water dispersible and hydrophobic polyester resin of claim 8, wherein said carboxy functional compound having
at least two carboxyl groups is selected from the group consisting of trimellitic acid, trimellitic anhydride, maleic
acid, maleic anhydride, fumaric acid and isophthalic acid.

14. The water dispersible and hydrophobic polyester resin of claim 8, wherein said hydrophobic compound is selected
50 from the group consisting of stearic acid, oleic acid, linoleic acid, behenic acid, lauric acid, palmitic acid, beef tallow,
lard, corn oil and soybean oil.

15. The water dispersible and hydrophobic polyester resin of claim 8, comprising the reaction product of 40-60% by
weight of polyethylene terephthalate polymer; 1-10% by weight of neopentylglycol; 5-10% pentaerythritol; 3 to 15%
55 by weight of trimellitic acid or trimellitic anhydride; and 10-45% by weight of stearic acid.

16. The water dispersible and hydrophobic polyester resin of claim 8, comprising a reaction product prepared in the

14
 EP 0 960 021 B1

presence of monobutyl stannoic acid or a tetraalkyl titanate, or a mixture thereof.

17. The water dispersible and hydrophobic polyester resin of claim 8, dispersed in water with an alkali metal or am-
monium hydroxide or carbonate.
5
18. The water dispersible and hydrophobic polyester resin of claim 15, dispersed in water with an alkali metal or
ammonium hydroxide or carbonate.

19. An article of manufacture comprising a substrate coated with a water dispersible and hydrophobic polyester coating
10 composition comprising a reaction product of 30-70% by weight of a terephthalate polymer; 5-40% by weight of a
hydroxy functional compound having at least two hydroxyl groups; 1-20% by weight of a carboxy functional com-
pound having at least two carboxyl groups and 10 - 60% by weight of a hydrophobic compound selected from the
group consisting of C6-C24 straight chain or branched fatty acid or triglycerides thereof.

15 20. The article of manufacture of claim 19, wherein said substrate is a fibrous substrate.

21. The article of manufacture of claim 19, wherein said substrate is a paper substrate.

22. The article of manufacture of claim 19, wherein said substrate is a textile substrate.
20
23. The article of manufacture of claim 19, wherein said substrate is food packaging.

24. The article of manufacture of claim 19, wherein said substrate is release paper.

25 25. The article of manufacture of claim 19, wherein said substrate is concrete.

26. The coated article of manufacture of claim 19, wherein said terephthalate polymer is a waste terephthalate of the
unit formula

30

35
wherein R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbons of or oxygenated glycol of the formula

HO(C x N 2x O) n C x H 2x OH (2)
40

wherein x is an integer from 2-4 and n is 1-10.

27. The coated article of manufacture of claim 26 wherein the waste terephthalate polymer is polyethylene terephtha-
late, poly 1,2 propylene terephthalate, poly1,3 propylene terephthalate, polybutyleneterephthalate, poly(cyclohex-
45 anedimethanol terephthalate) or a mixture thereof.

28. The coated article of manufacture of claim 19, wherein said hydroxy functional compound having at least two
hydroxyl groups is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, cy-
clohexanedimethanol, propylene glycol, 1,2-propylene glycol, 1,3-propane diol, 1,2-butylene glycol, 1,3-butanedi-
50 ol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylo-
lethane, pentaerythritol, erythritol or a monosaccharide.

29. The coated article of manufacture of claim 19, wherein said hydroxy functional compound having at least two
hydroxyl groups is selected from the group consisting of derivatives of glycerol, trimethylolpropane, trimethylo-
55 lethane, pentaerythritol, erythritol or a monosaccharide oxyalkylated with 5-30 moles of ethylene oxide, propylene
oxide or a mixture thereof, per hydroxyl of the hydroxy functional compound.

15
 EP 0 960 021 B1

30. The coated article of manufacture of claim 19, wherein said carboxy functional compound having at least two
carboxyl groups is selected from the group consisting of trimellitic acid, trimellitic anhydride, maleic acid, maleic
anhydride, fumaric acid and isophthalic acid.

5 31. The coated article of manufacture of claim 19, wherein said hydrophobic compound is selected from the group
consisting of stearic acid, oleic acid, linoleic acid, behenic acid, lauric acid, palmitic acid, beef tallow, lard, corn oil
and soybean oil.

32. An article of manufacture comprising a substrate coated with a water dispersible and hydrophobic polyester coating
10 composition comprising a reaction product of 40-60% by weight of polyethylene terephthalate polymer; 1-10% by
weight of neopentylglycol; 5-10% pentaerythritol; 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and
10-45% by weight of stearic acid.

33. The article of manufacture of claim 32, wherein said substrate is a fibrous substrate.
15
34. The article of manufacture of claim 32, wherein said substrate is a paper substrate.

35. The article of manufacture of claim 32, wherein said substrate is a textile substrate.

20 36. The article of manufacture of claim 32, wherein said substrate is food packaging.

37. The article of manufacture of claim 32, wherein said substrate is release paper.

38. The article of manufacture of claim 32, wherein said substrate is concrete.
25
39. A water repellent polyester coating composition, comprising a reaction product of 30-70% by weight of a tereph-
thalate polymer; 5-40% by weight of a hydroxy functional compound having at least two hydroxyl groups; 1-20%
by weight of a carboxy functional compound having at least two carboxyl groups and 10 - 60% by weight of a
hydrophobic compound selected from the group consisting of C6-C24 straight chain or branched fatty acid or trig-
30 lycerides thereof.

40. A water repellent polyester coating composition, comprising a reaction product of 40-60% by weight of polyethylene
terephthalate polymer; 1-10% by weight of neopentylglycol; 5-10% pentaerythritol; 3 to 15% by weight of trimellitic
acid or trimellitic anhydride; and 10-45% by weight of stearic acid.
35
41. A method for imparting water repellency to substrates selected from the group consisting of fibrous substrates and
leather comprising applying to such susbtrates a composition comprising the reaction product of 30-70% by weight
of a terephthalate polymer; 5-40% by weight,of a hydroxy functional compound having at least two hydroxyl groups;
1-20% by weight of a carboxy functional compound having at least two carboxyl groups and 10 - 60% by weight
40 of a hydrophobic compound selected from the group consisting of C6-C24 straight chain or branched fatty acid or
triglycerides thereof.

Patentansprüche
45
1. Ein wasserdispergierbares und hydrophobes Polyesterharz mit der Formel

I n -P-A m
50
in welcher I eine ionische Gruppe ist; n=1-3 die Anzahl der ionischen Gruppen ist; P ein Polyesterrückgrat ist; A
eine fettartige aliphatische Gruppe ist; m=3-8 die Anzahl der fettartigen aliphatischen Gruppen ist und in welcher
I in einer Menge von ungefähr 1-20 Gewichts-% vorhanden ist; das Polyesterrückgrat in einer Menge von ungefähr
30-80 Gewichts-% vorhanden ist und die fettartige aliphatische Gruppe in einer Menge von ungefähr 10-60 Ge-
55 wichts-% vorhanden ist; wobei die Polyesterharze eine große Wasserabstoßung zeigen, wie dies durch einen
anfänglichen Berührungswinkel von wenigstens 98 gezeigt ist, wenn ein Wassertropfen auf die Oberfläche eines
Zelluloseträgermaterials aufgebracht wird, das mit dem Harz überzogen worden ist.

16
 EP 0 960 021 B1

2. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem I in einer Menge vorhan-
den ist, die sich zwischen 5 und 10 Gewichts-% bewegt.

3. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem das Polyesterrückgrat P
5 in einer Menge vorhanden ist, die sich zwischen 50 und 60 Gewichts-% bewegt.

4. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem die Fettsäuregruppe A in
einer Menge vorhanden ist, die sich zwischen 20 und 40 Gewichts-% bewegt.

10 5. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem I von Polycarbonsäure
oder Anhydriden, die aus der Gruppe gewählt sind, die Trimellit-Anhydrid, Trimellitsäure und Maleinsäureanhydrid
umfasst, abstammt.

6. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem das Polyesterrückgrat P
15 ein polyalkyliertes Terephtalat ist, das aus der Gruppe gewählt ist, die Polyethylen-Terephtalat, Polypropylen-Ter-
ephtalat und Polybutylen-Terephtalat umfasst.

7. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 1, in welchem die Fettsäuregruppe A
aus der Gruppe gewählt ist, die Stearinsäure, Behensäure, Palmitinsäure, Laurinsäure, Ölsäure und Linoisäure
20 umfasst.

8. Ein wasserdispergierbares und hydrophobes Polyesterharz, bestehend aus einem Reaktionsprodukt von 30-70
Gewichts-% eines Terephtalat-Polymers; 5-40 Gewichts-% einer hydroxyfunktionalen Verbindung, die wenigstens
zwei Hydroxylgruppen hat; 1-20 Gewichts-% einer carboxyfunktionalen Verbindung, die wenigstens zwei Carboxyl-
25 gruppen hat, und 10-60 Gewichts-% einer hydrophoben Verbindung, die aus der Gruppe ausgewählt ist, die Fett-
säure mit C6-C24 geraden oder verzweigten Ketten oder Triglyceride davon umfasst; wobei das Harz weiter da-
durch gekennzeichnet ist, dass die hydroxyfunktionale Verbindung 1-3 mal gegenüber den Äquivalenten der
hydrophoben Teile vorhanden ist.

30 9. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, umfassend aus dem Reaktionspro-
dukt von Abfall-Terephtalat mit dem Formelzeichen

35

40

wobei R der Rest eines aliphatischen oder cykloaliphatischen Glykols mit 2-10 Kohlenstoffatomen oder eines
oxygenierten Glykols mit der Formel

45
HO(C x H 2x O) n C x H 2x OH (2)

ist, wobei x eine ganze Zahl von 2-4 und n=1-10 ist.

50 10. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, in welchem das Abfall-Terephtalat-
Polymer Polyethylen-Terephtalat, Poly-1,2-Propylen-Terephtalat, Poly-1,3-Propylen-Terephtalat, Polybutylen-Ter-
ephtalat, Poly(Cyclohexandimethanol-Terephtalat) oder eine Mischung davon ist.

11. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, in welchem die hydroxyfunktionale
55 Verbindung, die wenigstens zwei Hydroxylgruppen hat, aus der Gruppe gewählt ist, die Ethylenglykol, Diethylen-
glykol, Triethylenglykol, Cyclohexan-Dimethanol, Propylenglykol, 1,2-Propylenglykol, 1,3-Propandiol, 1,2-Butylen-
glykol, 1,3-Butandiol, 1,4-Butandiol, Neopentylglykol, 1,5-Penandiol, 1,6-Hexandiol, Glycerin, Trimethylolpropan,

17
 EP 0 960 021 B1

Trimethylolethan, Pentaerythrit, Erythrit oder ein Monosacharid umfasst.

12. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, in welchem die hydroxyfunktionale
Verbindung, die wenigstens zwei Hydroxylgruppen hat, aus der Gruppe gewählt ist, die Derivate von Glycerin,
5 Trimethylolpropan, Trimethylolethan, Pentaerythrit, Erythrit oder ein Monosacharid oxyalkyliert mit 5-30 Mol Ethy-
lenoxid, Propylenoxid oder einer Mischung davon pro Hydroxyl der hydroxyfunktionalen Verbindung.

13. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, in welchem die carboxyfunktionale
Verbindung, die wenigstens zwei Carboxylgruppen hat, aus der Gruppe gewählt ist, die Trimellitsäure, Trimellit-
10 Anhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure und Isophtalsäure umfasst.

14. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, in welchem die hydrophobe Verbin-
dung aus der Gruppe gewählt ist, die Stearinsäure, Ölsäure, Linolsäure, Behensäure, Laurinsäure, Palmitinsäure,
Rindertalg, Schweinefett, Maisöl und Sojabohnenöl umfasst.
15
15. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, bestehend aus dem Reaktionsprodukt
von 40-60 Gewichts-% Polyethylen-Terephtalat-Polymer; 1-10 Gewichts-% Neopentylglykol; 5-10 % Pentaerythrit;
3-15 Gewichts-% Trimellitsäure oder Trimellit-Anhydrid; und 10-45 Gewichts-% Stearinsäure.

20 16. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, bestehend aus einem Reaktionspro-
dukt, das in Anwesenheit von Monobutyl-Zinnsäure oder einem Tetraalkyltitanat oder einer Mischung davon her-
gestellt ist.

17. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 8, das in Wasser mit einem Alkalimetall
25 oder Ammoniumhydroxid oder Carbonat dispergiert ist.

18. Das wasserdispergierbare und hydrophobe Polyesterharz nach Anspruch 15, das in Wasser mit einem Alkalimetall
oder Ammoniumhydroxid oder Carbonat dispergiert ist.

30 19. Ein Erzeugnis umfassend ein Substrat bzw. Trägermaterial, das mit einer wasserdispergierbaren und hydrophoben
Polyesterbeschichtungs-Zusammensetzung beschichtet ist, das ein Reaktionsprodukt von 30-70 Gewichts-% ei-
nes Terephtalat-Polymers; 5-40 Gewichts-% einer hydroxyfunktionalen Verbindung, die wenigstens zwei Hydro-
xylgruppen hat; 1-20 Gewichts-% einer carboxyfunktionalen Verbindung, die wenigstens zwei Carboxylgruppen
hat, und 10-60 Gewichts-% einer hydrophoben Verbindung aufweist, die aus der Gruppe gewählt ist, die Fettsäure
35 mit C6-C24 geraden oder verzweigten Ketten oder Triglyceriden davon umfasst.

20. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial ein fasriges Trägermaterial ist.

21. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial ein Papier-Trägermaterial ist.
40
22. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial ein Gewebe-Trägermaterial ist.

23. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial eine Lebensmittelverpackung ist.

45 24. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial ein Abziehpapier ist.

25. Das Erzeugnis nach Anspruch 19, in welchem das Trägermaterial Beton ist.

26. Das beschichtete Erzeugnis nach Anspruch 19, in welchem das Terephtalat-Polymer ein Abfall-Terephtalat ist mit
50 dem Formelzeichen

55

18
 EP 0 960 021 B1

10 wobei R der Rest eines aliphatischen oder cycloaliphatischen Glykols mit 2-10 Kohlenstoffatomen oder eines
oxygenierten Glykols mit der Formel

HO(C x H 2x O) n C x H 2x OH (2)
15

ist, wobei x eine ganze Zahl von 2-4 und n=1-10 ist.

27. Das beschichtete Erzeugnis nach Anspruch 26, in welchem das Abfall-Terephtalat-Polymer Polyethylen-Tereph-
talat, Poly-1,2-Propylen-Terephtalat, Poly-1,3-Propylen-Terephtalat, Polybutylen-Terephtalat, Poly(Cyclohexandi-
20 methanol-Terephtalat) oder eine Mischung davon ist.

28. Das beschichtete Erzeugnis nach Anspruch 19, in welchem die hydroxyfunktionale Verbindung, die wenigstens
zwei Hydroxylgruppen aufweist, aus der Gruppe gewählt ist, die Ethylenglykol, Diethylenglykol, Triethylenglykol,
Cyclohexan-Dimethanol, Propylenglykol, 1,2-Propylenglykol, 1,3-Propandiol, 1,2-Butylenglykol, 1,3-Butandiol,
25 1,4-Butandiol, Neopentylglykol, 1,5-Pentandiol, 1,6-Hexandiol, Glycerin, Trimethylolpropan, Trimethylolethan,
Pentaerythrit, Erythrit oder ein Monosacharid umfasst.

29. Das beschichtete Erzeugnis nach Anspruch 19, in welchem die hydroxyfunktionale Verbindung, die wenigsten
zwei Hydroxylgruppen aufweist, aus der Gruppe gewählt ist, umfassend Derivate von Glycerin, Trimethylolpropan,
30 Trimethylolethan, Pentareythrit, Erythrit oder ein Monosacharid oxyalkyliert mit 5-30 Mol Ethylenoxid, Propylenoxid
oder einer Mischung davon pro Hydroxyl der hydroxyfunktionalen Verbindung.

30. Das beschichtete Erzeugnis nach Anspruch 19, in welchem die carboxyfunktionale Verbindung, die wenigstens
zwei Carboxylgruppen hat, aus der Gruppe gewählt ist, die Trimellitsäure, Trimellit-Anhydrid, Maleinsäure, Mal-
35 einsäureanhydrid, Fumarsäure und Isophtalsäure umfasst.

31. Das beschichtete Erzeugnis nach Anspruch 19, in welchem die hydrophobe Verbindung aus der Gruppe gewählt
ist, die Stearinsäure, Ölsäure, Linolsäure, Behensäure, Laurinsäure, Palmetinsäure, Rindertalg, Schweinefett,
Maisöl und Sojabohnenöl umfasst.
40

32. Ein Erzeugnis umfassend ein Trägermaterial, das mit einer wasserdispergierbaren und hydrophoben Polyester-
beschichtungs-Zusammensetzung beschichtet ist, das ein Reaktionsprodukt von 40-60 Gewichts-% Polyethylen-
Terephtalat-Polymer; 1-10 Gewichts-% Neopentylglykol; 5-10 % Pentaerythrit; 3-15 Gewichts-% Trimellitsäure
oder Trimellit-Anhydrid; und 10-45 Gewichts-% Stearinsäure umfasst.
45

33. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial ein faseriges Trägermaterial ist.

34. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial ein Papier-Trägermaterial ist.

50 35. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial ein Gewebe-Trägermaterial ist.

36. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial eine Lebensmittelverpackung ist.

37. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial ein Abziehpapier ist.
55

38. Das Erzeugnis nach Anspruch 32, in welchem das Trägermaterial Beton ist.

19
 EP 0 960 021 B1

39. Ein wasserabweisendes Polyester-Beschichtungsmittel, umfassend ein Reaktionsprodukt von 30-70 Gewichts-%
eines Terephtalat-Polymers; 5-40 Gewichts-% einer hydroxyfunktionalen Verbindung, die wenigstens zwei Hydro-
xylgruppen hat; 1-20 Gewichts-% einer carboxyfunktionalen Verbindung, die wenigstens zwei Carboxylgruppen
hat, und 10-60 Gewichts-% einer hydrophoben Verbindung, die aus der Gruppe gewählt ist, die Fettsäure mit
5 C6-C24 geraden oder verzweigten Ketten oder Triglyceriden davon umfasst.

40. Ein wasserabweisendes Polyester-Beschichtungsmittel, umfassend ein Reaktionsprodukt von 40-60 Gewichts-%
Polyethylen-Terephtalat-Polymer; 1-10 Gewichts-% Neopentylglykol; 5-10 % Pentaerythrit; 3-15 Gewichts-% Tri-
mellitsäure oder Trimellit-Anhydrid; und 10-45 Gewichts-% Stearinsäure.
10
41. Ein Verfahren zur Übertragung von wasserabweisenden Eigenschaften auf Trägermaterialien, die aus der Gruppe
gewählt sind, die faserige Trägermaterialien und Leder umfasst, bei dem auf solche Trägermaterialien eine Zu-
sammensetzung aus dem Reaktionsprodukt von 30-70 Gewichts-% eines Terephtalat-Polymers; 5-40 Gewichts-
% einer hydroxyfunktionalen Verbindung, die wenigstens zwei Hydroxylgruppen hat; 1-20 Gewichts-% einer car-
15 boxyfunktionalen Verbindung, die wenigstens zwei Carboxylgruppen hat, und 10-60 Gewichts-% einer hydropho-
ben Verbindung, die aus der Gruppe gewählt ist, die Fettsäure mit C6-C24 geraden oder verzweigten Ketten oder
Triglyceride davon umfasst aufgebracht wird.

20 Revendications

1. Résine polyester dispersible dans l'eau et hydrophobe ayant la formule :

I n -P-A m
25

dans laquelle I est un groupe ionique ; n = 1 à 3 est le nombre de groupes ioniques ; P est un squelette de polyester ;
A est un groupe aliphatique gras ; m = 3 à 8 est le nombre de groupes aliphatiques gras et dans laquelle I est
présent à raison d'environ 1% à 20% en poids ; le squelette de polyester est présent à raison d'environ 30% à
30 80% en poids et le groupe aliphatique gras est présent à raison d'environ 10% à 60% en poids ; lesdites résines
polyester présentant une propriété hydrofuge élevée comme présenté par un angle de contact initial d'au moins
98° quand une goutte d'eau est appliquée à la surface d'un substrat cellulosique qui a été revêtu avec ladite résine.

2. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle I est présent à raison
35 de 5% à 10% en poids.

3. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle le squelette polyester
P est présent à raison de 50% à 60% en poids.

40 4. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle le groupe A d'acide
gras est présent à raison de 20% à 40% en poids.

5. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle I est dérivé d'un
acide polycarboxylique ou de ses anhydrides choisis dans le groupe formé par l'anhydride trimellitique, l'acide
45 trimellitique et l'anhydride maléique.

6. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle le squelette de
polyester P est un poly(téréphtalate d'alkylène) choisi dans le groupe formé par le poly(téréphtalate d'éthylène),
le poly(téréphtalate de propylène) et le poly(téréphtalate de butylène).
50
7. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 1, dans laquelle le groupe A d'acide
gras est choisi dans le groupe formé par l'acide stéarique, l'acide béhénique, l'acide palmitique, l'acide laurique,
l'acide oléique et l'acide linoléique.

55 8. Résine polyester dispersible dans l'eau et hydrophobe, comprenant un produit de la réaction d'un polymère té-
réphtalate à raison de 30 à 70% en poids; d'un composé à fonction hydroxy ayant au moins deux groupes hydroxyle
à raison de 5 à 40% en poids ; d'un composé à fonction carboxy ayant au moins deux groupes carboxyle à raison
de 1 à 20% en poids et d'un composé hydrophobe à raison de 10 à 60% en poids choisi dans le groupe formé par

20
 EP 0 960 021 B1

un acide gras à chaîne droite ou ramifiée en C6 à C24 ou les triglycérides de celui-ci ; ladite résine étant de plus
caractérisée en ce que le composé à fonction hydroxy est présent à raison de 1 à 3 fois les équivalents de la
fraction hydrophobe.

5 9. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, comprenant le produit de la réaction
d'un téréphtalate usagé de formule unitaire :

10

15
dans laquelle R est le résidu d'un glycol aliphatique ou cycloaliphatique de 2 à 10 atomes de carbone ou de glycol
oxygéné de formule :

20
HO(C x H 2x O) n C x H 2x OH (2)

dans laquelle x est un nombre entier valant de 2 à 4 et n vaut de 1 à 10.

10. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, dans laquelle le polymère téréph-
25 talate usagé est le poly(téréphtalate d'éthylène), le poly(téréphtalate de 1,2-propylène), le poly(téréphtalate de
1,3-propylène), le poly(téréphtalate de butylène), le poly(téréphtalate de cyclohexanediméthanol) ou leurs mélan-
ges.

11. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, dans laquelle ledit composé à
30 fonction hydroxy ayant au moins deux groupes hydroxyle est choisi dans le groupe formé par l'éthylèneglycol, le
diéthylèneglycol, le triéthylèneglycol, le cyclohexanediméthanol, le propylèneglycol, le 1,2-propylèneglycol, le
1,3-propanediol, le 1,2-butylèneglycol, le 1,3-butanediol, le 1,4-butanediol, le néopentylglycol, le 1,5-pentanediol,
le 1,6-hexanediol, le glycérol, le triméthylolpropane, le triméthyloléthane, le pentaérythritol, l'érythritol ou un mo-
nosaccharide.
35

12. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, dans laquelle ledit composé à
fonction hydroxy ayant au moins deux groupes hydroxyle est choisi dans le groupe formé par les dérivés du gly-
cérol, du triméthylolpropane, du triméthyloléthane, du pentaérythritol, de l'érythritol ou un monosaccharide oxyalk-
ylé avec 5 à 30 moles d'oxyde d'éthylène, d'oxyde de propylène ou un mélange de ceux-ci, par groupe hydroxyle
40 du composé à fonction hydroxy.

13. Résine polyester dispersible dans l'eau ou hydrophobe selon la revendication 8, dans laquelle le composé à fonc-
tion carboxy ayant au moins deux groupes carboxyle est choisi dans le groupe formé par l'acide trimellitique,
l'anhydride trimellitique, l'acide maléique, l'anhydride maléique, l'acide fumarique et l'acide isophtalique.
45

14. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, dans laquelle ledit composé hy-
drophobe est choisi dans le groupe formé par l'acide stéarique, l'acide oléique, l'acide linoléique, l'acide béhénique,
l'acide laurique, l'acide palmitique, le suif de boeuf, le saindoux, l'huile de maïs et l'huile de soja.

50 15. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, comprenant le produit de la réaction
d'un polymère poly(téréphtalate d'éthylène) à raison de 40 à 60% en poids ; de néopentylglycol à raison de 1 à
10% en poids ; de pentaérythritol à raison de 5 à 10% ; d'acide trimellitique ou d'anhydride trimellitique à raison
de 3 à 15% en poids ; et d'acide stéarique à raison de 10 à 45% en poids.

55 16. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, comprenant un produit réactionnel
préparé en présence d'acide monobutylstannoïque ou d'un tétraalkyltitanate, ou un de leurs mélanges.

21
 EP 0 960 021 B1

17. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 8, dispersée dans l'eau avec un
hydroxyde ou un carbonate de métal alcalin ou d'ammonium.

18. Résine polyester dispersible dans l'eau et hydrophobe selon la revendication 15, dispersée dans l'eau avec un
5 métal alcalin ou l'hydroxyde ou carbonate d'ammonium.

19. Article manufacturé comprenant un substrat revêtu d'une composition de revêtement polyester dispersible dans
l'eau et hydrophobe comprenant un produit de la réaction d'un polymère téréphtalate à raison de 30 à 70% en
poids ; d'un composé à fonction hydroxy ayant au moins deux groupes hydroxyle à raison de 5 à 40% en poids ;
10 d'un composé à fonction carboxy ayant au moins deux groupes carboxyle à raison de 1 à 20% en poids et d'un
composé hydrophobe, à raison 10 à 60% en poids, choisi dans le groupe formé par un acide gras à chaîne droite
ou ramifiée en C6 à C24 ou les triglycérides de celui-ci.

20. Article manufacturé selon la revendication 19, dans lequel ledit substrat est un substrat fibreux.
15
21. Article manufacturé selon la revendication 19, dans lequel ledit substrat est un substrat de papier.

22. Article manufacturé selon la revendication 19, dans lequel ledit substrat est un substrat de textile.

20 23. Article manufacturé selon la revendication 19, dans lequel ledit substrat est un emballage alimentaire.

24. Article manufacturé selon la revendication 19, dans lequel ledit substrat est un papier anti-adhésif.

25. Article manufacturé selon la revendication 19, dans lequel ledit substrat est du ciment.
25
26. Article manufacturé revêtu selon la revendication 19, dans lequel ledit polymère téréphtalate est un téréphtalate
usagé de formule unitaire :

30

35

dans laquelle R est le résidu d'un glycol aliphatique ou cycloaliphatique de 2 à 10 atomes de carbone ou d'un
glycol oxygéné de formule :
40

HO(C x H 2x O) n C x H 2x OH (2)

dans laquelle x est un nombre entier valant de 2 à 4 et n est vaut de 1 à 10.

45

27. Article manufacturé revêtu selon la revendication 26, dans lequel le polymère téréphtalate usagé est le poly(téré-
phalate d'éthylène), le poly(téréphtalate de 1,2-propylène), le poly(téréphtalate de 1,3-propylène), le poly(téréph-
talate de butylène), le poly(téréphtalate de cyclohexanediméthanol) ou leurs mélanges.

50 28. Article manufacturé revêtu selon la revendication 19, dans lequel ledit composé à fonction hydroxy ayant au moins
deux groupes hydroxyle est choisi dans le groupe formé par l'éthylèneglycol, le diéthylèneglycol, le triéthylènegly-
col, le cyclohexanediméthanol, le propylèneglycol, le 1,2-propylèneglycol, le 1,3-propanediol, le 1,2-butylènegly-
col, le 1,3-butanediol, le 1,4-butanediol, le néopentylglycol, le 1,5-pentanediol, le 1,6-hexanediol, le glycérol, le
triméthylolpropane, le triméthyloléthane, le pentaérythritol, l'érythritol ou un monosaccharide.
55

29. Article manufacturé revêtu selon la revendication 19, dans lequel ledit composé à fonction hydroxy ayant au moins
deux groupes hydroxyle est choisi dans le groupe formé par les dérivés du glycérol, du triméthylolpropane, du

22
 EP 0 960 021 B1

triméthyloléthane, du pentaérythritol, de l'érythritol ou un monosaccharide oxyalkylé avec 5 à 30 moles d'oxyde

d'éthylène, d'oxyde de propylène ou un mélange de ceux-ci, par groupe hydroxyle du composé à fonction hydroxy.

30. Article manufacturé revêtu selon la revendication 19, dans lequel ledit composé à fonction carboxy ayant au moins
5 deux groupes carboxyle est choisi dans le groupe formé par l'acide trimellitique, l'anhydride trimellitique, l'acide
maléique, l'anhydride maléique, l'acide fumarique et l'acide isophtalique.

31. Article manufacturé revêtu selon la revendication 19, dans lequel ledit composé hydrophobe est choisi dans le
groupe formé par l'acide stéarique, l'acide oléique, l'acide linoléique, l'acide béhénique, l'acide laurique, l'acide
10 palmitique, le suif de boeuf, le saindoux, l'huile de maïs et l'huile de soja.

32. Article manufacturé comprenant un substrat revêtu d'une composition de revêtement polyester dispersible dans
l'eau et hydrophobe comprenant un produit de la réaction d'un polymère poly(téréphtalate d'éthylène) à raison de
40 à 60% en poids ; de néopentylglycol à raison de 1 à 10% en poids ; de pentaérythritol à raison de 5 à 10% ;
15 d'acide trimellitique ou d'anhydride trimellitique à raison de 3 à 15% en poids ; et d'acide stéarique à raison de 10
à 45% en poids.

33. Article manufacturé selon la revendication 32, dans lequel ledit substrat est un substrat fibreux.

20 34. Article manufacturé selon la revendication 32, dans lequel ledit substrat est un substrat de papier.

35. Article manufacturé selon la revendication 32, dans lequel ledit substrat est un substrat de textile.

36. Article manufacturé selon la revendication 32, dans lequel ledit substrat est un emballage alimentaire.
25
37. Article manufacturé selon la revendication 32, dans lequel ledit substrat est un papier anti-adhésif.

38. Article manufacturé selon la revendication 32, dans lequel ledit substrat est du ciment.

30 39. Composition de revêtement polyester hydrofuge, comprenant un produit de la réaction d'un polymère téréphtalate
à raison de 30 à 70% en poids ; d'un composé à fonction hydroxy ayant au moins deux groupes hydroxyle à raison
de 5 à 40% en poids ; d'un composé à fonction carboxy ayant au moins deux groupes carboxyle à raison de 1 à
20% en poids et d'un composé hydrophobe, à raison de 10 à 60% en poids, choisi dans le groupe formé par un
acide gras à chaîne droite ou ramifiée en C6 à C24 ou ses triglycérides.
35
40. Composition de revêtement polyester hydrofuge, comprenant un produit de la réaction d'un polymère poly(téréph-
talate d'éthylène) à raison de 40 à 60% en poids ; de néopentylglycol à raison de 1 à 10% en poids ; de pentaé-
rythritol à raison de 5 à 10% en poids ; d'acide trimellitique ou d'anhydride trimellitique à raison de 3 à 15% en
poids ; et d'acide stéarique à raison de 10 à 45% en poids.
40
41. Procédé pour conférer une propriété hydrofuge à des substrats choisis dans le groupe formé par des substrats
fibreux et du cuir consistant à appliquer à de tels substrats une composition comprenant le produit de la réaction
d'un polymère téréphtalate à raison de 30 à 70% en poids ; d'un composé à fonction hydroxy ayant au moins deux
groupes hydroxyle à raison de 5 à 40% en poids ; d'un composé à fonction carboxy ayant au moins deux groupes
45 carboxyle à raison de 1 à 20% en poids et d'un composé hydrophobe, à raison de 10 à 60% en poids, choisi dans
le groupe formé par un acide gras à chaîne droite ou ramifiée en C6 à C24 ou ses triglycérides.

50

55

23