EP1084030A1

EP1084030A1 - Water dispersible/redispersible hydrophobic polyester resins and their application in coatings

Info

Publication number: EP1084030A1
Application number: EP99914316A
Authority: EP
Inventors: Robert Keith Salsman; Timothy Shouting Wang
Original assignee: Seydel Research Inc
Current assignee: Seydel Research Inc
Priority date: 1998-04-07
Filing date: 1999-03-31
Publication date: 2001-03-21
Also published as: AU747282B2; AU3219399A; CA2327294A1; AU3219499A; EP1084030A4; WO1999051431A1; WO1999051430A1; CN1298347A; AU743591B2

Abstract

This invention relates to the synthesis from PET (Virgin, recycled, post consumer, or precursor raw materials) of novel water dispersible or water emulsifiable polyester resins having improved hydrophobicity or non-polar characteristics. The polyester resins can be combined with other polymers to give blends having improved properties when coated onto substrates. These characteristics give the applied film of these dispersions or emulsions much improved water repellency while at the same time retaining their redispersible or re-emulsifiable properties. Such resins can be used for many applications in the paper, textile, coatings, paint, construction, and other industries.

Description

WATER DISPERSIBLE/REDISPERSIBLE HYDROPHOBIC POLYESTER RESINS AND THEIR APPLICATION IN COATINGS

FIELD OF THE INVENTION

The present application is a continuation-in-part of pending U.S. Serial

No. 08/792,635 filed January 31 , 1997. 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 excellent

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 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, construction, and other

industries.

BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE PRIOR ART

Several patents have been written relating to the synthesis of water

soluble, dispersible, or emulsifiable polyester 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 hydroxyl groups. A resulting intermediate is alkoxylated with 1-4 moles of ethylene oxide and/or propylene oxide. The final

product is useful in making polyurethane and polyisocyanurate foams.

Sperenza etal. 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.

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.

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 glycol, and 20-50% by weight of

isophthalic acid.

U.S. 5,252,615 to Rao et al teaches coating compositions derived from

alcoholysis of polyethylene terephthalate (PET). Most preferably, the PET is

recycled or reclaimed from plastic articles.

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 dispersing the resulting melt in an aqueous alkali solution. The products are used

as coating and impregnating agents.

References proposing the use of copolymers containing terephthalic

units and units derived from alkylene and polyoxyalkylene glycols forfiber orfabric

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).

Marshall et al., in U.S. Pat. No. 3,814,627, have proposed applying an

ester, based on polyethylene glycol, to polyester yarn.

In our other patent U.S. 5,281 ,630 (Salsman), we disclose sulfonated

water-soluble or water-dispersible polyester resin compositions made by treating

a polyester glycolysis product with an alpha, beta-ethylenically unsaturated

dicarboxylic acid and then with a sulfite.

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.

The resins described in the above prior art have found applications in

textiles, coatings, and adhesive. All of 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.

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-linking occurs between chains, and the applied coating becomes insoluble.

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.

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

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 expose

sufficient areas of the oil modified chain to provide hydrophobic and water

repellent properties to the coatings produced from this chemistry. The resins described in this invention have overcome the problem of

chain termination by using a highly modified polyester backbone. In this way

polyester resins can be made containing 30 percent or more of mono-functional

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 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.

The prior art is silent regarding the new water dispersible and polyester

resins of the present invention which are derived from polyethylene terephthalate

and which exhibits high water repellency as evidenced by high contact angles.

OBJECTS OF THE INVENTION

It is a primary object of the invention to provide water-soluble or

water-dispersible polyester resin compositions having improved hydrophobicity. 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.

It is an additional object of the invention to provide water-soluble or

5 water-dispersible polyester resin compositions having improved water repellency.

It is yet another object of the invention to provide water-soluble or

water-dispersible polyester resin compositions having improved oil and

water-repellency.

An additional object of the invention is to utilize waste polyester

o material in the production of polyester resins having improved hydrophobicity and

non-polar characteristics.

It is still another object of the invention to use the water-dispersible

polyester compositions as coatings for fiber, paper or fabric.

It is yet a further object of the invention to produce water-soluble or

5 water-dispersible polyester coating compositions having improved oil and

water-repellency.

SUMMARY OF THE INVENTION

Briefly, the present invention relates to water dispersible/and

o redispersible hydrophobic polyester resins derived 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: 'n ^" ' ^" "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 backbone; A is an aliphatic group; and

m is an integer in the range of 3-8 and defines the number of aliphatic groups.

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.

The backbone P of the polymer is composed of polyester groups. It

can be any linear or branched polyester made using polyacids and polyalcohols.

The preferred method is to generate the backbone using polyester from recycled

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.

The aliphatic groups A consist of straight or branched 6-24 carbon

chain fatty acids or triglycerides thereof. The weight percent of the aliphatic

moiety can be 10-60% with 20-40% by weight being the preferred amount.

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.

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 times the equivalents of the hydrophobic

moiety.

The instant invention is also directed to substrates such as paper,

paperboard, food packaging, textiles, concrete 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 selected from the group consisting of C₆-C₂₄ straight chain or branched

fatty acid or triglycerides thereof.

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

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.

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

fatty acid or triglycerides thereof.

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%

10-45% by weight of stearic acid.

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

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.

Still another novel aspect of the invention is a composition for imparting

water and oil repellency to substrates comprising (a) a water dispersible and

hydrophobic polyester resin having the formula:

'n " ' " A_m 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 aliphatic group is present in an amount of about 10% to 60%

by weight; said polyester resins exhibiting high water and oil repellency; and (b)

at least one other polymer in an amount effective to impart additional water and

oil repellency to said substrates.

The polymer of part (b) includes two kinds of polymers: one is polymer

(c) that itself can render the substrates treated therewith additionally repellent to

water and oil, and the other is a polymer (d) that can react with the water

dispersible polyester resin (a).

The present invention also provides a method for imparting water and

oil repellency to substrates selected from the group consisting of fibrous

substrates and leather comprising applying to such substrates the aforementioned

compositions. This invention further provides water and oil repellent fibrous

substrate or leather or other substrate articles.

The invention also describes polyester resins which can be made

containing 30 percent or more of mono-functional monomers, such as stearic acid ,

to provide a much improved non-polar nature.

10 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The objects of the present invention and many of the expected

advantages of the present invention will be readily appreciated as the same

becomes better understood by reference to the following detailed description.

The novel water dispersible resins of the present invention can be

represented as shown by the following structure:

- P - Λ,

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.

There are four necessary requirements for the polyester chemistry of

the present invention:

1. A polyester backbone.

2. A multi-functional glycol in the backbone providing additional

hydroxyl functionality present at 1-3 times the equivalent 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 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.

11 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 in

water.

The physical properties that make the resins of the present invention

unique are:

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.

The water dispersible and hydrophobic polyester compositions of this

invention imparts desirable water and 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 repellency to fibrous substrates such as textiles, papers,

non-woven articles or leather or to other substrates such as plastic, wood, metals,

glass, stone and concrete.

The water-dispersible resins of the present invention are synthesized

by condensation polymerization with original or recycled PET or

polyacid-polyalcohol [mutli-functional acids or alcohols] used to make polyesters

along with aliphatic acids or hydrogenated or unhydrogenated animal or vegetable

triglycerides.

12 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

O ROOC- -co - (1 )

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

or oxygenated glycol of the formula

H O (C χH ₂χO ) nC χH₂χO H (2)

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

Preferably the waste terephthalate polymer is a polyalkylene

terephthalates such as polyethylene terephthalate and polybutylene

terephthalate, polycyclohexanedimethanol terephthalate or a mixture thereof.

Other suitable polyester polymers which can be used in the practice of the present

invention include polyl ,2 and polyl ,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.

The ionic group l_n needed for water-dispersibility can be a carboxylic

acid which is introduced into the resin by polyacid monomers such as Trimellitic

anhydride, Trimellitic acid, or Maleic Anhydride or sulfonate groups which come

13 from monomers such as dimethyl 5-sulfoisophthalate (DMSIP or dimethyl

5-sulfo,1 ,3-benzenedicarboxylate), sulfoisophthalate ethylene glycol (SIPEG or

dihydroxyethyl 5-sulfo1 ,3-benzenedicarboxylate, or from sulfonated alkenically

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

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.

The backbone of the polymer is composed of polyester groups. It can

be any linear or branched polyester made using polyacids and polyalcohols. The

preferred method is to generate the backbone using polyester from recycled

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,

cyclohexanedimethanol, propylene glycol, 1 ,2-propylene glycol, 1 ,3-propanediol,

1 ,2-butylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, neopentyl glycol,

1 ,5-pentanediol, 1 ,6-hexanediol, glycerol.trimethylolpropane, trimethylolethane,

14 pentaerythritol, erythritol or a monosaccharide. In another embodiment, other

hydroxy compounds having at least two 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.

The aliphatic groups consist of 6-24 carbon chain fatty acids or

triglycerides thereof such as stearic, oleic, 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. 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:

Route 1

(1 ) Aliphatic Acids or Esters + Multifunctional Glycol — > esterification

or transesterification = Hydrophobic Glycol

(2) Hydrophobic Glycol + PET (or Diacid with Dialcohol) — > esterification

or transesterification = Hydrophobic Polyester

(3) Hydrophobic Polyester + Ionic monomer → esterification or

transesterifcation = Water Dispersible and Hydrophobic Polyester Resin

15 Route 2

(1 ) Diacid or PET + Multifunctional Glycol — » esterification or

transesterification = grafting polyester with hydroxyl groups throughout chain

and/or as end groups

5 (2) Grafting polyester + Aliphatic Acids or Esters — > esterification or

transesterification = Hydrophobic Polyester Resin

(3) Hydrophobic Polyester + ionic monomer — > esterification or

transesterification = Water Dispersible and Hydrophobic Polyester Resin

o 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 stearic acid, behenic acid,

palmitic acid, lauric acid, oleic acid, linoleic acid, etc.; triglycerides from animal or

5 vegetable 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 multi-

0 functional hydroxyl component or components such as pentaerythritol, sorbitol,

glycerol, etc. at levels consistent with but not limited to 1 to 3 times the reactive

equivalent of components from group 1.

16 3. Esterification or transesterification of ingredients typical of those

used to make polyester polymers. These ingredients 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 ethylene glycol, diethylene glycol, neopentyl

glycol, propylene glycol, etc.

4. Incorporation of an 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 aamount of base, if

needed, to neutralize the pendant acid groups.

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.

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 titanates, 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 ortetrabutyl titanate, or a mixture thereof.

The resulting resinous products obtained are generally taken up in

relatively concentrated aqueous solutions of alkali metal or ammonium hydroxides

17 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.

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.

The incorporation of polymer (c) that exhibits water and oil repellent

properties into the water-dispersible polyester resins of the present invention

would render the substrates treated therewith with higher repellency to water and

oil. Generally, the polymer (c) useful in the present invention comprises

fluoropolymers, silicone resins and mixtures thereof.

Fluoropolymers useful in the present invention include any of the

fluorochemical radical-containing polymeric and oligomeric compounds known in

the art to impart water and oil repellency to the substrates. These polymeric and

oligomeric fluorochemical radical-containing compounds comprise one or more

fluorochemical radicals that contain a perfluorinated carbon chain having from 3

to about 20 carbon atoms, more preferably from about 6 to about 14 carbon

atoms. These fluorochemical radicals can contain straight chain, branched chain,

18 or cyclic fluorinated alkylene groups or any combination thereof. Fully fluorinated

radicals are preferred.

Suitable fluoropolymers include, but are not limited to, fluorinated

urethane, ureas, non-aromatic esters, ethers, alcohols, epoxides, allophanates,

amides, amines, acids, carbodiiides, carbamates, guanidines, oxazolidinones,

isocyanurates, biurets, and acrylate and substituted acrylate homopolymers and

copolymer. Representative fluoropolymers are fluoroaliphatic radical-containing

polyesters, polyamide, polyepoxides, vinyl polymers, polyurethanes, and

polycarbodiimides. Examples of some suitable fluoropolymers include: polymers

0 and copolymers of vinylidene fluoride, tetrafluoroethylene, perfluoroalkylethyl

acrylates, perfluoroalkylethyl methacrylate, mixtures of the same; blends of the

foregoing polymers and copolymers with: polymers and copolymers of alkyl

acrylates and alkylmethacrylates, copolymers of vinylidene fluoride.

Suitable silicone resins include, but are not limited to,

5 organopolysiloxane comprising monovalent R₃SiO₀₅ and R'R₂SiO₀₅ units and

tetravalent SiO₂ units, the ratio of monovalent units to tetravalent units being from

0.4/1 to 2/1 , wherein R and R' each are independently selected from the group

consisting of a substituted or unsubstituted alkyl, an aryl, an alkaryl, an aralkyl, a

cycloalkyl, an alkenyl and a mixture of any of the foregoing.

o Many commercially available fluoropolymers can be used as effective

oil-repellents and water-repellents including, but not limited to, commercially

available proprietary products sold under the trade names of "Teflon"® and

"Zonyl"® from DuPont, "Milease"® from ICI, "Asahigard"® from Asahi,

19 "Scotchgard"® from 3M, "Softech"® from Dyetech, "Tex-Tel"® from Atochem and

"NK Guard"® from Nicca. Suitable commercially available silicone-based

repellents include, but are not limited to, C2-0563 from Dow Corning, which is a

silicone repellent mixture of polydialkylsiloxanes.

The relative amount of the fluoropolymers used in the water and oil

repellent imparting composition is not critical to the present invention. However,

the composition should contain, relative to the amount of water dispersible

polyester resins, at least about 3 weight percent, preferably at least about 5

weight percent, carbon-bound fluorine in the form of said fluorochemical radical

groups.

When adding polymer (d) that can react with polyester resin of this

invention is (e.g. cross-linking reaction) into the water dispersible polyester

composition, the resulting system would provide additional barrier properties to

moisture and water. Said polymer (d) can be any conventionally used polymer

that can react with polyester resin, especially cross-link with polyester resin.

Suitable polymer (d) includes, but are not limited to, phenol-formaldehyde resins,

either of the resole or novalac type; urea-formaldehyde resins; melamine urea

formaldehyde resins; tannin-phenol-formaldehyde resins; diisocyanate resin;

epoxy resins; crosslinkable polyvinyl acetate; polyvinylalcohol, polyvinyl chloride,

ethylene/vinylacetate copolymers, starches, cellulose derivatives such as

cellulose esters and cellulose ethers, polyester polyols; polyether polyols;

polycarbonates; polyhydroxy polyester; polyhydroxy polyester amides;

20 polyhydroxy polyamides; polyhydroxy polyacetals; polyhydroxy polythioethers;

polyurea; polyurethane; polyamines; and blends thereof.

The above general types of resins are commercially available from a

number of commercial sources and these commercial sources may provide their

proprietary compositions to help meet the desired characteristics of the coating

composition.

The water and oil repellent coating composition may also contain

various crosslinking monomers. There is a wide range of such crosslinking

monomers, including monomers having functional groups that can form covalent

bonds through an addition or condensation reaction with the polyester resin (a),

and monomers having functional groups that can cure through the action of a

curing catalyst or the like. Examples include N-methylol acrylamide, N-methylol

methacrylamide, N-(isobutoxymethyl) acrylamide, glycidyl acrylate, glycidyl

methacrylate, aziridinyl acrylate, aziridinyl methacrylate, diacetone acrylamide,

diacetone methacrylamide, methylolated diacetone acrylamide, methylolated

diacetone methacrylamide, ethylene diacrylate, ethylene dimethacrylate,

hydroxyalkyl acrylate, and hydroxylalkyl methacrylate.

The composition for imparting water and oil repellency to substrates

may be prepared by mixing an aqueous dispersion of the instant polyester resin

with an aqueous emulsion of a suitable polymer (c) or polymer (d) or mixture

thereof. Forming the coating composition emulsion may require using one or

more emulsifiers compatible with the particular chosen treatment.

21 The application of the composition stated above as a coating to the

substrate such as a fibrous substrate or leather may comprise contacting the

substrate with an aqueous emulsion of said water and oil repellent imparting

composition. Alternatively, the coating can be carried out by first applying a water

5 dispersible and hydrophobic polyester resin composition of this invention to the

surface of said substrate, and then coating said surface with a polymer (c) or

polymer (d) or mixture thereof.

EXAMPLES

i o 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,

percentage, etc. in the examples and the rest of the specification, are by weight

unless otherwise noted.

15 Throughout all the Examples described below, a 1000 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:

20

22 EXAMPLE 1

Ineredients Wt% Grams

Recycled PET 56.29 598.8

Pentaerythritol 6.71 71.4

Neopentyl Glycol 2.6 27.7

Tetra Propyl 0.08 0.8 Titanate(TPT)

Stearic Acid 28.24 300.4

Monobutyl Stannic Acid 0.08 0.9 Trimellitic Anhydride 6 63.8

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 last for 5

to 12 hours. The obtained resin is dispersed in diluted 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.

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 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.

23 EXAMPLE 2

Inαredients Wt% Grams

Recycled PET 56.29 598.8

Pentaerythritol 6.71 71.4

Neopentyl Glycol 2.6 27.7

Tetra Propyl 0.08 0.8 Titanate(TPT)

Oleic Acid/stearic acid 28.24 300.4

Monobutyl Stannic 0.08 0.9 Acid 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 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.

EXAMPLE 3

A recipe containing a triglyceride is shown as follows:

24 Inσredients Weiαht % Grams

Recycled PET 48.80 480

Pentaerythritol 6.83 67.17

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

Trimellitic Anhydride or 9.83 96.67 Maleic Anhydride Isophthalic acid 6.76 66.45

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 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

In this example the same formula is used as in Example 3 except the

hydrogenated is tallow triglycerides are substituted with corn oil or soy-bean oil.

Care must be taken to prevent cross-linking reactions from occurring. The resin

25 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

triglycerides.

EXAMPLE 5

The formula is shown as follows:

Inqredients Weiαht% Grams

Pentaerythritol(PE) 7.07 67.7

Neopentyl Glycol 19.18 182.26

Diethylene Glycol 3.35 31.84

Stearic Acid 24.98 245.7

Monobutyl Stannic Acid 0.1 0.96

Trimellitic 10.17 96.67

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°C until the acid value is less than 100.

The Isophthalic acid, the Neopentyl Glycol, and the Diethylene 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.

26 EXAMPLE 6

The same formula is used as in Example 5 except the Isophthalic acid

is replaced with Terephthalic acid with the same results.

EXAMPLE 7

The same formula is used as in Example 5 except the Isophthalic is

replaced with Phthalic acid with similar results.

EXAMPLE 8

The formula is shown as follows:

Inαredients Weiαht% Grams

Pentaerythritol(PE) 7.07 67.7

Neopentyl Glycol 19.18 182.26

Diethylene Glycol 3.35 31.84

Stearic Acid 24.98 245.7

Monobutyl Stannic Acid 0.1 0.96

Trimellitic 10.17 96.67

Anhydride(TMA) or Maleic Anhydride(MA) Phthalic acid 34.27 325.64

to the vessel and reacted at 160 to 270 °C until the acid value is less than 100.

The Phthalic acid, the Neopentyl Glycol, and the Diethylene 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

27 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.

EXAMPLE 9

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

described above.

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:

I. PAPER

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 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

28 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 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:

A. Paper or paperboard for food packaging

Some food packages (fresh products, 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 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 repulsing. 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.

29 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.

In the Frozen Food Industry paper containers are used to store food

for use in instant cooking, microwave 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

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 with

these resins alone have excellent water repellency and ink holdout as well as

increased strength and gloss.

30 C. Paper or Paperboard for storage or transport

Paper Bags for carrying consumer purchases, etc. have a problem in

that if they get wet they lose their strength and tear easily. Making these bags

water repellent or just water resistant would help solve this problem. Letters,

envelopes, 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.

D. Release Paper

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

used for this purpose as well since the hydrophobic properties make them ideally

suited as adhesive release agents.

E. Miscellaneous Paper Items

Other paper products which could benefit from an inexpensive

waterproofing system would be fiber drums, 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.

3 1 II. TEXTILES

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, re-application of waterproofing agents

and footwear.

III. WOOD

Wood products especially those used in outdoor applications, need to

be protected from rain and weather. 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.

IV. CONCRETE

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

32 used for this purpose. 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

In some instances it is desirable for a paint (or protective coating) to

exhibit a certain amount of water repellency. 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

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

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.

33 VIM. GLASS

Fiberglass is used as the structural material for a great deal of

commonly used items such as shower stalls, 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.

IX. METAL COATINGS

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.

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 substrate.

The amount which is sufficient to impart desired repellency can be determined

empirically and can be increased as necessary or desired.

The treatment of fibrous substrates using the water and oil repellency

imparting composition of the present invention is carried out by using well-known

34 methods including dipping, spraying, padding, knife coating, and roll coating.

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.

The effectiveness of the coatings resulting from the resins of the

present invention is illustrated in Example 10.

EXAMPLE 10

Contact Angle Comparisons

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-l 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.

PROCEDURE

A 0.1 ml sample of distilled water was place on the surface of a piece

of uncoated (control) and coated paperboard 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 values calculated. The difference between the two

average values was calculated as the Lose of Angle.

35 RESULTS

The following chart reflects the results using uncoated paper and

various coating formulas.

TEST SAMPLE Initial 5 min. Lose of Angle Angle Angle

Control: No coating 78.2 64.3 13.9

Graphsize: polyurethane size 91.3 84.4 6.9

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

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

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

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.

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.

36 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.

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, 3.47 wt% neopentylglycol, 1.96 wt%

diethyleneglycol.

EXAMPLE 11

Water Resistance Test

The following film formulations were prepared by mixing 25% WXP

(polyester resin of instant invention) with 63.4% CAS4 and pure calcium

carbonate to form a polymer blend. According to conventional film-forming

37 procedures, the film was made from the polymer blend above for evaluating its

water resistance.

Table I

Film Formulations

Film 63.4% CAS 4 25% XWP 100% CaCO, Final Sample ΛVeight % Grams Weight % Grams Weight % Grams Weight

A 61.2 5.000 — — 38.8 3.170

B 56.4 4.500 6.3 0.500 37.3 2.978

C 53.9 4.250 9.5 0.750 36.6 2.882

D 51.4 4.000 12.8 1.000 35.8 2.786

E 48.8 3.750 16.3 1.250 34.9 2.690

F 46.1 3.500 19.8 1.500 34.1 2.594

G 43.3 3.250 23.3 1.750 33.4 2.498 8.47

H 40.5 3.000 22.0 2.000 32.5 2.402 8.36

I 37.6 2.750 30.8 2.250 31.6 2.304 8.25

J 34.7 2.500 34.7 2.500 30.6 2.210 8.18

K 31.6 2.250 38.7 2.750 29.7 2.114 8.09

28.5 2.000 42.7 3.000 28.8 2.018 8.01

In the table above, the resin compositions of the polymer blend are

defined as follows:

CAS 4: This resin is 63.4% dispersion of styrene/butadiene resin.

XWP: This resin is Resin 2141 used in Example 10, 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.

38 Water resistance of films as prepared above was measured by

weighing the films before and after drying, then soaking the films in water for 30

minutes, 1 hour and 2 hours, respectively, and then weighing the films after

soaking and calculating the added moisture. The results were listed in Tables ll-IV.

Table II

Water Resistance Test 1

Soaking Time: 30 minutes

Film Sample Weight Before Weight After Weight After Added Drying (g) Drying (g) Soaking (g) Moisture %

A 9.01 7.257 7.345 1.198

B 8.90 6.932 7.015 1.183

C 8.78 6.725 6.794 1.016

D 8.75 6.578 6.640 0.934

E 8.65 6.374 6.432 0.902

F 8.56 6.190 6.244 0.865

G 8.47 6.080 6.124 0.718

H 8.36 5.863 5.882 0.323

I 8.25 5.877 5.912 0.592

J 8.19 5.514 5.566 0.934

K 8.09 5.438 5.464 0.476

L 8.01 5.277 5.425 2.728

39 Table III

Water Resistance Test 2

Soakine Time: 2 Hours

A 2.704 3.163 14.54

B 2.847 3.479 18.19

C 2.976 3.344 11.00

D 3.422 4.310 20.60

E 3.118 3.983 21.72

F 2.549 3.642 30.01

G 8.47 5.936 6.082 2.401

H 8.40 5.787 5.875 1.498

I 8.30 5.618 5.712 1.646

J 8.20 5.425 5.504 1.435

K 8.04 5.190 5.277 1.649

L 7.97 4.995 5.098 2.020

The results in Tables II and III show that the added moisture into the

soaked films become less and less with the increase in the levels of XWP in the

film formulations. This further demonstrates that the water dispersible and

hydrophobic polyester resins of this invention have superior water repellent

properties.

40 EXAMPLE 12

Compatibility Test

The compatibility test was performed by mixing resin of this invention

(XWP) with other polymers, then measuring the desize time. The results were

listed in Tables IV and V.

Table IV

Ratio Desize: l%Na₂CO₃+ 0.1% Desize: 0.85% Na₂CO₃ +

Sample LC XWP TDA-18, 65°C, pH 11.1 0.05% TDA-18, 65°C, pH 10.7

A 50/50 Not all All dissolved dissolved

B 60/40 Most dissolved All dissolved

C 70/30 Most dissolved —

D 80/20 Not dissolved —

E 90/10 Not dissolved All dissolved p* 50/50 All dissolved All dissolved

G* 80/20 All dissolved All dissolved

Samples F and G are PE-23OIXWP.

In the Table VI above, LC represents sulphoisophthalate polyester

resin.

41 Table V

Polymer Blend

Sample Constituents Ratio Compatible Rank

A XWP/PVA 90/10 Yes 1

B XWP7PVA 80/20 Viscous 2

C XWP/PVA 70/30 Thick 3

D XWP/Starch-K66F 90/10 Yes 1

E XWP/Starch-K66F 80/20 Viscous 2

F XWP/Starch-K66F 70/30 Thick 3

The physical properties that make this resin unique are:

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.

EXAMPLE 13

With stirring, an aqueous dispersion of instant polyester resin such as

25% WXP was mixed with a solution of fluoropolymer such as fluoroaliphatic

radical-containing polymethacrylate in an organic solvent or solvents mixture, e.g.

ethylacetatelheptane, in different ratios to form an emulsion of instant composition

having improved water and oil repellent properties.

42 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 concepts

of the present invention. Accordingly, it should be cleariy 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.

43

Claims

What is claimed is:

1. A composition for imparting water and oil repellency to

substrates comprising:

(a) a water dispersible and hydrophobic polyester resin having the

formula:

'n " P " An

wherein I is an ionic group; n=l-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 aliphatic group is present in an amount of about 10% to 60% by

weight; said polyester resins exhibiting high water and oil repellency; and,

(b) at least one polymer in an amount effective to impart additional

water and oil repellency to said substrates.

2. The composition of claim 1 wherein I in the polymer of part (a)

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

3. The composition of claim 1 wherein the polyester backbone P

in the polymer of part (a) is present in an amount ranging from 50% to 60% by

weight.

4. The composition of claim 1 wherein the fatty acid group A in the

polymer of part (a) is present in an amount ranging from 20% to 40% by weight.

44

5. The composition of claim 1 wherein I in the polymer of part (a)

is derived from polycarboxylic acid or anhydrides selected from the group

consisting of trimellitic anhydride, trimellitic acid and maleic anhydride.

6. The composition of claim 1 wherein the polyester backbone P

in the polymer of part (a) is a polyalkylene terephthalate selected from the group

consisting of polyethylene terephthalate, polypropylene terephthalate and

polybutylene terephthalate.

7. The composition of claim 1 wherein the fatty acid group A in the

polymer of part (a) is selected from the group consisting of stearic acid, behenic

0 acid, palmitic acid, lauric acid, oleic acid and linoleic acid.

8. The composition of claim 1 wherein the polymer of part (b) is

selected from the group consisting of polymer (c) that provides additional water

and oil repellence to the substrates, and/or a polymer (d) that can react with

polyester resin (a). 5

9. The composition of claim 8 wherein the polymer (c) is selected

from the group consisting of fluoropolymers, silicone resins or mixture thereof.

10. The composition of claim 9 wherein said fluoropolymers

comprise fluorochemical radical-containing polymers.

11. The composition of claim 10 wherein said fluorochemical

o radical-containing polymers are selected from the group consisting of fluorinated

urethanes, ureas, non-aromatic esters, ethers, alcohols, epoxides, allophanates,

amides, amines, acids, carbodiimides, carbamates, guanidines, oxazolidinones,

45 isocyanurates, biurets, and acrylate and substituted acrylate homopolymers and

copolymer.

12. The composition of claim 9 wherein said fluoropolymers are

selected from the group consisting of fluoroaliphatic radical-containing polyesters,

polyamides, polyepoxides, vinyl polymers, polyurethanes, and polycarbodiimides.

13. The composition of claim 12 wherein said fluoropolymer is

selected from the group consisting of polymers and copolymers of vinylidene

fluoride, tetrafluoroethylene, perfluoroalkylethyl acrylates, perfluoroalkylethyl

methacrylate, mixtures of the same; blends of the foregoing polymers and

copolymers with: polymers and copolymers of alkyl acrylates and

alkylmethacrylates, copolymers of vinylidene fluoride.

14. The composition of claim 8 wherein the polymer (d) is selected

from the group consisting of phenol-formaldehyde resins, urea-formaldehyde

resins, melamine urea formaldehyde resins, tannin-phenol-formaldehyde resins,

diisocyanate resin, epoxy resins, crosslinkable polyvinyl acetate, polyvinyl alcohol,

starches, polyester polyols, polyether polyols, polycarbonates, polyhydroxy

polyester, polyhydroxy polyester amides, polyhydroxy polyamides, polyhydroxy

polyacetals, polyhydroxy polythioethers, polyurea, polyurethane, polyamines, and

blends thereof.

15. A composition for imparting water and oil repellence comprising:

(a) 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;

46 1-20% by weight to substrates 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; said resin being further characterized in that the hydroxy

functional compound is present at 1-3 times the equivalents of the hydrophobic

moiety; and,

(b) at least one polymer selected from polymer (c) and (d) as

claimed in claim 8 in an amount effective to impart additional water and oil

repellency to said substrates.

16. The composition of claim 15, wherein said water dispersible and

hydrophobic polyester resin (a) comprises the reaction product of waste

terephthalate of the unit formula

O ROOC ^'Γûá^ ΓÇö ( OCJ )╬│>HΓÇö^~ C^┬╗O4-r-- (1 )

or oxygenated glycol of the formula

H O (C ╧çH_{2 X}0 )_nC ╧çH ₂╧çO H (2)

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

17. The composition of claim 15, wherein the terephthalate polymer

is polyethylene terephthalate, polyl ,2 propylene terephthalate, polyl ,3 propylene

47 terephthalate, polybutylene terephthalate, poly(cyclohexanedimethanol

terephthalate) or a mixture thereof.

18. The composition of claim 15, wherein said hydroxy functional

compound having at least two hydroxyl groups is selected from the group

consisting of ethylene glycol, diethylene glycol, triethylene glycol,

1 ,2-butylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, neopentyl glycol,

1 ,5-pentanediol, 1 ,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane,

pentaerythritol, erythritol or a monosaccharide.

19. The composition of claim 15, 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 oxyalkylated with 5-30 moles of

ethylene oxide, propylene oxide or a mixture thereof, per hydroxyl of the hydroxy

functional compound.

20. The composition of claim 15, 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.

21. The composition of claim 15, 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.

48

22. The composition of claim 15, wherein polymer (c) is selected

from fluoropolymers, silicone resins or mixture thereof.

23. The composition of claim 15, wherein polymer (d) is selected

from the group consisting of phenol-formaldehyde resins, urea-formaldehyde

resins, melamine urea formaldehyde resins, tannin-phenol-formaldehyde resins,

diisocyanate resin, epoxy resins, crosslinkable polyvinyl acetate, polyester

polyols, polyether polyols, polycarbonates, polyhydroxy polyester, polyhydroxy

polyester amides, polyhydroxy polyamides, polyhydroxy polyacetals, polyhydroxy

polythioethers, polyurea, polyurethane, polyamines, and blends thereof.

24. A composition for imparting water and oil repellency to

substrates comprising:

(a) a water dispersible and hydrophobic polyester resin, 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% by weight of

trimellitic acid or trimellitic anhydride; and 10-45% by weight of stearic acid; and,

(b) at least one polymer selected from polymer (c) and (d) as

claimed in claim 8 in an amount effective to impart additional water and oil

repellency to said substrates.

25. An article of manufacture comprising a substrate having on the

surface thereof an amount of a composition according to claim 1 effective to

impart water and is oil repellent properties thereto.

49

26. The article of manufacture of claim 25, wherein the substrate is

selected from the group consisting of paper, textile fabrics, fibers, non-wovens,

leather, wood, concrete, and metals.

27. The article of manufacture of claim 25, wherein the substrate is

food packaging.

28. The article of manufacture of claim 25, wherein the substrate is

release paper.

29. An article of manufacture comprising a substrate having on the

surface thereof an amount of a composition according to claim 15 effective to

impart water and oil repellent properties thereto.

30. The article of manufacture of claim 29, wherein the substrate is

leather, wood, concrete, and metals.

31. The article of manufacture of claim 29, wherein the substrate is

5 food packaging.

32. The article of manufacture of claim 29, wherein the substrate is

release paper.

33. An article of manufacture comprising a substrate having on the

surface thereof an amount of a composition according to claim 24 effective to

o impart water and oil repellent properties thereto.

34. The article of manufacture of claim 33, wherein the substrate is

leather, wood, concrete, and metals.

50

35. The article of manufacture of claim 33, wherein the substrate is

food packaging.

36. The article of manufacture of claim 33, wherein the substrate is

release paper.

37. A water and oil repellent coating composition, comprising:

(a) 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; and,

(b) at least one polymer selected from polymer (c) and (d) as

claimed in claim 8 in an amount effective to impart additional water and oil

repellency to said substrates.

38. A water and oil repellent coating composition, comprising:

(a) a reaction product of 40-60% by weight of polyethylene

terephthalate polymer; 1-10% byweightof neopentyiglycol; 5-10% pentaerythritol;

3 to 15% by weight of trimellitic acid or trimellitic anhydride; and 10-45% by weight

of stearic acid; and,

(b) at least one polymer selected from polymer (c) and (d) as

claimed in claim 8 in an amount effective to impart additional water and oil

repellency to said substrates.

51

39. A method for imparting water and oil repellency to substrates

selected from the group consisting of fibrous substrates and leather comprising

applying to such substrates a composition comprising:

(a) 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 of a hydrophobic compound

or triglycerides thereof; and,

(b) at least one polymer selected from polymer (c) and (d) as

claimed in claim 8 in an amount effective to impart additional water and oil

repellency to said substrates.

40. A method for imparting water and oil repellency to substrates

selected from the group consisting of fibrous substrates and leather comprising:

(i) first applying to such substrates a composition comprising the

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; and then,

(ii) applying to the surfaces of said substrates coated with the

polymer (i) above at least one polymer selected from polymer (c) and (d) as

52 claimed in claim 8 in an amount effective to impart additional water and oil repellency to said substrates.

53