Title of Invention

A PROCESS FOR PREPARATION OF HYDROXYL CARBOXYL FUNCTIONAL AQUEOUS POLYURETHANE DISPERSIONS AND PRODUCTS THEREOF

Abstract Abstract The present invention describes synthesis of Hydroxyl / carboxyl functional polyurethane dispersion (PUD), with low volatile organic content (VOC), based on poly(ethylene) glycol (PEG), dimethylol propionic acid (DMPA), and m-tetramethyl xylene diisocyanate (m-TMXDI) . The coating materials are formulated with varying concentration of hexakis(methoxymethyl)melamine resin (HMMM) and cured at elevated temperatures (120-180 °C) to obtain three dimensionally crosslinked thermosetting networks. The reactions are catalyzed with different concentrations of amine-blocked p-toluene sulphonic acid (p-TSA). These coatings are particularly useful for application on mild steel, aluminum and plastic materials.
Full Text FORM 2
THE PATENT ACT 1970
(39 OF 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and rule 13)
1. TITLE OF THE INVENTION
SURFACE COATINGS BASED ON WATER BORNE POLYURETHANE DISPERSION WITH HYDROXYL/ CARBOXYL FUNCTIONALITY CROSS-LINKED BY HEXAKIS(METHOXYMETHYL) MELAMINE (HMMM)
2. APPLICANTS Nationality: Address:
Name :
a) PROF. DR. VILAS DATTATRAY ATHAWALE a) INDIAN a) C-702 ASTER, VALLEY OF FLOWERS,
THAKUR VILLAGE, KANDIVALI (EAST), MUMBAI-400101
b) MR. SUNIL NAMDEV PESHANE b) INDIAN b) 301 SAI DARSHAN, BLDNG NO. 3,
ADARSH VIDYA MANDIR ROAD, BADLAPUR (WEST), 421503.
3. PREAMBLE TO THE DESCRIPTION
COMPLETE
The following specification particularly describes the invention and the manner in which it is to be performed.

Description
BACKGROUND OF THE INVENTION
Waterborne Polyurethane coatings is a vital component in the industry-wide efforts to reduce volatile organic compounds (VOC) in surface coatings industry. The major factors are the versatility of polyurethane (PU) systems and their effectiveness in the production of 'tailor-made' coatings for a wide range of demanding applications. The development of these aqueous coating systems has been motivated primarily by environmental considerations and legislation aimed increasingly towards waterborne and high solids systems.
Many commercially available aqueous PUR dispersions are predominantly linear thermoplastic polymers that are dispersed in water as a continuous phase. They specifically lack the crosslinking and high molecular weight obtainable by the their solventborne counterparts because of some major constraints like rheology of prepolymer and poor coalescence of particles leading to poor film integrity. The final consequence of this is usually a lack of water and solvent resistance shown by most of the coating films. The main disadvantage of PUDs and other water-based coatings is their inherent water sensitivity due to the hydrophilic modification of the backbone polymer. In order to heave these properties the use of cross-linking agents that are capable to react through the carboxyl functionality are needed.
The carboxyl acid functionality of anionic PUDs mainly responsible for the poor water and solvent resistance can be exploited through cross-linking by melamine resin. Melamine resin is used for cross-linking purpose mainly because of its stability as a
2.

single pack system and a wide range of manipulations possible to tune the film properties and curing schedules. The present work mainly emphasizes on this aspect of HMMM cross-linking agent. The base resin employed for the present study was a hydroxyl /carboxyl functional polyurethane synthesized from m-TMXDI. The asymmetrical structure of TMXDI and the steric hindrance of the isocyanate group by the DESCRIPTION OF THE PRIOR ART
The various technique of synthesizing waterborne polyurethane dispersion are discussed in an article by D. Dieterich in Porgress in Organic Coatings, vol. 9, (1981), p. 281- 340.
In U. S. Patent 4, 451, 622 issued on May 29, 1984 to DiDomenico, Jr.; Edward a composition of matter comprising a hydroxyl terminated urethane prepolymers derived from a polyisocyante and a polyol selected from the group consisting of hydroxylmethyl polyols are discussed. The prepolymers are obtained by mixing the ingredients at room temperature. These prepolymers are crosslinked by amino crosslinking agent namely
3

Cymel 303. In these coatings mainly isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and a trifunctional aliphatic isocyanate Z 4370 (manufactured by Mobay Chemical Co.) are used. The organic solvents used for dilution are mainly Methyl normal amyl ketone (MnAK) and ethylene glycol monoethyl ether acetate. The films are characterized for hardness which is found to be in the range of H - 4H and impact resistance which is found to be in the range of 2 - 60 inch lbs (direct) and 0.5- 60 inch lbs (reverse).
In U. S. patent 4, 125, 570 issued on November 14, 1978 to Chang; Wen-Hsuan, Porter, Jr.; Samuel, Wismer; Macro, thermosetting resins containing hydroxyl groups which can be cured with aminoplast resins are stabilized by the addition of l,4-diazo[2,2,2]-bicyclooctane. This method is particularly useful in stabilizing the gloss retention of extensible coatings formed by curing a hydroxyl-containing urethane product with an aminoplast resin. Such coatings can be applied to virtually any solid substrate and are especially useful on rubbery, resilient substrates such as polyurethane or polyethylene foam, natural or synthetic rubber or rubber foam, and various elastomeric plastic materials. They are also particularly useful on other substrates such as mild steel or aluminum.
In U. S. patent 4, 017, 556 issued on April 12, 1977 to Wang; Samuel S., coatings with compositions of matter consisting of the acid catalyzed reaction product of a urethane prepolymer having terminal hydroxy groups produced from a diol of a molecular weight of 200 - 3,000, an organic diisocyanate, a polyhydric alcohol having 2-6 hydroxyl groups and a polyalkyl ether of a polymethylol melamine, are disclosed.
4

In U. S. Patent 3, 959, 201 issued on May 25, 1976 to Chang; Wen-Hsuan, high solids, aqueous solvent-thinnable compositions are prepared by combining relatively low molecular weight, hydroxyl-containing organic materials with aminoplast resins. In general, the hydroxyl-containing materials are characterized by a room temperature water thinnability of 3 or more parts of water per 100 parts of organic material. The compositions can be used in a wide variety of different applications, and find particular utility in the formulation of unique coating compositions.
In U. S. 3, 962, 521 issued on June 8, 1976 to Chang; Wen-Hsuan and Hartman; Marvis E., cured coatings having a high degree of extensibility and other desirable properties are obtained from compositions comprising a hydroxyl-containing, urethane reaction product containing a polyether component and an amine-aldehyde resin. Preferred compositions contain a polyether polyol of low glass transition temperature. These compositions are storage-stable in one package, and the cured coatings are adherent, durable and highly extensible. These coatings are particularly useful on resilient and rubbery substrates, such as foam rubber, polyurethane foam and vinyl foam, and on soft metal surfaces such as mild steel and aluminum.
In U. S. patent 3, 960, 983 issued on June 1, 1976 to Blank; Werner Josef, the composition of matter comprising blends of certain polyether polyols with a class of compatible aminoplast cross-linking agents and the use of such compositions with or without diluents is disclosed.

SUMMARY OF THE INVENTION
Hydroxyl / carboxyl functional polyurethane dispersion was prepared by using slightly modified form of 'prepolymer mixing' technique. Predetermined quantity of poly(ethylene) glycol was first reacted with m-TMXDI precursor to form polyurethane prepolymer. The prepolymer was then hydrophilically modified using DMPA to introduce ionic centers. The ionomer thus formed was further subjected to chain extension followed by introduction of the hydroxyl functionality and its subsequent dispersion in water. Dibutyl tin dilaurate (DBTDL) was employed as a catalyst and N-methyl-2-pyrrolidone (NMP) as a co-solvent and processing aid during the synthesis.
Tensile strength and elongation were measured using computerized tensile testing machine "Tensilon" (R&D Electronics, India) as per ASTM D 2370. Impact resistance was measured on Falling Block Impact Tester (Komal Scientific, India) as per ASTM D 2794 and hardness was measured by Shore A Hardness Tester as per ASTM D 2240-75
To evaluate tensile strength and % elongation at break, films were cast on thermoplastic olefin (TPO) substrate and were first air dried for 20 min. to remove some of the water (flash off) and subsequently cured at different cure schedules viz. 120 ° C - 25 min., 160 ° C - 20 min. and 180 ° C - 15 min. The films were of thickness ranging from 25-30 microns. All the other properties were checked on previously degreased and zinc phosphated mild steel panels coated by brushing and curing them at different time temperature schedules (as specified above) to get dry films of thickness 30 urn.
6

EXAMPLE -1

Parts (On Solids)
Prepolymer (PUD) 85
HMMM 15
Amine blocked p-TSA 0.6
# Cure Schedule 120 °C - 25 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 1200 psi
% Elongation at Break 3 8 %
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 67 / 3H
MEK Rub Test, 2X 60
EXAMPLE -2
Parts (On Solids)
Prepolymer (PUD) 80
HMMM 20
Amine blocked p-TSA 0.6
# Cure Schedule 120 °C - 25 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 2150 psi
% Elongation at Break 27 %
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 89 / 3H
MEK Rub Test, 2X 100
7

EXAMPLE -3
Parts (On Solids)
Prepolymer (PUD) 75
HMMM 25
Amine blocked p-TS A 0.6
# Cure Schedule 120 °C - 25 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 2630 psi
% Elongation at Break 18 %
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 92 / 4H
MEK Rub Test, 2X > 200
EXAMPLE -4
Parts (On Solids)
Prepolymer 70
HMMM 30
Amine blocked p-TS A 0.6
# Cure Schedule 120 °C - 25 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 3150 psi
% Elongation at Break 12 %
Impact resistance, D/R 140/80 in-lb
Hardness (Shore A) / pencil 95 / 5H
MEK Rub Test, 2X > 200
%

EXAMPLE -5
Parts (On Solids)
Prepolymer (PUD) 65
HMMM 35
Amine blocked p-TSA 0.6
# Cure Schedule 120 °C - 25 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM

Tensile Strength 3250 psi
% Elongation at Break 5%
Impact resistance, D/R 120/60in-lb
Hardness (Shore A) / pencil 97/5H
MEK Rub Test, 2X >200
EXAMPLE -6
Parts (On Solids)
Prepolymer (PUD) 85
HMMM 15
Amine blocked p-TSA 0.4
# Cure Schedule 160 °C - 20 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 1320 psi
% Elongation at Break 34 %
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 70 / 3H
MEK Rub Test, 2X 85
9

EXAMPLE -7
Parts (On Solids)
Prepolymer (PUD) 80
HMMM 20
Amine blocked p-TSA 0.4
# Cure Schedule 160 °C - 20 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM

Tensile Strength 2450 psi
% Elongation at Break 22%
Impact resistance, D/R 160/160in-lb
Hardness (Shore A) / pencil 89/3H
MEK Rub Test, 2X 135
EXAMPLE -8
Parts (On Solids)
Prepolymer (PUD) 75
HMMM 25
Amine blocked p-TSA 0.4
# Cure Schedule 160 °C - 20 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 2970 psi
% Elongation at Break 15 %
Impact resistance, D/R 160/140 in-lb
Hardness (Shore A) / pencil 97 / 4H
MEK Rub Test, 2X > 200
\0

EXAMPLE -9
Parts (On Solids)
Prepolymer (PUD) 70
HMMM 30
Amine blocked p-TSA 0.4
# Cure Schedule 160 °C - 20 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM

Tensile Strength 3450 psi
% Elongation at Break 8%
Impact resistance, D/R 140 / 80 in-lb
Hardness (Shore A) / pencil Full Scale / 5H
MEK Rub Test, 2X >200
AMPLE -10
Parts (On Solids)
polymer (PUD)HMMM 6535
Amine blocked p-TSA 0.4
# Cure Schedule 160 °C - 20 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 3450 psi
% Elongation at Break 3 %
Impact resistance, D/R 120/60 in-lb
Hardness (Shore A) / pencil Full Scale / 5H
MEK Rub Test, 2X > 200

EXAMPLE-11
Parts (On Solids)
Prepolymer (PUD) 85
HMMM 15
Amine blocked p-TSA 0.2
# Cure Schedule 180 °C - 15 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM

Tensile Strength 1625 psi
% Elongation at Break 25%
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 85/4H
MEK Rub Test, 2X 150
EXAMPLE -12
Parts (On Solids)
Prepolymer (PUD) 80
HMMM 20
Amine blocked p-TSA 0.2
# Cure Schedule 180 °C - 15 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 2875 psi
% Elongation at Break 18 %
Impact resistance, D/R 160/160 in-lb
Hardness (Shore A) / pencil 98 / 4H
MEK Rub Test, 2X > 200

EXAMPLE -13
Parts (On Solids)
Prepolymer (PUD) 75
HMMM 25
Amine blocked p-TSA 0.2
# Cure Schedule 180 °C - 15 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM

Tensile Strength 3450 psi
% Elongation at Break 12%
Impact resistance, D/R 140 / 80 in-lb
Hardness (Shore A) / pencil Full Scale / 5H
MEK Rub Test, 2X >200
EXAMPLE -14
Parts (On Solids)
Prepolymer (PUD) 70
HMMM 30
Amine blocked p-TSA 0.2
# Cure Schedule 180 °C - 15 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 4150 psi
% Elongation at Break 5 %
Impact resistance, D/R 120/60 in-lb
Hardness (Shore A) / pencil Full Scale / 6H
MEK Rub Test, 2X > 200

EXAMPLE -15
Parts (On Solids)
Prepolymer (PUD) 65
HMMM 35
Amine blocked p-TSA 0.2
# Cure Schedule 180 °C - 15 min.
SURFACE AND BULK MECHANICAL PROPERTIES OF THE FILM
Tensile Strength 4750 psi
% Elongation at Break 2 %
Impact resistance, D/R 80 / 20 in-lb
Hardness (Shore A) / pencil Full Scale / 6H
MEK Rub Test, 2X > 200

References Cited (Patent Documents)
1) DiDomenico, Jr.; Edward, US patent 4,451,622 (1984).
2) Chang; Wen-Hsuan, Porter, Jr.; Samuel, Wismer; Macro, US patent 4, 125, (1978).
3) Wang; Samuel S., US patent 4, 017, 556 (1977).
4) Chang; Wen-Hsuan, US patent 3,959,201 (1976).
5) Chang; Wen-Hsuan, Hartman; Marvis E., US patent 3,962, 521 (1976).
6) Blank; Werner Josef, US patent 3, 960, 983 (1976).
Other References
1) D. Dieterich, Prog. Org. Coatings, 9, (1981), 281- 340.

Claims
1. A hydroxyl carboxyl functional prepolymer is derived from a macrodiol, a monomeric diol with carboxylic acid functionality on tertiary carbon atom and diisocyanate of the formula






2. In the composition of Claim 1. wherein the said macrodiol is 2000 MW poly(ethylene) glycol (PEG)
3. In the composition of Claim 1. wherein the said monomeric diol is dimethylol propionic acid of the formula

4. In the composition of Claim 1. wherein the said diisocyanate is m-tetramethyl xylene diisocyanate of the formula
16


5. The coating material consists of prepolymer of Claim 1 in the amount ranging from 65 % to 85 % by weight on solids and hexakis(methoxymethyl)melamine resin in the amount ranging from 15 % to 35 % by weight on solids.
6. The curing reactions for the composition of Claim 5 are catalyzed by amine blocked p-toluene sulphonic acid in the concentration range of 0.2 -0.6 % on resin solids.
. The composition of Claim 5 are cured at elevated temperatures from 120-180 °C to yield coatings with high solid, low volatile organic compound and excellent surface and bulk mechanical properties which are highly desired for surface coatings.


Abstract
The present invention describes synthesis of Hydroxyl / carboxyl functional polyurethane dispersion (PUD), with low volatile organic content (VOC), based on poly(ethylene) glycol (PEG), dimethylol propionic acid (DMPA), and m-tetramethyl xylene diisocyanate (m-TMXDI) . The coating materials are formulated with varying concentration of hexakis(methoxymethyl)melamine resin (HMMM) and cured at elevated temperatures (120-180 °C) to obtain three dimensionally crosslinked thermosetting networks. The reactions are catalyzed with different concentrations of amine-blocked p-toluene sulphonic acid (p-TSA). These coatings are particularly useful for application on mild steel, aluminum and plastic materials.


Documents:

826-mum-2006-abstract.doc

826-mum-2006-abstract.pdf

826-MUM-2006-AMENDED(OTHER DOCUMENT)-(18-3-2009).pdf

826-mum-2006-cancelled pages(25-1-2009).pdf

826-MUM-2006-CLAIMS(18-3-2009).pdf

826-MUM-2006-CLAIMS(AMENDED)-(25-1-2010).pdf

826-mum-2006-claims(granted)-(12-4-2010).pdf

826-mum-2006-claims.doc

826-mum-2006-claims.pdf

826-MUM-2006-CORRESPONDENCE(18-3-2009).pdf

826-mum-2006-correspondence(25-1-2010).pdf

826-mum-2006-correspondence(ipo)-(12-4-2010).pdf

826-MUM-2006-CORRESPONDENCE(IPO)-(19-3-2009).pdf

826-mum-2006-correspondence-others.pdf

826-mum-2006-correspondence-received.pdf

826-mum-2006-description (complete).pdf

826-MUM-2006-DESCRIPTION(COMPLETE)-(18-3-2009).pdf

826-mum-2006-description(granted)-(12-4-2010).pdf

826-MUM-2006-FORM 1(30-5-2006).pdf

826-mum-2006-form 13(18-3-2009).pdf

826-mum-2006-form 18(1-12-2006).pdf

826-mum-2006-form 2(18-3-2009).pdf

826-mum-2006-form 2(granted)-(12-4-2010).pdf

826-MUM-2006-FORM 2(TITLE PAGE)-(18-3-2009).pdf

826-MUM-2006-FORM 2(TITLE PAGE)-(25-1-2010).pdf

826-mum-2006-form 2(title page)-(granted)-(12-4-2010).pdf

826-mum-2006-form-1.pdf

826-mum-2006-form-2.doc

826-mum-2006-form-2.pdf

826-mum-2006-form-3.pdf

826-mum-2006-form-9.pdf

826-MUM-2006-REPLY TO HEARING(25-1-2010).pdf

826-mum-2006-specification(amanded)-(18-3-2009).pdf

826-MUM-2006-SPECIFICATION(AMENDED)-(25-1-2010).pdf


Patent Number 239924
Indian Patent Application Number 826/MUM/2006
PG Journal Number 16/2010
Publication Date 16-Apr-2010
Grant Date 12-Apr-2010
Date of Filing 30-May-2006
Name of Patentee VILAS DATTATRAY ATHAWALE
Applicant Address C-702 ASTER, VALLEY OF FLOWERS, THAKUR VILLAGE, KANDIVALI(EAST), MUMBAI-400101
Inventors:
# Inventor's Name Inventor's Address
1 VILAS DATTATRAY ATHAWALE C-702 ASTER, VALLEY OF FLOWERS, THAKUR VILLAGE, KANDIVALI(EAST), MUMBAI-400101
2 SUNIL NAMDEV PESHANE 301 SAI DARSHAN, BLDNG NO.3, ADARSH VIDYA MANDIR ROAD, BADLAPUR(WEST), 421503,
PCT International Classification Number C08G 71/04
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA