IP Library Granted Patent US 6,984,675
Granted Patent B2
US 6,984,675 · App. 10/101,038 · Granted Jan 10, 2006

Formaldehyde-free binder compositions for simultaneous warp sizing and coloration of filament yarns

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Quick Facts
Patent No.
US 6,984,675
App. No.
10/101,038
Granted
Jan 10, 2006
Kind
B2
Abstract

An aqueous dispersion has an addition polymer (B) formed in situ on a sulfopolyester (A). The sulfopolyester (A) is formed as a polycondensation product of first and second reaction mixtures. The first reaction mixture includes at least about 70 mol. % of terephthalic acid or an ester thereof, and about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus, wherein the functional groups are selected from the group consisting of hydroxyls, carboxyls and alkyl esters. The second reaction mixture includes at least two different glycols, at least about 20 mol. % of the second reaction mixture being ethylene glycol. The addition polymer (B) is formed in situ on the sulfopolyester (B) by polymerizing styrene monomer.

Claims (61)

1. An aqueous dispersion, comprising:

(A) a sulfopolyester formed as a polycondensation product of:

(1) a first reaction mixture comprising:

(a) at least about 70 mol. % of terephthalic acid or an ester thereof, and

(b) about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus, and functional groups selected from the group consisting of hydroxyls, carboxyls and alkyl esters; and

(2) a second reaction mixture comprising ethylene glycol, diethylene glycol and triethylene glycol, at least about 20 mol. % of the second reaction mixture being ethylene glycol; and

(B) an addition polymer formed in situ on the sulfopolyester from polymerizing styrene monomer.

2. An aqueous dispersion according to claim 1 , wherein the aqueous dispersion contains substantially no hydroxyethyl acrylate.

3. An aqueous dispersion according to claim 1 , wherein the aqueous dispersion contains substantially no formaldehyde.

4. An aqueous dispersion according to claim 1 , wherein the aqueous dispersion has a total polymer content (A+B) of about 50 weight % or less.

5. An aqueous dispersion according to claim 1 , wherein the aqueous dispersion has a total polymer content (A+B) of about 60 weight % or less.

6. An aqueous dispersion according to claim 1 , wherein based on the total polymer content (A+B), the aqueous dispersion contains from about 40 weight % to about 95 weight % of the sulfopolyester (A) and from about 60 weight % to about 5 weight % of the addition polymer (B).

7. An aqueous dispersion according to claim 1 , wherein based on the total polymer content (A+B), the aqueous dispersion contains from about 60 weight % to about 80 weight % of the sulfopolyester (A) and from about 40 weight % to about 20 weight % of the addition polymer (B).

8. An aqueous dispersion according to claim 1 , wherein the first reaction mixture (A)(1) further comprises from about 0.1 mol. % to about 5 mol. % of a saturated aliphatic or a saturated alicyclic dicarboxylic acid, or ester thereof.

9. An aqueous dispersion according to claim 1 , wherein the first reaction mixture (A)(1) contains from about 85 to about 90 mol. % terephthalic acid (A)(1)(a) and from about 10 to about 15 mol. % of the difunctional ester forming sulfomonomer (A)(1)(b).

10. An aqueous dispersion according to claim 1 , wherein the second reaction mixture (A)(2) contains at least about 25 mol. % ethylene glycol.

11. An aqueous dispersion according to claim 1 , wherein the second reaction mixture (A)(2) contains from about 40 mol. % to about 60 mol. % ethylene glycol.

12. An aqueous dispersion according to claim 1 , wherein the sulfopolyester (A) has an inherent viscosity of at least about 0.20 dL/g measured at 250° C. in 60/40 parts by weight of a phenol/tetrachloroethane solvent at a concentration of 0.25 g/dL.

13. An aqueous dispersion, comprising:

(A) a sulfopolyester formed as a polycondensation product of:

(1) a first reaction mixture comprising:

(a) at least about 70 mol. % of terephthalic acid or an ester thereof, and

(b) about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus and functional groups selected from the group consisting of hydroxyls, carboxyls and alkyl esters: and

(2) a second reaction mixture comprising ethylene glycol, diethylene glycol and triethylene glycol, at least about 20 mol. % of the second reaction mixture being ethylene glycol; and

(B) an addition polymer formed in situ on the sulfopolyester from polymerizing a plurality of monomers comprising at least about 50 weight % styrene monomer.

14. An aqueous dispersion according to claim 13 , wherein the plurality of monomers comprises at least one carboxylic acid or ester thereof, the carboxylic acid being selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.

15. An aqueous dispersion according to claim 13 , wherein the addition polymer (B) is formed from polymerizing styrene monomer and from about 0.1 weight % to about 15 weight % of a carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and mixtures thereof.

16. An aqueous dispersion according to claim 13 , wherein the addition polymer (B) is formed from polymerizing styrene monomer and from about 0.1 weight % to about 50 weight % of an ester of a carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and mixtures thereof.

17. The aqueous dispersion of claim 1 wherein the difunctional ester forming sulfomonomer (A)(1)(b) is 5-sodiosulfoisophthalic acid or an ester thereof.

18. The aqueous dispersion of claim 1 wherein the second reaction mixture (A)(2) comprises contains from about 0.1 mol. % to about 5 mol. % of a poly(ethylene glycol).

19. The aqueous dispersion of claim 1 wherein

the difunctional ester forming sulfomonomer (A)(1)(b) is 5-sodiosulfoisophthalic acid or an ester thereof,

the mol. ratio of terephthalic acid (A)(1)(a) to 5-sodiosulfoisophthalic acid (A)(1)(b) is approximately 85/15,

the addition polymer (B) is derived solely from styrene monomer, and

the weight ratio of sulfopolyester (A) to addition polymer (B) is approximately 70/30.

20. The aqueous dispersion of claim 13 wherein

the difunctional ester forming sulfomonomer (A)(1)(b) is 5-sodiosulfoisophthalic acid or an ester thereof, the mol. ratio of terephthalic acid (A)(1)(a) to 5-sodiosulfoisophthalic acid (A)(1)(b) is approximately 87/13,

the addition polymer (B) is formed from polymerizing styrene monomer and itaconic acid,

the weight ratio of styrene monomer to itaconic acid is approximately 99.5/0.5, and

the weight ratio of sulfopolyester (A) to addition polymer (B) is approximately 68/32.

21. A process of preparing an aqueous dispersion, comprising: forming a sulfopolyester by conducting polycondensation of:

(1) a first reaction mixture comprising:

(a) at least about 70 mol. % of terephthalic acid or an ester thereof, and

(b) about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus and functional groups selected from the group consisting of hydroxyls, carboxyls and alkyl esters; and

(2) a second reaction mixture comprising at least two different glycols, at least about 20 mol. % of the second reaction mixture being ethylene glycol; and

conducting in situ polymerization of styrene monomer in the presence of the sulfopolyester.

22. A process of preparing an aqueous dispersion according to claim 21 , further comprising adding a free radical initiator before conducting in situ polymerization of styrene monomer.

23. An aqueous dispersion, comprising:

(A) a sulfopolyester formed as a polycondensation product of:

(1) a first reaction mixture comprising:

(a) at least about 70 mol. % of terephthalic acid or an ester thereof, and

(b) about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus and functional groups selected from the group consisting of hydroxyls, carboxyls and alkyl esters; and

(2) a second reaction mixture comprising at least two different glycols, at least about 20 mol. % of the second reaction mixture being ethylene glycol and from about 0.1 mol. % to about 5 mol. % being a poly(tetramethylene glycol); and

(B) an addition polymer formed in situ on the sulfopolyester from polymerizing styrene monomer.

24. An aqueous dispersion, comprising:

(A) a sulfopolyester formed as a polycondensation product of:

(1) a first reaction mixture comprising:

(a) at least about 70 mol. % of terephthalic acid or an ester thereof, and

(b) about 4–20 mol. % of a difunctional ester forming sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus and functional groups selected from the group consisting of hydroxyls, carboxyls and alkyl esters; and

(2) a second reaction mixture comprising at least two different glycols, at least about 20 mol. % of the second reaction mixture being ethylene glycol and from about 0.1 mol. % to about 5 mol. % being a poly(tetramethylene glycol); and

(B) an addition polymer formed in situ on the sulfopolyester from polymerizing a plurality of monomers comprising at least about 50 weight % styrene monomer.

Assignments (25)
RELEASE OF SECURITY INTEREST IN PATENTS PREVIOUSLY RECORDED AT REEL/FRAME (030146/0970) Recorded Jul 9, 2019
From: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT
To: HEXION INC. (FORMERLY KNOWN AS MOMENTIVE SPECIALTY CHEMICALS INC.)
Reel/Frame 049706/0264 →
RELEASE OF SECURITY INTEREST Recorded Feb 23, 2017
From: WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT
To: HEXION INC. (FORMERLY KNOWN AS HEXION SPECIALTY CHEMICALS INC.); BORDEN CHEMICAL FOUNDRY, LLC; HEXION INVESTMENTS INC. (FORMERLY KNOWN AS BORDEN CHEMICAL INVESTMENTS, INC.); HEXION U.S. FINANCE CORP.; HSC CAPITAL CORPORATION; LAWTER INTERNATIONAL INC.; HEXION INTERNATIONAL INC. (FORMERLY KNOWN AS BORDEN CHEMICAL INTERNATIONAL INC.); OILFIELD TECHNOLOGY GROUP, INC.; HEXION CI HOLDING COMPANY (CHINA) LLC
Reel/Frame 041793/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 24, 2017
From: HEXION INC.
To: SYNTHOMER USA LLC.
Reel/Frame 041057/0634 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: WILMINGTON TRUST, NATIONAL ASSOCIATION
To: HEXION INC.
Reel/Frame 039259/0696 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: JPMORGAN CHASE BANK, N.A.
To: HEXION INC.
Reel/Frame 039260/0011 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: JPMORGAN CHASE BANK, N.A.
To: HEXION INC.
Reel/Frame 039260/0069 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: JPMORGAN CHASE BANK, N.A.
To: HEXION INC.
Reel/Frame 039260/0158 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: JPMORGAN CHASE BANK, N.A.
To: HEXION INC.
Reel/Frame 039259/0940 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: WILMINGTON TRUST, NATIONAL ASSOCIATION
To: HEXION INC.
Reel/Frame 039258/0913 →
RELEASE OF SECURITY INTEREST Recorded Jul 26, 2016
From: WILMINGTON TRUST COMPANY
To: HEXION INC.
Reel/Frame 039259/0628 →
RELEASE OF SECURITY INTEREST Recorded Jul 15, 2016
From: WILMINGTON TRUST COMPANY
To: HEXION INC.
Reel/Frame 039360/0724 →
CHANGE OF NAME Recorded Jan 29, 2015
From: MOMENTIVE SPECIALTY CHEMICALS INC.
To: HEXION INC.
Reel/Frame 034859/0314 →
PATENT SECURITY AGREEMENT Recorded Apr 3, 2013
From: MOMENTIVE SPECIALTY CHEMICALS INC.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 030146/0946 →
PATENT SECURITY AGREEMENT Recorded Apr 3, 2013
From: MOMENTIVE SPECIALTY CHEMICALS INC.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 030146/0970 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS Recorded Mar 28, 2013
From: JPMORGAN CHASE BANK, N.A.
To: MOMENTIVE SPECIALTY CHEMICALS INC. (F/K/A HEXION SPECIALTY CHEMICALS, INC.)
Reel/Frame 030111/0021 →
MERGER Recorded Mar 5, 2012
From: RESOLUTION SPECIALTY MATERIALS LLC
To: HEXION SPECIALTY CHEMICALS, INC.
Reel/Frame 027805/0616 →
CHANGE OF NAME Recorded Mar 5, 2012
From: HEXION SPECIALTY CHEMICALS, INC.
To: MOMENTIVE SPECIALTY CHEMICALS INC.
Reel/Frame 027805/0865 →
SECURITY AGREEMENT Recorded Feb 5, 2010
From: HEXION LLC; HEXION SPECIALTY CHEMICALS, INC.; BORDEN CHEMICAL FOUNDRY, LLC; BORDEN CHEMICAL INVESTMENTS, INC.; HEXION U.S. FINANCE CORP.; HSC CAPITAL CORPORATION; LAWTER INTERNATIONAL INC.; BORDEN CHEMICAL INTERNATIONAL, INC.; OILFIELD TECHNOLOGY GROUP, INC.; HEXION CI HOLDING COMPANY (CHINA) LLC
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 023905/0451 →
SECURITY INTEREST Recorded Jan 29, 2010
From: HEXION SPECIALTY CHEMICALS, INC.; BORDEN CHEMICAL FOUNDRY, LLC; BORDEN CHEMICAL INVESTMENTS, INC.; HEXION U.S. FINANCE CORP.; HSC CAPITAL CORPORATION; LAWTER INTERNATIONAL INC.; BORDEN CHEMICAL INTERNATIONAL, INC.; OILFIELD TECHNOLOGY GROUP, INC.; HEXION CI HOLDING COMPANY (CHINA) LLC
To: WILMINGTON TRUST FSB, AS COLLATERAL AGENT
Reel/Frame 023963/0038 →
SECURITY AGREEMENT Recorded Nov 21, 2006
From: HEXION SPECIALTY CHEMICALS, INC.
To: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT
Reel/Frame 018535/0556 →
SECURITY AGREEMENT Recorded Nov 21, 2006
From: HEXION SPECIALTY CHEMICALS, INC.
To: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT
Reel/Frame 018535/0701 →
SECURITY AGREEMENT Recorded Jul 14, 2006
From: HEXION SPECIALTY CHEMICALS, INC.
To: JPMORGAN CHASE BANK, N.A. AS COLLATERAL AGENT
Reel/Frame 017946/0151 →
SECURITY AGREEMENT Recorded Aug 31, 2005
From: RESOLUTION PERFORMANCE PRODUCTS LLC; RESOLUTION SPECIALTY MATERIALS LLC; BORDEN CHEMICAL, INC.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 016480/0648 →
SECURITY AGREEMENT Recorded Aug 31, 2005
From: RESOLUTION PERFORMANCE PRODUCTS LLC; RESOLUTION SPECIALTY MATERIALS LLC; BORDEN CHEMICAL, INC.
To: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT
Reel/Frame 016522/0428 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 30, 2004
From: EASTMAN CHEMICAL COMPANY
To: RESOLUTION SPECIALTY MATERIALS LLC
Reel/Frame 015201/0335 →