Composition and method for treating substrates to reduce electrostatic charge and resultant article

• US 5,534,192 A
• Filed: 02/22/1995
• Issued: 07/09/1996
• Est. Priority Date: 11/18/1993
• Status: Expired due to Fees

• Current Assignee: Cognis Corporation (BASF SE)
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Fischer, Stephen A., Incorvia, Michael J.
• Primary Examiner(s): GREEN, ANTHONY J
• Application Number:
  US08/392,712
• Time in Patent Office: 503 Days
• Field of Search: 252/8.6, 252/8.7, 252/8.8, 252/8.75, 252/500, 57/901, 524/910, 524/911, 428/289, 428/290, 428/412, 428/474.4, 428/475.5, 428/480, 428/423.1, 428/413, 427/394, 427/393.5, 427/430.1, 427/434.2, 562/605, 564/291
• US Class Current: 252/500
• CPC Class Codes: C07C 217/50 Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
• CPC Class Codes: C07C 53/18 containing fluorine
• CPC Class Codes: C07C 53/21 containing fluorine
• CPC Class Codes: C08J 2471/00 Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08J2459/00; of epoxy resins C08J2463/00; of polythioether-ethers C08J2481/02; of polyethersulfones C08J2481/06; Derivatives of such polymers
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/044 Forming conductive coatings; Forming coatings having anti-static properties
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2201/04 Antistatic
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C09K 3/16 Anti-static materials
• CPC Class Codes: D06M 13/17 Polyoxyalkyleneglycol ethers
• CPC Class Codes: D06M 13/236 containing halogen atoms
• CPC Class Codes: D06M 13/33 containing halogen atoms
• CPC Class Codes: D06M 13/463 derived from monoamines
• CPC Class Codes: D06M 2200/00 Functionality of the treatment composition and/or properties imparted to the textile material
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H05F 1/00 Preventing the formation of electrostatic charges
• CPC Class Codes: H05F 1/02 by surface treatment
• CPC Class Codes: Y10S 57/901 Antistatic
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31725 : Of polyamide
• CPC Class Codes: Y10T 428/31739 : Nylon type
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 442/2434 : Linear polyether group chain containing

Abstract

Antistatic agents and their use in processing textiles or formed plastic substrates. The antistatic agent comprises a compound having a fluorocarbon moiety and an ethoxylated quaternary ammonium moiety. The antistatic composition increases the electrolytic conductivity of textile or plastic materials treated therewith, thereby increasing the rate of electrostatic charge dissipation thereof. The coatings remain effective after exposure of the treated substrate to an aqueous environment.

Claims

1. An antistatic agent of the formula (Q--L--R)_d --X, wherein Q represents a straight or branched, saturated or unsaturated perfluoroaliphatic radical, L represents a linkage selected from the group consisting of ester, ether, amide or alkylene amine linkages, R represents a straight or branched alkylene-oxyalkylene or a straight or branched alkylene-poly(oxyalkylene) group, and d is 1 or 2, and, when d is 1, X represents at least one quaternary ammonium group of the formula ##STR12## and, optionally, a tertiary amine-forming group of the formula ##STR13## and, when d is 2, X represents a quaternary amine-forming group of the formula ##STR14## and, optionally, a tertiary amine-forming group of the formula

View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21)

2. An antistatic agent as claimed in claim 1 comprising an ester having as its reactive components at least one saturated perfluoroaliphatic carboxylic acid and at least one quaternary ammonium compound of the formula ##STR17## wherein R_a is as previously defined, g and k may be the same or different and are each integers from 1 to 50, j is an integer from 1 to 4, R₆ represents a straight or branched, saturated or unsaturated C₆ -C₂₂ aliphatic group, R_b and R_c independently represent H, straight or branched alkylene primary amine or straight or branched alkylene secondary amine, and A is an organic or inorganic anion, and, optionally, a tertiary amine of the formula ##STR18## wherein R_a, R_b and R_c are as defined above, m and n may be the same or different and are each integers from 1 to 50 which may be the same or different, R₇ represents a straight or branched, saturated or unsaturated, C₆ -C₂₂ aliphatic group;

said antistatic agent further containing at least one of (i) said saturated perfluoroaliphatic carboxylic acid in unreacted form, (ii) said quaternary ammonium compound in unreacted form and, optionally, (iii) said tertiary amine in unreacted form.

3. An antistatic agent as claimed in claim 2 comprising an ester having as its reactive components at least one acid of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

at least one quaternary ammonium compound of the formula ##STR19## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR20## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of halide and lower alkyl sulfate; and

at least one tertiary amine of the formula ##STR21## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are nominally 8, R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and

said antistatic agent further containing at least one of (i) said acid in unreacted form, (ii) said quaternary ammonium compound in unreacted form, and (iii) said tertiary amine in unreacted form.

4. An antistatic agent as claimed in claim 1 wherein said amide linkage has been formed by reacting a polyalkoxylated quaternary ammonium compound with ethyleneimine or a N-alkylated derivative of ethyleneimine, and then reacting the resulting product with a fluorocarboxylic acid of the formula C_q F_2q+1 --COOH wherein q represents an integer from 1 to 17.

5. An antistatic agent as claimed in claim 1 wherein said amide linkage has been formed by reacting a fluoroalcohol with ethyleneimine or a N-alkylated derivative of ethyleneimine, and then reacting the resulting product with an alkoxylated quaternary ammonium compound having one or more substituent carboxyl groups.

6. An antistatic agent as claimed in claim 1 wherein said alkylene amine linkage has been formed by reacting a halogenated derivative of a polyalkoxylated quaternary ammonium compound with a primary amine, and then reacting the resulting product with a fluoroalkylated olefin of the formula H₂ C=CH-C_q F_2q+1 wherein q represents an integer from 1 to 17.

7. A method for dissipating an electrostatic charge on a static-prone substrate selected from the group consisting of a textile substrate, a formed, thermoplastic substrate and a formed thermoset substrate, comprising the step of applying to said substrate an antistatic agent as claimed in claim 1 in an amount effective to impart to said substrate a surface resistivity value in the range of from about 10⁶ to about 10¹² ohms, a 90% electrostatic charge decay time of 10 seconds or less, or both.

8. A method as claimed in claim 7 wherein said antistatic agent is applied to a textile substrate.

9. A method as claimed in claim 8 wherein said textile substrate is selected from the group consisting of nylon, rayon, acetate, cotton, wool, linen, and mixtures thereof.

10. A method as claimed in claim 7 wherein said substrate is selected from the group consisting of polycarbonate, polyamide, polyphenylene oxide, polyester, polyolefin, and mixtures thereof.

11. A method as claimed in claim 7, wherein said antistatic agent comprises an ester having as its reactive components at least one acid of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

and at least one quaternary ammonium compound of the formula ##STR22## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR23## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of halide and lower alkyl; and

at least one tertiary amine of the formula ##STR24## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are each integers from 2-16, R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and

said antistatic agent further containing at least one of (i) said acid in unreacted form, (ii) said quaternary ammonium compound in unreacted form, and (iii) said tertiary amine in unreacted form.

12. A method as claimed in claim 7 wherein said antistatic agent is applied to a surface of said substrate.

13. A method as claimed in claim 8 wherein said antistatic agent is applied to said substrate by passing said textile substrate through a bath comprising said antistatic agent.

14. A method as claimed in claim 7 wherein said antistatic agent is applied to a formed, thermoplastic substrate.

15. A method as claimed in claim 14 wherein an antistatic agent comprising an ester having as its reactive components at least one acid of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

and at least one quaternary ammonium compound of the formula ##STR25## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR26## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of chloride and lower alkyl sulfate; and

at least one tertiary amine of the formula ##STR27## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are each integers from 2-16, R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and

said antistatic agent further containing at least one of (i) said acid in unreacted form, (ii) said quaternary ammonium compound in unreacted form, and said tertiary amine in unreacted form is applied to said thermoplastic substrate.

16. A method as claimed in claim 15, wherein said antistatic agent is applied to a surface of said substrate.

17. A method as claimed in claim 7, wherein said antistatic agent is applied to a formed thermoset substrate.

18. A method as claimed in claim 17, wherein an antistatic agent comprising an ester having as its reactive components at least one acid of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

and at least one quaternary ammonium compound of the formula ##STR28## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR29## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of chloride and lower alkyl sulfate; and

at least one tertiary amine of the formula ##STR30## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are each integers from 2-16, R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and

said antistatic agent further containing at least one of (i) said acid in unreacted form (ii) said quaternary ammonium compound in unreacted form and (iii) said tertiary amine in unreacted form is applied to said thermoset substrate.

19. A method as claimed in claim 17, wherein said antistatic agent is applied to a surface of said substrate.

20. An article of manufacture comprising a substrate selected from the group consisting of a textile substrate, a formed, thermoplastic substrate and a formed, thermoset substrate having applied thereto the antistatic agent of claim 1.

21. An article of manufacture as claimed in claim 20, wherein an antistatic agent comprising an ester having as its reactive components at least one acid of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

at least one quaternary ammonium compound of the formula ##STR31## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR32## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of halide and lower alkyl sulfate; and

a tertiary amine of the formula ##STR33## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are each integers from 2-16, R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and

said antistatic agent further containing at least one of (i) said acid in unreacted form, (ii) said quaternary ammonium compound in unreacted form, and (iii) said tertiary amine in unreacted form is applied to said substrate.

22. A composition comprising the product of the reaction between at least one straight or branched, saturated or unsaturated perfluoroaliphatic carboxylic acid and at least one quaternary ammonium compound of the formula ##STR34## wherein R_a represents H or CH₃, g and k may be the same or different and are each integers from 1 to 50, j is an integer from 1 to 4, R₆ represents a straight or branched, saturated or unsaturated C₆ -C₂₂ aliphatic group, R_b and R_c represent H, straight or branched alkylene primary amine or straight or branched alkylene secondary amine, and A is an organic or inorganic anion, and, optionally, a tertiary amine of the formula ##STR35## wherein R_a, R_b and R_c are as defined above, m and n may be the same or different and are each integers from 1 to 50 which may be the same or different, and R₇ represents a straight or branched, saturated or unsaturated, C₆ -C₂₂ aliphatic group;

and said antistatic agent further containing any of said acid, said quaternary ammonium compound, or said tertiary amine in unreacted form.

23. A composition as claimed in claim 22 which further includes a vehicle for application of said reaction product into a static-prone substrate.

24. A composition as claimed in claim 22 wherein said acid is of the formula (C_q F_2q+1)--COOH, wherein q represents an integer from 1-17;

said quaternary ammonium compound is of the formula ##STR36## wherein R_a is as previously defined, s and w may be the same or different and are each integers from 2-16, t is 1 or 2, R₈ represents a straight or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group, R_d and R_e independently represent H or ##STR37## wherein R_f is H or a C₁ -C₄ alkyl group, A represents an anion selected from the group consisting of halide and lower alkyl sulfate; and

said tertiary amine is of the formula ##STR38## wherein R_a, R_d and R_e are as defined above, y and z may be the same or different and are each integers from 2-16, and R₉ represents a straight or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group.