Fluorocarbon modification of fibers

Claim 2

Claim 2 continued -OH, halogen, or hydrogen and wherein x1 and x2, R1 and R2 are as defined in paragraph (2G), with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1; (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from the group consisting of hydrogen and Z, in which Z is alkyl of 1 to 4 carbon atoms; Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms; and R1, R2, R3 and R4 are the same or different and are as defined for the R groups of paragraph (2A); (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wherein x1, R1, R2, Z1, Z2 and Q" are as defined in paragraphs (2G) and (2I), and x3 is 0 or 1.

Claim 3

The fibrous articles of claim 2 wherein the fiber additives are incorporated therein in an amount of up to about 2.5 percent by weight of the fibrous article.

Claim 4

The fibrous articles of claim 2 wherein the article comprises filarnents prepared from a fiber-forming theromoplastic resin.

Claim 5

The fibrous articles of claim 4 wherein the fiber-forming thermoplastic resin is selected from the group consisting of polypropylene, polyethylene, polybutylene, polyester, polyamide, polyacrylonitrile and blends thereof. 6. A process for producing a water and/or oil repellent fibrous article which comprises contacting the fibrous article with a liquid medium containing a fiber additive selected from the group consisting of compounds having the formula: (A) wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1(CHOH)f2(CH2)f3OH, wherein f1 and f3 are the same or differer and are lntegers of from 1 to 4 and wherein f2 is either zero or 1, Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals inde-pendéntly selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O-, -C6H4(CH2)p1-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, wherein P1 and P2 are integers and are independently selected from the group consisting of 1 to 4; and R1, R1' and R2 are independently selected from the group cons;sting of -(CmF2m+1), -(CmF2m-1) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms; (B) wherein n, Q, D1 and R1 are as defined in paragraph (6A); Z is alkylene of 1 to 4 carbon atoms, and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of: (i) >O, aim 6 continued (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2, (vi) (vii) >CHOH, (viii) -CH2(OCH2CH2)rCH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is or ; and Y is when t is 4, provided that Z is not -CH2- when Y is oxygen; wherein q is 1 or 2, Z' is alkylene of 2 to 4 carbon atoms, and n, Q, D1 and R1 are as defined in paragraph (6A); (D) wherein A1 and A2 are independently selected from the group consisting of -R1, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, D1 and R1 are as defined in paragraph (6A), and T is a member selected from the group consisting of: (i) , (ii) , laim 6 continued (iii) , and (iv) wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4; (E) wherein B is a member selected from the group consisting of: (i) -CO2D1R1 (ii) , and (iii) -CON(Z")2 where D3 and D4 are divalent radicals independently selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)P1 CH(OH)(CH2)p2 O-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, R3 and R4 are independently selected from the group consisting of -(CmF2m+1)-, -(CmF2m-1)- and -(CF2)mOX, Z" is alkyl of 1 to 4 carbon atoms, wherein P1m P2, m, D1, D2, R1, R1 ', R2 and X are as defined in paragraph (6A), with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must contain at least 3 methylene groups; (F) wherein R1 and D1 are as defined in paragraph (6A), and Y' is selected from the group consisting of oxygen and alkylene of 1 to 6 carbon atoms; (G) laim 6 continued wherein two E groups are E1, and two E groups are E2, in which E1 is -CON(D1R1)2 or -CO2DlR1 and E2 is -CO2(CH2)x1 (CHOH)x2 CH2Q" wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to 4, Q" is -OH or halogen and D1 and R1 are as defined in paragraph (6A); (H) ? and wherein R2' is selected from the group consisting of -(CH2)x1 , hydrogen, -(CH2)x1 (CHOH)x2 CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q" are as defined in paragraph (6G); (I) wherein Z1, Z2 and Z3 are the same or different and are alkylene of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, and -O(CH2)x1(CHOH)x2 CH2Q"', wherein Z is alkyl of 1 to 4 carbon atoms; Q"' is -OH, halogen, or hydrogen and wherein x1, x2, R1,R2 are as defined in paragraph (6G), with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1; (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from

Claim 6

Claim 6 continued the group consisting of hydrogen and Z, in which Z is alkyl of 1 to 4 carbon atoms; Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms; and R1, R2, R3 and R4 are the same or different and are as defined for the R groups of paragraph (6A); and (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wherein x1, R1, R2, Z1, Z2 and Q" are as defined in paragraphs (6G) and (6I), and X3 is 0 or 1.

Claim 7

The process of clalm 6 wherein the heated fibrous article is annealed at a temperature of from 90° to 230°C.

Claim 8

The process of claim 6 wherein said liquid medium contains said fiber additive in an amount sufficient to provide a fibrous article having said fiber additive incorporated therein in a amount of up to about 2.5 percent by weight of said fibrous article.

Claim 9

The process of claim 8 wherein said liquid medium contains said fiber additive in an amount of from about 0.1 to 50 percent by weight. 10. The process according to claim 6 wherein said fiber additive comprises an additive selected from the group consisting of compounds having the formula: (a) wherein L is -(CH2)f1(CHOH)f2CH2f3OH, wherein f1, f2, f3, n, Q, D1 and R1 are as defined in claim (6A); laim 10 continued (b) wherein t is 2 or 3, and Y (1) is selected from the group consisting of >C(CH2OH)2 and >CHOH when t is 2 and (2) is >COH when t is 3, wherein n, Q, D1, R1 and Z are as defined in claim (6B); (c) mixtures of wherein two E groups are E1 and two E groups are E2 in which E2 is -CO2(CH2)x1(CHOH)x2CH2Q", and wherein E1, x1, x2 and Q" are as defined in claim (6G), under the proviso that where x2 is 0, Q" is -OH; (d) mixtures of and wherein R'2 is selected from the group consisting of -(CH2)x1(CHOH)x2CH2Q" and -CH2(CHOH)CH2OCH2(CHOH)CH2OH, wherein x1, x2, Q", D1 and R1 are as defined in claim (6G), with the proviso that Q" is -OH when x2 is 0; (e) wherein M1 is -O(CH2)x1(CHOH)x2CH2Q"', wherein x1, x2, Q"', Z1, Z2 Z3, R1 and R2 are as defined in claim (6I), with the proviso that Q"' is -OH when x2 is 0; and

Claim 10

Claim 10 continued (f) wherein M1 is -(CH2)x1(CHOH)x2(CH2)Q" wherein x1, x2, R1, Y", R2, Z1, Z2 and Q" are as defined previously, with the proviso that Q" us -OH when x2 is 0; and wherein said liquid medium contains (1) a functional reactant selected from the group consisting of epoxide compounds having at least two functional epoxide groups, isocyanate oompounds having at least two functional isocyanate groups, and mix-tures thereof, and (2) an amine selected from the group consisting of tertiary amines, amino acids and mixtures thereof. 11. A process of producing a water and/or oil repellent fiber which comprises extruding said fiber from a fiber-forming thermoplastic resin containing an additive selected from the group consisting of compounds having the formula: (A) wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1(CHOH)f2(CH2)f3OH, wherein f1 and f3 are the same or different and are integers of from 1 to 4 and wherein f2 is either zero or 1, Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals independently selected from the group consisting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O--C6H4(CH2)P1-, -C6H4O(CH2)P1-, -C6H4-, and -C6H4O-, wherein P1 and P2 are integers and are independently selected from the group Claim 11 continued consisting of 1 to 4: and R1, R1' and R1 are independently selected from the group consisting of -(CmF2m+1), -(CmF2m-1) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms; (B) wherein n, Q, D1 and R1 are as defined above; Z is alkyl of 1 to 4 carbon atoms, and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of: (i) >O, (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2, (vi) , (vii) >CHOH, (viii) -CH2(OCH2CH2)1CH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is or ; and Y is when t is 4, provided that z is not methyl when Y is oxygen; (C) wherein q is 1 or 2, Z' is alkyl of 2 to 4 carbon atoms, n Q, D1 and R1 are as previously defined; (D) Claim 11 continued wherein A1 and A2 are independently selected from the group consisting of -R1, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, D1 and R1 are as previously defined, and T is a member selected from the group consisting of: (i) (ii) (iii) , and (iv) wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4; (E) wherein B is a member selected from the group consisting of: (i) -CO2D1R1 (ii) , and (iii) -CON(Z")2 where D3 and D4 are divalent radicals independently selected from the group consisting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)P1CH(OH)(CH2)P2O-, -C6H4O(CH2)P1-, -C6H4-, and -C6H4O-, R3 and R4 are independently selected from the group consisting of -(CMF2m+1)-,-(CmF2m-1)- and -(CF2)mOX, Claim 11 continued Z" is alkyl of 1 to 4 carbon atoms, wherein P1, P2, m, D1, D2, R1, R1', R2 and X are as previously defined, with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must contain at least 3 methylene groups; (F) wherein R1 and D1 are as defined previously and Y' is selected from the group consisting of oxygen and alkyl of 1 to 6 carbon atoms; (G) . wherein two E groups are E1, and two E groups are E2, in which E1 is -CON(D1R1)2 or -CO2D1R1 and E2 is -CO2(CH2)x1(CHOH)x2CH2Q" or -CO2H wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to 4, Q" is -OH or halogen and D1 and R1 are a previously defined, (H) and wherein R2' is selected from the group consisting of , hydrogen, -(CH2)x1(CHOH)x2CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q" are as defined above; (I)

Claim 11

Claim 11 continued wherein Z1, Z2 and Z3 are the same or different and are alkyl of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, and -O(CH2))x1(CHOH)x2CH2Q"', wherein Q"' is -OH, halogen, or hydrogen and wherein x1 and x2, R1 and R2 are as defined above, with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1; (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from the group consisting of hydrogen and Z, in which Z is as defined previously, Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkyl of from 1 to 4 carbon atoms, and R1, R2, R3 and R4 are the same or different and are as defined above; and (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wberein x1, R1, R2, Z1m Z2 and Q" are as defined above and x3 is 0 or 1.

Claim 12

The process according to claim 11 wherein said additive is contained in said resin in an amount of up to about 3 percent by weight of the resin.