Substrate having high initial water repellency and a laundry...

Details Substrate having high initial water repellency and a laundry... Substrate having high initial water repellency and a laundry...

1999-01-14

2001-10-30

Dawson, Robert (Department: 1712)

Stock material or miscellaneous articles

Composite

Of fluorinated addition polymer from unsaturated monomers

C428S392000, C428S394000, C428S424200, C428S424600, C428S475800, C428S483000, C428S522000, C428S537500, C442S085000, C442S091000, C524S589000, C524S599000, C525S124000, C525S129000, C526S242000, C526S245000, C526S248000, C526S310000

Reexamination Certificate

active

06309752

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to aqueous compositions containing fluorochemical oil- and water-repellent agents. This invention also relates to agents that improve fluorine efficiency of fluorochemical oil- and water-repellent agents. This invention also relates to processes for providing oil- and water-repellency to fibrous substrate materials.
DESCRIPTION OF THE RELATED ART
Water-, oil- and soil-repellent finishes containing fluorochemical agents or compositions are well known. A considerable disadvantage of such finishes, however, is their high price. So-called “extenders” have therefore been developed in order to reduce cost. Modified synthetic resins, waxes, paraffin emulsions, and similar products have been used for this purpose.
U.S. Pat. No. 3,849,521 (Kirimoto et al.) describes oil- and water-repellent compositions containing a polymer containing fluoroalkyl-containing monomer units and an additive copolymer containing monomer units having the formula
CR
1
R
2
═CR
3
R
4
wherein R
1
, R
2
and R
3
represents hydrogen atoms or methyl groups, and R
4
represents a C
1-18
alkyl group; and monomer units having the formula:
CH
2
═CR
5
CONHCH
2
OH
wherein R
5
represents a hydrogen atom or a methyl group
U.S. Pat. No. 4,834,764 (Deiner et al.) describes the use of blocked isocyanate compounds as extenders, the isocyanate compound before blocking being diphenylmethane diisocyanate or an isocyanate compound having a molecular weight of at least 450.
SUMMARY OF THE INVENTION
This invention provides fluorine-efficient oil- and water-repellent compositions comprising:
(A) a fluorochemical oil-and water-repellent agent;
(B) a copolymer extender comprising:
(i) polymerized units derived from a monomer of Formula V:
CR
1
R
2
═CR
3
R
4
  (V)
 wherein each of R
1
, R
2
, R
3
and R
4
independently represents hydrogen, halogen, or an organic group such as alkyl, carboxyl, or acyloxyalkyl (i.e., —CO
2
alkyl); and
(ii) polymerized units derived from a monomer of Formula VII:
CH
2
═CR
5
X   (VII)
 wherein R
5
represents a hydrogen atom or a methyl group, and X represents a moiety comprising a functional group that can interact with a fibrous substrate; and
(C) a blocked isocyanate extender.
This invention also provides substrates treated with a fluorine-efficient composition as described above, and methods of improving the fluorine-efficiency of a fluorochemical oil- and water-repellent agent, comprising the step of formulating the fluorochemical agent with components (B) and (C) described above.
The compositions of the invention comprise at least one member of each of two classes of extenders. The combination improves the fluorine-efficiency of fluorochemical agents, and thus reduces the cost of fluorochemical treatment, to a greater extent than would be expected based on the properties of each individual class of extenders.
DETAILED DESCRIPTION OF THE INVENTION
Component (A) in a composition of the invention is a fluorochemical oil- and water-repellent agent generally comprising a plurality of fluoroaliphatic (i.e., R
f
) groups. Such agents are well known to those skilled in the art, and many (e.g., SCOTCHGARD™ fabric protector, Minnesota Mining and Manufacturing Company) are commercially available as ready-made formulations.
In general, fluorochemical agents useful in this invention comprise fluorochemical compounds or polymers containing one or more fluoroaliphatic groups R
f
, which are fluorinated, stable, inert, non-polar, preferably saturated, monovalent and both oleophobic and hydrophobic. R
f
preferably contains at least about 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms. R
f
can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic alkylene groups. R
f
is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that R
f
contain about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight. The terminal portion of the R
f
group contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, e.g., CF
3
CF
2
CF
2
—, (CF
3
)
2
CF—, —CF
2
SF
5
, or the like. Perfluorinated aliphatic groups (i.e., those of the formula C
n
F
2n+1
) are the most preferred embodiments of R
f
.
Examples of fluorochemical agents include, for example, R
f
-containing urethanes, ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, and compounds containing two or more of these groups, as well as mixtures and blends thereof.
Useful fluorochemical polymers containing R
f
groups include copolymers of fluorochemical acrylate and/or methacrylate monomers with the following co-polymerizable monomers including fluorine-containing and fluorine-free hydrophobic monomers such as methyl methacrylate, butyl acrylate, octadecylmethacrylate, acrylate and methacrylate esters of poly)oxyalkylene) polyol oligomers and polymers, e.g., poly(oxyethylene)glycol dimethacrylate, glycidyl methacrylate, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile, vinylchloroacetate, isoprene, chloroprene, styrene, butadiene, vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, acrylic and methacrylic acid, 2-hydroxyethyl acrylate, N-methylolacrylamide; 2-(N,N,N-trimethylammonium)ethyl methacrylate and the like.
Particular fluorochemical agents include those described in Pat. Nos. 2,803,615 (Ahlbrecht et al.), 2,934,450 (Brown), 3,068,187 (Bolstad et al.), 3,094,547 (Heine), 3,329,661 (Smith et al.), 3,341,497 (Sherman et al.), 3,398,182 (Guenthner et al.), 3,458,571 (Tokoli), 3,462,296 (Raynolds et al.), 3,574,791 (Sherman et al.), 3,728,151 (Sherman et al.), 3,896,251 (Landucci), 3,916,053 (Sherman et al.), 4,013,627 (Temple), 4,024,178 (Landucci), 4,029,585 (Dettre), 4,034,964 (Sherman et al.), 4,144,367 (Landucci), 4,160,777 (Loudas), 4,165,338 (Katsushima et al.), 4,190,545 (Marshall), 4,215,205 (Landucci), 4,264,484 (Patel), 4,325,857 (Champaneria et al.), 4,340,749 (Patel), 4,401,780 (Steel), 4,426,476 (Chang), 4,525,305 (Patel), 4,525,423 (Lynn et al.), 4,529,658 (Schwartz et al.), 4,540,497 (Chang et al.), 4,560,487 (Brinkley), 4,564,366 (Patel), 4,565,641 (Chang et al.), 4,566,981 (Howells), 4,579,924 (Schwartz et al.), 4,582,882 (Lynn et al.), 4,606,737 (Stern), 4,668,406 (Chang), 4,668,726 (Howells), 5,276,175 (Dams), each of which is incorporated herein by reference.
Particularly useful compositions impart high initial water repellency and laundry durable water repellency to treated substrates. High initial water repellency can be indicated by initial Water Spray Test Ratings of a treated substrate of about 90%. “High laundry durability” in the context of this invention means that the treated substrate has at least a 10% higher Water Spray Test Rating after 5 launderings (performed according to the Laundering Procedure described herein) than the same type of substrate treated with (a) a composition containing the fluorochemical agent alone, or (b) a composition containing the fluorochemical agent and copolymer extender alone, or (c) a composition containing the fluorochemical agent and the blocked isocyanate extender alone after five launderings. The particularly useful compositions can be prepared using fluorochemical agents selected from the group consisting of: R
f
-containing carbodiimides, R
f
-containing melamines; R
f
-containing polyisocyanates with one or more blocked isocyanate groups; and copolymers of fluorochemical acrylates, and/or methacrylates with copolymerizable fluorine-containing monomers, and/or hydrophobic, fluorine-free monomers. Examples of suitable hydrophobic, fluorine-free monomers include: methyl meth

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