Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-06-18
2001-02-20
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S303100, C526S304000, C526S318400, C428S375000, C428S378000, C428S511000, C442S083000, C442S152000, C442S164000
Reexamination Certificate
active
06191244
ABSTRACT:
This invention relates to polymer compositions, more specifically this invention relates to polymer compositions which are useful as binders in fiber, nonwoven, textile, and paper compositions.
Fiber, nonwoven, textile, and paper compositions typically are coated with polymeric binders to provide water repellency and durability. Self cross-linking acrylic polymers and styrene/acrylic polymers are typically used in these applications. There is a need for polymeric binders which provide improved water repellency and durability in fiber, nonwoven, textile, and paper compositions.
U.S. Pat. No. 5,521,266 discloses a method for forming polymers from hydrophobic monomers. The disclosed method utilizes macromolecular organic compounds which have a hydrophobic cavity to complex monomers which have low water solubility. This enables the formation of polymers from low water solubility monomers by emulsion polymerization. Suitable monomers for use in the method for forming polymers include lauryl methacrylate.
U.S. Pat. No. 3,915,921 discloses interpolymers made by solution polymerization. The interpolymers contain hydrophobic monomers including stearyl methacrylate, and certain carboxylic monomers including acrylic acid. The interpolymers are taught to be effective thickeners.
Despite the disclosure of the prior art, there is a continuing need for polymeric binders which provide improved water repellency and durability in fiber, nonwoven, textile, and paper compositions.
We have surprisingly found that the use of the polymer compositions of this invention provide improved water repellency and durability in fiber, nonwoven, textile, and paper compositions.
The present invention provides a composition comprising an emulsion polymer comprising as polymerized units:
i) a) from 9.5 to 99.9 parts by weight of at least one C
12
to C
40
alkyl ester of (meth)acrylic acid;
b) from 0 to 90 parts by weight of at least one less than C
15
ethylenically unsaturated nonionic monomer;
c) from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof; and
d) from 0.1 to 10 parts by weight of at least one cross-linking monomer; and
ii) from 0 to 10 parts by weight, based on the polymer weight of at least one cross-linking agent,
provided that the composition contains 0.1 to 10 parts by weight, based on the polymer weight cross-linking monomer and cross linking agent.
In another embodiment, the present invention provides a method of improving water repellency and durability in fiber, nonwoven, textile, and paper compositions comprising:
a) providing a composition comprising an emulsion polymer comprising as polymerized units:
i) from 9.5 to 100 parts by weight of at least one C
12
to C
40
alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one less than C
15
ethylenically unsaturated nonionic monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof; and
from 0 to 10 parts by weight of at least one cross-linking monomer; and
ii) from 0 to 10 parts by weight, based on the polymer weight of at least one cross-linking agent;
b) providing a substrate selected from the group consisting of fiber, nonwoven, textile, and paper;
c) coating the substrate with the polymer composition; and
d) drying the coated substrate.
The present invention also provides an article comprising:
a substrate selected from the group consisting of fiber, nonwoven, textile, and paper coated with an emulsion polymer composition comprising as polymerized units:
i) from 9.5 to 100 parts by weight of at least one C
12
to C
40
alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one less than C
15
ethylenically unsaturated nonionic monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof; and
from 0 to 10 parts by weight of at least one cross-linking monomer; and
ii) from 0 to 10 parts by weight, based on the polymer weight of at least one cross-linking agent.
The compositions of this invention may be prepared by a single stage or multi-stage process. The process may be an emulsion polymerization such as the process described in U.S. Pat. No. 5,521,266. The process may also be solution polymerization followed by emulsification as described in U.S. Pat. No. 5,539,021, mini-emulsion polymerization, or micro-emulsion polymerization. Emulsion polymerization is preferred. In the process utilized for preparing the samples within this application, a first stage was prepared by adding a monomer emulsion and sodium persulfate to a solution containing methyl-&bgr;-cyclodextrin (“CD”), deionized water, and surfactant. The first stage was reacted at 85° C. A second stage was prepared by making a second monomer emulsion and feeding the second monomer emulsion and a sodium persulfate solution to the reacted first stage. The second stage was reacted at 85° C.
The compositions of this invention contain as polymerized units from 9.5 to 100 parts by weight, preferably from 15 to 80 parts by weight, more preferably 20 to 70 parts by weight of at least one C
12
to C
40
alkyl ester of (meth)acrylic acid. It is preferred that the alkyl ester of (meth)acrylic acid be a C
12
to C
30
alkyl ester of (meth)acrylic acid. It is more preferred that the alkyl ester of (meth)acrylic acid be a C
12
to C
18
alkyl ester of (meth)acrylic acid. Suitable alkyl esters of (meth)acrylic acid include cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, and eicosyl (meth)acrylate. Beneficial properties may be obtained by utilizing more than one C
12
to C
40
alkyl ester of (meth)acrylic acid.
The compositions of this invention also contain as polymerized units from 0 to 90 parts by weight, preferably 15 to 90 parts by weight, more preferably 20 to 80 parts by weight of at least one less than C
15
ethylenically unsaturated nonionic monomer. Suitable less than C
15
ethylenically unsaturated nonionic monomers for use in the preparation of the polymer compositions of this invention include, but are not limited to (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate; acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile. Butyl acrylate, methyl methacrylate, and styrene are preferred. More preferred are butyl acrylate and methyl methacrylate.
The compositions of this invention also contain as polymerized units from 0 to 90 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight ethylenically unsaturated acid containing monomer or salts thereof. Suitable ethylenically unsaturated acid containing monomers include, but are not limited to acrylic acid, methacrylic acid, crotonic acid, phosphoethyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydride. Acrylic acid and methacrylic acid are preferred. Methacrylic acid is more preferred.
The compositions of this invention also contain as polymerized units from 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on the polymer weight of a cross-linker selected from a cross-linking agent and a cross-linking monomer. By cross-linker is meant a compound which has at least 2 reactive groups which will react with acid groups found on the monomers of the compositions of this invention. Cross-linking agents useful in this invention include a polyaziridine, polyisocyanate, polycarbodiimide, polyamine, and a polyvalent metal. The cross-linking agent is optional, and may be added after polymerization has been completed.
Finley Maureen Joanne
Lau Willie
Morris Hal Conley
Williams Martin Marion
Pezzuto Helen L.
Rohm and Haas Company
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