Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-10-27
2003-03-18
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C526S279000, C526S911000, C106S287160, C427S387000
Reexamination Certificate
active
06534590
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a silicone-grafted vinyl copolymer emulsion composition. More particularly, this invention relates to a highly storage-stable silicone-grafted vinyl copolymer emulsion composition that has the ability to form highly water-resistant coatings and films.
BACKGROUND OF THE INVENTION
Silicone-grafted vinyl copolymers have in the past been produced by solution polymerization techniques in which vinyl monomer is polymerized in organic solvent with a straight-chain silicone macromonomer bearing a radically polymerizable functional group (referred to below simply as silicone macromonomer). However, due to issues associated with the use of organic solvents, i.e., safety, toxicity, and environmental issues, there has quite recently been underway a transition to the emulsion-type products produced by emulsion polymerization technology. The corresponding silicone-grafted vinyl copolymer emulsions have generally been prepared by first emulsifying the vinyl monomer and silicone macromonomer and then adding radical polymerization initiator and effecting polymerization. Unfortunately, silicone macromonomers, being poorly diffusible within the micelle due to their high molecular weight and also being encumbered by large steric hindrance, have exhibited a low reactivity with vinyl monomers. As a consequence, large amounts of the silicone macromonomer have remained unpolymerized after termination of the reaction, which has reduced the purity of the reaction system. In addition, the unpolymerized silicone macromonomer has a low solubility in vinyl monomer and the post-polymerization polymer and as a result will bleed out onto the film surface when the silicone-grafted vinyl copolymer emulsion product is coated on substrate. This outmigration not only serves to impair the printability, the compatibility with other materials, and the adhesiveness for other substrates, but also generates a lubricity in excess of that required. Finally, higher degrees of polymerization (DP) by the silicone macromonomer increase the likelihood that aggregates or coagulates will be produced during emulsion polymerization and also cause an unsatisfactory post-polymerization emulsion stability.
To counter these problems, Japanese Patent Application Laid Open (Kokai) Number Hei 5-9248 (9,248/1993) has disclosed a method that seeks to effectively convert silicone macromonomer through the use of oil-soluble radical initiator in combination with silicone macromonomer and vinyl monomer. This notwithstanding, even with the use of this method the conversion remains unsatisfactory and unpolymerized silicone macromonomer still remains available to impair such properties as the printability and compatibility with other materials.
The acrylic emulsion composition proposed by Japanese Patent Application Laid Open (Kokai) Number Hei 1-284513 (284,513/1989) does provide a high conversion through the use of low-DP silicone macromonomer, but at the expense of rendering unsatisfactory those properties, such as water repellency, that originate with silicone.
Thus, it has been substantially impossible using prior-art silicone macromonomers to produce a high-purity, high-performance silicone-grafted vinyl copolymer emulsion that is also highly storage, stable and does not produce aggregates or coagulates.
SUMMARY OF THE INVENTION
The present inventors achieved this invention as the result of extensive investigations directed to solving the problems described above.
In specific terms, the object of this invention is to provide a highly storage-stable silicone-grafted vinyl copolymer emulsion composition that can produce a film or coating that itself is highly water repellent, water resistant, adhesive, and printable.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to silicone-grafted vinyl copolymer emulsion compositions as afforded by the emulsion polymerization of components comprising
(A) vinyl monomer;
(B) carbosiloxane dendrimer that contains a radically polymerizable organic group and has the following general formula
wherein Y is a radically polymerizable organic group, R
1
is C
1
to C
10
alkyl or aryl, and X
1
is the silylalkyl group with the following formula when i=1
(R
1
is defined as above; R
2
is C
2
to C
10
alkylene; R
3
is C
1
to C
10
alkyl; X
i+1
is selected from the group consisting of hydrogen, C
1
to C
10
alkyl, aryl, and the above-defined silylalkyl group; i is an integer with a value from 1 to 10 that specifies the generation of said silylalkyl group; and a
i
is an integer from 0 to 3), wherein the component (A); component (B) weight ratio is 0:100 to 99.9:0.1;
(C) surfactant, at from 0.01 to 20 weight parts for each 100 weight parts of the total of components (A) and (B); and
(D) radical polymerization initiator, at from 0.01 to 20 weight parts for each 100 weight parts of the total of components (A) and (B).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Each component of the inventive composition will be explained in detail in the following.
The vinyl monomer (A) should contain a radically polymerizable vinyl group, but the type and properties of this monomer are not otherwise critical. Vinyl monomer (A) can be exemplified by lower alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate; lower alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate; higher acrylates such as n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, and stearyl acrylate; higher methacrylates such as n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, and stearyl methacrylate; the vinyl esters of lower aliphatic acids, such as vinyl acetate and vinyl propionate; the vinyl esters of higher aliphatic acids, such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate; aromatic vinyl monomers such as styrene, vinyl toluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, and vinyl pyrrolidone; amino-functional vinyl monomers such as dimethylaminoethyl acrylate, dimethylamninoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate; amide-functional vinyl monomers such as acrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, isobutoxymethoxyacrylamide, N,N-dimethylacrylamide, methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, and N,N-dimethylmethacrylamide; hydroxyl-functional vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, and 2-hydroxypropyl methacrylate; fluorinated vinyl monomers such as trifluoropropyl acrylate, perfluorobutylethyl acrylate, perfluorooctylethyl acrylate, trifluoropropyl methacrylate, perfluorobutylethyl methacrylate, and perfluorooctylethyl methacrylate; epoxy-functional vinyl monomers such as glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, glycidyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; ether linkage-containing vinyl monomers such as tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol monoacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate; alkoxysilanes that contain a radically polymerizable unsaturated group, such as
CH
2
═CHCOOC
3
H
6
Si(OCH
3
)
3
,
CH
2
═C(CH
3
)COOC
3
H
6
Si(OCH
3
)
3
,
CH
2
═C(CH
3
)COOC
3
H
6
Si(CH
3
)(OCH
3
)
2
,
CH
2
═C(CH
3
)COOC
3
H
6
Si(CH
3
)
2
0CH
3
,
CH
2
═C(CH
3
)COOC
2
H
4
OC
Aso Takayuki
Furukawa Haruhiko
Morita Yoshitsugu
Dow Corning Toray Silicone Co. Ltd.
Duane Morris LLP
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