Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1999-06-02
2002-06-04
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S171000, C522S173000, C522S178000, C522S179000, C522S181000, C522S096000, C522S180000, C428S500000, C428S513000, C428S704000
Reexamination Certificate
active
06399672
ABSTRACT:
BACKGROUND
1. Field of the Invention
This invention relates to radiation curable coatings, adhesives, inks, and molded articles. The invention also relates to clear, transparent molded articles useful as lenses, laminating resins, and novel unsaturated metal sulfates.
2. Description of the Prior Art
The use of metal (meth)acrylates such as zinc, calcium, and magnesium salts of acrylic or methacrylic acids as crosslinking monomers for use with elastomers to promote adhesion to substrates is well known. As described in Proudfit, U.S. Pat. No. 5,314,187, for example, zinc acrylate, zinc diacrylate, and zinc methacrylate are particularly suitable crosslinking agents for elastomers such as EPDM, 1,4-butadiene, isoprene, chloroprene, and the like. Ahmad et al., U.S. Pat. No. 5,506,308, teaches use of unsaturated carboxylic metal salts such as zinc diacrylate in curable elastomeric compositions wherein the elastomer may be a nitrile rubber, EPDM, EVA, and the like. Other prior patents which teach zinc acrylate, zinc diacrylate, zinc methacrylate, calcium diacrylate, and calcium dimethacrylate as crosslinking agents for elastomers include U.S. Pat. Nos. 5,731,371; 5,721,304; 5,656,703; 5,208,294; 5,126,501; 4,918,144; 4,770,422; 4,720,526; 4,715,607; 4,716,409; 4,529,770; 4,500,466; 4,495,326; 4,165,877; 4,065,537; and 4,264,075.
One disadvantage of such metal salts of carboxylic acids is their poor oil solubility. For example, they are relatively insoluble in organic monomers and oligomers.
Soluble zinc and calcium salts of ethylene glycol-methacrylate-phthalate (EMD) prepared in aqueous solution, and then copolymerized with methyl methacrylates (MMA), styrene (ST), and hydroxyethyl methacrylate (HEMA) were disclosed by Matsuda, et al., Preparation and Copolymerization of Divalent Metal Salts of Ethylene Glycol-Methacrylate-Phythalate,
J. App. Poly. Sci.,
17, 1941-1952 (1973), as ionic crosslinkers. The resultant crosslinked copolymers are shown to have improved physical properties.
U.S. Pat. No. 3,847,846 assigned to Kansai Paint Co., Ltd., teaches electrically conductive resins prepared from metal salts of certain sulphonates, phosphates, or phosphoric acid diesters, with an epoxide, optional solvent, polymerization initiator, and/or photosensitizer, and useful for magnetic tape and the like.
Matsuda, et al., U.S. Pat. No. 3,899,382, teaches polyvalent metal salts of compounds such as diethylene glycol methacrylate phthalate, mixed with an organic peroxide.
Matsuda, et al., Metal-Containing Cured Resins Based on Divalent Metal Salts of Ethylene Glycol-Methacrylate-Maleate,
Poly Eng. and Sci.,
18, No. 8, 628-633, June 1978, teach solubility of such salts in St., MMA, and EA, and copolymerization with such vinyl monomers to produce polymers having high heat distortion temperature, tensile strength, compressive strength, impact strength, and Rockwell hardness, as well as resistance to chemical attack.
Japanese Kokai 295285 of May 7, 1991, teaches use of magnesium, aluminum, or calcium salts of unsaturated phosphate compounds as additives for coatings to improve adhesion to metals.
Okamoto, et al., Effect of divalent metal salts of dibasic acid mono (methacryloyloxy propyl) esters on adhesive properties,
Int. J. Adhesion and Adhesives,
9, No. 1, January 1989, teach peroxide cured adhesives prepared by copolymerizing such monomers with hydroxy propyl methacrylate (HPM).
The art of radiation curable coatings, adhesives, and inks is different from the art of peroxide curable polymers. In the radiation curable field, the current art uses only oil insoluble metal salts as adhesion promoters. No one has previously proposed oil soluble metal salts of carboxylic acids in the radiation curable art.
3. Objects
It is, therefore, an object of the present invention to provide improved radiation curable adhesives, coatings, and inks, transparent molded articles useful as lenses, and thermoset laminating resins.
It is another object to provide novel polymerizable, unsaturated metal sulfates which are oil soluble and useful in such compositions.
SUMMARY OF THE INVENTION
These objects, and others which will become apparent from the following disclosure, are provided by the invention which, in one aspect, includes a composition suitable for a radiation cured coating, adhesive, ink, or photoresist comprising (A) at least one polymerizable, ethylenically unsaturated compound of the formula
wherein
M is one or more metal atoms of valence n, wherein n=y·w, and wherein M is optionally more than one metal atom, with the proviso that the global equivalent metal valence is n=w·y;
n is an integer of about 1-6;
R is a residue of a compound having anhydride and/or carboxylic acid groups with an initial equivalent carboxy equivalent functionality defined by the equation f=x+y+z, wherein f is an integer of about 2 to 30;
R
1
is a residue of a hydroxy-containing ethylenically unsaturated compound;
R
2
is H or a residue of a hydroxy containing ethylenically unsaturated compound different from R
1
;
R
3
is a residue of a hydroxy-containing ethylenically unsaturated compound;
w is the number of moieties having residue R required for metal valence n;
x is an integer of about 1 to f−1;
y is an integer of about 1 to 2 (the number of intramolecular carboxylates bonded to M);
z is an integer of about 0 to f−2;
Y is H or R
3
; and
(B) at least one copolymerizable ethylenically unsaturated monomer or oligomer.
In another aspect, the invention includes a polymer, especially in the form of a coating, adhesive, ink, or molded article prepared by curing such a composition in the presence of a free radical initiator and/or radiation.
A further aspect of the invention is a solution of compound (A) in copolymerizable ethylenically unsaturated monomer or oligomer (B), alone or in an inert solvent. Such solutions can be prepared by forming compound (A) in the presence of the copolymerizable ethylenically unsaturated monomer or oligomer (B) and optionally in the presence of an inert solvent.
Still another aspect of the invention is a molded article polymerized from such a composition, the article having a refractive index useful for lenses.
A still further aspect is a process of preparing polymerizable, ethylenically unsaturated compounds (A) of formula (I), (II), (III) comprising reacting a hydroxy compound with a polyacid, anhydride, sulfur oxide, or phosphorus oxide compound to form an acid functional compound, and reacting the acid functional compound with a metal compound.
In another aspect, the invention includes a thermoset copolymer of a monomer mixture comprising (A) a compound according to formula (I), (II), or (III), and a (B) a polyfunctional (meth)acrylate or allylic compound.
Another aspect is a composition suitable for laminating resins having high heat distortion temperature, comprising an ethylenically unsaturated monomer, a free radical initiator, and a crosslinking monomer according to formula (I), (II), or (III).
The invention also comprises a compound of formula (III), i.e., a polymerizable, ethylenically unsaturated sulfate compound of the formula
wherein
M=metal;
n=valence of M; and
R
3
=a residue of an unsaturated hydroxy compound; the compound being useful in making certain of the radiation curable compositions.
DETAILED DESCRIPTION OF THE INVENTION
The oil soluble metal salts of formula (I), (II), or (III) useful in the radiation curable compositions of the invention can be prepared by any appropriate process. A preferred process comprises reacting a hydroxy compound with a carboxylic polyacid or anhydride, a sulfur oxide compound, or a phosphorus oxide compound to form an acid functional compound, and reacting that acid functional compound with a metal compound. The compounds of formula (I) are prepared, from carboxylic polyacids or anhydrides, whereas the compounds of formula (II) are prepared from phosphoric acids, and the compounds of formula (II) are prepared from sulfuric acids.
The hydroxy compounds used in such preparation can b
Ceska Gary W.
Hazell Thomas W.
Horgan James P.
Schaeffer William R.
Fein Michael B.
McClendon Sanza
O'Connor Cozen
Sartomer Technologies Co., Inc.
Seidleck James J.
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