Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1999-01-29
2001-01-09
Berman, Susan W. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S173000, C522S103000, C526S258000, C526S260000, C526S263000, C252S182130, C252S182180, C544S106000, C544S129000, C544S130000, C544S171000, C546S248000, C546S184000
Reexamination Certificate
active
06172129
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to aminoacrylate monomers, process for preparation of monomers and polymers, coatings, and inks made with aminoacrylate monomers.
2. Description of the Prior Art
Coatings, inks, and adhesives can be prepared from (meth)acrylate monomers and oligomers by radiation curing. Radiation curing is generally done under UV or EB radiation, optionally in the presence of photoinitiators, and proceeds by a free radical mechanism. A problem in this art is that air retards or inhibits the cure, leading to tacky surfaces. German patent DE 3706355 suggests that amines and acrylated amines can enhance the surface cure, even in the presence of oxygen. U.S. Pat. No. 3,876,518 and Canadian Pat. 1011891 teach that the modification of acrylated epoxidized soybean oil with amine at low level can enhance the surface cure which is especially useful in ink applications. Robson, et al. U.S. Pat. No. 4,045,416 assigned to Union Carbide Corporation teaches preparation of amine acrylates from primary and secondary amines and polyacrylates, preferably diacrylates and their use directly or as part of radiation curable formulations. Meixner, et al. U.S. Pat. No. 5,482,649, assigned to Bayer Ak., disclosed that the modification of acrylates with primary amines at low level leads to low viscosity aminoacrylates. U.S. Pat. No. 3,876,518 teaches low acrylate functionality for amine acrylates in radiation cure applications.
The prior art did not teach low viscosity, low volatility, high cure rate compositions comprising multifunctional acrylates. According to the prior art, it would have been expected that modification of multifunctional acrylates with amines would lead to high viscosity or gel-like materials.
An object of the present invention was to provide reactive acrylates having low viscosity which can be used in radiation, especially UV and EB, cure.
SUMMARY OF THE INVENTION
These objects, and others which will become apparent from the following disclosure, are achieved by the present invention which comprises in one aspect a (meth)acrylate (i.e., acrylate, methacrylate, or mixtures thereof) functional compound which is the reaction product of a cyclic secondary amine and a poly(meth)acrylate having at least three (meth)acrylate groups, useful for radiation curable coating or ink composition having low viscosity, low volatility, and high cure rate under radiation.
Other aspects of the invention include the process for preparing such coating and ink composition, the coatings and inks, articles coated with the coating or printed with the ink.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The multifunctional reactive amine acrylates of the invention can be prepared by reacting (meth)acrylates having at least three (meth)acrylate groups with a cyclic secondary amine compound such as morpholine and/or piperidine. The reaction between acrylates and amines is known as Michael addition reaction, both primary and secondary amines are suitable.
Multifunctional acrylates are well known in the art which can be prepared from (meth)acrylic acid and tri- or tetra-hydroxy polyols in the presence of catalysts. Suitable (meth)acrylates include propoxylated glyceryl triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylol propane triacrylate, pentaerythritol triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaeytliritol tetraacrylate, urethane acrylates, and epoxy acrylates. The general formula for acrylates are shown below
where R is hydrogen or methyl, A is the residue of a polyol, and n is an integer having a value of 3 to 6.
The production of polyacrylate esters is well known to those of normal skill in the art. It is known that an acid such as acrylic acid or methacrylic acid will react with a polyhydroxyl compound to produce the polyacrylate ester. The polyacrylate esters can also be produced by transesterification reactions. These reactions are known in the art and the conditions under which they are carried out are so well known that they need not be set forth in detail.
The polyols that are reacted with acrylic acid or methacrylic acid to produce the polyacrylate esters can be any of the compounds containing three or more hydroxyl groups that will undergo esterification. These are well known and include the aliphatic-type polyols having from three to about 20 carbon atoms, triols such as trimethylol propane, glycerol, 1,2,6-hexanetriol; tetrols such as pentaerythritrol; and the like; the ether polyols having a molecular weight of from about 106 to about 15,000, including the block polyoxyalkylene polyols.
Hence, the residue of the polyol used to produce the polyacrylate ester can be a saturated or unsaturated linear or branched polyvalent alkylene.
Suitable secondary cyclic amines include morpholine, substituted morpholines, piperidine, substituted piperidines, and the like. The preferred amines are morpholine and piperidine. The morpholine or piperidine can be modified, for example the reaction product of piperazine or alkyl substituted piperazines with mono-epoxides such as epichlorohydrin, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, and the like, or poly-epoxides such as diglycidyl ether of bisphenol A, 4-vinyl-1-cyclohexene dioxide, and the like; the reaction product of said piperazines with an isocyanate such as phenyl isocyanate, methyl isocyanate, tolylene diisocyanate, bis(2-isocyanatoethyl)bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylate, bis(2-isocyanatoethyl)4-cyclohexene-1,2-dicarboxylate, and the like. In these instances only one of the >NH groups of the piperazine compound is reacted and there is always an >NH group available from the piperazine molecule.
The reaction between the acrylates and secondary cyclic amine can take place without any catalyst or solvent. The reaction can be carried out at temperature between −30 to 150° C., the preferred temperature is from 25 to 100° C. Although solvent is not required it may be used to facilitate the heat and mass transfer. The reaction of the polyacrylate ester with the amine is preferably carried out in an inert gas atmosphere, for example, under nitrogen or argon, to prevent or minimize unwanted side reactions. However, this is not necessary for a successful reaction. The reaction can be carried out at a temperature of from about −30° C. or lower to about 150° C. or higher. The preferred temperature range is from about −10° C. to about 75° C. and the most preferred range is from about 15° C. to about 60° C. The pressure of the reaction system can be maintained at atmospheric pressure or superatmospheric pressure.
To prevent acrylate polymerization various inhibitors or stabilizers may also be used during the reaction. Typical inhibitors such as hydroquinone, hydroqinone methyl ether, butylated hydroqinone can be used.
Solvent may be used to facilitate heat and mass transfer during the reaction which was exothermic. Non-reactive solvents such as hydrocarbons, esters, and halogenated solvents may be used. Examples are toluene, hexane, heptane, ethyl acetate, butyl acetate, chloroform, chlorobenzene. The reaction can be carried out in the absence of a solvent or in the presence of an inert solvent. Among the suitable inert organic solvents that can be used one can mention methanol, ethanol, acetone, benzene, toluene, xylene, hexane, octane, and the like. Any inert solvent can be used that does not interfere with the reaction. In order to minimize side reactions, the reaction is preferably carried out in the absence of light.
In the reaction, one or more of the acrylyl groups of the polyacrylate ester reacts to displace the amino hydrogen atom while the rest of acrylyl group of the polyacrylate ester is not affected. The molar amount of arnines charged to the reaction system can vary from about 0.9 mole to about 3 mol
Ceska Gary
Fan Ming Xin
Horgan James P.
Jurczak Edward A.
Miller Henry C.
Berman Susan W.
Cozen & O'Connor
Fein Michael
Sartomer Technologies Inc.
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