Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-06-21
2002-03-19
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C525S524000, C525S525000, C525S530000, C525S531000
Reexamination Certificate
active
06359029
ABSTRACT:
RELATED APPLICATIONS
This application claims priority to German Application No. 199 28 436.9, filed Jun. 23, 1999, herein incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to solvent-free or low-solvent two-component binders, in particular for road-marking paints.
2. Background of the Invention
Nowadays road-markings are predominantly made using spray paints based on synthetic rubber and/or synthetic resins. These single-component paints are applied at a thickness of about 0.4 mm to the surface of the road, using spray assemblies. Abrasion gives them a typical service life of about one year.
Ways have been sought to prolong the service life of the marking. Essentially the service life can only be increased by increasing the thickness.
One development was that of thermoplastic paint compositions known as hot plastics, which are applied or sprayed at about 150-180° C. This allows markings to be applied at thicknesses of up to about 3 mm, and it is also possible to drive over these immediately once they have cooled. The disadvantage is that at low temperatures these layers tend to become brittle and to flake away from the pavement surface. Pools of water frequently form at the edges of the markings and increase the risk of aquaplaning.
Better performance is shown by what are known as cold plastics, which are polymers dissolved in olefinically unsaturated monomers and mostly based on acrylic or methacrylic resins or on unsaturated polyesters, with fillers added. The result is a paste-like composition which is applied to the road surface. Immediately prior to application a hardener is admixed, and this initiates the (free-radical) polymerization of the monomers.
SUMMARY OF THE INVENTION
It has now been found that the ease of flow, and therefore the surface uniformity, of cold-plastic material can be significantly improved if the (meth)acrylate copolymer dissolved in the monomer or, respectively, in the monomer mixture contains units which form, during or after the polymerization to give the (meth)acrylic copolymers, as a result of the reaction of cyclic low molar mass compounds selected from the class consisting of monoepoxides, lactones and lactams, with vinyl monomers containing acid groups. Adding these specific starting materials to an otherwise unchanged formulation also considerably reduces the viscosity of the paint compositions, so that homogenization of the composition is easier and more efficient.
The invention, therefore, provides for binders for road-marking paints, comprising a (meth)acrylate copolymer A and one or more olefinically unsaturated monomers B which can be cured by adding free-radical initiators C. The invention also provides for road-marking paints which comprise the novel binders and their customary additions, such as color pigments, fillers, other additives, adhesion promoters and added reflective materials.
DETAILED DISCUSSION OF THE INVENTION
The novel binders are usually used in the form of a highly filled composition. For the purposes of the present invention, these are compositions in which the mass fraction of fillers is at least about 30%. The mass ratio of the mixture made from polymer A and monomers B to the filler is preferably from about 1:1 to about 1:6.
The binders comprise mass fractions from about 20 to about 80%, preferably from about 25 to about 75% and in particular from about 30 to about 70% of the (meth)acrylate copolymer A and from about 80 to about 20%, preferably from about 75 to about 25%, in particular from about 70 to about 30%, of the olefinically unsaturated monomers B.
The (meth)acrylate copolymers A are obtainable by reacting mass fractions of,
from about 10 to about 50%, preferably from about 15 to about 40%, in particular from about 17 to about 35%, of compounds A1 selected from the class consisting of monoepoxides, lactones and lactams having preferably from 4 to 18 carbon atoms, most preferably from glycidyl esters and glycidyl ethers of &agr;-branched aliphatic monocarboxylic acids having from 4 to 12 carbon atoms and, respectively, of aliphatic alcohols, preferably having from 4 to 13 carbon atoms, lactones and lactams having, preferably from 5 to 12 carbon atoms,
from about 1 to about 25%, preferably from about 3 to about 20%, in particular from about 5 to about 18%, of olefinically unsaturated monomers A2 which contain at least one acid group selected from the class consisting of carboxyl groups, sulfonic acid groups and phosphonic acid groups,
from about 5 to about 70%, preferably from about 8 to about 60%, in particular from about 10 to about 55%, of methacrylates A3 of linear, branched or cyclic aliphatic alcohols having, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms,
from about 2 to about 84%, preferably from about 5 to about 75%, in particular from about 7 to about 65%, of acrylates A4 of linear, branched or cyclic aliphatic alcohols having preferably from 2 to 20 carbon atoms, more preferably from 4 to 10 carbon atoms, and also, if desired,
up to about 70% of other vinyl monomers A5 by free-radical polymerization, where the compounds A1 are first charged and the monomers A2 to A5,and also a free-radical initiator A7, are added. If desired, up to about 10% by weight of a solvent A6 may also be added to component A1 or to the monomers A2 to A5. However, it is preferable to operate without a solvent. The sum of the mass fractions mentioned of A1 to A5 is, of course, always 100%. The polymerization usually takes place at temperatures of from about 100 to about 220° C., preferably at from about 110 to about 200° C., in particular at from about 120 to about 185° C.
The compounds A1 here are monoepoxides, cyclic esters, such as lactones or carbonates of 1,2- or 1,3-diols, or lactams, and these form adducts by reacting with the monomers A2 containing acid groups, with ring opening. This gives double-bond compounds which can copolymerize with the other monomers. Particular preference is given to &egr;-caprolactone, and also to monoglycidyl esters of an industrial mixture of &agr;-alkyl- and &agr;,&agr;-dialkylalkane-monocarboxylic acids with an average of from about 4 to 11 carbon atoms. These are obtainable, for example, as ®Cardura E5 or E10 (Shell Chemie) or Glydexx N10 (Exxon) or from other producers.
The monomers A2 are preferably &agr;,&bgr;-unsaturated carboxylic acids having, preferably from 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, vinylacetic acid or crotonic acid, monoesters of olefinically unsaturated dicarboxylic acids with aliphatic alcohols, in particular with linear aliphatic alcohols, preferably having from 1 to 4 carbon atoms, such as methanol, ethanol, isopropanol or n-butanol, for example monomethyl maleate or monobutyl itaconate. Particular preference is given to acrylic or methacrylic acid, and also to monomethyl maleate and mixtures of these.
The monomers A3 are preferably methacrylates of aliphatic alcohols, preferably having from 1 to 10 carbon atoms in the alkyl group; for example, methyl, ethyl, n- or isopropyl, tert-butyl, isoamyl, hexyl or cyclohexyl methacrylate. Use is particularly made of methyl, ethyl, isopropyl or tert-butyl methacrylate.
The monomers A4 are preferably acrylates of aliphatic alcohols, preferably having from 2 to 10 carbon atoms in the alkyl group; such as ethyl, n-propyl, n-butyl, 2-ethylhexyl or decyl acrylate. It is also possible to use subordinate proportions (up to about 20% of the mass of the monomers A4) of acrylates of oligomeric or polymeric propylene glycols with degrees of polymerization of from about 2 to about 20. The residual hydroxyl group in these may also have been etherified with low molar mass aliphatic alcohols, preferably having from 1 to 4 carbon atoms.
The monomers A5 include styrene, vinyltoluene, vinyl versatate, other vinyl esters, vinyl ethers, such as methyl and butyl vinyl ether, (meth)acrylonitrile and (meth)acrylamide.
Suitable solvents A6 are: aromatic hydrocarbons or mixtures of these, in particular certain cuts from the fractionatio
Epple Ulrich
Klintschar Gerfried
Kriessmann Ingo
Labenbacher Adolf
Frommer & Lawrence & Haug LLP
Sanders Kriellion A.
Solutia Resins GmbH
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