Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
1999-08-25
2001-07-24
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...
C522S084000, C522S086000, C522S104000, C522S108000, C522S179000, C524S845000, C525S437000, C525S444000
Reexamination Certificate
active
06265461
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to radiation-curable water-soluble combinations of polyester resins with high mass fraction of solids.
2. Description of the Related Art
From EP-A 0 574 775 self-emulsifying polymerizable binders are known which can be made by reacting pre-polymers containing (meth)acryloyl groups (A) and unsaturated polyesters (B) which are emulsifiable in water with multifunctional isocyanates. The preferred pre-polymers (A) containing (meth)acryloyl groups are polyester (meth)acrylates which are condensation products of aromatic and/or aliphatic dicarboxylic acids (A1), especially those of malonic, succinic, glutaric, adipic, sebacic, hexahydrophthalic, terephtalic, maleic, fumaric, citraconic and itaconic acids or their anhydrides, of polyols (A2), especially glycol, 1,2- and 1,3-propanediol, diglycol, dipropylene glycol, butanediol, etc., and &agr;, &bgr;-unsaturated monocarboxylic acid derivatives (A3). The polyesters which are emulsifiable in water are the condensation products of the dicarboxylic acids referred to under (A1) and the polyols referred to under (A2) as well as of a polyether alcohol such polyethylene and polypropylene glycol and alcohols having, an allyl ether functionality. Using these polyesters, dispersions with a mass fraction of solids of approx. 50% can be produced.
From EP-A 0 425 974, water-soluble binders with at least one polymerizable double bond are known which may be produced by condensation of at least one polyoxy-alkylene glycol with a molar mass of from 300 to 800 g/mol, or optionally from one polyoxy-alkylene glycol with a molar mass of less than 300 g/mol, at least one alkoxylated trivalent alcohol, or optionally at least one alkoxylated tetra to hexavalent alcohol, at least one polycarboxylic acid or a derivative of a polycarboxylic acid and at least one monocarboxylic acid of a derivative thereof.
From DE-A 33 40 589, radiation-curable water-soluble polyesters containing acryloyl groups are known which contain co-condensed units of a dicarboxylic anhydride, a polyether alcohol, a bivalent alcohol and a trivalent alkoxylated alcohol and acrylic acid. Dispersions with a mass fraction of solids of approx. 50% can be produced using these polyesters.
OBJECT OF THE INVENTION
However, it was now discovered that a composition comprising an emulsifying resin A containing acid groups and a radiation-curable water-insoluble polymer B, which is either a mixture of these two components without chemical reaction or a reaction product which can be produced from these two component by means of a condensation reaction, can homogeneously be dissolved or dispersed in water up to a mass fraction of solids of about 75%; and that coatings which can be made from it can be hardened by high-energy radiation (UV light or electron beams) into a covering which is resistant to mechanical and chemical influences.
SUMMARY OF THE INVENTION
Therefore, the subject matter of the invention is a radiation-curable polyester composition AB which dissolves in water or can be dispersed in water to solutions or dispersion with a high solid content. The inventive polyester composition AB is produced by mixing or pre-condensing of a water-soluble radiation-curable emulsifying resin A, which contains ester and/or acid groups and has an acid number from about 20 to about 300 mg/g (preferably from about 60 to about 250 mg/g), and of a radiation-curable water-insoluble polymer B, which contains ester and/or ether groups. Resin A is a reaction product of an alkoxylated polyol A1 with at least 3 hydroxyl groups per molecule and 3 to 10 oxyalkylene units per molecule, these oxyalkylene units containing 2 to 4 carbon atoms, with an &agr;, &bgr;-unsaturated carboxylic acid A2, with one free carboxyl group per molecule, and a carboxylic acid A3. Carboxylic acid A3 is selected from carboxylic acids A31, having at least two carboxylic groups wherein at least one of these is a secondary or tertiary carboxylic group (i.e. the carboxylic group is linked to a carbon atom which in turn are linked to two or three carbon atoms) as well as a further acid group selected from carboxylic acid groups, sulphonic and phosphoric acid groups, and carboxylic acids A32 with at least two carboxylic groups and at least one hydroxyl group which is acidic by adjacent electronegative substitution (with a pKa-value of up to about 8). Polymer B is a reaction product of aliphatic, linear, branched or cyclic alcohols B1 with compounds B2 selected from alkylene oxides B21 having 2 to 4 carbon atoms, aliphatic, linear, branched or cyclic dicarboxylic acids B22, having 3 to 8 carbon atoms, and aliphatic lactones B23 having 4 to 12 carbon atoms, as well as compounds B3 selected from &agr;, &bgr;-unsaturated carboxylic acids with 1 to 2 carboxyl groups in the molecule.
In this context a “high solid content” means having a mass fraction of solids exceeding about 55%, preferably exceeding about 65% and particularly preferred in excess of about 70%.
DESCRIPTIONS OF THE PREFERRED EMBODIMENTS
The alkoxylated polyols A1 are conversion products produced in the known manner from alkylene oxides A11 and aliphatic, linear, branched or cyclic compounds A12 with at least three hydroxyl groups per molecule.
The alkylene oxides A11 are aliphatic 1,2-epoxides, selected from ethylene oxide (oxirane), 1,2-propylene oxide (methyloxirane) and 1,2-butylene oxide (ethyloxirane). Particularly preferred is oxirane.
The aliphatic polyols A12 have at least three carbon atoms and at least three, preferably 3 to 6 hydroxyl groups per molecule. Examples are glycerine, trimethylol ethane and trimethylol propane, erythritol, pentaerythritol, arabitol, xylitol and adonitol, sorbitol, mannitol and dulcitol as well as the ether polyols such as ditrimethylol propane and dipentaerythritol. Mixtures of these polyols may also be used.
As &agr;, &bgr;-unsaturated carboxylic acids A2 are suited, for example, aliphatic monocarboxylic acids such as acrylic and methacrylic acid as well as crotonic, isocrotonic and vinylacetic acids, furthermore the monoesters of &agr;, &bgr;-unsaturated dicarboxylic acids and aliphatic alcohols with 1 to 8, preferably with 1 to 4 carbon atoms. Among the latter monomethylmaleate and fumarate as well as monomethyl-, monoethyl-, monobutylesters of the itaconic, citraconic and mesaconic acids should be named. Particularly preferred are acrylic and methacrylic acids as well as monomethylmaleate. Mixtures of these acids may also be used.
The carboxylic acids A3, which can be used for the invention, have at least two carboxyl groups and a further acidic group per molecule. In this context the acidic groups are of differing reactivity which is characterised, for example, by the pK
a
value. Preferably, they should at least possess one additional acidic hydroxyl group (A32) or an additional acidic group (A31) per molecule. They possess preferably at least 3 carbon atoms and may possess an aliphatic, linear, branched or cyclic or an aromatic as well as mixed aromatic-aliphatic structure. Suitable among the hydroxycarboxylic acids are A32 tartronic (hydroxymalonic acid) and malic acid (hydroxysuccinic acid), the isomers of tartaric acid (dihydroxysuccinic acid) as well as the citric and isocitric acids. Among the acids A31 with differing reactivity the tricarballylic and sulfoisophthalic acids should be named.
For the synthesis of the water-insoluble radiation-curable polymers B, aliphatic, linear, branched or cyclic alcohols B1, with not less than two hydroxyl groups per molecule, are used in the first stage. These alcohols are preferably selected from the dihydroxy compounds with two to six carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol and neopentyl glycol. Also preferred are hydroxy compounds with three or more hydroxy groups (such as named hereafter) and mixtures of hydroxy compounds with an average hydroxyl functionality of about 2.1 to about 3.5. Such mixtures comprise, for example, o
Awad Rami-Raimund
Gerlitz Martin
Kuttler Ulrike
Urbano Edmund
Berman Susan W.
Frommer & Lawrence & Haug LLP
Vianova Resins AG
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