Process for the preparation of coatings composed of polyhydroxy compounds

• US 4,177,183 A
• Filed: 04/21/1977
• Issued: 12/04/1979
• Est. Priority Date: 04/29/1976
• Status: Expired due to Term

• Current Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Dalibor, Horst
• Primary Examiner(s): Pertilla, Theodore E.
• Application Number:
  US05/789,660
• Time in Patent Office: 957 Days
• Field of Search: 260/31.4, 260/77.5 CR, 260/836 GL, 260/18 EP, 260/21, 260/32.8 R, 260/856, 260/859 R, 526/49, 526/16, 528/46
• US Class Current: 524/317
• CPC Class Codes: C08G 18/6258 the acid groups being esterified with polyhydroxy compounds or epoxy compounds during or after polymerization
• CPC Class Codes: C08K 5/29 Compounds containing one or more carbon-to-nitrogen double bonds
• CPC Class Codes: C08L 2666/36 Nitrogen-containing compounds
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer

Abstract

The subject of the invention is a process for the production, by shaping while removing the solvent, of coatings composed of polyhydroxy compounds based on copolymers which contain hydroxyl groups and which are reaction products from mixtures of polymerizable vinyl compounds which contain α, β-ethylenically unsaturated monocarboxylic or dicarboxylic acids and styrene, or derivatives thereof, and of glycidyl esters, as well as polyisocyanates in solvents which do not contain active hydrogen atoms.

Claims

1. A coating binder composition, dissolved in solvents which do not contain active hydrogen atoms, composed of a binder (A) comprising a mixture of a copolymer which contains hydroxyl groups and which is a reaction product from mixtures of polymerizable vinyl compounds which contain α

,β

-ethylenically unsaturated monocarboxylic acids and styrene and glycidyl esters and (B), polyisocyanate wherein component A consists of 60-80 percent by weight of hydroxyl group containing copolymers, having a total hydroxyl group content of 3.5 to 6.5 percent by weight, prepared in the presence of a mixture of a diacyl peroxide or perester and an alkyl hydroperoxide or dialkyl peroxide as polymerization initiators, from;

(a) 5-24 percent by weight of glycidyl ester of alkanemonocarboxylic acids selected from the group consisting of α

-alkyl-alkanemonocarboxylic acids and α

,α

-dialkylalkanemonocarboxylic acids of the following empirical formula C_12-14 H_20-26 O₃, and slow, uniform addition to said glycidyl esters (a) of

(b) 12-30 percent by weight of compounds selected from the group consisting of hydroxyethyl acrylate and hydroxyethyl methacrylate,

(c) 1-10 percent by weight of acrylic acid,

(d₁) 20-50 percent by weight of styrene, and

(d₂) 5-35 percent by weight of methyl methacrylate,

the components a, b, c, d₁, and d₂, based on 100 percent by weight of components a to d₂, and the polymerization and condensation reactions taking place simultaneously and jointly, with the additional condition that components a, b, and c are employed in such quantities that the copolymer component A has a hydroxyl group content of 3.5 to 6.5 percent by weight, and component B consists of 20 to 40 precent by weight of an organic polyisocyanate, it being necessary that components A and B together give a numerical value of 100 percent by weight.

2. A composition according to claim 1, wherein component A contains 63 to 68 percent by weight of the copolymers which contain hydroxyl groups and component B contains 32 to 37 percent by weight of an organic triisocyanate which has been obtained by reacting 3 mols of hexamethylene diisocyanate and 1 mol of water, it being necessary that A and B together give a numerical value of 100 percent by weight.

3. A composition according to claim 1, wherein 1 to 10 percent by weight of reactive melamine resins, relative to the weight of the binder component, are used as an additional binder.

4. A composition according to claim 1, wherein component A is a solution containing 10 to 30 percent by weight of inert organic solvents which are customary in the lacquer industry and 70 to 90 percent by weight of copolymers, it being necessary that the percentages of components A and B add up to 100 percent by weight.

5. A coating composition according to claim 1, wherein component A comprises a copolymer which has a hydroxyl group content of 4.5±

0.3 percent by weight and which component A copolymer is obtained from a mixture consisting of

A"--20-25 percent by weight of ethylglycol acetate and

B"--75-80 percent by weight of a reaction mixture of the components a to d₂ ;

(a) 11-12 percent by weight of glycidyl ester of α

,α

-dialkylalkanemonocarboxylic acids of the following empirical formula C₁₃ H₂₄ O₃ which have been obtained by reacting tripropylene, carbon monoxide and water and which consist essentially of monocarboxylic acids with highly branched C₁₀ chains, being heated with the ethylglycol acetate to 165°

to 170°

C., and a mixture consisting of

(b) 25-26 percent by weight of compounds selected from the group consisting of hydroxyethyl acetate and hydroxylethyl methacrylate,

(c) 3-4 percent by weight of acrylic acid,

(d₁) 44-48 percent by weight of styrene,

(d₂) 10-16 percent by weight of methyl methacrylate,

(e) 2-2.5 percent by weight of tert.-butyl perbenzoate, and

(e'"'"') 1-1.5 percent by weight of cumene hydroperoxide,

dissolved to form an 80 percent strength solution in a mixture of alcohols, ketones and cumene,

it being necessary that the sum of the monomers a to d₂ add up to 100 percent by weight, said reaction mixture B" being added slowly and uniformly to component A" in the course of 6 to 10 hours and the temperature of said mixture A" plus B" being kept at 170±

5°

C. in the course thereof, until the solids content of the solution has reached a value of 80±

1 percent by weight, the polymerization and condensation reactions taking place jointly and simultaneously and the copolymer having a hydroxyl group content of 4.5±

0.3.

6. A coating composition according to claim 5, wherein compound a of component B" is a mixture of glycidyl esters of α

,α

-dialkylalkanemonocarboxylic acids having up to about 10 percent by weight of glycidyl ester of α

,α

-dialkylalkanemonocarboxylic acids of the said empirical formula, the mixture having an epoxide equivalent of 240 to 250.

7. A coating composition according to claim 1, applied to a sheet-like structure, and from which composition so applied, solvents are removed by air drying.