Polyester prepolymer useful for coating anda method of preparing thesame

Claim 1

26,285 m Claims defining the invention are as follows:- 1. A orie li~ing 1 h polyester prepolymer com- prising a backbone chain formed from a non-crystalline polyrster of a molecular weight of 300 to 5,000 which is a polycondensa- tion product of a polybasic carboxylic acid component and a polyol component and contains a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH/g; and at least one pendent side chain substituting said hydroxyl group of said backbone chain with an ester bonding in a proportion of not lower than 0.5 but not exceeding 7.0 of said pendent side chains with respect to 1,000 molecular weight of said backbone chain, containing at least two ester groups and being terminated with at least one cN, 9-olefinically unsaturated group. 2. A polyester prepolymer as set forth in claim 1, wherein said polybasic carboxylic acid component of said backbone chain is a member selected from aliphatic polybasic carboxylic acids having a straight or branched chain of 2 to 20 carbon atoms, aromatic polybasic carboxylic acids, alicyclic poly- basic carboxylic acids and aralkyl polybasic carboxylic acids. 3. A polyester prepolymer as set forth in claim 1, wherein said polybasic acid component of said backbone chain is a member selected from the class consisting of malonic acid, oxalic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, itaconic acid, rA-methylene glutaric acid, adipic acid, sobacic acid, phthalic acid, isophthalic acid, tetrabromophthalic acid, tetrahydrophthalic acid, dimethyl tetraphthalic acid, naphthalene dicarboxylic acid, endo- methylene tetrahydrophthalic acid, citraconic acid, muconic acid, diglycollic acid, pimelic acid, malic acid, p-carboxy- phenyl carboxylic acid, benzophenone-4-4'-dicarboxylic acid, 2 4 ,o 0 7 26, 2 8 5 M and dicarboxylic acid of the formula: CH2 01H- \I2 C CH2 CH2 CH COOH COOH 4. A polyester prepolymer as set forth in claim 1, wherein said polyol component of said backbone chain is a polyol mixture containing 1 to 85% by mol of tri- or more-hydric alcohol. A polyester prepolymer as set forth in claim 4, wherein said tri- or more-hydric alcohol is a member selected from the class consisting of glycerol, trirethylol propane, 1,3,6- hexane triol, trimethylol ethane, pentaerythritol, sorbitol, glucose and mixtures of the above polyols. 6. A polyester propolymer as set forth in claim 4, wherein said polyol mixture contains a diol member selected from the class consisting of ethylene glycol, propylene glycol, 1,3- butylene glycol, diethyl glycol, 1,4-cyclohexane diol, neopentyl glycol, bis-phenol A, hexamethylene glycol, p-dihydroxy di- methyl benzene, hexahydroresorcinol,'hydroquinone, polyalkylene glycols and mixtures of the above diols. 7; A polyester prepolymer as set forth in claim 1, wherein said pendent side chain is of the formula: R OOC R COOCH CH- CH 2 OOC -C CH2 OH or R I 00C R1 COOCH 2 CH OOC C CH2 wherein R represents a hydrogen atom or methyl group, and R 1 represents a di-valent organic group, therefore, OOC R1 COO represents a polybasic carboxylic acid residue. 40 455,0 2 8 26, 2 8 Claims defining the invention are as follows:- 1. A erco li.1:c1; r±niig polyoster prepolymer com- prising a backbone chain formed from a non-crystalline polyrster of a molecular weight of 300 to 5,000 which is a polycondensa- tion product of a polybasic carboxylic acid component and a polyol component and contains a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH/g; and at least one pendent side chain substituting said hydroxyl group of said backbone chain with an ester bonding in a proportion of not lower than 0.5 but not exceeding 7.0 of said pendent side chains with respect to 1,000 molecular weight of said backbone chain, containing at least two ester groups and being terminated with at least one cq, ,-olefinically unsaturated group. 2. A polyester prepolymer as set forth in claim 1, wherein said polybasic carboxylic acid component of said backbone chain is a member selected from aliphatic polybasic carboxylic acids having a straight or branched chain of 2 to 20 carbon atoms, aromatic polybasic carboxylic acids, alicyclic poly- basic carboxylic acids and aralkyl polybasic carboxylic acids. 3. A polyester prepolymer as set forth in claim 1, wherein said polybasic acid component of said backbone chain is a member selected from the class consisting of malonic acid, oxalic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, itaconic acid, 'X-methylene glutaric acid, adipic acid, sobacic acid, phthalic acid, isophthalic acid, tetrabromophthalic acid, tetrahydrophthalic acid, dimethyl tetraphthalic acid, naphthalene dicarboxylic acid, endo- methylene tetrahydrophthalic acid, citraconic acid, muconic acid, diglycollic acid, pimelic acid, malic acid, p-carboxy- phenyl carboxylic acid, benzophenone-4-4'-dicarboxylic acid, 455.028 26,2 85 m and dicarboxylic acid of the formula: 2CH 2 CH II C CH 2 C COOH COOH 4. A polyester prepolymer as set forth in claim 1, wherein said polyol component of said backbone chain is a polyol mixture containing 1 to 85% by mol of tri- or more-hydric alcohol. A polyester prepolymer as set forth in claim 4, wherein said tri- or more-hydric alcohol is a member selected from the class consisting of glycerol, trinethylol propane, 1,3,6- hexane triol, trimethylol ethane, pentaerythritol, sorbitol, glucose and mixtures of the above polyols. 6. A polyester propolymer as set forth in claim 4, wherein said polyol mixture contains a diol member selected from the class consisting of ethylene glycol, propylene glycol, 1,3- butylone glycol, diethyl glycol, 1,4-cyclohexane diol, neopentyl glycol, bis-phenol A, hexamethylene glycol, p-dihydroxy di- methyl benzene, hexahydroresorcinol, hydroquinone, polyalkylene glycols and mixtures of the above diols. 7; A polyester prepolymer as set forth in claim 1, wherein said pendent side chain is of the formula: R OOC- R- COOCH2 CH CH2 OOC -C CH2 OH or R OOC RI COOCH 2 CH OOC C CH2 CH2 0H wherein R represents a hydrogen atom or methyl group, and R 1 represents a di-valent organic group, therefore, OOC R1 COO represents a polybasic carboxylic acid residue. 40 45.5, 02 26,2 85 8. A polyester propolymer as sct forth in claim 1, wherein pendent side chain is attachod to said backbone chain with a residue of a polybasic carboxylic acid selected from the class consisting of maleic acid, chlorinated malcic acid, succinic acid, itaconic acid, :)(-mothylene glutaric acid, citraconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, naphthalone dicarboxylic acid, dodecenyl succinic acid, endo-mothylene totrahydrophthalic acid, methyl-endo-methylone tetraphydrophthalic acid, hexa- hydrophthalic acid, and 1,4,5,6,7,7-hexachloro-bi-cyclo- (2,2,l1 hept-6-en-2,3-dicarboxylic acid. 9. A polyester propolymer as set forth in claim 1, wherein said pendent side chain is terminated with a residue of a member selected from glycidyl esters of 6, -olefinically unsaturated acids and glycidyl ethers of hydroxyl group- containing vinyl monomers. A polyester prepolymer as set forth in claim 9, wherein said glycidyl ester is glycidyl acrylate ester or glycidyl methacrylate ester. 11. A polyester prepolymer as set forth in claim 9, wherein said glycidyl ether is allyl glycidyl ether, methallyl glycidyl ether or vinyl cyclohexane monoxide. 12. A method of preparing a =Q hae-g poly- ester propolymer comprising the steps of first reacting a backbone polymer of a molecular weight of 300 to 5,000 which is a polycondensation product of a polybasic carboxylic acid component and a polyol component and contains a hydroxyl group wvrith a hydroxyl value of 20 to 200 mgKOH/g, with-a polybasic c&By3ic acid anhydride in a proportion of at least 0.1 mol of said polybasic carboxylic -41 45,028 26,285 n1 acid anhydride with respect to 1.0 nol of said hydroxyl group in said backbone polymer, and second reacting said result of said stop with a vinyl monomer being terminated at -"thoreof with a glycidyl group and an 3 -olcfinically unsaturated group.in a proportion of at least 0.1 mol of said vinyl monomer with respect to 1.0 mol of said hydroxyl group of said backbone polymer. 13. A method as set forth in claim 12, wherein said poly- basic carboxylic acid component for said backbone polymer is selected from aliphatic polybasic carboxylic acids having a straight or branched chain of 2 to 20 carbon atoms, aromatic polybasic carboxylic acids, alicyclic polybasic carboxylic acids and aralkyl polybasic carboxylic acids. 14. A method as set forth in claim 12, wherein said poly- basic acid component for said backbone polymer is a member selected from the class consisting of malonic acid, oxalic acid, succinic acid, maleic acid, succinic acid anhydride, dodecenyl succinic acid anhydride maleic acid .nhydrido, glutaric acid, fumaric acid, itaconic acid, c.-mothylone glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrabromophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid dinethyl tetraphthalic acid, naphthalene dicarboxylic acid, endo-methylene totrahydro-- phthalic acid, citraconic acid, muconic acid, diglycollic acid, pimelic acid, malic acid, p-carboxyphenyl carboxylic acid, benzophenone 4,4'-dicarboxylic acid and dicarboxylic acid of the formula: CH2 CH C CH2CH2 CH COOH COOH A method as set forth in claim 12, wheroin said polyol component for said backbone polymer is polyol mixture con- aL. taining 10 to 85% by mol of tri- or more-hydric alcohol. 16. A method as set forth in claim 15, wherein said tri- or.more-hydric alcohol is a member selected from the class consisting of glycerol, trimethylol propane, 1,3,6-hexanetriol, trimethylol ethane, pentacrythritol, sorbitol, glucose and mixtures of the above polyols. 17. A method as set forth in claim 15, wherein said polyol mixture contains a diol seleqted from the class consisting of ethylene glycol, propylone gl col, 1,3-butylene glycol, diethyl A, glycol, 1,4-cyclohexane diol, ncopentyl glycol, bis-phenol hexamothylone glycol, p-dihydroxy dimethyl benzone, hoxahydro- resorcinol, hydroquinone, polyalkylene glycols, and mixtures of the above diols. 18. A method as set forth in claim 12, wherin said poly- basic carboxylic acid anhydride to be reacted to said backbone polymer is a member selected from the class consisting of anhydrides of maleic acid, chlorinated maleic acid, succinic acid, itaconic acid, 0(-methylene glutarin acid, citraconic ,acid, phthalic acid, tetrahydrophthalic acid, hexahydro- phthalic acid, tetrabromophthalic acid, naphthalene dicar- boxylic acid, dodecenyl succinic acid, endo-mothylene tetra- hydrophthalic acid, mothyl-endo-methylene tetraphydrophthalic acid, hexahydrophthalic acid, and.1,4,5,6,7,7-hexachloro-bi- cyclo-[2,2,13 hept-6-cn-2,3-dicarboxylic acid. 19. A method as set forth in claim 12, wherein said vinyl monomer is a member selected from glycidyl esters of olefinically unsaturated acids and glycidyl others of hydroxyl group-containing vinyl monomers. 43 455, 028 2 6,285 nt A method as set forth in claim 19, wherein said gly- cidyl ester is glycidyl acrylate ester or glycidyl methacrylate ester. 21. A method as set forth in claim 19, wherein said gly- ether cidyl ether is allyl glycidyl ether, methallyl glycidyl or vinyl cyclohexane monoxide. 22. A coating composition comprising ac')e"-i-r-ndly chain hardeni g polyester propolyncr comprising a backbone formed from a non-crystalline polyester of a molecular weight a of 300 to 5,000 which is a polycondensation product of polybasic carboxylic acid component and a polyol component and contains a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH/g; and at least one pendent side chain substituting said hydroxyl group of said backbone chain with an ester bond- ing in a proportion of not lower than 0.5 but not exceeding of said side chains with respect to 1,000 molecular weight of said backbone chain, containing at least two ester groups and being terminated with at least one P-olefinically unsaturated group; and organic solvent for said prepolymer. 23. A coating composition as sot forth in claim 22, wherein said organic solvent is a mixture of 30 to 100% by weight of an acrylic or methacrylic ester and 0 to 70% by weight of a monomer capable of copolymerization with said acrylic or methacrylic ester. 24. A coating composition as set forth in claim 22, wherein said organic solvent is a member selected from reaction pro- ducts of A, P-olefinically unsaturated carboxylic acids and/or polybasic carboxylic acids and vinyl monomers being terminated with an epoxy group. A coating composition as set forth in claim 22, wherein 455,028 26,285 1 said organic solvent is a member selcct-d from reaction pro- ducts of a condensation product of vinyl monomers being terminated with a hydroxyl group and/or polyhydric alcohols having at least two pendent hydroxyl groups and polybasic carboxylic acid anhydrides, and vinyl monomers being terminated with an epoxy group. 26. A coating composition as set forth in claim 22, wherein said organic solvent is a member selected from reaction pro- ducts of condensation products of vinyl monomers being terminated vith a hydroxyl group and polybasic carboxylic acid anhydrides and polyepoxides. 27. A coating composition as set forth in claim 22, wherein said organic solvent is a member selected from condensation products of- a reaction product of vinyl monomers being terminated with a hydroxyl group and polybasic carboxylic acid anhydrides and polyhydric alcohols. 28. A coating composition as set forth in claim 22, wherein said organic Colvent is a member selected from condensation products of -reaction products of one or more parts by mol of polyhydric alcohols and two parts by mol of polybasic carboxylic acids and vinyl monomers being terminated with a hydroxyl group. 296 A coating composition as set forth in claim 23, wherein said acrylic and methacrylic ester is selected from the acrylic and methacrylic esters wherein a hydrogen atom of the carboxylic group thereof is substituted with a member selected from straight or branched hydrocarbon groups of 6 to 12 carbon atoms, cyclohexyl group, benzyl group and phenetyl group. 455.02 26,2 Dated this 14th day of March, 1971. MITSUBISHI RAYON COMPAN'Y LIMITED By its Patent Attorneys DAVIES COLLISON 455,0 28a