CA2101244A1 - Epoxy phosphate ester resin, its production and coating composition containing the resin - Google Patents
Epoxy phosphate ester resin, its production and coating composition containing the resinInfo
- Publication number
- CA2101244A1 CA2101244A1 CA002101244A CA2101244A CA2101244A1 CA 2101244 A1 CA2101244 A1 CA 2101244A1 CA 002101244 A CA002101244 A CA 002101244A CA 2101244 A CA2101244 A CA 2101244A CA 2101244 A1 CA2101244 A1 CA 2101244A1
- Authority
- CA
- Canada
- Prior art keywords
- epoxy
- phosphate ester
- resin
- phosphoric acid
- epoxy phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
- C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
Abstract
The present invention provides a process for preparing an epoxy phosphate ester resin, which comprises (1) reacting an epoxy resin having an average of greater than one vicinal epoxy group with a phosphoric acid source material to obtain an epoxy phosphate ester; and (2) further reacting the obtained epoxy phosphate ester with a phosphoric acid source material. The present invention provides epoxy phosphate ester resins obtained by the above process, which exhibit good water-solubility. The coating compositions containing such epoxy phosphate ester resin show good coating properties such as good corrosion resistance, chemical resistance, heat resistance and flexibility.
Description
WO 93/12156 PCI`/IJS92/10197 ```- 21~12~4 EPOXY PHOSPHATE ESTER RESIN, ITS PRODUCTION AND
COATING COMPOSITION CONTAINING THE RESIN
Technical Field The present invention relates to a water- soluble epoxy phosphate ester resin which can be used as a water-borne coating material, its production process and a coating composition containing the resin. - .
'.: .
Backaround Art Epoxy resins have been used in a wide variety of applicationssuch ascoating applications, for example, because of their superiority in corrosion resistance, chemical resistance and flexibility. In order to improve workability, the epoxy resins are usually diluted with an organic solvent to decrease thei r viscosities. -Recently, various laws and regulations regarding use of organic soh/ents, such as 15 organic solvent intoxication prevention regulations and fire regulations, have become more stringent. Because of such regulations, it is desired to make epoxy resins for coating compositions water soluble or water dispersible. Several attempts have been madeto modify ..
conventional epoxy resins which per se are not water soluble. For example, self-dispersi on type epoxy resins modified with an acrylic resin have been proposed and disclosed in Japanese :
20 PatentApplication Laid Open Gazettes Nos. Sho 55-003,481 and Sho 58-198,513.
Further, for simplification of steps, studies have been carried out to rnake an epoxy resin per se water dispersible. For example, in Japanese Patent Application Laid-Open Gazette No. Hei 2-212,570, an epoxy resin is reacted with phosphoric acid to make the resin water dispersible. However, phosphoric acid has three hydroxyl groups and thus triesters of 25 phosphoric acid are easily formed. For this reason, to obtain an epoxy phosphate ester resin having low viscosity and good dispersion stability, excess arnounts of phosphoric acid must be : - -employed. Therefore, unreacted phosphoric acid may remain in the resin product resulting in problems such as blushing of resultant coatings.
:
: .
WO93/12156 ~ ~ ~ PCl/US92/10197 Japanese Patent Publication Gazette No. Hei 1-055,299 discloses an epoxy phosphate ester resin prepared by reacting an epoxy resin with phosphoric acid, and then hydroly~ing the phosphoric acid modified epoxy resin fot monoesteri~ication. The resultant resin per se can be made water dispersible. However, the resins have unduly large particle size 5 v~hen dispersed in water, resulting in poor dispersion stability. Accordingly, if the amount of organic solvent used is restricted, sufficient dispersion stability cannot be obtained. In particular, in paints prepared using an aromatic epoxy resin, a completely transparent aqueous solution cannot be obtained. In the case of relatively low molecular weight epoxy resins having a weight average molecular weight of 340 to 4,000, there is a problem that they are difficult to 10 hydrolyze and their viscosities increase when r~ispersed in water.
In view of the deficiencies of the pric,r art described above, it would be desirable to provide an epoxy phosphate ester resin which exhibits good water-solubility, and its production process.
It would also be desirable to provide a coating ¦composition having good coating15 properties such as a good anti-rust property and good flexibility. ;.
Summar~of Invention According to the present invention, there is now provided a process for preparing an epoxy phosphate ester resin, which comprises (1) reacting an epoxy resin having an average 2û of greaterthanonevicinalepoxygroupwithaphosphoricacidsourcematerialtoobtainanepoxy phosphate ester; and (2) further reacting the obtained epoxy phosphate ester with a phosphoric acid source material.
Another aspect of the present invention pertai ns to an epoxy phosphate ester resin prepared by the above process.
Another aspect of the present i nventi on relates to a coati ng composition comprising:
(a) the epoxy phosphate ester resin obtained as above;
(b) an acrylic resin and/or a polyester resin, miscible with the epoxy phosphateester resi n;
3û ~c) at least one curing agent; and (d) water and/or an organic solvent.
According to the process of the present invention, water-soluble epoxy phosphate ester resins having low viscosity can be obtained while !estricting the amount of free phosphoric acid, diesters of phosphoric acid and triesters of pnosphoric acid to a minimum 35 level.
The water-soluble resins of the present invention can be used to form a more stable aqueous solution when compared with conventional epoxy ¦phosphate ester resin. The water-borne coating compositions according to the prFsent invention, provides a resultant - .
: ' 2 1 ~12 ~ ~ PCI/VS92/10197 ~ '`.`............................................................ :
:."j. ::
coating film with improved corrosion resistance and flexibility as compared with a conventional paint such as an acrylic resin-based paint. Accordingly, the coating compositions of the present invention can be effectively used, particularly, in the fields of coating applications such as spray coating and roll coating.
Detailed Exolanation of the Invention In the present invention, any known epoxy resins having an average of more than one epoxy group per molecule, can be used. Suitable epoxy resins include, for example, thosehavinganepoxyequivalentweightoffrom t70to3,500,moresuitablyfromaboutl75 10 to1,000,andaweightaveragemolecularweightoffrom340tol8,000,moresuitablyfrom340to 5,000. Preferred epoxy resins which can be used herein, are those having two vicinal epoxy groups such as diglycidyl ethers of bisphenol A, bisphenol K, bisphenol F, bisphenol S, bisphenol AD, aliphatic phenols and mixturesthereof. The most preferred epoxy resin are diglycidyl ethers of bisphenoi A and diglycidyl ethers of aliphat;c phenols.
in the present invention, the epoxy resi ns are not li mited to the above-mentioned epoxy resir,s, but include any known epoxy resins. Such epoxy resins are well described in, for example, U .S. Patent Nos.4,289,812,4,397,970,4,~68,059 and 5,070,174, and "The Handbook of Epoxy Resins" by H. Lee and K. Neville, published in 1967 by McGraw-Hill, New York, all of which are incorporated herein by reference.
Ascommerciallyavailableepoxyresins, D.E.R."' 331L; D.E.R. '~ 3~3J; D.E.R."^ 661;D.E.R."' 664; D.E.R.T" 732; and D.E.N."' 438 (trademarks of The Dow Chemical Company) resins, available from The Dow Chemical Company, can be used.
The epoxy resins which can be used i n the present i nvention may be prepared bythe reaction of a commercially available epoxy resin and a phenolic compound havin~ an 25 average of more than one hydroxyl group. In this case, the epoxy resin and the phenolic compound may be used in an amount to provide an epoxy: phenolic component ratio by weight of preferably from 6û:4û to 99: 1, more preferably from 75:25 to 99: 1.
Also, if the amount of the phenolic compound used exceeds 40 percent by ~ :~
weight, the next reaction, i.e., phosphorylation is difficult to conduct.
In the reaction between the epoxy component and the phosphoric acid component, according to the present invention, any known catalyst can be used. Such known catalysts include, for example, imidazoles such as 2-methylimidazole; tertiary amines such as triethylamine, tripropylamine and tributylamine; phosphonium salts such as ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and 35 ethyltriphenylphosphonium acetate-acetic acid complex; and ammonium salts such as benzyltrimethylammonium chloride and benzyltrimethylammonium hydroxide.
. .
COATING COMPOSITION CONTAINING THE RESIN
Technical Field The present invention relates to a water- soluble epoxy phosphate ester resin which can be used as a water-borne coating material, its production process and a coating composition containing the resin. - .
'.: .
Backaround Art Epoxy resins have been used in a wide variety of applicationssuch ascoating applications, for example, because of their superiority in corrosion resistance, chemical resistance and flexibility. In order to improve workability, the epoxy resins are usually diluted with an organic solvent to decrease thei r viscosities. -Recently, various laws and regulations regarding use of organic soh/ents, such as 15 organic solvent intoxication prevention regulations and fire regulations, have become more stringent. Because of such regulations, it is desired to make epoxy resins for coating compositions water soluble or water dispersible. Several attempts have been madeto modify ..
conventional epoxy resins which per se are not water soluble. For example, self-dispersi on type epoxy resins modified with an acrylic resin have been proposed and disclosed in Japanese :
20 PatentApplication Laid Open Gazettes Nos. Sho 55-003,481 and Sho 58-198,513.
Further, for simplification of steps, studies have been carried out to rnake an epoxy resin per se water dispersible. For example, in Japanese Patent Application Laid-Open Gazette No. Hei 2-212,570, an epoxy resin is reacted with phosphoric acid to make the resin water dispersible. However, phosphoric acid has three hydroxyl groups and thus triesters of 25 phosphoric acid are easily formed. For this reason, to obtain an epoxy phosphate ester resin having low viscosity and good dispersion stability, excess arnounts of phosphoric acid must be : - -employed. Therefore, unreacted phosphoric acid may remain in the resin product resulting in problems such as blushing of resultant coatings.
:
: .
WO93/12156 ~ ~ ~ PCl/US92/10197 Japanese Patent Publication Gazette No. Hei 1-055,299 discloses an epoxy phosphate ester resin prepared by reacting an epoxy resin with phosphoric acid, and then hydroly~ing the phosphoric acid modified epoxy resin fot monoesteri~ication. The resultant resin per se can be made water dispersible. However, the resins have unduly large particle size 5 v~hen dispersed in water, resulting in poor dispersion stability. Accordingly, if the amount of organic solvent used is restricted, sufficient dispersion stability cannot be obtained. In particular, in paints prepared using an aromatic epoxy resin, a completely transparent aqueous solution cannot be obtained. In the case of relatively low molecular weight epoxy resins having a weight average molecular weight of 340 to 4,000, there is a problem that they are difficult to 10 hydrolyze and their viscosities increase when r~ispersed in water.
In view of the deficiencies of the pric,r art described above, it would be desirable to provide an epoxy phosphate ester resin which exhibits good water-solubility, and its production process.
It would also be desirable to provide a coating ¦composition having good coating15 properties such as a good anti-rust property and good flexibility. ;.
Summar~of Invention According to the present invention, there is now provided a process for preparing an epoxy phosphate ester resin, which comprises (1) reacting an epoxy resin having an average 2û of greaterthanonevicinalepoxygroupwithaphosphoricacidsourcematerialtoobtainanepoxy phosphate ester; and (2) further reacting the obtained epoxy phosphate ester with a phosphoric acid source material.
Another aspect of the present invention pertai ns to an epoxy phosphate ester resin prepared by the above process.
Another aspect of the present i nventi on relates to a coati ng composition comprising:
(a) the epoxy phosphate ester resin obtained as above;
(b) an acrylic resin and/or a polyester resin, miscible with the epoxy phosphateester resi n;
3û ~c) at least one curing agent; and (d) water and/or an organic solvent.
According to the process of the present invention, water-soluble epoxy phosphate ester resins having low viscosity can be obtained while !estricting the amount of free phosphoric acid, diesters of phosphoric acid and triesters of pnosphoric acid to a minimum 35 level.
The water-soluble resins of the present invention can be used to form a more stable aqueous solution when compared with conventional epoxy ¦phosphate ester resin. The water-borne coating compositions according to the prFsent invention, provides a resultant - .
: ' 2 1 ~12 ~ ~ PCI/VS92/10197 ~ '`.`............................................................ :
:."j. ::
coating film with improved corrosion resistance and flexibility as compared with a conventional paint such as an acrylic resin-based paint. Accordingly, the coating compositions of the present invention can be effectively used, particularly, in the fields of coating applications such as spray coating and roll coating.
Detailed Exolanation of the Invention In the present invention, any known epoxy resins having an average of more than one epoxy group per molecule, can be used. Suitable epoxy resins include, for example, thosehavinganepoxyequivalentweightoffrom t70to3,500,moresuitablyfromaboutl75 10 to1,000,andaweightaveragemolecularweightoffrom340tol8,000,moresuitablyfrom340to 5,000. Preferred epoxy resins which can be used herein, are those having two vicinal epoxy groups such as diglycidyl ethers of bisphenol A, bisphenol K, bisphenol F, bisphenol S, bisphenol AD, aliphatic phenols and mixturesthereof. The most preferred epoxy resin are diglycidyl ethers of bisphenoi A and diglycidyl ethers of aliphat;c phenols.
in the present invention, the epoxy resi ns are not li mited to the above-mentioned epoxy resir,s, but include any known epoxy resins. Such epoxy resins are well described in, for example, U .S. Patent Nos.4,289,812,4,397,970,4,~68,059 and 5,070,174, and "The Handbook of Epoxy Resins" by H. Lee and K. Neville, published in 1967 by McGraw-Hill, New York, all of which are incorporated herein by reference.
Ascommerciallyavailableepoxyresins, D.E.R."' 331L; D.E.R. '~ 3~3J; D.E.R."^ 661;D.E.R."' 664; D.E.R.T" 732; and D.E.N."' 438 (trademarks of The Dow Chemical Company) resins, available from The Dow Chemical Company, can be used.
The epoxy resins which can be used i n the present i nvention may be prepared bythe reaction of a commercially available epoxy resin and a phenolic compound havin~ an 25 average of more than one hydroxyl group. In this case, the epoxy resin and the phenolic compound may be used in an amount to provide an epoxy: phenolic component ratio by weight of preferably from 6û:4û to 99: 1, more preferably from 75:25 to 99: 1.
Also, if the amount of the phenolic compound used exceeds 40 percent by ~ :~
weight, the next reaction, i.e., phosphorylation is difficult to conduct.
In the reaction between the epoxy component and the phosphoric acid component, according to the present invention, any known catalyst can be used. Such known catalysts include, for example, imidazoles such as 2-methylimidazole; tertiary amines such as triethylamine, tripropylamine and tributylamine; phosphonium salts such as ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and 35 ethyltriphenylphosphonium acetate-acetic acid complex; and ammonium salts such as benzyltrimethylammonium chloride and benzyltrimethylammonium hydroxide.
. .
3 ::
., . . ,:
..... ..
: ' ' , !, , ~, . ' . ! , ~ , . , ' ~? '~ PCI/US9~/10197 In addition, known catalysts other than the above-mentioned catalysts can be used. Such catalysts include those described in, for example, U.S. Patent Nos. 4,289,812;
., . . ,:
..... ..
: ' ' , !, , ~, . ' . ! , ~ , . , ' ~? '~ PCI/US9~/10197 In addition, known catalysts other than the above-mentioned catalysts can be used. Such catalysts include those described in, for example, U.S. Patent Nos. 4,289,812;
4,397,970 and 4,868,059, all of which are incorporated herein by reference.
in the present invention, acidic catalysts are ¦preferable. The amount of the catalysts used generally ranges from 0.001, preferably 0.01 to 1, preferably to 0.3 percent by weight, based on the total solid weight of the reaction mixture.
In the present invention, the above-mentioned epoxy r esin is reacted with a phosphoric acid source material and the reaction product obtained is further reac~ed with a phosphoric acid sou rce material The obtained product is then subjected to hydrolysis 10 treatmentto produce an epoxy phosphate monoester resin.
Phosphoric acid source materials which can be employed in the present invention include, for example, 100 percent phosphoric acid, the semi-hydrate (2H3PO4-H2O) and aqueous solutions cc ntaining at least 18 weight percent HP304 (at least 1 mole H3poA per 25 moles of water). ~he various condensed forms (polymeric, partial anhydrides) of phosphoric acid, pyrophosphoric acid, orthophosphoric acid and tri phosphoric acid can also be used.
Preferred are phosphoric acid having an H3PO4 concentration of from 85 to 120 percent, and more preferred are superphosphoric acids having an H3PO4 concentration of from 105 to 1 16 ~i percent.
For the reaction of the epoxy component and the phosphoric acid component, 20 the phosphoric acid source material may be added dropwise to the epoxy component at, for example, 50C to 1 50C for a period of from 1, preferably 5 to 110, preferably to 15 minutes.
After the dropwise addition, the reaction mixture may be heated and stirred for 1 to 120 minutes. If desired, these procedures rrlay be repeated as many times as necessary.
Water-dispersible epoxy phosphate ester resins can be obtained even if the whole25 amount of phosphoric lacid source material for the two-step reaction is simultaneously reacted in a single step with an epoxy resin. However, in such a case the reaction products have high viscosity and also contain unreacted phosphoric acid, triesters and diesters of phosphoric acid, resulting in poor stability when dispersed in an aqueous sol ution.
In the present invention, when producing high molecular weight epoxy 30 phosphate ester resins, it is possible to perform a uniform reaction by decreasing the viscosity of the reaction mixture with an organic solvent to improve stirring efficiency.
Suitablesolventsforusehereinincludeorganicsolventshavinggood compa~ibility with an epoxy resin and a boiling point higher than 110C, especially higherthan 140C. Examples of the organic solvents used herein are glycol type solvents such as ethylene 35 glycol and propylene glycol; glycol monoether type solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether, diethylene glycol ~ . -butyl ether, propylene glycol n-butyl ether; acetate type solvents such as propylene glycol monomethyl ether acetate, butyl acetate and propylene glycol methyl ether acetate; alcohol :~ .
-4- :
:
. . .
WO 93/12156 2 ~ ~ ~ 2 ~ ~ PCI /US9~/10197 type solvents such as n-butanol, amyl alcohol and cyclohexanol; ketone type solvents such as cyclohexanone and diisobutyl ketone; and aromatic solvents such as xylene and SOLVESSO~'^
100 (supplied by Exxon Chemical). Of these solvents, a glycol type solvent and an alcohol type solvent are especially preferred. These solvents can be used singly or as a mixture of two or 5 more thereof The non-volatiles concentration of the diluted reaction system is preferably from 50 to 100 percent, based on the total reaction mixture. The higher solids concentration is ~ -preferable within the viscosity range where the reaction mixture is not gelled.
In the reaction between the above-mentioned phosphoric acid component and the above-mentioned epoxy component, in the first reaction step an epoxy resin may be 10 reacted with a phosphoric acid source material in an amount to provide from 0.2 to 0.4, preferably from 0.25 to 0.35 hydroxyl group per epoxy group; and in the second reaction step the obtained epoxy phosphate ester is reacted with a phosphoric acid source material in an amount to provide from 0.05 to 0.4, preferably from 0.05 to 0.20 hydroxyl group per epoxy : .
group. `
More specifically, in the case of using 100 percent phosphoric acid, the amount of the phosphoric acid source material used for one reaction may preferably range from 0.1 to 6.0 percent by weight, rnore preferably from 0.3 to 5.5 percent by weight, most preferably from 0.4 to 4.8 based on the total solid content of the reaction mixture. If the amount of the phosphoric acid source material used is less than 0.1 percent by weight, the resultant resins have a large 20 amount of unreacted epoxy groups, resulting in increased viscosity or poor dispersion stability when dispersed in water. If the amount of unreacted epoxy groups exceeds 6.0 percent by weight, gelation may occur during the reaction or free phosphoric acid will be formed during the next reaction step. These are disadvantageous and free phosphoric acid will cause blushing when a coating of the resultant resi n is subjected to retort treatment. :
The phosphoric acid source materials per se can be added dropwise. However, it is effective to use the phosphoric acid source material diluted with a hydroxylic solvent such as the above-mentioned glycol monoether type jsolvent or a mixture thereof. The use of the hydroxyl group-containing solvents prevents self-condensation of the phosphoric acid source materials, resulting in a more uniform reaction. These solvents can be used in an amount to 30 provide a molar ratio of the solvent to the phosphoric acid source material of at least 2:1, preferably at least 4:1.
The epoxy phosphate ester resins prepared as above are mainly in the form of triesters or di esters, and thus can be changed to monoesters by subjecti ng them to partial hydrolysis to reduce them to monoesters. Monoesterification reduces the viscosity of the :
35 resultant hydrolyzed modified epoxy phosphate ester resin to make handling easier. . :.
Further, the phosphate groups existing atthe end of molecules can provide good corrosic n resistance inherently possessed by the phosphoric acid. Further, the phosphoric acid residuesmayca~alyzecuringoftheresultantcoatedfiimandprovideflexibilitytothecoated -- ~
in the present invention, acidic catalysts are ¦preferable. The amount of the catalysts used generally ranges from 0.001, preferably 0.01 to 1, preferably to 0.3 percent by weight, based on the total solid weight of the reaction mixture.
In the present invention, the above-mentioned epoxy r esin is reacted with a phosphoric acid source material and the reaction product obtained is further reac~ed with a phosphoric acid sou rce material The obtained product is then subjected to hydrolysis 10 treatmentto produce an epoxy phosphate monoester resin.
Phosphoric acid source materials which can be employed in the present invention include, for example, 100 percent phosphoric acid, the semi-hydrate (2H3PO4-H2O) and aqueous solutions cc ntaining at least 18 weight percent HP304 (at least 1 mole H3poA per 25 moles of water). ~he various condensed forms (polymeric, partial anhydrides) of phosphoric acid, pyrophosphoric acid, orthophosphoric acid and tri phosphoric acid can also be used.
Preferred are phosphoric acid having an H3PO4 concentration of from 85 to 120 percent, and more preferred are superphosphoric acids having an H3PO4 concentration of from 105 to 1 16 ~i percent.
For the reaction of the epoxy component and the phosphoric acid component, 20 the phosphoric acid source material may be added dropwise to the epoxy component at, for example, 50C to 1 50C for a period of from 1, preferably 5 to 110, preferably to 15 minutes.
After the dropwise addition, the reaction mixture may be heated and stirred for 1 to 120 minutes. If desired, these procedures rrlay be repeated as many times as necessary.
Water-dispersible epoxy phosphate ester resins can be obtained even if the whole25 amount of phosphoric lacid source material for the two-step reaction is simultaneously reacted in a single step with an epoxy resin. However, in such a case the reaction products have high viscosity and also contain unreacted phosphoric acid, triesters and diesters of phosphoric acid, resulting in poor stability when dispersed in an aqueous sol ution.
In the present invention, when producing high molecular weight epoxy 30 phosphate ester resins, it is possible to perform a uniform reaction by decreasing the viscosity of the reaction mixture with an organic solvent to improve stirring efficiency.
Suitablesolventsforusehereinincludeorganicsolventshavinggood compa~ibility with an epoxy resin and a boiling point higher than 110C, especially higherthan 140C. Examples of the organic solvents used herein are glycol type solvents such as ethylene 35 glycol and propylene glycol; glycol monoether type solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether, diethylene glycol ~ . -butyl ether, propylene glycol n-butyl ether; acetate type solvents such as propylene glycol monomethyl ether acetate, butyl acetate and propylene glycol methyl ether acetate; alcohol :~ .
-4- :
:
. . .
WO 93/12156 2 ~ ~ ~ 2 ~ ~ PCI /US9~/10197 type solvents such as n-butanol, amyl alcohol and cyclohexanol; ketone type solvents such as cyclohexanone and diisobutyl ketone; and aromatic solvents such as xylene and SOLVESSO~'^
100 (supplied by Exxon Chemical). Of these solvents, a glycol type solvent and an alcohol type solvent are especially preferred. These solvents can be used singly or as a mixture of two or 5 more thereof The non-volatiles concentration of the diluted reaction system is preferably from 50 to 100 percent, based on the total reaction mixture. The higher solids concentration is ~ -preferable within the viscosity range where the reaction mixture is not gelled.
In the reaction between the above-mentioned phosphoric acid component and the above-mentioned epoxy component, in the first reaction step an epoxy resin may be 10 reacted with a phosphoric acid source material in an amount to provide from 0.2 to 0.4, preferably from 0.25 to 0.35 hydroxyl group per epoxy group; and in the second reaction step the obtained epoxy phosphate ester is reacted with a phosphoric acid source material in an amount to provide from 0.05 to 0.4, preferably from 0.05 to 0.20 hydroxyl group per epoxy : .
group. `
More specifically, in the case of using 100 percent phosphoric acid, the amount of the phosphoric acid source material used for one reaction may preferably range from 0.1 to 6.0 percent by weight, rnore preferably from 0.3 to 5.5 percent by weight, most preferably from 0.4 to 4.8 based on the total solid content of the reaction mixture. If the amount of the phosphoric acid source material used is less than 0.1 percent by weight, the resultant resins have a large 20 amount of unreacted epoxy groups, resulting in increased viscosity or poor dispersion stability when dispersed in water. If the amount of unreacted epoxy groups exceeds 6.0 percent by weight, gelation may occur during the reaction or free phosphoric acid will be formed during the next reaction step. These are disadvantageous and free phosphoric acid will cause blushing when a coating of the resultant resi n is subjected to retort treatment. :
The phosphoric acid source materials per se can be added dropwise. However, it is effective to use the phosphoric acid source material diluted with a hydroxylic solvent such as the above-mentioned glycol monoether type jsolvent or a mixture thereof. The use of the hydroxyl group-containing solvents prevents self-condensation of the phosphoric acid source materials, resulting in a more uniform reaction. These solvents can be used in an amount to 30 provide a molar ratio of the solvent to the phosphoric acid source material of at least 2:1, preferably at least 4:1.
The epoxy phosphate ester resins prepared as above are mainly in the form of triesters or di esters, and thus can be changed to monoesters by subjecti ng them to partial hydrolysis to reduce them to monoesters. Monoesterification reduces the viscosity of the :
35 resultant hydrolyzed modified epoxy phosphate ester resin to make handling easier. . :.
Further, the phosphate groups existing atthe end of molecules can provide good corrosic n resistance inherently possessed by the phosphoric acid. Further, the phosphoric acid residuesmayca~alyzecuringoftheresultantcoatedfiimandprovideflexibilitytothecoated -- ~
6 P~/US92/10197 film. The hydrolyzed, modified epoxy phosphate ester resins may contain a small quantity of diesters, triesters and free phosphoric acid in addition to monoesters, but normally contain almost no epoxy groups.
In the process of the present invention, the epoxy phosphale ester resins can be5 madewater-solublebyaddingatleastoneaminecompoundtotheresintoadjustitspHto between 6 and 11, adding dropwise water, and then stirring the obtained product. If the pH o~
the adj usted epoxy phosphate ester resi n i s outside the pH range of G to 1 1, the resultant solution may have poor stability.
Suitable amine compounds which can be used in ¦the present invention include 10 those described in U.S. Patent Nos. 4,289,812 and 4,397,970; for example, alkanol amines such as N,N-dimethylethanol amine. Particularly preferred is an amine mixture prepared by mixing N,N-dimethylethanol amine and diethanol amine at a weight ratio of between 50:50 ancl 70:30.
In the present invention, neutralization can be effected at room temperature.
However, if the reaction mixture has hi~h viscosity due to its high solids content or use of resins of high molecular weight, the reaction mixture can be heated at a temperature below the boiling point of the amine compound used.
In the present invention, the epoxy phosphate ester resin may be incorporated with, for example, an acrylic resin and/or a polyester resin, a curing agent, water and/or an 20 organic solvent to prepare a coating composition.
Acrylic resins which can be used in the present invention include any acrylic resin known as a coating material, such as a polymer of alkyl acrylate or methacrylate and a monomer copolymerizable therewith. Suitable alkyl (meth)acrylate polymers include, for example, those prepared from methyl (meth)acrylate, ethyl (meth~acrylate, butyl 25 (meth)acrylate and 2-ethylhexyl (meth)acrylate and a monomer copolymerizable with these esters. Suitable copolymerizable monomers used herein include, for example, (meth)acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acryl-amide, N-methylol acryl-amide, styrene, vinyltoluene, acrylonitrile and vinylacetate.
Polyester resins which can be used in the present invention include polyester 30 resins known as coating materials, which are prepared from a suitable alcohol component and a suitable acid component. Suitable alcohol components include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, .:
1,4-cyclohexanedimethanol, glycerol, anthrol, trimethylolethane, hexanetriol and ~ .
35 pentaer.ythritol. Suitable acid components include, for example, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid and anhydrides of these acids.
.. .
WO 93/12156 2 ~ PCr/US92/1~197 Curing agents which can be incorporated into the composition for solvent-borne coatings according to the present invention include, for example, amino resins such as melamine-formaldehyde and urea-formaldehyde; alkyl-etherified amino resins such as those prepared from the etherification of the above amino resins with lower alcohols such as :
5 methanol or ethanol; polyisocyanates such as isophorone diisocyanate and m-xylene diisocyanate; blocked isocyanates such as those formed by introducing blocking agents such as alcohols, including methanol, or phenols, includ;ng cresol, intothe above polyisocyanates; and alkyl-etherified phenol resins such as an aryl ether monomethylol phenol. For water-borne coatings, any known water-soluble curing agents can be used.
Theepoxyresinsofthepresentinventioncanbeusedasrawmaterialsforwater-borne coating compositions, which are considered preferable from an lenvironmental view point, as well as raw materials for solvent-borne coating compositions.
The epoxy phosphate ester resins of the present invention can be incorporated with water and known water-soluble curing agents to prepare a water-borne coating composition The epoxy phosphate ester resins of the present invention can also be used to prepare a solvent-borne coating composition. Suitable organic solvents which can be used as diluent to adjust viscosity include, for example, the above~mentioned glycol-type solvents;
glycol monoether-type solvents, alcohol type solvents, aromatic- type solvents and ketone-type ..
20 solvents (such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone). These solvents can be used alone or in combination.
The epoxy phosphate ester resins of the present invention can be used in combination with a known epoxy resin as long as the resin mixture keeps good performance . . .
derived from the epoxy phosphate ester resins. . . -The preferable component ratio of a coating composition of the present invention is as follows:
(a) from 1, preferably 5 to 30, preferably 20 percent by weight of an epoxy phosphate ester resin;
(b) from 50, preferably 70 to 90, preferably 80 percent by weight of an acryli c ;
30 resin and/or a polyester resin; and .(c) from 10, preferably ~ 5 to 30, preferably 20 percent by weight of a curing agent for Components (a) and (b).
To the above composition, ~d) water and/or an organic solvent may be added to provide a volatiles content of, for example, from l O, preferably 15 to 80, preferably 40 percent 35 by weight.
If desired, these coating compositions may cornprise an appropriate arnount of apigment, plasticizer, coloring agent, flow modifier and/or curing accelerator.
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..
:' ~'0 93/121S6 PCI`/USg2/10197 2~
Examples and ComParative Examples The present invention will now be described in more detail with reference to thefollowing Examples and Comparative Examples, which are not to be construed as limiting the invention.
In the Examples and Comparative Examples, all of the percentages and parts are by weight unless otherwise indicated.
Example 1 A reaction vessel equipped with a condenser was charged with 777 parts of a 10 diglycidyl ether of bisphenol A ~D.E.R.'~ 331 resin: trademark of The Dow Chemical Company), 323 parts of bisphenol A and 0.2 parts of a catalyst, a 70 percent me~hanol solution of ethyltriphenylphosphonium acetate-acetic acid complex. The reaction was carried out in a nitrogen current at 1 75C for 1 hour.
A mixed solvent containing DOWANOL'~ PM (propylene glycol methyl ether) and 15 DOWANOL'~ DPM (dipropylene glycol methyl ether) ( 1:1 weight ratio) was then added to the reaction mixture to adjust the solids concentration to 90 percent and to cool the reaction mixture to 1 25C. Then, 20 parts of a solution prepared by diluting superphosphoric acid having a concentration of 105 percent in 4 times as many moles of the same mixed ¦solvent (DOWANOL"' PM and DOWANOL"' DPM 1:1 weight ratio) as phosphoric acid, were added20 dropwise to the reaction product over a period of 30 minutes. To the reaction product obtained, 20 parts of the same superphosphoric acid solution were added in the same way as : .
above for further reaction, under the same conditions.
Then, 20 parts of water were added to the reaction product for hydrolysis to obtain an epoxy phosphate monoester resin. The epoxy phosphate ester resin obtained as 25 above was subjected to neutralization with dimethylethanol amine, and then incorpora~ed into water to prepare a transparent aqueous solution having a volatiles content of 34.2 percent and pH of 7.3.
To the aqueous solution of the epoxy phosphate ester resin obtained, as indicated in Table 1, an acrylic resin and a melamine curing agent were added. Further, to the mixture, 30 deionized water was added for dilution to prepare a coating composition having volatiies content of 25 percent.
Example 2 In the fashion described in Example 1 and except as otherwise stated, using the 35 same reactants, amounts and conditions, 407 parts D.E.R."' 732 aliphatic diglycidyl ether resin supplied by The Dow Chemical Company and 43 parts bisphenol A were reacted in the presence of 0.6 parts of the same phosphonium-acid complex catalyst.
- - .
: ' ' ' WO 93/12156 PCI/l~S92/10197 ~ 2~2~
The reaction system was cooled to 125C and 9 parts of the same 1:4 . .
superphosphoric acid: mixed solvent solution were added dropwise over 30 minutes and then 9 parts of the superphosphoric acid solution were further added. The reaction product was hydrolyzed with 10 parts water, subjected to the amine neutralization and diluted with water to a transparent 32.2 percent volatiles solution of pH 7.5.
As in Example 1, a coating composition, indicated in Table 1, of 25 percent volatiles content was prepared.
Example 3 In the same fashion, 1û0 parts of D.E.R. '~ 331 diglycidyl ether supplied by TheDow Chemical Company was reacted by dropwise addition of D,.8 parts of the superphosphoric acid solution over 20 minutes at 1 25C. To the resulti ng product at 1 25C, another 4.8 parts of the superphosphoric acid solution were added dropwise and then 3 parts water were added to hydrolyze the product. Neutralization with the dimethylethanol amine and dilution with water was carried out to yield a transparent solution of pH 7.5 having 35.6 percent volatiles content.
As in Example 1, a coating composition, indicated in Table 1, of 25 percent volatiles content was prepared. :
20 Example 4 A coating composition was prepared in the same way as in Example 3 except that the kind of acrylic resin was changed as indicated in Table 1. - .
Reference Examole A reaction vessel equipped with a condenser was charged with 388 parts of an aliphaticdiglycidylether~D.E.R."'331:trademarkofTheDowChemicalCompany),112partsof i ~ -bisphenol A and 0.1 parts of a 70 percent methanol solution of ethyltriphenylphosphonium acetate-acetic acid complex. The reaction was carried out in a nitrogen current at 1 75C for 1 .:
hour. Thereafter, a mixed solvent containing DOWANOL'~ PM and DOWANOL'~ DPM (1:130 weight ratio) was added to the reaction mixture to adjust a solid concentration to 70 percent and to cool the reaction mixture to 1 25~C.
Then, a solution prepared bydiluting 10 parts of superphosphoric acid having a concentration of 105 percent in an amount 4 times as much moles of a mixed solvent containing DOWANOL"^ PM and DOWANOL'~ DPM ~1:1 weight ratio) as that of 35 superphosphoric acid, were added dropwise to the reaction product over a period of 30 minutes for reactic n.
Then, 10 parts of water were added to the reaction product obtai ned for hydrolysis to obtain an epoxy phosphate ester resin. The epoxy phosphate ester resi n obtained .
was subjected to neutralization with dimethylethanol amine, and then incorporated with water. However, the viscosity of the suspension liquid increased and it became a white solid product.
From the results of this Reference Example, it was found that the products 5 obtained through a single reaction with superphosphoric acid exhibit poor water-solubility compared with those obtained through a two-step reaction with superphosphoric acid as in the present Examples 1-4.
Comparative Example 1 The emulsion type acrylic resin (AR-l ) used in Examples 1 to 3 was incorporatedwith a melamine curing agent as indicated in Table 1. To the mixture, deionized water was added for dilution of the volatiles content to 25 percent, to prepare a coating composition. :
Comparative Exam~le 2 The emulsion type acrylic resin (AR-2) used in Example 4\~as incorporated with amelamine curing agent as indicated in Table 1. Deionized water was added to the mixture for dilution so that the volatiles content became 25 percent, to prepare a coating composition. M
Next, a coating composition consisting of an acrylic resin and a curing agent was prepared as comparison.
.
T~ble 1 Kind of Resin Component Ratios (wt./~) Epoxy Acrylic Epoxy Resin/ CYMEL'~
Resin ResinAcr~/lic Resin 303 Ex. 1 BisABased AR-l iOI15 15 Ex. 2 Aliphatic AR-1 70/15 15 Ex. 3 BisA aased AR-1 70/15 15 30 Ex. 4 Bis A Based AR-2 70/15 15 Comp. Ex. 1 - AR-1 0/85 15 Cornp. Ex.2 - AR-2 0/85 15 . :
AR-l: Emulsiontype acrylic resin havir1g a MW of 20,000.
35 AR-2: Water-soluble acrylic resin having a MW of 9,600.
CYMEL'~ 303: Melamine hardener supplied by Mitsui-Cyanamid.
, , Wo 93/12156 PC~/US92/10197 ~` 21~12~
Experiment The coati ng compositions prepared as above were coated on a ti n-plated steel sheet,andheatedtol80Cfor10minutesforheatcuring. Then,thepropertiesoftheresultant coatedfilmswereevaluated. Intheexperiment, pigmentwasnotused inordertoevaluatethe 5 properties of the resins themselves.
The evaluation methods used in the experiment are as follows.
(T-Bend Test) A coated specimen (3 cm X 3 cm) is bent so that the coated surface appears 10 outside, and a plurality of tin plates (spacer) having the same thickness as that of the specimen . .:
are inserted inside of the bent specimen. Then, the bent specimen is pressed. The bent speci men is re-pressed after the number of the spacers is reduced, one by one, until a crack ~ :
c ccurs in the coated film. The minimum number of the spacers where a crack did not occur is regarded as an index of flexibility. . ~ -(Xvlene Double Rubbinq Test) A specimen is subjected to a rubbing test using a rubbing testet wi th xylene at a ::
load of 2 pounds. The maximum number of rubbing is set as 100 times.
20 (Boilino Water Resistance) Pencil hardness is measured before and after a coated specimen is immersed in a boiling water for a period of 2 hours. The pencil hardness test is conducted in accordance with ~ .
JIS K-5400.
': ' :
25 (Salt Sprav Test) :m~; :
In accordance with J IS K-5400, width of rust formed S00 hours after spraying ismeasured. :
The results of the testing, carried out on coatings prepared from ~he coating 30 compositions described above, are shown in Table 2.
WO 93~12156 ~ PCl'/US92/10197 :
Tabie 2 Salt Spray Xylene DoubleBoiling Water Test Example/T-BendRubbing Resistance(500 hrs, Rust Comp. Ex.Test Test ~Before/After)width in mm~
Example 1lT >100 H/HB 1.0 Example 21T > 100 H/HB 2.0 Example 32T > 100 H/HB 2.0 Example 42T > 100 H/H 3.5 Comp. Ex. 1 2T >100 H/HB 4.0 Comp. Ex. 2 3T > 100 H~B 5.5 Apparent from the results, as shown in Table 2, it was found that the water-soluble epoxy resins of the present invention show good flexibility and corrosion resistance without sacrificing other properties such as chemical resistance and heat resistance.
Industrial Applicabilit~
The epoxy phosphate ester resins of the present invention exhibit an improved curing time, corrosion resistance, chemical resistance, flexibility and hardness, and can provide a transparent aqueous solution when the solution is newtralized. The resins exhibit good :
stability when dissolved in water. : .
Accordingly, the coating compositions of the present invention can be effectively -used in coating applications such as spray coating and roll coating. Particularly, the coating compositions show good performance in the fields of can coating, coil coating and post coati ng.
More specifical Iy, the coati ng compositions accordi ng to the present i nvention can be effectively used as coating materials on steel based plates or sheets such as a tin-plated steel (TPS) sheet, tin-free steel (TFS) sheet and galvanized steel sheet; and non-steel based plates or sheets such as an aluminum sheet.
Also, the resin compositions of the present invention can be effectively used asprimers for substrates. In this case, conventional coating rnaterials may be coated thereon as topcoatinglayers. Suchcoatingmaterialsfortopcoatingsinclucle,forexample,analkydresin-based paint, polyester resin-based paint, thermosetting acrylic resin-based paint, vinyl resin-based paint and silicon resin-based paint.
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W() 93/12156 2 1 ~12 ~ ~L PCl/US92/10197 '.
Further, the resin compositions of the present invention can be used as coatingmaterials for top coating when an aqueous solution of the resi n composition is blended with a water-soluble or water-dispersible acrylic resin or polyester resin. Therefore, the epoxy resins of the present invention can be used as additive for an acrylic resin-based paint or a polyester 5 resin- based paint, in which an epoxy resin was not previously used.
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In the process of the present invention, the epoxy phosphale ester resins can be5 madewater-solublebyaddingatleastoneaminecompoundtotheresintoadjustitspHto between 6 and 11, adding dropwise water, and then stirring the obtained product. If the pH o~
the adj usted epoxy phosphate ester resi n i s outside the pH range of G to 1 1, the resultant solution may have poor stability.
Suitable amine compounds which can be used in ¦the present invention include 10 those described in U.S. Patent Nos. 4,289,812 and 4,397,970; for example, alkanol amines such as N,N-dimethylethanol amine. Particularly preferred is an amine mixture prepared by mixing N,N-dimethylethanol amine and diethanol amine at a weight ratio of between 50:50 ancl 70:30.
In the present invention, neutralization can be effected at room temperature.
However, if the reaction mixture has hi~h viscosity due to its high solids content or use of resins of high molecular weight, the reaction mixture can be heated at a temperature below the boiling point of the amine compound used.
In the present invention, the epoxy phosphate ester resin may be incorporated with, for example, an acrylic resin and/or a polyester resin, a curing agent, water and/or an 20 organic solvent to prepare a coating composition.
Acrylic resins which can be used in the present invention include any acrylic resin known as a coating material, such as a polymer of alkyl acrylate or methacrylate and a monomer copolymerizable therewith. Suitable alkyl (meth)acrylate polymers include, for example, those prepared from methyl (meth)acrylate, ethyl (meth~acrylate, butyl 25 (meth)acrylate and 2-ethylhexyl (meth)acrylate and a monomer copolymerizable with these esters. Suitable copolymerizable monomers used herein include, for example, (meth)acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acryl-amide, N-methylol acryl-amide, styrene, vinyltoluene, acrylonitrile and vinylacetate.
Polyester resins which can be used in the present invention include polyester 30 resins known as coating materials, which are prepared from a suitable alcohol component and a suitable acid component. Suitable alcohol components include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, .:
1,4-cyclohexanedimethanol, glycerol, anthrol, trimethylolethane, hexanetriol and ~ .
35 pentaer.ythritol. Suitable acid components include, for example, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid and anhydrides of these acids.
.. .
WO 93/12156 2 ~ PCr/US92/1~197 Curing agents which can be incorporated into the composition for solvent-borne coatings according to the present invention include, for example, amino resins such as melamine-formaldehyde and urea-formaldehyde; alkyl-etherified amino resins such as those prepared from the etherification of the above amino resins with lower alcohols such as :
5 methanol or ethanol; polyisocyanates such as isophorone diisocyanate and m-xylene diisocyanate; blocked isocyanates such as those formed by introducing blocking agents such as alcohols, including methanol, or phenols, includ;ng cresol, intothe above polyisocyanates; and alkyl-etherified phenol resins such as an aryl ether monomethylol phenol. For water-borne coatings, any known water-soluble curing agents can be used.
Theepoxyresinsofthepresentinventioncanbeusedasrawmaterialsforwater-borne coating compositions, which are considered preferable from an lenvironmental view point, as well as raw materials for solvent-borne coating compositions.
The epoxy phosphate ester resins of the present invention can be incorporated with water and known water-soluble curing agents to prepare a water-borne coating composition The epoxy phosphate ester resins of the present invention can also be used to prepare a solvent-borne coating composition. Suitable organic solvents which can be used as diluent to adjust viscosity include, for example, the above~mentioned glycol-type solvents;
glycol monoether-type solvents, alcohol type solvents, aromatic- type solvents and ketone-type ..
20 solvents (such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone). These solvents can be used alone or in combination.
The epoxy phosphate ester resins of the present invention can be used in combination with a known epoxy resin as long as the resin mixture keeps good performance . . .
derived from the epoxy phosphate ester resins. . . -The preferable component ratio of a coating composition of the present invention is as follows:
(a) from 1, preferably 5 to 30, preferably 20 percent by weight of an epoxy phosphate ester resin;
(b) from 50, preferably 70 to 90, preferably 80 percent by weight of an acryli c ;
30 resin and/or a polyester resin; and .(c) from 10, preferably ~ 5 to 30, preferably 20 percent by weight of a curing agent for Components (a) and (b).
To the above composition, ~d) water and/or an organic solvent may be added to provide a volatiles content of, for example, from l O, preferably 15 to 80, preferably 40 percent 35 by weight.
If desired, these coating compositions may cornprise an appropriate arnount of apigment, plasticizer, coloring agent, flow modifier and/or curing accelerator.
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..
:' ~'0 93/121S6 PCI`/USg2/10197 2~
Examples and ComParative Examples The present invention will now be described in more detail with reference to thefollowing Examples and Comparative Examples, which are not to be construed as limiting the invention.
In the Examples and Comparative Examples, all of the percentages and parts are by weight unless otherwise indicated.
Example 1 A reaction vessel equipped with a condenser was charged with 777 parts of a 10 diglycidyl ether of bisphenol A ~D.E.R.'~ 331 resin: trademark of The Dow Chemical Company), 323 parts of bisphenol A and 0.2 parts of a catalyst, a 70 percent me~hanol solution of ethyltriphenylphosphonium acetate-acetic acid complex. The reaction was carried out in a nitrogen current at 1 75C for 1 hour.
A mixed solvent containing DOWANOL'~ PM (propylene glycol methyl ether) and 15 DOWANOL'~ DPM (dipropylene glycol methyl ether) ( 1:1 weight ratio) was then added to the reaction mixture to adjust the solids concentration to 90 percent and to cool the reaction mixture to 1 25C. Then, 20 parts of a solution prepared by diluting superphosphoric acid having a concentration of 105 percent in 4 times as many moles of the same mixed ¦solvent (DOWANOL"' PM and DOWANOL"' DPM 1:1 weight ratio) as phosphoric acid, were added20 dropwise to the reaction product over a period of 30 minutes. To the reaction product obtained, 20 parts of the same superphosphoric acid solution were added in the same way as : .
above for further reaction, under the same conditions.
Then, 20 parts of water were added to the reaction product for hydrolysis to obtain an epoxy phosphate monoester resin. The epoxy phosphate ester resin obtained as 25 above was subjected to neutralization with dimethylethanol amine, and then incorpora~ed into water to prepare a transparent aqueous solution having a volatiles content of 34.2 percent and pH of 7.3.
To the aqueous solution of the epoxy phosphate ester resin obtained, as indicated in Table 1, an acrylic resin and a melamine curing agent were added. Further, to the mixture, 30 deionized water was added for dilution to prepare a coating composition having volatiies content of 25 percent.
Example 2 In the fashion described in Example 1 and except as otherwise stated, using the 35 same reactants, amounts and conditions, 407 parts D.E.R."' 732 aliphatic diglycidyl ether resin supplied by The Dow Chemical Company and 43 parts bisphenol A were reacted in the presence of 0.6 parts of the same phosphonium-acid complex catalyst.
- - .
: ' ' ' WO 93/12156 PCI/l~S92/10197 ~ 2~2~
The reaction system was cooled to 125C and 9 parts of the same 1:4 . .
superphosphoric acid: mixed solvent solution were added dropwise over 30 minutes and then 9 parts of the superphosphoric acid solution were further added. The reaction product was hydrolyzed with 10 parts water, subjected to the amine neutralization and diluted with water to a transparent 32.2 percent volatiles solution of pH 7.5.
As in Example 1, a coating composition, indicated in Table 1, of 25 percent volatiles content was prepared.
Example 3 In the same fashion, 1û0 parts of D.E.R. '~ 331 diglycidyl ether supplied by TheDow Chemical Company was reacted by dropwise addition of D,.8 parts of the superphosphoric acid solution over 20 minutes at 1 25C. To the resulti ng product at 1 25C, another 4.8 parts of the superphosphoric acid solution were added dropwise and then 3 parts water were added to hydrolyze the product. Neutralization with the dimethylethanol amine and dilution with water was carried out to yield a transparent solution of pH 7.5 having 35.6 percent volatiles content.
As in Example 1, a coating composition, indicated in Table 1, of 25 percent volatiles content was prepared. :
20 Example 4 A coating composition was prepared in the same way as in Example 3 except that the kind of acrylic resin was changed as indicated in Table 1. - .
Reference Examole A reaction vessel equipped with a condenser was charged with 388 parts of an aliphaticdiglycidylether~D.E.R."'331:trademarkofTheDowChemicalCompany),112partsof i ~ -bisphenol A and 0.1 parts of a 70 percent methanol solution of ethyltriphenylphosphonium acetate-acetic acid complex. The reaction was carried out in a nitrogen current at 1 75C for 1 .:
hour. Thereafter, a mixed solvent containing DOWANOL'~ PM and DOWANOL'~ DPM (1:130 weight ratio) was added to the reaction mixture to adjust a solid concentration to 70 percent and to cool the reaction mixture to 1 25~C.
Then, a solution prepared bydiluting 10 parts of superphosphoric acid having a concentration of 105 percent in an amount 4 times as much moles of a mixed solvent containing DOWANOL"^ PM and DOWANOL'~ DPM ~1:1 weight ratio) as that of 35 superphosphoric acid, were added dropwise to the reaction product over a period of 30 minutes for reactic n.
Then, 10 parts of water were added to the reaction product obtai ned for hydrolysis to obtain an epoxy phosphate ester resin. The epoxy phosphate ester resi n obtained .
was subjected to neutralization with dimethylethanol amine, and then incorporated with water. However, the viscosity of the suspension liquid increased and it became a white solid product.
From the results of this Reference Example, it was found that the products 5 obtained through a single reaction with superphosphoric acid exhibit poor water-solubility compared with those obtained through a two-step reaction with superphosphoric acid as in the present Examples 1-4.
Comparative Example 1 The emulsion type acrylic resin (AR-l ) used in Examples 1 to 3 was incorporatedwith a melamine curing agent as indicated in Table 1. To the mixture, deionized water was added for dilution of the volatiles content to 25 percent, to prepare a coating composition. :
Comparative Exam~le 2 The emulsion type acrylic resin (AR-2) used in Example 4\~as incorporated with amelamine curing agent as indicated in Table 1. Deionized water was added to the mixture for dilution so that the volatiles content became 25 percent, to prepare a coating composition. M
Next, a coating composition consisting of an acrylic resin and a curing agent was prepared as comparison.
.
T~ble 1 Kind of Resin Component Ratios (wt./~) Epoxy Acrylic Epoxy Resin/ CYMEL'~
Resin ResinAcr~/lic Resin 303 Ex. 1 BisABased AR-l iOI15 15 Ex. 2 Aliphatic AR-1 70/15 15 Ex. 3 BisA aased AR-1 70/15 15 30 Ex. 4 Bis A Based AR-2 70/15 15 Comp. Ex. 1 - AR-1 0/85 15 Cornp. Ex.2 - AR-2 0/85 15 . :
AR-l: Emulsiontype acrylic resin havir1g a MW of 20,000.
35 AR-2: Water-soluble acrylic resin having a MW of 9,600.
CYMEL'~ 303: Melamine hardener supplied by Mitsui-Cyanamid.
, , Wo 93/12156 PC~/US92/10197 ~` 21~12~
Experiment The coati ng compositions prepared as above were coated on a ti n-plated steel sheet,andheatedtol80Cfor10minutesforheatcuring. Then,thepropertiesoftheresultant coatedfilmswereevaluated. Intheexperiment, pigmentwasnotused inordertoevaluatethe 5 properties of the resins themselves.
The evaluation methods used in the experiment are as follows.
(T-Bend Test) A coated specimen (3 cm X 3 cm) is bent so that the coated surface appears 10 outside, and a plurality of tin plates (spacer) having the same thickness as that of the specimen . .:
are inserted inside of the bent specimen. Then, the bent specimen is pressed. The bent speci men is re-pressed after the number of the spacers is reduced, one by one, until a crack ~ :
c ccurs in the coated film. The minimum number of the spacers where a crack did not occur is regarded as an index of flexibility. . ~ -(Xvlene Double Rubbinq Test) A specimen is subjected to a rubbing test using a rubbing testet wi th xylene at a ::
load of 2 pounds. The maximum number of rubbing is set as 100 times.
20 (Boilino Water Resistance) Pencil hardness is measured before and after a coated specimen is immersed in a boiling water for a period of 2 hours. The pencil hardness test is conducted in accordance with ~ .
JIS K-5400.
': ' :
25 (Salt Sprav Test) :m~; :
In accordance with J IS K-5400, width of rust formed S00 hours after spraying ismeasured. :
The results of the testing, carried out on coatings prepared from ~he coating 30 compositions described above, are shown in Table 2.
WO 93~12156 ~ PCl'/US92/10197 :
Tabie 2 Salt Spray Xylene DoubleBoiling Water Test Example/T-BendRubbing Resistance(500 hrs, Rust Comp. Ex.Test Test ~Before/After)width in mm~
Example 1lT >100 H/HB 1.0 Example 21T > 100 H/HB 2.0 Example 32T > 100 H/HB 2.0 Example 42T > 100 H/H 3.5 Comp. Ex. 1 2T >100 H/HB 4.0 Comp. Ex. 2 3T > 100 H~B 5.5 Apparent from the results, as shown in Table 2, it was found that the water-soluble epoxy resins of the present invention show good flexibility and corrosion resistance without sacrificing other properties such as chemical resistance and heat resistance.
Industrial Applicabilit~
The epoxy phosphate ester resins of the present invention exhibit an improved curing time, corrosion resistance, chemical resistance, flexibility and hardness, and can provide a transparent aqueous solution when the solution is newtralized. The resins exhibit good :
stability when dissolved in water. : .
Accordingly, the coating compositions of the present invention can be effectively -used in coating applications such as spray coating and roll coating. Particularly, the coating compositions show good performance in the fields of can coating, coil coating and post coati ng.
More specifical Iy, the coati ng compositions accordi ng to the present i nvention can be effectively used as coating materials on steel based plates or sheets such as a tin-plated steel (TPS) sheet, tin-free steel (TFS) sheet and galvanized steel sheet; and non-steel based plates or sheets such as an aluminum sheet.
Also, the resin compositions of the present invention can be effectively used asprimers for substrates. In this case, conventional coating rnaterials may be coated thereon as topcoatinglayers. Suchcoatingmaterialsfortopcoatingsinclucle,forexample,analkydresin-based paint, polyester resin-based paint, thermosetting acrylic resin-based paint, vinyl resin-based paint and silicon resin-based paint.
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';~
W() 93/12156 2 1 ~12 ~ ~L PCl/US92/10197 '.
Further, the resin compositions of the present invention can be used as coatingmaterials for top coating when an aqueous solution of the resi n composition is blended with a water-soluble or water-dispersible acrylic resin or polyester resin. Therefore, the epoxy resins of the present invention can be used as additive for an acrylic resin-based paint or a polyester 5 resin- based paint, in which an epoxy resin was not previously used.
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Claims (9)
1. A process for preparing an epoxy phosphate ester resin, which comprises (1) reacting an epoxy resin having an average of greater than one vicinal epoxy group with a phosphoric acid source material to obtain an epoxy phosphate ester; and (2) further reacting the obtained epoxy phosphate ester with a phosphoric acid source material.
2. A process according to Claim 1, wherein in the first reaction the epoxy resinis reacted with a phosphoric acid source material in an amount to provide from about 0.2 to about 0.4 hydroxyl group per epoxy group; and in the second reaction the obtained epoxy phosphate ester is reacted with a phosphoric acid source material in an amount to provide from about 0.05 to about 0.4 hydroxyl group per epoxy group.
3. A process according to Claim 1, wherein each of the first and second reaction are carried out at 50°C to 150°C for a period of from 1 to 110 minutes.
4. A process according to Claim 1, which further comprises subjecting the epoxy phosphate ester resin obtained to hydrolysis treatment with water to produce an epoxy phosphate monoester; and then subjecting the obtained epoxy phosphate monoester to neutralization treatment.
5. A process according to Claim 1, wherein the epoxy resin is a glycidyl ether of bisphenol A, glycidyl ether of bisphenol K, glycidyl ether of bisphenol F, glycidyl ether of bisphenol S, glycidyl ether of bisphenol AD or a mixture thereof.
6. A process according to Claim 1, wherein the phosphoric acid source material is 100 percent phosphoric acid, a semi-hydrate of phosphoric acid, a polymeric phosphoric acid, a partial anhydride of phosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, superphosphoric acid or a mixture thereof.
7. An epoxy phosphate ester resin prepared by any one of the methods set forth in Claims 1 to 6.
8. A coating composition comprising:
(a) the epoxy phosphate ester resin of Claim 7;
(b) an acrylic resin or a polyester resin, miscible with the epoxy phosphate ester resin;
(c) at least one curing agent; and (d) water.
(a) the epoxy phosphate ester resin of Claim 7;
(b) an acrylic resin or a polyester resin, miscible with the epoxy phosphate ester resin;
(c) at least one curing agent; and (d) water.
9. A coating composition comprising:
(a) the epoxy phosphate ester resin of Claim 7;
(b) an acrylic resin or a polyester resin, miscible with the epoxy phosphate ester resin;
(c) at least one curing agent; and (d) an organic solvent.
(a) the epoxy phosphate ester resin of Claim 7;
(b) an acrylic resin or a polyester resin, miscible with the epoxy phosphate ester resin;
(c) at least one curing agent; and (d) an organic solvent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35184891A JPH05163330A (en) | 1991-12-16 | 1991-12-16 | Epoxy phosphate resin, its production and coating composition containing said resin |
| JP03/351848 | 1991-12-16 | ||
| PCT/US1992/010197 WO1993012156A1 (en) | 1991-12-16 | 1992-11-30 | Epoxy phosphate ester resin, its production and coating composition containing the resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2101244A1 true CA2101244A1 (en) | 1993-06-17 |
Family
ID=18420019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002101244A Abandoned CA2101244A1 (en) | 1991-12-16 | 1992-11-30 | Epoxy phosphate ester resin, its production and coating composition containing the resin |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0571606A1 (en) |
| JP (1) | JPH05163330A (en) |
| AU (1) | AU658710B2 (en) |
| BR (1) | BR9205627A (en) |
| CA (1) | CA2101244A1 (en) |
| TW (1) | TW219943B (en) |
| WO (1) | WO1993012156A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087751C (en) * | 1998-04-09 | 2002-07-17 | 中国科学院化学研究所 | Epoxy resin composition |
| EP1310534A1 (en) * | 2001-11-07 | 2003-05-14 | Sigma Coatings S.A. | Treating primer for coil coating |
| SG188141A1 (en) * | 2008-02-08 | 2013-03-28 | Lam Res Corp | A protective coating for a plasma processing chamber part and a method of use |
| JP5859726B2 (en) * | 2010-10-05 | 2016-02-16 | 日本鋳鉄管株式会社 | Method for manufacturing pipe component with anticorrosion coating on outer surface |
| KR101525867B1 (en) * | 2013-08-29 | 2015-06-03 | (주)에프티씨코리아 | Method of manufacturing water soluble modified epoxy ester resin composition and water soluble resin composition manufactured thereby |
| US20210130663A1 (en) * | 2017-09-12 | 2021-05-06 | Ddp Specialty Electronics Materials Us, Inc. | One-component toughened epoxy adhesives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4600754A (en) * | 1983-05-18 | 1986-07-15 | Scm Corporation | Phosphate epoxy acrylic copolymers |
| CA1262794A (en) * | 1984-09-10 | 1989-11-07 | Terence J. Hart | Blends of phosphated epoxy and acrylic resins and the use thereof in coating compositions |
| US4638020A (en) * | 1984-11-23 | 1987-01-20 | Ppg Industries, Inc. | Aqueous composition comprising a phosphated epoxy and non-self dispersible resin |
-
1991
- 1991-12-16 JP JP35184891A patent/JPH05163330A/en active Pending
-
1992
- 1992-11-30 CA CA002101244A patent/CA2101244A1/en not_active Abandoned
- 1992-11-30 AU AU32261/93A patent/AU658710B2/en not_active Ceased
- 1992-11-30 EP EP19930900671 patent/EP0571606A1/en not_active Ceased
- 1992-11-30 BR BR9205627A patent/BR9205627A/en not_active Application Discontinuation
- 1992-11-30 WO PCT/US1992/010197 patent/WO1993012156A1/en not_active Application Discontinuation
- 1992-12-15 TW TW81110050A patent/TW219943B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| AU3226193A (en) | 1993-07-19 |
| WO1993012156A1 (en) | 1993-06-24 |
| EP0571606A1 (en) | 1993-12-01 |
| JPH05163330A (en) | 1993-06-29 |
| AU658710B2 (en) | 1995-04-27 |
| BR9205627A (en) | 1994-11-08 |
| TW219943B (en) | 1994-02-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |