AU612458B2 - Modified advanced epoxy resins - Google Patents

Description

Note: No legalization or other witness required.

i

PCT

WOE

INTERNATIONAL APPLICATIOb (51) International Patent Classification C08G 59/02, 59/14, 59/30 OPI D E 04 89 LN- ID 29454 89 AO JDA{ 0 o 9%5 b NUMBER PCT/US88/04677 (11) International Publication Number: WO 89/ 06661 S (43) International Publication Dare: 27 July 1989 (27.07.89) (21) International Application Number: PCT/US88/04677 (22) International Filing Date: 28 December 1988 (28.12.88) (81) Designated States: AU, BR, JP, KR, NO.

Published With international search report.

Before the expiratton of the time limit fr amnending the claims and to be republished in the event of the receipt of amendments.

(31) Priority Application Number: (32) Priority Date: (33) Priority Country: 143,558 13 January 1988 (13.01.88) (71) Applicant: THE DOW CHEMICAL COMPANY [US/ US]; 2030 Dow Center Abbott Road, Midland, MI 48640 (US).

(72)Inventors: MASSINGILL, John, Jr. 410 Forest Drive. Lake Jackson, TX 77566 PABON, Raul, Jr, 106 Mesquite, Lake Jackson, TX 77566 (US).

(74) Agent: DAMOCLES, Nemia, The Dow Chemical Company, P.O. Box 1967, Midland, MI 48641-1967

(US).

(54) Title: MODIFIED ADVANCED EPOXY RESINS (57) Abstract Modified advanced epoxy resins are prepared by reacting an advanced epoxy resin prepared by reacting an epoxy resin having at least one aromatic 'ing, an average of more than one, but not more than two vicinal epoxy groups per molecule and which contains at least one oxyalkylene or substituted oxyalkylene group per molecule; with a dihydric phenol; with a phosphorus-containing compound. Curable compositions comprising the modified advanced epoxy resin and cured products resulting from curing the curable compositions are also disclosed.

WO 89/06661 PCT/US88/04677 -1- MODIFIED ADVANCED EPOXY RESINS The present invention concerns advanced epoxy resins prepared from dihydric phenols and compounds having an average of more than one glycidyl ether group per molecule, at least one aromatic group per molecule and at least two alkoxy groups per molecule which advanced epoxy resins have been reacted with phosphoric acid or a phosphate ester.

Advanced aromatic epoxy resins are well known for their extremely useful combination of properties such as flexibility, adhesion, resistance to corrosion, and chemical and solvent resistance. Unfortunately, they also have some well known disadvantages such as sensitivity to ultraviolet light, relatively high viscosities, and limited formability. Advanced aliphatic epoxy resins are well known for their low viscosities and flexibility; however, they lack physical strength and are sensitive to water and chemicals. It would be desirable to have available advanced epoxy resins which have unique combinations of viscosity (low), and when cured with a WO 89/06661 PCT/US88/04677 -2suitable curing agent, good flexibility, strength and resistance to water and chemicals and solvents.

One asDect of the present invention pertains to a modified advanced epoxy resin which results from reacting an advanced epoxy resin which results from reacting an epoxy resin composition comprising at least one epoxy resin having at least one aromatic ring, an average of more than one, but not more than two vicinal epoxy groups per molecule and which contains at least one oxyalkylene or substituted oxyalkylene group per molecule; and optionally at least one epoxy resin which has an average of more than one but not more than about two vicinal epoxy groups per molecule and which is different from the epoxy resin of (a) above; wherein components and are present in amounts such that from 5 to 100 equivalent percent of the epoxide groups are derived from component and from zero to 95 equivalent percent of the epoxide groups are derived from component 30 with at least one compound having two aromatic hydroxyl groups per molecule; wherein components and are employed in C amounts which provide a ratio of aromatic i WO 89/06661 PCT/US88/04677 -3hydroxyl groups per epoxy group of from Q.005:1 to 200:1; with a phosphorus-containing compound reiec!ed from phosphoric acid; super phosphoric acid; phosphate esters; or any combination of components (B-2) or wherein components and are present in an amount such that the ratio of moles of component to epoxy groups contained in component is from 0.1:1 to 5:1.

Another aspect of the present invention pertains to a curable composition which comprises (I) the aforesaid reaction product of the advanced epoxy resin and phosphorus-containing compound and (II) a curing amount of a suitable curing agent for component

(I)

The compositions of the present invention have unique combinations of viscosity (low), and when cured with a suitable curing agent, good flexibility, strength and resistance to water and chemicals and solvents.

The advanced epoxy resins employed in the present invention are prepared by reacting the epoxy resin or mixture of epoxy resins with the compound having two aromatic hydroxyl groups per molecule or mixture of such compounds at a temperature suitably from 25°C to 300°C, more suitably from 50 0 C to 250°C, most suitably from 50 0 C to 225 0 C for a time sufficient to complete the reaction, suitably from 1 to 8, more suitably from 1 to 6, most suitably from 1 to 4 hours.

.1 i WO 89/06661 PCT/US88/04677 -4- The higher the temperature, the shorter the reaction time and the lower the temperature the longer the reaction time. The reaction is usually conducted in the presence of a catalyst and Lf desired, one or more solvents. The reactants are employed in amounts such that the ratio of phenolic hydroxyl groups to epoxide group is suitably from 0.005:1 to 200:1, more suitably from 0.5:1 to 5:1, most suitably from 0.5:1 to 1:1.

The epoxy resin which is advanced with the compound having two aromatic hydroxyl groups has suitably from 5 to 100, more suitably from 10 to 100, most suitably from 25 to 100 percent of the epoxy groups derived from an epoxy resin which contains oxyalkylene or substituted oxyalkylene groups and suitably from zero to 95, more suitably from zero to most suitably from zero to 75 perlcent of the epoxy groups derived from an epoxy resin which is different from the aforementioned epoxy resin.

Suitable epoxy resins having at least cne aromatic ring, an average of more thaa one, but not more than two glycidyl ether groups per moletule and which contain at least one oxyalkylene or substituted oxyalkylene group per molecule include those represented by the following formula I L 1 i WO 89/06661 PCT/US88/04677 Formula I 0 0

H

2 C C-OHZ 2 CH C -CH 2

R

wherein each R is independently hydrogen or an alkyl group having from 1 to 4 carbon atoms, preferably hydrogen or methyl, most preferably hydrogen; Z is a divalent aromatic group represented by the following formulas II and III Formula II Formula III 2C (X) 4 (X (X) 4 S(A)n wherein A is a divalent hydrocarbyl group having suitably from 1 to 12, more suitably from 1 to 6, most suitably from 1 to 3, carbon atoms, -S0 2 or each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12, more suitably from 1 to 6, most suitably from 1 to 3 carbon atoms, or a halogea, more suitably chlorine or bromine, most suitably bromine; n is zero or 1; each Z' is WO 89/06661 PCT/US88/04677 -6independently a group represented by the following formula IV Formula IV

-CH-CH-

R

2

RI

wherein each RI and R 2 are independently hydrogen or a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12, more suitably from 1 to 6, most suitably from 1 to 3 carbon atoms or an -CH 2 -O-R3 group wherein R3 is a hydrocarbyl group having suitably from 1 to 12, more suitably from 1 to 9, most suitably from 1 to 6 carbon atoms; and each m and m' independently has a value suitably from 1 to more suitably from 1 to 10, most suitably from 1 to The term hydrocarbyl as employed herein means any aliphatic, cycloaliphatjc, aromatic, aryl substituted aliphatic or cycloaliphatic, or aliphatic or cyoloaliphatic substituted aromatic groups. The aliphatic groups can be saturated or unsaturated.

Likewise, the term hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the object to which it is attached.

Particularly suitable epoxy resins which have an average of more than one but not more than two vicinal epoxy groups and at least one aromatic ring per molecule and at least one oxyalkylene group or substituted oxyalkylene group per molecule include, for example, the glycidyl ethers of the reaction products of an aromatic compound having two aromatic hydroxyl groups per molecule or mixture of such I i Mir WO 89/06661 PCT/US88/04677 compounds and an alkylene or substituted alkylene oxide or monoglycidyl ether or any combination thereof.

Suitable compounds having two aromatic hydroxyl groups per molecule which can be employed herein include, for example, those represented by the following formulas V ana VI Formula 7r

OH

Formula VI

(X)

4 (X) 4 wherein A, X and n are as defined above.

Particularly suitable aromatic compounds having two aromatic hydroxyl groups per molecule include, for example, catechol, hydroquinone, resorcinol, biphenol, bisphenol A, bisphenol F, bisphenol K, bisphenol S and 3 combinations thereof. Particularly suitable alkylene oxides include, for example, ethylene oxide, 1,2propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and combinations thereof. Particularly suitable substituted alkylene oxides include, for example, styrene oxide, t-butyl styrene oxide, isopropenyl WO 89/06661 PCT/US88/04677 benzene oxide, and combinations thereof. Sui table monoglycidv! ethers -include, for example, glycidy] ethers of ethylenically unsaturated monocarboxyl.ic acidz, alkyl 9lyci-1yl ethers Aryli zivcid'il ethers, and combinations thereof. Particularly suitable monoglycidyl ethers include, for example. phenyL glycidyl ether, butyl glycidrl, ether, glyci dyl acrylate, g.Lyidyl methacrylate, dodecyl glycidyl ether combinations thereof, Suitable epoxy resino which have an average of mnove than one but not more than two vicinal epoxy groups per molecule and which are different from tL-he aforementioned epoxy resins include, for example, those aromatic epoxy resins represented by the following formulas VII and VIII as well as those aliphatic epoxy resins represented by the following formula IX 0 00 Formula VII 0

H

2 C C-CH 2 0

(X)

4

OH

O-CH2-C-CH2 0 R O CUJ2-C--12

R

Formula V III 0

H

2 C- C-CH 2

-O

I

(X)4 la(A)n

(X)

4

(X)

4 -0 -q (04 0

CH

2 -C CH'1 WO 89/06661 WO 8906661PCT/US88/04677 Formula I C.0j 31 CH-CH-0nC wherein A, R. R1, R 2 X, m and n are as defined above and n' suitably has an average value from zero to more suitably from 0.01 to 0.5, most suitably from 0.03 to 0.15.

Particularly suitable as the other epoxy resins are those epoxy resins which have an average of~ more than one but not more than two vicinal epoxy groups and at least one aromatic ring per molecule which are free of oxyalkylene or 5ubstitu~ted oxyalkylene groupz:.

The term free of oxyalkyleno or substituted oxyalkylene groups means that the epoxy resin is free of groups represented by the following formulas X and

XI

Formula X -CH-OH-O- R12 11 -O-CH-CH- Formula XI M1 MO .l .3

L

wheeinR 1andR 2are as defined above, and the term oxyalkylene or substituted oxyal!iwlene group is defined accordingly.

0 *0.

0 0.00 0S 0 *00 S

S

66 S S 00 00 S 0*

OS

S

00055*

S

056* S S *6 S 6

S

S.

55 0 6 *5 S. S S

S.

at least one epOxY resin having an ./2 WO 89/06661 PCT/US88/04677 More partcularly suitable epoxy resins whit,,h have an average of: mnore than one but not more than a-:boutu t"wo viciral epoxy groups and at least one aromatic- rinq oe- A lec ulIe and w hi chI are "i oxyalkvlene urouos include, for exampole, the =Ivc-dvL etherc- of catechol, resorcinol, hydrouuinone, biphenol, bisphenol A, b,14sphenol F7, bisphenol K. bi sphenoi S, and any combirat.J.on Uee The eooxy; resins which are prepared from oompounds having aliphatic hydroxyl groups wchare reac ted .,jith an epihalolhydrin can be preparea by any of the known methods for preparing aliphatic epoxy resins such as conducting the reaction in the presence of a Lewis acid such as, for example, st-.nnic chloride, boron trifluoride and combinations thereof; followed by dehydrohalogenation with a baisic acting compound sucb as an alkali metal hydroxide., Most preferably, these epoxy resins are pre pared by the method disclosed in GB 2, 137',205A.

Suitable cataly3ts which can be employed to prepare the advanced epoxy reL'iins include, for example, tertiary amnines, phosphines, amonium, compounds, phosphonium compounds, and metal hydroxides.

Particularly suitably catalysts include, ethyl triphenyl phosphonium chloride, ethyl triphenyl phosphoniun bromide, ethyl triphenyl phusphoniun iodide, ethyl triphenyl phosphonium acetateeacetic acid complex, tetrabutyl phosphoniun chloride, tetrabutyl phosphohiun bromide, tetrabuty. phosphonium iodide., tetrabutyl phosphoniuin acetateeacetic acid complex, and combinations thereof. The catalyst is suitably employed in a catalytic amount which in mo:s.t instancea is an amount which coi-rts ponds to from 0.0001 to 0.02, i:- -*i WO 89/06661 PCT/US88/0467 7 -12more suitably from 0.002 to 0.02, most suitably from 0.002 to 0.01, moles of catalyst per mole of epoxy resin.

Suitable solvents which can be employed in the preparation of the advanced epoxy resins include, for example, alcohols, ketones. glycol ethers, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons and combinations thereof.

Particularly suitable solvents include, for example, toluene, xylene, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol monotertiarybutyl ether, ethylene glycol monobutyl ether (2-butoxyethanol) and combinations thereof. The 1 solvent can be employed suitably in amounts of from zero to 50, more suitably from 3 to 30, most suitably from 3 to 20 percent by weight based upon the combined weight of the epoxy resin and the phenolic compound.

Suitable phosphorus-containing compounds which can be employed herein to react with the advanced epoxy resins include, for example, phosphoric acid, super phosphoric acid, phosphate esters and combinations thereof. Suitable phosphate esters include those represented by the following formula XII.

V

I

WO 89/06661 PCT/US88/04677 -13- Formula XII 0 i

R

3 -0-P-OH

OH

wherein R 3 is hydrogen or a hydrocarbyl group having suitably from I to 20, more suitably from I to 8, most suitably from 1 to 4 carbon atoms.

Particularly suitable phosphorus-containing compounds which can be employed to modify the advanced epoxy resins to prepare the modified advanced epoxy re'sins of the present invention include, for example, phosphoric acid, super phosphoric acid, phosphorus pentoxide, butyl phosphate ester, butyl ether of ethylene glycol phosphate ester and combinations thereof.

The phosphorus-containing compound is employed in an amount which provides a ratio of moles of the phosphorus-containing compound, component to epoxy groups contained in the advanced epoxy resin, component is suitably from 0.lMI to 5:1, more suitably from 0.1:1 to 1.5:1, most suitably from 0.1:1 to 1:1.

The modified advanced epoxy resins of the present invention can be cured with any suitable curing agent for epoxy resins including, for example, primary and secondary polyamines, carboxylic acids and anhydrides thereof, phenolic hydroxyl-containing

J

'.13 WO 89/06661 PCT/US88/04677 -14compounds, guanidines, biguanides, urea-aldehyde resins, melamine-aldehyde resins, alkoxylated ureaaidehyde resins, alkoxylated melamine-aldehyde resins.

phenol-aldehyde (resole) resins and comDinations thereof. Particularly suitable curing agents include, for example, diethylenetriamine, Madic methyl anhydride, phenol-formaldehyde (resole) resins, cresolformaldehyde (resole) resins, bisphenol A-formaldehyde (resole) resins, melamine-formaldehyde resins, methoxylated melamine-formaldehyde resins, ureaformaldehyde resins, methoxylated urea-formaldehyde resins and combinations thereof. The curing agents are employed in an amount which will effectively cure the composition containing the epoxy resin. These amounts will depend upon the particular epoxy resin and curing agent employed; however, suitable amounts include, for example, from 0.025 to 4, more suitably from 0.5 to 2, most suitably from 0.75 to 1.25 equivalents of curing agent per epoxide equivalent for those curing agents which cure by reacting with the epoxy group of the epoxy resin or per hydroxyl group for those curing agents which cure by reacting with the aliphatic hydroxyl groups along the backbone of the epoxy resin.

The advanced epoxy resins of the present invention can be blended with other materials such as solvents or diluents, fillers, pigments, dyes, m=e±f-"-e-,-th-iokonors, reinforcing agents, ag accelerators end combinations thereof.

These additives are aed in functionally equivalent amounts e. h e pigments and/or dyes are added in qu ities which will provide the Scomposiei with the desired color; however, they a suitabhly emplnyer in amoun s of from 1 to 200, -14aflow modifiers, thickeners, dispersing agents, reinforcing agents, accelerators and combinations thereof. Monoamines are preferred as dispersing agents.

These additives are added in functionally equivalent amounts the pigments and/or dyes are added in quantities which will provide the composition with the desired color; however, they are suitably employed in amounts of from 1 to 200, 0 0 5

S

WO 89/06661 PCT/US88/04677 more suitably from 10 to 100, most suitably from to 100 percent by weight based upon the weight of the resin binder.

Solvents or diluents which can be employed herein include, for example, hydrocarbons, ketones, glycol ethers, esters, chlorinated hydrocarbons and combinations thereof. Particularly suitable solvents or diluents include, for example, toluene, benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, 1,1,itrichloroethane, DuPont DBE dibasic ester, ethylacetate, propylene glycol t-butyl ether and combinations thereof.

Reinforcing materials which can be employed herein include natural and synthetic fibers in the form of woven, mat, monofilament, and multifilament. Suitable reinforcing materials include, glass, ceramics, nylon, rayon, cotton, aramid, graphite, and combinations thereof.

Suitable fillers which can be employed herein include, for example, inorganic oxides, ceramic microspheres, plastic microspheres and combinations thereof.

The fillers can be employed in amounts suitably from 1 to 200, more suitably from 10 to 100, most suitably from 50 to 100 percent by weight based upon the weight of the resin binder.

The advanced epoxy resin compositions of the present invention can be employed in the preparation of WO 89/06661 -16coatings, castings, laminates, composites, encapsulants, and potting compositions.

PCT/US88/04677 WO 89/06661 PCT/US88/04677 -17- EXAMPLE 1 Preparation of Glycidyl Ether of Reaction Product of Bisohenol A and Propylene Oxide Into a reaction vessel equipped with stirrer, temperature controller, condenser, and nitrogen pad containing 500 g of ethylene dichioride was dissolved, at 750C, 172 g (1 OH equiv.) of the reaction product of propylene oxide and bisphenol A in a molar ratio of 2 to 1, respectively. Stannic chloride, 5 g (0.02 equiv.) was added and the temperature was raised to reflux, 880C. Epichlorohydrin, 194 g (1.2 equiv.) was added over a 45 minute period from a dropping funnel.

The solution turned black. The reaction mixture was cooled to 700C and 6 ml (0.0166 moles) of a 60% aqueous solution of benzyl trimethylammonium chloride and 500 g moles) of a 20% aqueous solution of sodium hydroxide were added and the reaction mixture cooled to 50°C. Stirring was continued and the mixture maintai ed at 500C for 2 hours. The reaction mixture was cooled to 350C and the aqueous layer was separated from the organic layer. To the organic layer was added an additional 250 g (1.25 moles) of 20 percent aqueous sodium hydroxide and 3 ml (0.008 moles) of a 60 percent aqueous solution of benzyl trimethylammonium chloride catalyst was added. The reaction mixture was heated to and maintained thereat with stirring for 2 hours.

The reaction mixture was cooled to 35°C and the aqueous layer was separated from the organic layer. The organic layer was washed three times with 150 ml portions of water. The ethylene dichloride was removed under vacuum in a rotary evaporator at 1500C. The resultant product had an epoxide equivalent weight (EEW) of 301.75, an aliphatic hydroxyl content of 1.86 -I I: III I iq~ r WO 89/06661 PCT/U$488/04677 -18wt. percent and a viscosity of 4040 ops (4.04 Pa.s) at Preparation of Advanced Ecoxy Resin SiA diglycidyl ether of bisphenol A having an EEW of 180, 152.7 g (0.85 epoxy equiv.), was blended with 356.2 g (1.18 epoxy equiv.) of the product from A above. This mixture was heated to 80°C at which time 191.2 g (1.68 equiv.) of bisphenol A was added. After the hinphenol A had dissolved, 0.727 g of a 70 wt.

percent methanolic solution of ethyl triphenyl phosphonium acetate*acetic acid complex catalyst was added. The reaction mixture was heated to 150"C and the heat source was turned off. The reaction exotherm causes the temperature to rise to 190 0 C, which temperature was maintained for 4 hours. The resultant advanced epoxy resin had an EEW of 1839.

Modification of Advanced Epoxy Resin To 95 g (0.052 equiv.) of the advanced epoxy resin prepared in above was mixed 10.3 g of ethylene glycol monobutyl ether in a three neck 500 ml round bottom flask equipped with a mechanical stirrer, a temperature controller, condenser and a nitrogen pad.

The mixture was heated to 125°C with stirring to dissolve the resin. A mixture of 0.95 g (1 percent by weight based on advanced epoxy resin solids) super phosphoric acid and 4.75 g ethylene glycol monobutyl ether was added to the resin solution all at once.

The reaction mixture exothermed to 130 0 C. The reaction mixture was stirred and the temperature maintained at 125°C for 30 minutes. Deionized water, 2 g, was then added to hydrolyze the di- and tri-esters thus formed.

The reaction mixture was then stirred and heated at WO 89/06661 PCT/US88/04677 -19- 125°C for an additional 2 hours. Additional ethylene glycol monobutyi ether solvent, 16 g, was added to give a solid solution of the modified advanced epoxy resin phosphate ester containing 78 percent by weight nonvolatiles.

Preaaration of Base Formulation A base formulation was prepared by blending 57 g of the resin solution from C above with the 1 following.

8.9 g ofMethylon 75108 resole curing agent available from BTL Chemical Specialties.

1.12 g of dimethylethanolamine as a dispersing agent.

3.1 g of CYMEL 247-10 available from American Cyanamid Company as a flow additive/curing agent.

g of DBE dibasic ester available from DuPont as a solvent.

Preparation of Coating The Base Formulation from D above was blended with 4 g of DuPont dibasic ester, DBE, solvent and 90 g of water was added over a period of 10 minutes. An aqueous dispersion with a bluish tinge was obtained.

The particle size of the dispersion was 0.1 micron and the volatile organic component (VOC) was 2.6 lbs/gal.

(3.14 kg/m3). This coating contained 50 percent by weight nonvolatiles. This dispersion was coated onto tin free steel can stock with a drawdown bar to give a 0.2 mil dry film thickness coating. The coated panel was baked at (400 0 F) 204°C for 10 minutes in an electric oven. The properties of the resultant coating are given in the Table.

WO 89/06661 PCT/US88/04677 Preparation of Coating The Base Formulation from D above except that it did not contain any melamine (CYMEL)

T

was blended with 4 g of DuPone aiasic ester, DBE, solvent, 30 g of ethylene glycol monobutyl ether and 5 grams of butanol.

The formulation contained 50 Dercent by weight nonvolatiles and a Gardner viscosity of X+ (1400 cps, 1.2 Pa-s). This solution was then diluted with 15 g of OBE solvent to give a 45 percent by weight nonvolatiles solution with an application viscosity of Gardner R (480 ops, 0.48 Pa-s). This solvent-borne coating was coated onto tin free steel can stock with a drawdown bar to give a 0.2 mil dry film thickness coating. The coating was baked for 10 minutes at 204.4 0 C (400°F). The properties of the resultant coating are given in the Table.

SOLVENT RESISTANCE was measured by rubbing the coating with a 2-pound (0.9 Kg) ballpein hammer where the hammer head was covered with gauze and soaked in methyl ethyl ketone (MEK). The number of double rubs, push-pull motion, observed until a marring of the coating occurs was recorded.

FLEXIBILITY was measured by the wedgebend test according to ASTM D3281-84 or T-bend test according to ASTM D4145-83.

AUTOCLAVE STEAM PROCESS RESISTANCE was measured by subjecting a stressed panel (about 2" x 50.8 mm x 101.6 .am) to 14.5 psig (100 kPa) steam for 90 minutes.

The panels were then removed from the autoclave or pressure cooker and dried with paper towels. The mI a, II WO 89/06661 PCT/US88/04677 -21coatings were observed for any signs of blush as evidenced by a white tinge to the coating.

ADHESION was then tested by cutting an X in the stressed area. Cellophane tape, SCOTCH

T

610, was then rubbed into each of the X's and removed with a smooth rapid pull. Any coating loss is noted.

The properties are given in the Table.

t COMPARATIVE EXPERIMENT A For comparative purposes, a coating was prepared using the unmodified resin from 1B employing the solvent-borne procedure of Example 1F. Note the improvem:.t in autoclave blush resistance for the two modified resins of Examples 1E and 1F compared to unmodified Comparative Experiment A.

Ex.or MEK Wedge Autoclave Comp. ME Bend Comp. Double Bend T Bend Expt. s Loss, Desig. Rubs mm Blusha Adhesion 1E 100+ 51 T2 none passb 1F 50 13 T2 none pass A* 30 24 T2 slight pass Not an example of the invention.

aAmount of white appearance on the coating surface.

bNo coating was removed when the tape was pulled off.

A

Claims (6)

1. A modified advanced epoxy resin which results from reacting an advanced epoxy resin which results from reacting an epoxy resin composition comprising at least one epoxy resin having an average of more than one, but not more than two vicinal epoxy groups per molecule and which contains at least one oxyalkylene or substituted oxyalkylene group per molecule; and at least one compound having two aromatic hydroxyl groups per molecule; wherein components and are employed in amounts which provide a ratio of aromatic hydroxyl groups per epoxy group of from 0.005:1 to 200:1; with a phosphorus-containing compound selected from phosphoric acid; super phosphoric acid; phosphate esters; or any combination of components (B-2) or wherein components and are present in an amount such that the ratio of moles of component 252 1 WO 89/.'6661 PCT/US88/04677 -23- to epoxy groups contained in component is f'rom 0.1:1 to 5:.1. modfiedadvanc-,-:d epoxy resin of Claim1 wherein component (0-11)1 furthe,, cornprises at least r-ne epoxy resin which has an average of more than one but not mire than about two viiaj epoxy groups per molecule and which is different from the eooxv resin of wherein components and are orese::t in amounts such that from 95 to 5 equi valent: percent of the epoxide groups are dierived from component (A-i-a) and from 5 to 95 equivalent percent of the epoxicde groups are derived from component

3. A-)advanced epoxy resin of Claim 2 wherein component is an epoxy resin or mixtur'e of~ epoxy resins represented by the following formula I Formula I 0 0 H 2 C 0 CH 2 (0-Z 0Z0-((Z 0O)m CH 2 C -C{ R wherein each R is i!ndependently hydrogen or an alkyl group having from 1 to 4 cebon atoms; Z is a divalent aromatic group reprecpnted'by the following formulas II andl III WO 89/06661 PCT/US88/046.77 -24- Formula II Formula III 4 (X) 4 X Tt 77 IU wherein A is a divalent hydrocarbyl group having fromn 1 to 12 carbon atoms, -SO2-, or each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, or a nalogen- n is zero or 1; each Z' is independently a group represented by the following formula IV Formula IV -CH-CH- I I R2 R1 wherein each RI and R 2 are independently hydrogen or a hydrocarbyl or hydrocarbyloxy group having 1 to 12 carbon atoms or a -CH2-0-R 3 group wherein R 3 is a hydrocarbyl group having from 1 to 12 carbon atoms; and each m an m' independently has a value from 1 to component is an epoxy resin or mixture of epoxy resins represented by the following formulas VII, VIII or IX or combinations thereof; Formula VII 0 H 2 C -C-CH2 R 0 X) 4 OH O-CH2-C-CH 2 I 0 nlI C(0) 4 0 0 CH'r-1C- CH2~ RI Formula V III (X) 4 H 2 C- C-CH 2 -0 I (X) 4 a(A)n (X) 4 0 0 C11 2 -0 ,I k0 O WO 89/06661 PCT/US88/04677 Formula 1X a /1 -ZC CH CH -Ji -J wherein A, R, RI, R 2 X, m and n are as def ined above and n has a.n averagze value f romi zero to 5: n (c component i3 a iompound or a= mxtur of compounds represented by the following formulas V and VI Formula V Formula VI (X) 4 (X) 4 wherein A, X and n are as defined abovte a4- -27-

4. A modified advanced epoxy resin of Claim 3 wherein component is a diglycidyl ether of the reaction product of bisphenol A with ethylene oxide, propylene oxide, butylene oxide, phenyl glycidyl ether, butyl glycidyl ether or a combination thereof; component is a diglycidyl ether of bisphenol A, bisphenol F or a combination thereof; and component is bisphenol A, bisphenol F or a combination thereof. io 0as e aocct Cccnpr n r 0 Amodified advanced epoxy rsin of Claim 1 or 2 444Ch- has -Additionally b- n rected ith-a monoamine ki-\ CL.

6. A curable composition which comprises a modified advanced epoxy resin of Claim 1 or 2 and a curing quantity of a suitable curing agent for said advanced epoxy resin. es

7. A curable composition which comprises a modified advanced epoxy resin of Claim =\and a curing quantity of a I o suitable curing agent for said advanced epoxy resin. te S8. A cured product resulting from curing the curable -7 composition of Claim

9. A modified advanced epoxy resin substantially as hereinbefore described with reference to Example 1. DATED: 27 February, 1991 SO THE DOW CHEMICAL COMPANY By their Patent Attorneys: A PHILLIPS ORMONDE FITZPATRICK INTERNATIONAL SEARCH REPORT international Application No. PCT/US88/04677 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) 6 According to Inlernaiional Patent Classiication (IPC) or to both National Classircation and IPC IPC4: C08G 59/02, 59/14, 59/30 U.S. CL: 525/523; 528/103 104, 108 iI. FIELDS SEARCHED Clasificati Sym Minimum Documentation Searched 7 Classification System Classification Symbols US. CL. _52 /523; 528/103, 104, i0.8 Documentation Searched other than Minimum Documentation to the Extent innr such Oocuments are Includea in me Fields Searcheda Ill. DOCUMENTS CONSIDERED TO BE RELEVANT o Category 1 Citation of Document, i with indication, where approoriate, of the relevant passages 12 Relevant to Claim No. 13 A US, A, 3,937,679 (BOSSO) 10 FEBRUARY 1976 (NOTE COLUMN 13) A US, A, 4,164,487 (MARTIN) 14 AUGUST 1979 (SEE ENTIRE DOCUMENT) A US, A, 4,256,844 (MARTIN) 17 MARCH 1981 (SEE ENTIRE DOCUMENT) A US,A, 4,289,812 (MARTIN) 15 SEPTEMBER 1981 (SEE ENTIRE DOCUMENT) A US, A, 4,316,922 (PERINE) 23 FEBRUARY 1982 (SEE ENTIRE DOCUMENT) A US, A, 4,360,613 (SHIMP) 23 NOVEMBER 1982 (SEE ENTIRE DOCUMENT) A US, A, 4,397,970 (CAMPBELL) 09 AUGUST 1983 (SEE ENTIRE DOCUMENT) A US, A, 4,481,347 (BERTRAM) 06 NOVEMBER 1984 (SEE ENTIRE DOCUMENT) SSpecial categories of cited documents; 10 later document published after the International filing date Sthe general sate oo the art which is not r priority date and not in conflict with the application but documen defining the general sate of the art which s notcited to understand the principle or theory underlying the considered to be of particular relevance Invention earlier document but published on or alter the International document of particular relevance; the claimed Invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority clalm(s) or Involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed Invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the International filing date but In the art. later than the priority date claimed document member of the same patent family IV, CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of tws l neWltlfaJt SsjilReiport 06 APRIL 1989 2 3 MAY 1989 International Searching Authority Signature of Auth r t -off International Application No. PCT/US8 8/04 677 ill._DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE 5ECOND SHEET) Cdlegory Citation of Documeiti, with jnaiCati~it. where aporoortate, ortine relevant passages Relevant to Claim Nho US,A 5,0-7o. GDTH M-ARCH ,SE ENTIRFIE DOC"UMENT) UOS,A ,b 0 8, 3 H ICKNER) 2 6 AUG U ST 198 6 !kSEE ENTIRE DOCUMENT) A US, A, 4, 613 661 (L-AN ER) 2 n3 SEPTEMBER 1 (SEE ENTIRE DOCUMENT) A US; A 4 692, 3 82 (1s CHMITT) 0 8 S EPT EMBER 1987 (SEE ENTIRE DOCUMENT) Farm PCT/ISAt2t0 (extr a sheet) (Flev.1 1-87)