Method for making a blocked amine

BACKGROUND OF THE INVENTION

[0002] The present invention relates generally to epoxy coatings, and more particularly to the use of blocked amine compounds in making epoxy coatings.

[0003] Curable epoxy resin systems are known. Conventional two component epoxy resin systems involve mixing of the epoxy resin and hardener and subsequent application of such mixtures as coatings by various techniques. Once mixed, such systems have short pot lives and must be used within a few hours.

[0004] As a result, efforts have been made to develop what are called one component systems. In one component systems, the curing agent is mixed with the epoxy but is inactive. It can be activated at a later time. One type of one component system involves the use of elevated temperature to activate the cross-linking reaction. However, the use of high temperatures is undesirable in many applications.

[0005] Another type uses latent cure, blocked amine systems in an attempt to alleviate the problem of reduced shelf life. In blocked amine systems, the amine is reacted with a ketone or aldehyde to form a blocked amine which is mixed with the epoxy resin. The system is activated by the addition of water, typically in the form of ambient moisture. This reverses the blocking reaction, forming the amine and the ketone or aldehyde. The amine then reacts with the uncured epoxy resin, and the ketone or aldehyde either evaporates or co-reacts with the epoxy. In the absence of moisture, such blocked amines systems afford a slight improvement in storage stability over conventional two component systems. However, commercial ketimine-based epoxy resin systems still suffer from limited storage stability, typically having a pot life of less than 24 hours. (Shell, 1986, EPON Curing Agents).

[0006] Furthermore, many systems include volatile organic compounds (VOC) or hazardous air pollutants (HAP), which are regulated. Commercial ketimine-based epoxy resin systems have elevated levels of VOCs, generally in excess of 3.5 lbs/gal. Under the current VOC standard for many industrial and maintenance coating applications, the limit is 3.1 lbs/gal of VOCs. This limit is likely to be reduced in the future to less than 2.8 lbs/gal of VOCs.

[0007] The use of ketimines as curing agents for epoxy resins is described in R. T. Holm, “Ketimines as Latent Epoxy Curing Agents,” J. of Paint Tech., Vol. 39, No. 509, June 1967, pp. 385-388. The VOC levels of these compounds is over 3.5 lbs/gal. The reported viscosity of the formulations containing the various ketimines ranged from about 3 to about 36 stokes after storage for 20 days at 25° C. However, these formulations do not provide the long term stability desired for commercial products. The long term stability of the formulations can be evaluated using accelerated aging testing at 55° C. Two weeks storage at 55° C. is equivalent to a shelf life of about six months, while 30 days storage is equivalent to a shelf life of over 1 year. The shelf life at 55° C. is estimated to be only about 12% of the value at 25° C.

[0008] British Patent No. 960,236, which is incorporated herein by reference, attempts to improve the shelf life of ketimine-based single component epoxy coatings by using hydroxyl-containing imines as blocked curing agents. The imines are obtained by reacting one or more imines possessing at least one amino hydrogen and one or more compounds having at least one epoxy group. No shelf life or VOC level is reported for these formulations. U.S. Pat. No. 5,837,785, which is incorporated herein by reference, discloses the use of heterocyclic containing curing agents for use in single component epoxy resin compositions. The heterocycle-containing compound has a backbone chain selected from the group consisting of polyether, polyvinyl, polyester, polyamide, polycarbonate, and novalac chains and at least two heterocyclic groups of the following general formula as side chains:

[0009] wherein R1 and R2 may be the same or different and each represents hydrogen, straight chain or branched C1 to C6 alkyl or alkenyl, or C6 to C8 aryl; or R1 and R2 taken together with the adjacent carbon atom, represents C5 to C7 cycloalkyl: R3 represents C, to C10 alkylene. A shelf life of 6 months at 40° C. is reported, but no VOC level is given. The viscosity of coating formulations is not disclosed, but it appears to be high for conventional coating applications.

[0010] Therefore, there is a need for a single component epoxy coating precursor having improved shelf life and a method for making such a precursor. There is also a need for a low VOC epoxy coating and for a method of making such a coating. There is also a need for a method of making a blocked amine which can be used in a single component epoxy coating precursor.

SUMMARY OF THE INVENTION

[0011] The present invention solves this need by providing a single component epoxy coating precursor and a method for making such a precursor, a low VOC epoxy coating and a method for making such a coating, and a method for making a blocked amine which is more stable than previously known ones.

[0012] The single component epoxy coating precursor includes an epoxy resin, a first solvent, and a blocked amine. The single component epoxy coating precursor has a viscosity after 30 days at a temperature of 55° C. of less than 16 stokes. It can have a viscosity after 30 days at a temperature of 55° C. of less than 13 stokes, or a viscosity after 30 days at a temperature of 55° C. of less than 7 stokes.

[0013] The method for making a single component epoxy coating precursor includes drying an epoxy resin and a blocked amine, combining and mixing the epoxy resin, the blocked amine, and a first solvent to form the single component epoxy coating precursor, wherein the single component epoxy coating precursor has a viscosity after 30 days at a temperature of 55° C. of less than 16 stokes. It can have a viscosity after 30 days at a temperature of 55° C. of less than 13 stokes, or a viscosity after 30 days at a temperature of 55° C. of less than 7 stokes. This level of viscosity stability at 55° C. generally corresponds to over one year of shelf life at room temperature storage conditions.

[0014] A reactive diluent optionally can be added to the single component epoxy coating precursor. Reactive diluents include, but are not limited to, modified glycidyl ethers, acrylates, methacrylates, urethane acrylates and combinations thereof. A water scavenger optionally can be added to the single component epoxy coating precursor. Water scavengers include, but are not limited to, molecular sieves, monocyclic bifunctional oxazolidines and combinations thereof. Pigments may be optionally added to the single component epoxy coating precursor. Pigments include, but are not limited to, titanium dioxide, diarylide yellow, iron oxide, raw umber, burnt umber, phthalocyanine blue, cobalt blue, chinese blue, phthalocyanine green, toluidine red, quinacridone red, dicerylide orange, carbon black, furnale black, lampblack, leafing aluminum and non-leaving aluminum.

[0015] Other formulating aids such as wetting agents, flow and rheology modifiers, light stability additives, etc., known in the art can be also incorporated.

[0016] First solvents which are useful in the present invention include, but are not limited to acetone, p-chlorobenzotrifluoride, t-butyl acetate, methyl isobutyl ketone, methyl propyl ketone and combinations thereof.

[0017] Epoxy resins include, but are not limited to, aliphatic epoxy resins, cycloaliphatic epoxy resins, aromatic epoxy resins and combinations thereof.

[0018] The single component epoxy coating precursor can have a VOC level of less than about 3 lbs/gal, or a VOC level of less than about 2.8 lbs/gal.

[0019] The method of making a low VOC epoxy coating includes drying an epoxy resin and a blocked amine, combining and mixing the epoxy resin, the blocked amine, and a first solvent to form the single component epoxy coating precursor, the single component epoxy coating precursor having a VOC level of less than about 3 lbs/gal, and exposing the single component epoxy coating precursor to water, the single component epoxy coating precursor and water reacting to form the low VOC epoxy coating. The water can be present in any form desired, including, but not limited to liquid water, and moisture in the air. The VOC level can be less than about 2.8 lbs/gal. The single component epoxy coating precursor described above and the blocked amine described below can be used to make the low VOC epoxy coating.

[0020] The method for making the blocked amine includes mixing a solvent capable of forming an azeotrope with water, an amine, and an amine blocker selected from ketones and aldehydes in a reaction vessel to form a reaction mixture. Ambient moisture is removed from the reaction vessel. The amine and the amine blocker are reacted to form the blocked amine and water of reaction, and the water of reaction is removed from the reaction mixture while the amine and the amine blocker are reacted. The blocked amine is recovered while maintaining the absence of moisture.

[0021] The solvent capable of forming an azeotrope with water includes solvents which can form binary or ternary azeotropes with water. These include, but are not limited to, toluene, xylene and combinations thereof.

[0022] The amine can be a polyamine, and it includes but is not limited to, diethylenetriamine, m-xylylenediamine and combinations thereof.

[0023] The amine blocker is selected from ketones and aldehydes. The ketones and aldehydes may have a molecular weight in the range of about 30 to about 600. They may have between about 2 and 14 carbon atoms. Suitable ketones include, but are not limited to, methyl isobutyl ketone, methyl ethyl ketone, acetone, phorone, heptanedione, tetramethylheptanedione, adamantone, acetonyl acetone, methylpropylketone and combinations thereof. Suitable aldehydes include, but are not limited to benzaldehyde, salicylaldehyde and combinations thereof.

[0024] The yield of blocked amine can be greater than about 90% of the theoretical yield, or greater than about 95% of the theoretical yield, or greater than about 97% of the theoretical yield.

[0025] The low VOC epoxy coating includes a reaction product of a single component epoxy coating precursor and water, the single component epoxy coating precursor comprising an epoxy resin and a blocked amine, the single component epoxy coating precursor having a VOC level of less than about 3 lbs/gal. The low VOC epoxy coating can have a VOC level of less than about 2.8 lbs/gal.

DETAILED DESCRIPTION OF THE INVENTION

[0026] The blocked amines were prepared according to the following procedure. The chemicals to be used were dried over molecular sieves. A solvent capable of forming an azeotrope with water was placed in a suitably sized round bottom flask fitted with a stir bar, magnetic stir plate, heating mantel, reflux condenser, and a Dean-Stark tube. The solvent capable of forming an azeotrope with water includes, but is not limited to, solvents which can form binary or ternary azeotropes with water. Examples of suitable solvents include, but are not limited to, toluene, xylene and combinations thereof. Toluene was used in these experiments as the solvent capable of forming an azeotrope with water. However, it is to be understood that other solvents capable of forming azeotropes with water could also be used. The flask was charged with an amine, a ketone or aldehyde, and a catalyst. Any appropriate catalyst can be used. Generally, acid based catalysts are used, such as p-toluene sulfonic acid. The neck of the reaction flask was wiped with a small amount of toluene to remove any trace reactants. The flask walls were also rinsed with a small amount of toluene to minimize exposure of the reactants to ambient moisture.

[0027] After the reaction mixture was added to the flask, it was purged under a stream of argon for about 5 minutes while stirring to remove ambient moisture and oxygen. The reflux condenser was quickly put in place and fitted with a gas inlet tube to provide a very slight positive pressure. Alternatively, the reflux condenser can be fitted with a drying tube containing Drierite™ to avoid incorporation of atmospheric water during the reaction or the subsequent cooling period before the flask is transferred to a distillation apparatus, such as a Rotovap™. No significant difference was observed in the efficiency of azeotrope or the theoretical mass of water recovered using either arrangement.

[0028] Water flow to the condenser was started, and the reaction flask and the Dean-Stark tube were wrapped in foil to improve water azeotroping efficiency. The reaction mixture was then stirred and heated. The mixture was maintained under steady state conditions at about 116° C. while stirring until either 100% of the theoretical water of reaction was recovered or until water ceased to azeotrope. The temperature will depend on the particular solvent used, and it should be about the boiling point of the solvent. Here, with toluene as the solvent (BP about 111° C.), the temperature was about 116° C. Water was drained from the Dean-Stark tube as required to prevent overfilling. The water of reaction recovered was over 90% of the theoretical amount, typically over 95%, and generally in the range of 96% to 99%.

[0029] At the end of each run, the reaction flask was cooled overnight to room temperature under a slight increase in initial argon pressure or with the drying tube in place. The positive increase in argon pressure was to prevent the transport of trap oil and moisture into the reaction flask. After cooling to room temperature, the reaction mixture was placed in a Rotovap™ to remove toluene and any unreacted ketone or aldehyde. The bath temperature was 70° C., and the vacuum was increased slowly to about 2 mm Hg over one hour. The reaction flask was returned to ambient pressure under argon, removed from the Rotovap™, and placed in a vacuum oven for two days at 70° C. and about 2 mm Hg to remove any remaining traces of toluene, ketone, or aldehyde. Heat to the vacuum oven was turned off, and the flask was cooled to ambient temperature while maintaining a vacuum. Under a stream of argon, the flask was returned to ambient pressure, placed over mole sieves, and capped. The reaction product was evaluated by infrared analysis for free amine.

[0030] Amines made using this procedure were blocked with a variety of different ketones and aldehydes. These blocked amines were then used to make single component epoxy resin precursors. The properties of the precursors and the coatings made from them were then evaluated.

[0031] The viscosity of the single component epoxy coating precursors in two solvents, toluene and methylisobutylketone (MIBK), at ambient temperature was monitored. In addition, the viscosity was monitored for the epoxy coating precursors in MIBK at 55° C. The accelerated aging samples were tested on a daily basis for the first 30 days, except on weekends, in order to determine viscosity. The process included removing the samples from the oven, cooling the samples to room temperature, and then measuring the samples in direct comparison with Gardner bubble viscosity tubes. The Gardner bubble viscosity tubes use bubble velocity to determine the viscosity of a sample. The viscosity of the sample is determined by finding the standard tube of known viscosity where the air bubble rises at the same rate with that of the test sample. A viscosity of less than 16 stokes is desirable because formulations remain sprayable with conventional spray equipment at this viscosity.

[0032] Coating properties were also evaluated. Draw-down panels were prepared using a #54 wire bound rod over Bonderite iron phosphate treated 3″×6″×0.0032″ steel panels and stored at 23° C. and 50% relative humidity to evaluate cure time and the physical properties of the films.

[0033] The pencil hardness test is described in Paint Testing Manual by H. A. Gardner and G. G. Sward, 13th Ed. (1972) p. 283-284, which is incorporated herein by reference. The ratings from worst to best are: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H.

[0034] For the MEK double rubs, a pad made from 10 plies of gauze material is attached to the ball end of a 2 lb ball peen hammer. The pad is saturated with methyl ethyl ketone (MEK) and rubbed across the coated substrate. A constant back and forth motion is used so that only the weight of the hammer applies the force. One double rub is equal to one back and forth movement. The movement is continued until the film is marred and/or begins to be removed by the solvent. One hundred double rubs are required to pass this test.

[0035] Other standard tests were also run.

[0036] Table 1 shows the formulation of the blocked amine and the epoxy coating precursor, and Tables 2 and 3 show the results of the initial evaluation of the epoxy coating precursors and the epoxy coatings.

[0037] The control formulation containing unblocked diethylenetriamine (DETA) cured in 2 hrs as a thin film from MIBK. The bottled control in toluene gelled in 24 hrs, while the control in MIBK gelled in 48 hours under ambient conditions. The control in MIBK stored at 55° C. gelled between 1 and 18 hrs.

[0038] In Run 1, an experimental DETA-based curing agent blocked with acetone was used. The experimental DETA-based curing agent was supplied by Shell with the designation S42686, and contained a mixture of DETA, a proprietary amine, and an alkyl phenol amine (hereafter referred to as “experimental DETA”). The film dried to the touch between 0-24 hrs. The toluene and MIBK formulations stored at room temperature gelled in 7 days and 9 days, respectively. The accelerated aging sample gelled within 24 hrs.

[0039] In Run 2, the experimental DETA-based curing agent was blocked with MIBK. The drying time for this film was 0-24 hrs. Additional films were prepared from this formulation after 3 weeks of aging at room temperature and after 16 days at 55° C. The films were dry to the touch at 6 hrs and 2 hrs. The films made from the aged formulations were blush-free and showed increased gloss with aging of the bottled formulations. Both samples stored at room temperature remained water like with no change in viscosity. The accelerated aging sample showed no change in viscosity until after 15 days. At that time, the viscosity went from about 0.5 to 4.4 stokes within 24 hrs. The sample remained pourable for 2 more days. Gel time was between 17 and 19 days. A replicate sample gelled in 22-24 days with a similar cure profile.

[0040] Run 4 used reagent grade DETA blocked with acetone. The drying time was slow, over 48 hrs, and the accelerated aging sample gelled in less than 24 hrs. These results are similar to the ones with experimental DETA. (Run 2).

[0041] DETA (reagent grade) blocked with MIBK was used in Run 5. Two panels were prepared from this formulation, one fresh and the other aged for two days. The drying time for the first panel was 0-24 hrs. The first panel showed a slight blush and a low gloss on cure. The second panel was monitored at 2 hr intervals to more accurately assess drying time. It was dry to the touch in 4 hrs, and showed no blush and excellent gloss (the wet look) after cure. The bottled samples stored at room temperature remained water like for over 8 weeks. The accelerated aging sample gelled after 24 days. A replicate sample also gelled in about 24 days.

[0042] In Run 6, lysine [H2N(CH2)4CH(NH2)COOH] was blocked with MIBK. One panel containing a 5% excess of blocked amine based upon 4 primary amines, and another containing a 5% excess based on all reactive hydrogens (typically 5) were prepared. The panels remained tacky after 8 hrs, but were dry to the touch the next morning. Pencil hardness was B at 24 hrs and 1 week. The panels showed poor resistance to MEK. The accelerated aging samples showed no increase in viscosity after 29 days. The sample with the lower concentration of blocked amine gelled in less than 6 months, while the sample with the higher level gelled in less than 5 months.

[0043] Run 7 involved the use of DETA blocked with phorone [(CH3)C═CHCOCH═C(CH3)2]. Films were dry to the touch in about 8 hrs. The panel containing less blocked amine required 8-10 hrs. Pencil hardness was <B after 24 hrs and 1 week, and solvent resistance was poor. The accelerated aging sample containing the lower level of blocked amine gelled in 25 days. The sample with the higher concentration of blocked amine gelled in 14 days.

[0044] In Run 8, DETA blocked with 2-heptanedione [CH3(CH2)4COCH3] was used. The films were dry to the touch is 8 hrs. Pencil hardness was B at 24 hrs increasing to F at 1 week. MEK resistance was good, especially for the sample with the higher concentration of blocked amine. The panels were glossy with a slight blush. The mixtures exhibited “crawling” during application. “Crawling” refers to coatings that draw away from the surface and leave holes or voids in the coating. Such bare areas are usually related to the wetting properties of the formulation. The accelerated aging sample with the lower concentration of blocked amine gelled in 25 days, while the sample with the higher concentration gelled at 14 days.

[0045] DETA blocked with tetramethyl heptanedione [(CH3)3CCOCH2COC(CH3)3] was used in Run 9 to evaluate the performance of a diketone. The panels required more than 48 hrs to cure and exhibited inadequate hardness and solvent resistance. The accelerated aging samples showed no change in viscosity after 29 days, and did not gel for more than 6 months.

[0046] In Run 10, panels made with DETA blocked with pyruvic aldehyde dimethyl acetyl were tacky, but nearly dry to the touch after 8 hrs, and they were completely dry the next morning. Pencil hardness was B after 24 hours for the lower concentration of the blocked amine, and it was F after 1 week. The panel made from the higher concentration had a pencil hardness that was <B and H for the same time intervals. The solvent resistance was 100 double rubs after 1 week. The panels had a good gloss and light blush. The sample with the higher concentration of blocked amine showed a change in viscosity from 0.5 to 13 strokes after 14 days of accelerated aging, and gelled in 17 days. The sample with the lower concentration gelled after more than 30 days.

[0047] Run 11 involved the use of DETA blocked with adamantone. After 8 hours, the panels were dry to the touch. The pencil hardness was H, and the MEK resistance was 100 double rubs after one week. The films were medium amber with a gloss <90 and a slight blush. The viscosity of the formulation with the lower concentration of blocked amine, increased from 0.5 to 4 stokes in 14 days, and it gelled at between 16 and 21 days. The formulation having the higher concentration of blocked amine gelled in 13 days.

[0048] In Run 12, DETA blocked with acetonyl acetone [CH3COCH2CH2COCH3] was used. The panels remained soft and too tacky for physical evaluation after one week. After 28 days, no change in viscosity was found in the accelerated aging samples.

[0049] Meta-xylylenediamine blocked with MIBK was used in Run 13. Within 8 to 9 hours the panels were dry to the touch. According to the literature, blocked amines prepared from meta-xylylenediamine and MIBK dry to the touch in 4 hours at room temperature in the presence of a phenol accelerator. The pencil hardness for the lower concentration of blocked amine was B after 24 hrs, HB after 48 hrs, and HB after 72 hrs. The MEK double rubs were 50 after 24 hrs, 100 after 48 hrs, and 100 after 72 hrs. The panel passed the direct impact tasting, cross hatch and ¼ inch mandrel bend test. The panel showed good gloss and appearance. The panel containing the higher concentration of blocked amine showed a pencil hardness of F after 24 hrs, F after 48 hrs, and H after 72 hrs. The MEK double rubs results were 90 after 24 hrs, 100 after 48 hrs, and 100 after 72 hrs. This panel also passed the direct impact, cross hatch and ¼ inch mandrel bend tests. No viscosity change occurred until after 30 days of accelerated aging. The formulation with the lower concentration of blocked amine remained unchanged after 40 days of accelerated aging and did not gel for more than 6 months. The formulation having the higher concentration of blocked amine had a viscosity of 2.8 stokes after 40 days, and it did not gel for more than 4.5 months.

[0050] Run 14 involved xylylenediamine blocked with diisobutylketone (DIBK). Both panels required more than 48 hrs to dry. They showed a pencil hardness of B after one week. At one week, the MEK double rubs were 20 for the lower concentration and 100 for the higher concentration. The panel passed the other tests. The films were water white with a gloss >90. The aging samples remained unchanged after 13 days.

[0051] In summary, Runs 2, 5, 7, 8, 11, and 13 resulted in thin film cure times of 8 hrs or less. Runs 7, 8, and 11 had reasonable viscosity stability at 55° C. The films that produced the best overall physical properties, cure rate, and with over 20 days of viscosity stability at 55° C. were Runs 2, 5, and 13.

[0052] From these studies, we found that the effectiveness of the blocking agent in providing long term stability for the single component epoxy coating precursors varies depending on the molecular weight of the blocking agents. A blocking agent having a molecular weight in the range of 30 to 600 provides good long term stability.

[0053] The blocked amine used in Run 5, DETA blocked with MIBK, was also evaluated with the addition of titanium dioxide (TiO2). Three formulations of DETA blocked with MIBK were tested under accelerated aging conditions: 3.5 g of DETA blocked with MIBK without TiO2, 3.5 g of DETA blocked with MIBK with 13% TiO2, and 3.8 g of DETA blocked with MIBK with 13% TiO2. The formulations containing TiO2 gelled in 18 days, as compared to 24 days for the sample without TiO2. The 3.5 g of DETA blocked with MIBK with 13% TiO2, was slower to cure than the control. However, by increasing the concentration of the blocked amine (3.8 g of DETA), a slight improvement in thin film cure times and physical properties occurred. Results are further described in Table 4.

[0054] Tests were run with reduced solvent (VOC) levels. The results are shown in Table 5 with regard to storage stability, thin film set time and the physical properties of formulations. Similar results occurred for cure and physical properties regardless of the solvent level. The data showed that under accelerated aging conditions, a sample containing half the MIBK concentration gelled in 12 to 14 days, compared to about 24 days for the normal level of MIBK in the control. The control contained 4.0 lbs/gal volatiles while the reduced solvent formulations contained 2.8 lbs/gal of volatiles.

1TABLE 1FormulationsRunControl12A2B2C45AAmineDETADETA-basedDETA-basedDETA-basedDETA-basedDETADETAexperimentalexperimentalexperimentalexperimentalamineamineamineamineBlocking AgentAcetoneMIBKMIBKMIBKAcetoneMIBKDraw-downFormulationSolventMIBKMIBKMIBKMIBKMIBKMIBKEpoxy resinBlocked AmineAgingNone3 weeks at RT16 days at 55° C.Run5B6A6B7A7B8A8BAmineDETALysineLysineDETADETADETADETABlocking AgentMIBKMIBKMIBKPhoronePhorone2-heptanedione2-heptanedioneDraw-downFormulationSolventMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gEpoxy resin 10 g 10 g 10 g 10 g 10 g 10 gBlocked Amine3.55 g4.42 g3.98 g4.96 g3.42 g4.26 gAgingRun9A9B10A10B11A11BAmineDETADETADETADETADETADETABlocking Agenttetramethyltetramethylpyruvic aldehydepyruvic aldehydeAdamantoneAdamantoneheptanedioneheptanedionedimethyl acetaldimethyl accetalDraw-downFormulationSolventMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gEpoxy resin 10 g10 g 10 g 10 g 10 g 10 gBlocked Amine5.05 g6.283.51 g4.38 g4.26 g5.30 gAgingRun12A12B13A13B14A14BAmineDETADETAXylylenediamineXylylenediamineXylylenediamineXylylenediamineBlocking AgentAcetonyl acetoneAcetonylMIBKMIBKDIBKDIBKacetoneDraw-downFormulationSolventMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gMIBK - 10 gEpoxy resin 10 g 10 g 10 g 10 g 10 g 10 gBlocked Amine3.42 g4.26 g3.5 g4.3 g4.41 g5.49 gAging

[0055]

2

TABLE 2

Evaluation Blocked Amines

Toluene
MIBK
MIBK

MEK

Cross
1/4″
Film

at RT
at RT
at 55° C.

Time
Dry to
Pencil
Dbl.

Hatch
Mandrel
Color
Gloss
(Daily/
(Daily/
(Daily/

Run
(hrs)
Touch
Hardness
Rubs
20 lbs
40 lbs
Adhesion
Bend
(1 wk)
(1 wk)
24 hrs)
24 hrs)
24 hrs)

Control

2 hrs

24

2H
Passed

Water

Gelled

Gelled

(100)

white

in 24 hrs

in 1-18

blush

hrs

48

3H

Gelled

in 48

hrs

168-

Passed
Passed
Passed
Some
Very

wk

(100)

linear
slight

failure; no
stress

squares
crack-

ing

1

0-24

hrs

24

2H
51, soft-

Gelled in

ening;

24 hrs

24 hr full

recovery

48

Passed (100)

168-

2H
Passed (100)
Passed
Partial
Passed
Failed;

Gelled in
Gelled

wk

“rim”

lost

7 days
in 9

failure

adhe-

days

sion

2A

0-24

hrs

24
Gummy
2B
0

Light

amber

high

gloss

48/72
Dry

0/0

1 wk

H
100;
Passed
Passed
Passed
Passed

softening

didn't go

to bare

metal

2 wk

H

Passed
Passed
Passed
Passed

3 wk

2H

Passed
Slight
Passed
Passed

“rim”

failure

2B

6 hrs

2
Sticky

Light

amber

good

gloss

4
Tacky

6
Dry to

touch,

FP

8
Dry to

touch,

FP,

recovers

2C

2 hrs

2
Dry to

Light

touch,

amber

slight

no

FP

blush

high

gloss

(wet

look)

4
Dry to

touch,

slight

FP

6
Dry to

touch,

slight

FP

8
Dry to

No change

touch,

after 14

slight

days,

FP,

Passed

recovers

aging test

24

Gelled

between

17-19 days

48/72

HB
80
Passed
Passed
Passed

Replicate

gelled in

22-24 days

96

HB
90

1 wk

F
100
Passed
Passed
Passed

4

24-48

Mod

Water

amber

like

hrs ?

mod

blush

orange

peel

24
Tacky
HB
42

Gelled in

24 hrs

48/72
Week-
HB
60/75

end

96
Dry

75

1 wk

F
100
Passed
Passed
Slight

No

failure

change

2 wk

Not

moni-

tored

5A

0-24

Water

hrs

like

24

HB
35

Clear

low

gloss

slight

blush

48/72

B/B
42/65

96

B
72

1 wk

B
90

2 wk

F
100,

slight

softening

5B

4 hrs

2
Wet

4
Dry to

touch,

slight

FP

6
Dry to

touch,

slight

FP

8
Dry to

touch,

no FP

24

Clear

high

gloss

no

blush

1 wk

Passed
Slight
Passed

Gelled in

“rim”

about 24

failure

days

6A

8-24

hrs

24
Dry to
<B
<10

touch,

slight

FP

1 wk

B
15
Passed
Passed
Passed
Passed
Water

Gelled in

white

less than 5

dull

months

slightly

bluish

6B

8-24

hrs

24/48

B
20

72/96

Water

Gelled in

white

less than 6

dull

months

slightly

bluish

1 wk

B
15
Passed
Passed
Passed
Passed

7A

8-10

hrs

24

90

Gelled in 25

amber

days

7B

8 hrs

24

90

Gelled in 14

Failure

amber

days

8A

7 hrs

8
7 hrs

dry

to touch

very

slight

FP

24

B
10

1 wk

F
100
Passed
Failed
Passed
Passed
Yellow
<90

Gelled in

(dulled

medium

14 days

film)

amber

blush

8B

6 hrs

6
dry to

touch

very

slight

FP

24

B
100

(dulled

film)

1 wk

F
100 (no
Passed
Failed
Passed
Failed
Yellow
<90

Gelled in

effect

medium

25 days

amber

blush

9A

>48 hrs

24
Tacky,
Gummy
Gummy

FP

1 wk

90

Gelled in

white

more than 6

months

9B

>48 hrs

24
Tacky,
Gummy
Gummy

FP

1 wk

90

Gelled in

(dulled

amber

more than

film)

blush

30 days

10B

8-24

8
nearly

dry

24

<B
5

1 wk

H
100
Passed
Passed
Passed
Failed
Light
<90

Gelled in

(dulled

amber

17 days

film)

11A

8-9 hrs

24

B
<10

1 wk

H
100
Passed
Passed
Passed
Failed
Medium
<90

Gelled

(dulled

amber

between

film)

blush

16 and 21

days

11B

8-9 hrs

24

B
10

1 wk

H
100
Passed
Passed
Passed
Failed
Medium
<90

Gelled in

(dulled

amber

13 days

film)

12A

>1 wk

12B

>1 wk

13A

9 hrs

24

B
50

48

HB
100

72

HB
100

1 wk

HB
100
Passed
Passed
Passed
Passed

Gelled in

(dulled

more than

film)

6 mths

13B

8 hrs

24

B
90

48

HB
100

72

HB
100

1 wk

HB
100
Passed
Passed
Passed
Passed

Gelled in

(dulled

more than

film)

4.5 mths

14A

>48 hrs

24

Sticky
Sticky

1 wk

B
20
Passed
Passed
Passed
Passed
Water
>90

white

14B

>48 hrs

24

Sticky
Sticky

1 wk

B
100
Passed
Passed
Passed
Passed
Water
>90

(slight

white

dulling)

[0056]

3

TABLE 3

Overall Film Evaluations Based on Visual Observation

Run
Comments

4
Moderate blush

6A
Excellent flow upon application, gloss diminished after 8 hrs

6B
Excellent flow upon application, gloss diminished after 8 hrs

7A
Good flow upon application, slight fisheyes

7B
Good flow upon application, slight fisheyes

8A
Poor flow, crawling

8B
Poor flow, crawling

9A
Fairly good flow, slight crawling

10A
Good flow upon application

10B
Good flow upon application

11A
Good flow upon application

11B
Good flow upon application

12A
Poor flow upon application, crawling, fisheyes

12B
Poor flow upon application, crawling, fisheyes

14A
Very good flow upon application

14B
Very good flow upon application

15A
Good flow upon application

15B
Good flow upon application

[0057]

4

TABLE 4

Physical Data for Epoxy Formulations With and Without Titanium Dioxide

Hardness (24 hours)
FORMULATION
Dry to touch
MEK Double Rubs
Gel time

Ingredients
Grams
(hours)
Day 1
Day 5
Day 6
Day 1
Day 5
Day 6
(days)
Comments

RUN 5

48262-38-16A

Passed direct impact, cross

48220-44-09

hatch and 1/4″ mandrel bend

3.9 VOC

testing after 1 week, gloss and

appearence excellent

MIBK-DETA
3.5
5 Hours, NFP
F
H
H
100
100
100
24 daysA

MIBK
10

EPON 828
10

TiO2
0

48262-41-13B

Sample very slow to cure after

48220-65-07

2 weeks achieved “HB” pencil

3.9 VOC

hardness and 100 MEK double

rubs with slight dulling. Passed

direct impact, cross hatch and

mandrel bend tests.

MIBK-DETA
3.5
8 hours, sl FP
Too
4.0 VOC

DTT, FP

MIBK-DETA
3.8

Passed direct impact, cross

hatch and 1/4″ mandrel bend

testing, gloss and appearence

excellent

MIBK
10

EPON 828
10

TiO2
˜13%

A
No gel time taken for this sample used gel time for identical formulation 48220-44-09

B
No gel time taken for this sample used gel time for identical formulation prepared with dried TiO2 48220-65-07

[0058]

5

TABLE 5

Physical Data for Epoxy Formulations With Different Concentrations of MIBK

FORMULATION

Hardness (24 hours)
MEK Double Rubs
Gel time

Ingredients
Grams
Dry to touch
Day 1
Day 5
Day 6
Day 1
Day 5
Day 6
(days)
Comments

Run 2

48262-38-07

Gel 17-19
Passed direct impact, failed 1/4

3.9 VOC

daysA
inch mandrel (rim failure)

Gel 22-24
amber appearance with good

daysB
gloss (>90)

MIBKxp-DETA
3.5
6 hours
B
H
H
40
100
100

MIBK
10
DTT. Very slight FP

EPON 828
10

48262-38-25

NONE

2.98 VOC

MIBKxp-DETA
3.5
9 hours
90)

EPON 828
10

Run 5

48262-38-16

2.98 VOC

MIBK-DETA
3.5
5 Hours, NFP
F
H
H
100
100
100
˜24 daysC

MIBK
10

EPON 828
10

48262-39-07

2.98 VOC

MIBK-DETA
3.5
4 hours
H
2H
2H
100
100
100
Gel time
Passed direct impact (20 lbs),

12-14 daysD
failed direct impact (40 lbs),

passed cross hatch, failed

1/4 inch mandrel bend (2 wks).

Amber appearance slight blush,

good gloss (<90)

MIBK
5

EPON 828
10

A
Reference sample 48220-28-13 used to determine gel time

B
Reference sample 48220-53-07 used to determine gel time

C
Reference samples 48262-44-09 and 49-07 used to determine gel time

D
Reference samples 48220-65-16 used to determine gel time

[0059] Another set of tests focused on evaluating reduced VOC formulations. The VOC exempt solvents that were evaluated included acetone and p-chlorobenzotrifluoride (available as Oxsol 100 from Occidental Chemical Corp.). Tertiary butyl acetate (t-butyl acetate), for which exempt status is pending, was also evaluated. The nonexempt solvents included methyl isobutyl ketone (MIBK) and methyl propyl ketone (MPK). The solvents were evaluated in combination with water scavengers, including molecular sieves and Incosol-2® (available from Industrial Copolymers, Ltd.), and several mono and multifunctional reactive diluents. Incosol-2® is a monocyclic bifunctional oxazolidine that reacts with water to form a linear aminoalcohol and an aldehyde.

[0060] Eight-five formulations were prepared from xylylenediamine blocked with MIBK. The formulations are shown in Table 6. The materials were dried over mole sieves prior to use. The epoxy resin (EPON 828 available from Miller Stevenson) and the solvent(s) were combined and vortexed for about one minute until the samples were homogenous. Next, the reactive diluent was added, if used. The water scavenger was then added, if used. The samples were vortexed again for about 0.5 to 1.0 minute each, and the blocked amine was added. The samples were vortexed for a third time after which aliquots were transferred to 8 ml glass culture tubes, capped and put in the oven at 55° C. for accelerated aging evaluation. The remaining mixtures were maintained at room temperature for approximately 13 to 14 hours.

[0061] The results of the testing of these formulations are shown in Tables 7 and 8.

6TABLE 6Storage Stability Test Matrix Run 20 (MIBK-Xylylenediamine Based System)No Reactive DiluentWith742746748757With Incosol +Incosol − 5.0%Reactive DiluentWithWithoutWithWithoutWithWithoutWithWithout2.5% ExcessExcessSolvent SystemIncosolIncosolIncosolIncosolIncosolIncosolIncosolIncosolAmineAmineMIBK45 C. 5 C.55 C.15 C.65 C.25 C.75 C.35 C.2 C.4 C.MPK47 C. 7 C.57 C.17 C.67 C.27 C.77 C.37 C.OXSOL 10049 C. 9 C.59 C.19 C.69 C.29 C.79 C.39 C.t-Butyl Acetate51 C.11 C.61 C.21 C.71 C.31 C.81 C.41 C.Acetone53 C.13 C.63 C.23 C.73 C.33 C.83 C.43 C.No Reactive DiluentWithWith Mole742/TMPTA746/TMPTA748/TMPTA757/TMPTAMole S. +S. − 5.0%Reactive DiluentWithWithoutWithWithoutWithWithoutWithWithout2.5% ExcessExcessSolvent SystemMole SMole SMole SMole SMole SMole SMole SMole SAmineAmineMIBK46 C. 6 C.56 C.16 C.66 C.26 C.76 C.36 C. 1 C.3 C.MPK48 C. 8 C.58 C.18 C.68 C.28 C.78 C.38 C.OXSOL 10050 C.10 C.60 C.20 C.70 C.30 C.80 C.40 C.t-Butyl Acetate52 C.12 C.62 C.22 C.72 C.32 C.82 C.42 C.Acetone54 C.14 C.64 C.24 C.74 C.34 C.84 C.44 C.MIBK/Oxsol 10085 C.*Ketimine at 2.5% excess unless otherwise indicated

[0062]

7

TABLE 7

Storage Stability and Physical Property Data Summary of Reduced VOC

Formulations Prepared from MIBK-Xylylenediamine

Viscosity

Hard-
Hard-

Sample
at 30

Reactive

Solvent

Drying
ness
ness

ID
Days
VOC
Diluent
Scavenger
System
DIT 20
DIT 40
Gloss
Time
(24H)
(1 WK)

1C
#N/A
2.68
None
Mole Sieve + 2.5%
MIBK
Fail
Fail
72.5
10-12
H
2H

Excess

hours

Amine

2C
#N/A
2.68
None
Incosol + 2.5%
MIBK
Pass
Fail
81.2
10 hours
H
2H

Excess

Amine

3C
19
2.7
None
Mole Sieve − 5.0%
MIBK
Pass
Fail
78
10-12
2H
3H

Excess

hours

Amine

4C
#N/A
2.67
None
Incosol − 5.0%
MIBK
Pass
Fail
85.5
10-12
H
2H

Excess Amine

hours

5C
5.5
2.69
742
None
MIBK
Pass
Pass
47.5
over 10
<B
H

hours

6C
#N/A
2.69
742/TMPTA
None
MIBK
Pass
Fail
103.5
over 10
3H
2H

hours

7C
3.2
2.69
742
None
MPK
Pass
Pass
52.5
over 10
<B
2H

hours

8C
#N/A
2.69
742/TMPTA
None
MPK
Pass
Fail
101
10-12
2H
2H

hours

9C
#N/A
1.33
742
None
OXSOL 100
Pass
Very
61.7
over 10
<B
B

Slight

hours

Fail

10C
#N/A
1.47
742/TMPTA
None
OXSOL 100
Fail
Fail
100.2
over 10
3H
2H

hours

11C
#N/A
1.48
742
None
t-Butyl
Pass
Pass
64.2
over 10
<B
H

Acetate

hours

12C
#N/A
1.61
742/TMPTA
None
t-Butyl
Pass
Fail
100
over 10
2H
2H

Acetate

hours

13C
0.85
1.53
742
None
Acetone
Pass
Slight
45.1
over 10
H
2H

Failure

hours

14C
#N/A
1.67
742/TMPTA
None
Acetone
Pass
Fail
102.5
10-12
3H
4H

hours

15C
2.8
2.69
746
None
MIBK
Pass
Pass
38.3
over 10
<B
2H

hours

16C
#N/A
2.7
746/TMPTA
None
MIBK
Fail
Fail
89.5
over 10
2H
2H

hours

17C
2.5
2.69
746
None
MPK
Pass
Pass
34.9
over 10
<B
F

hours

18C
#N/A
2.7
746/TMPTA
None
MPK
Pass
Fail
80.4
over 10
3H
2H

hours

19C
#N/A
1.3
746
None
OXSOL 100
Pass
Pass
48.2
over 10
<B
F

hours

20C
#N/A
1.43
746/TMPTA
None
OXSOL 100
Pass
Fail
97.4
over 10
2H
4H

hours

21C
6.8
1.44
746
None
t-Butyl
Pass
Pass
45.4
over 10
<B
2H

Acetate

hours

22C
#N/A
1.58
746/TMPTA
None
t-Butyl
Pass
Fail
95.4
over 10
2H
3H

Acetate

hours

23C
2.25
1.49
746
None
Acetone
Pass
Pass
25.5
over 10
<B
F

hours

24C
#N/A
1.63
746/TMPTA
None
Acetone
Pass
Fail
97.1
over 10
2H
2H

hours

25C
1.65
2.7
748
None
MIBK
Pass
Pass
17.6
over 10
<B
F

hours

26C
#N/A
2.69
748/TMPTA
None
MIBK
Pass
Fail
96.7
over 10
H
2H

hours

27C
2
2.7
748
None
MPK
Pass
Pass
31
over 10
<B
HB

hours

28C
#N/A
2.69
748/TMPTA
None
MPK
Pass
Fail
82.7
over 10
2H
2H

hours

29C
13
1.22
748
None
OXSOL 100
Pass
Pass
29.1
over 10
<B
HB

hours

30C
#N/A
1.42
748/TMPTA
None
OXSOL 100
Pass
Fail
90
over 10
2H
2H

hours

31C
5.5
1.37
748
None
t-Butyl
Pass
Pass
17.3
over 10
<B
<B

Acetate

hours

32C
#N/A
1.56
748/TMPTA
None
t-Butyl
Pass
Pass
93
over 10
2H
2H

Acetate

hours

33C
1.4
1.42
748
None
Acetone
Pass
Pass
33.2
over 10
<B
F

hours

34C
#N/A
1.62
748/TMPTA
None
Acetone
Pass
Pass
98
over 10
2H
4H

hours

35C
#N/A
2.69
757
None
MIBK
Pass
Fail
60.5
10-12
2H
2H

hours

36C
#N/A
2.68
757/TMPTA
None
MIBK
Pass
Fail
99.4
over 10
2H
4H

hours

37C
13
2.69
757
None
MPK
Pass
Slight
52.6
over 10
2H
2H

Failure

hours

38C
#N/A
2.68
757/TMPTA
None
MPK
Pass
Fail
99.1
10-12
2H
4H

hours

39C
#N/A
1.38
757
None
OXSOL 100
Pass
Slight
72
10-12
H
2H

Failure

hours

40C
#N/A
1.48
757/TMPTA
None
OXSOL 100
Pass
Pass
99.6
over 10
3H
4H

hours

41C
#N/A
1.53
757
None
t-Butyl
Pass
Very
63.3
over 10
F
2H

Acetate

Slight

hours

Fail

42C
#N/A
1.62
757/TMPTA
None
t-Butyl
Pass
Fail
99.4
over 10
2H
2H

Acetate

hours

43C
4.4
1.58
757
None
Acetone
Pass
Slight
60.8
10-12
H
H

Failure

hours

44C
#N/A
1.68
757/TMPTA
None
Acetone
Pass
Fail
101.9
over 10
4H
4H

hours

45C
5.5
2.69
742
Incosol
MIBK
Pass
Pass
35
10-24
<B
B

hours

46C
#N/A
2.69
742/TMPTA
Mole Sieve
MIBK
Pass
Fail
101.3
10-24
2H
4H

hours

47C
3.2
2.69
742
Incosol
MPK
Pass
Pass
29.6
10-24
<B
<B

hours

48C
#N/A
2.69
742/TMPTA
Mole Sieve
MPK
Pass
Fail
98.5
10-24
H
2H

hours

49C
#N/A
1.32
742
Incosol
OXSOL 100
Pass
Pass
54.5
10-24
<B
HB

hours

50C
#N/A
1.47
742/TMPTA
Mole Sieve
OXSOL 100
Pass
Fail
95.4
10-24
2H
2H

hours

51C
13
1.46
742
Incosol
t-Butyl
Pass
Pass
54.5
10-24
HB
HB

Acetate

hours

52C
#N/A
1.61
742/TMPTA
Mole Sieve
t-Butyl
Pass
Fail
88.4
10-24
2H
2H

Acetate

hours

53C
0.85
1.52
742
Incosol
Acetone
Pass
Very
42.5
10-24
<B
F

Slight

hours

Fail

54C
2.8
1.67
742/TMPTA
Mole Sieve
Acetone
Pass
Fail
101.2
10-24
2H
4H

hours

55C
2.5
2.69
746
Incosol
MIBK
Pass
Pass
32.3
10-24
<B
HB

hours

56C
#N/A
2.7
746/TMPTA
Mole Sieve
MIBK
Pass
Slight
84
10-24
2H
2H

Failure

hours

57C
1.65
2.69
746
Incosol
MPK
Pass
Pass
21
10-24
<B
B

hours

58C
13
2.7
746/TMPTA
Mole Sieve
MPK
Pass
Pass
94.5
10-24
2H
4H

hours

59C
#N/A
1.29
746
Incosol
OXSOL 100
Pass
Pass
45.6
10-24
<B
H

hours

60C
#N/A
1.43
746/TMPTA
Mole Sieve
OXSOL 100
Pass
Fail
92.3
10-24
H
4H

hours

61C
5.5
1.43
746
Incosol
t-Butyl
Pass
Fail
38.5
10-24
F
H

Acetate

hours

62C
#N/A
1.58
746/TMPTA
Mole Sieve
t-Butyl
Pass
Fail
93.2
10-24
3H
3H

Acetate

hours

63C
1.25
1.48
746
Incosol
Acetone
Pass
Pass
24.4
10-24
F
F

hours

64C
3.7
1.63
746/TMPTA
Mole Sieve
Acetone
Pass
Slight
99.2
10-24
2H
4H

Failure

hours

65C
2.25
2.7
748
Incosol
MIBK
Pass
Pass
16.9
10-24
H
B

hours

66C
#N/A
2.69
748/TMPTA
Mole Sieve
MIBK
Pass
Pass
94
10-24
H
4H

hours

67C
1.4
2.7
748
Incosol
MPK
Pass
Pass
15.3
10-24
<B
B

hours

68C
13
2.69
748/TMPTA
Mole Sieve
MPK
Pass
Pass
96.2
10-24
H
2H

hours

69C
#N/A
1.21
748
Incosol
OXSOL 100
Pass
Pass
21.6
10-24
<B
B

hours

70C
#N/A
1.42
748/TMPTA
Mole Sieve
OXSOL 100
Pass
Fail
91.2
10-24
2H
3H

hours

71C
4.7
1.36
748
Incosol
t-Butyl
Pass
Pass
22.8
10-24
<B
F

Acetate

hours

72C
#N/A
1.46
748/TMPTA
Mole Sieve
t-Butyl
Pass
Pass
83.6
10-24
H
2H

Acetate

hours

73C
0.65
1.41
748
Incosol
Acetone
Pass
Pass
36.9
10-24
<B
<B

hours

74C
3.7
1.62
748/TMPTA
Mole Sieve
Acetone
Pass
Pass
91
10-24
H
4H

hours

75C
#N/A
2.69
757
Incosol
MIBK
Pass
Slight
50.7
10-24
2H
2H

Failure

hours

76C
#N/A
2.68
757/TMPTA
Mole Sieve
MIBK
Pass
Fail
92.1
10-24
2H
4H

hours

77C
9
2.69
757
Incosol
MPK
Pass
Slight
45.5
10-24
F
F

Failure

hours

78C
#N/A
2.68
757/TMPTA
Mole Sieve
MPK
Pass
Pass
96.8
10-24
2H
4H

hours

79C
#N/A
1.37
757
Incosol
OXSOL 100
Pass
Pass
65
10-24
H
2H

hours

80C
#N/A
1.48
757/TMPTA
Mole Sieve
OXSOL 100
Pass
Pass
94.9
10-24
2H
4H

hours

81C
#N/A
1.51
757
Incosol
t-Butyl
Pass
Pass
62.7
10-24
4H

Acetate

hours

83C
2.5
1.68
757
Incosol
Acetone
Pass
Slight
49.6
10-24
F
F

Failure

hours

84C
5.5
1.63
757/TMPTA
Mole Sieve
Acetone
Pass
Pass
95.1
10-24
H
4H

hours

85C
0.5
3.05
None
Mole Sieve
MIBK/
Pass
Very
76.5
10-24
H
2H

OXSOL 100

Slight

hours

Fail

[0063]

8

TABLE 8

Overall Film Evaluations Based on Visual Observations

Sample

ID
Comments

1C
Irregular flow pattern & lower gloss indicate some

incompatibility

2C
Irregular flow pattern & high low gloss indicate some

incompatibility

3C
Fairly good flow and gloss but brittle film

4C
Good gloss and flow but brittle film

5C
Good flow but “high-low” gloss pattern indicates

incompatibility

6C
Excellent gloss, good flow but brittle film

7C
Good flow but “high-low” gloss pattern indicates

incompatibility

8C
Excellent flow & gloss but brittle film

9C
Good flow but “high-low” glass pattern indicates

incompatibility

10C
Excellent gloss, good flow but very brittle film

11C
Good flow but “high-low” gloss pattern indicates

incompatibility

12C
Excellent gloss & flow but brittle film

13C
Classic example of “high low” gloss pattern &

incompatibility

14C
Excellent gloss & flow but brittle film

15C
Good flow but poor gloss

16C
Good gloss, excellent flow but brittle film

17C
Good flow, poor gloss, good flexibility

18C
Good flow & gloss but slight haze; brittle film

19C
Excellent flow but poor gloss; flexible film

20C
Excellent gloss & flow but brittle film

21C
Excellent flow but poor gloss; flexible film

22C
Excellent flow & good but brittle film

23C
Good flow, poor gloss but brittle film

24C
Outstanding gloss & flow but brittle film

25C
Poor gloss & flow; blush

26C
Excellent gloss, moderate flow; brittle film

27C
Low gloss, moderately good flow; blush; flexible film

28C
Fairly good flow but irregular gloss indicates incompatibility

29C
Poor gloss; blush, but good flexible film

30C
Excellent gloss; irregular flow; brittle film

31C
Very poor gloss; film soft, mars easily

32C
Excellent gloss; erratic flow pattern; flexible film

33C
Poor flow pattern, low gloss due to incompatibility

34C
Outstanding gloss, flow hardness & flexibility (*)

35C
Classic “high-low” gloss pattern of incompatibility

36C
Outstanding gloss, erratic flow pattern; brittle film

37C
“high-low” gloss, erratic flow reflects incompatibility

38C
Good gloss & flow but brittle film

39C
“High-low” gloss, erratic flow reflects incompatibility

40C
Excellent gloss, slightly erratic flow, but good flexibility

41C
High-low gloss, erratic flow; incompatibility, flexible film

42C
Outstanding gloss & flow; brittle film

43C
“High-low” gloss; erratic flow reflect incompatibility

44C
Outstanding gloss, good-flow but brittle film

45C
Poor gloss, “high-low” gloss; incompatible but flexible

46C
Outstanding gloss, good flow but brittle film

47C
Poor gloss (“high-low”) reflect incompatibility flexible

film

48C
Outstanding gloss, very good flow but brittle film

49C
Good flow pattern & flexibility but poor gloss

50C
Very good gloss & flow but brittle film

51C
Good flow & flexibility but poor gloss

52C
Good gloss; fairly good flow but brittle film

53C
Classic “high-low” gloss pattern; incompatible flexible

film

54C
Outstanding gloss; very good flow but brittle film

55C
Poor flow and gloss; incompatible but flexible film

56C
Very good gloss, flow and relatively good flexibility

57C
Poor flow & gloss; incompatible but flexible film

58C
Outstanding gloss, flow, hardness & flexibility *

59C
Poor flow & gloss; blush, but flexible film

60C
Good gloss & flow but brittle film

61C
Good flow but poor gloss flexible film

62C
Good gloss & glow but brittle film

63C
Poor gloss & flow; incompatible but flexible films

64C
Excellent gloss & flow but brittle film

65C
Poor gloss and flow; soft film; mars easily; blush

66C
Very good gloss, flow & flexibility

67C
Poor gloss; good flow & flexible film

68C
Very good gloss, flow, hardness & flexibility *

69C
Poor gloss; film soft; mars easily, flexible film

70C
Good gloss & flow but brittle film

71C
Poor gloss; film soft, mars easily but flexible

72C
Gloss & flexibility good but “mottled” flow is a problem

73C
Poor gloss, poor flow film soft & mars easily

74C
Very good gloss, flow, hardness & flexibility *

75C
“High-low” gloss pattern reflects incompatibility

76C
Excellent gloss slightly erratic flow & brittle film

77C
Classic “high-low” gloss incompatibility

78C
Very good gloss, flow, hardness & flexibility *

79C
Nice looking film but poor gloss; film flexible

80C
Very good gloss, flow, hardness & flexibility *

81C
Nice looking film but poor gloss, film flexible

82C
Good gloss & flow, hardness & flexibility

83C
“High-low” gloss pattern reflects incompatibility

84C
Very good gloss, flow, hardness & flexibility *

85C
Nice looking film but haze hinders gloss flexible.

Note:

Incompatibility in the strictest sense refers to the fact that a portion of the film appears to be insoluble in the residual solvent or reactive diluents.

* Superior film in all aspects except (slightly reduced) gloss.

[0064] After 30 days of accelerated aging, thirty-five of the eighty-five formulation evaluated had measured viscosities of 16 stokes or less, as shown in Table 9. The VOC level of these formulations ranged from 1.22 to 3.05 lbs/gal.

[0065] Of those 35 formulations, 29 had viscosities of 7 stokes or less, as shown in Table 10. The VOC level for these formulations ranged from 1.36 to 3.05 lbs/gal.

[0066] Of the 29 formulations with viscosities of 7 stokes or less, 12 contained Incosol-2® as a water scavenger, 12 contained no water scavenger, and five contained mole sieves. Only the mole sieves were tested in combination with the reactive diluent trimethylolpropanetriacrylate (TMPTA). The formulations containing TMPTA gelled faster than formulations without TMPTA, regardless of the solvent. In addition, six of the 20 TMPTA/mole sieve formulations remained sprayable after thirty days of accelerated aging. None of the samples containing TMPTA without mole sieves maintained acceptable viscosities after thirty days of accelerated aging.

[0067] Five formulations had a viscosity of 1.25 stokes or less and remained water-like. The VOC level for these formulations ranged from 1.41 to 3.05 lbs/gal. Samples 13C, 53C, 63C, and 73C contained acetone as a solvent and sample 85C contained equal parts of acetone and p-chlorobenzotrifluoride as a solvent. None of the five samples contained a multifunctional reactive diluent. Thin films made from these formulations were characterized by low gloss and inadequate hardness.

[0068] Draw-down panels were prepared with a #54 wire bound rod over Bonderite 1000 iron phosphate treated steel panels that were 3″×6″×0.0032″. The panels were held at a constant temperature of 75° F./50 RH and then observed at two-hour increments for ten hours to determine drying time. The majority of the panels required 10-12 hours or more before they were dry to the touch. The samples evaluated in the first phase using the same ketimine dried in 8-10 hours. The slower drying time is attributable to three factors. First, formulations in the second phase had a 2.5 wt % excess amine instead of 5 wt % as used in the first phase experiments. Second, the average coating thickness was 1.83 mils, due to the higher percent solids associated with the panel, rather than about 0.8 mils as in the previous panels. Finally, the constant temperature room was 73° F./45% RH during the thin film dry period, whereas, the previous panels were maintained in a constant temperature room at 75° F./50% RH. These conditions are slightly less favorable and would slightly retard cure time.

[0069] Comparing the effects of the reactive diluents on the coatings, the panels containing TMPTA as a reactive diluent had better hardness and gloss. Among the Epodil™ reactive modifiers, Epodil™ 757, a bifunctional epoxy resin, also exhibited good gloss and hardness. Since the other reactive diluents are monofunctional, these results are consistent with conventional coating chemistry. In summary, independent of VOC levels and storage stability, many test panels show excellent hardness and gloss while still maintaining sufficient flexibility to pass the impact testing.

[0070] Four formulations remained sprayable after 30 days of accelerated aging at 55° C. regardless of base solvent, had gloss values of greater than or equal to 85, passed both 20/40 pound impact testing, and had a pencil hardness of greater than or equal to H after 1 week. The four formulations that met the above criteria are 58C, 68C, 74C, and 84C. Two of these contain MPK as a solvent (Samples 58C and 68C), and two contain acetone (Samples 74C and 84C). The viscosity of both MPK formulations was 13 stokes at day 30, which puts the viscosities around the middle of the acceptable range. As a result, these formulations should remain easily sprayable for months, have acceptable VOC levels (2.7 and 2.69 lbs/gal, respectively), and good physical properties. Samples 74C and 84C have very low VOC levels (1.62 and 1.63 lbs/gal, respectively) and retained near water-like viscosities after accelerated aging for 30 days. Many of the samples maintained acceptable viscosities for about six months or more, based on accelerated aging projection, with acceptable physicals and VOC levels.

9TABLE 9Formulations With Viscosities ≦ 16 Stokes After30 Days of Accelerated Aging At 55° C.SampleViscosity atReactiveSolventDITHardnessID30 DaysVOCDiluentScavengerSystem20Gloss(1 WK) 5C5.52.69742NoneMIBKPass47.5H 7C3.22.69742NoneMPKPass52.52H13C0.851.53742NoneAcetonePass45.12H15C2.82.69746NoneMIBKPass38.32H17C2.52.69746NoneMPKPass34.9F21C6.81.44746Nonet-ButylPass45.42HAcetate23C2.251.49746NoneAcetonePass25.5F25C1.652.7748NoneMIBKPass17.6F27C22.7748NoneMPKPass31HB29C131.22748NoneOXSOL 100Pass29.1HB31C5.51.37748Nonet-ButylPass17.3<BAcetate33C1.41.42748NoneAcetonePass33.2F37C132.69757NoneMPKPass52.62H43C4.41.58757NoneAcetonePass60.8H45C5.52.69742IncosolMIBKPass35B47C3.22.69742IncosolMPKPass29.6<B51C131.46742Incosolt-ButylPass54.5HBAcetate53C0.851.52742IncosolAcetonePass42.5F54C2.81.67742/TMPTAMole SieveAcetonePass101.24H55C2.52.69746IncosolMIBKPass32.3HB57C1.652.69746IncosolMPKPass21B58C132.7746/TMPTAMole SieveMPKPass94.54H61C5.51.43746Incosolt-ButylPass38.5HAcetate63C1.251.48746IncosolAcetonePass24.4F64C3.71.63746/TMPTAMole SieveAcetonePass99.24H65C2.252.7748IncosolMIBKPass16.9B67C1.42.7748IncosolMPKPass15.3B68C132.69748/TMPTAMole SieveMPKPass96.22H71C4.71.36748Incosolt-ButylPass22.8FAcetate73C0.651.41748IncosolAcetonePass36.9<B74C3.71.62748/TMPTAMole SieveAcetonePass914H77C92.69757IncosolMPKPass45.5F83C2.51.68757IncosolAcetonePass49.6F84C5.51.63757/TMPTAMole SieveAcetonePass95.14H85C0.53.05NoneMole SieveMIBK/Pass76.52HOxsol 100

[0071]

10

TABLE 10

Formulations With Viscosities ≦ 7 Stokes After

30 Days of Accelerated Aging At 55° C.

Sample
Viscosity

Reactive

Solvent
DIT

Hardness
Hardness

ID
@ 30 days
VOC
Diluent
Scavenger
System
20
DIT 40
Gloss
(24H)
(1 WK)

5C
5.5
2.69
742
None
MIBK
Pass
Pass
47.5
<B
H

7C
3.2
2.69
742
None
MPK
Pass
Pass
52.5
<B
2H

13C
0.85
1.53
742
None
Acetone
Pass
Slight Failure
45.1
H
2H

15C
2.8
2.69
746
None
MIBK
Pass
Pass
38.3
<B
2H

17C
2.5
2.69
746
None
MPK
Pass
Pass
34.9
<B
F

21C
6.8
1.44
746
None
t-Butyl Acetate
Pass
Pass
45.4
<B
2H

23C
2.25
1.49
746
None
Acetone
Pass
Pass
25.5
<B
F

25C
1.65
2.7
748
None
MIBK
Pass
Pass
17.6
<B
F

27C
2
2.7
748
None
MPK
Pass
Pass
31
<B
HB

31C
5.5
1.37
748
None
t-Butyl Acetate
Pass
Pass
17.3
<B
<B

33C
1.4
1.42
748
None
Acetone
Pass
Pass
33.2
<B
F

43C
4.4
1.58
757
None
Acetone
Pass
Slight Failure
60.8
H
H

45C
5.5
2.69
742
Incosol
MIBK
Pass
Pass
35
<B
B

47C
3.2
2.69
742
Incosol
MPK
Pass
Pass
29.6
<B
<B

53C
0.85
1.52
742
Incosol
Acetone
Pass
Very Slight
42.5
<B
F

Fail

54C
2.8
1.67
742/TMPTA
Mole Sieve
Acetone
Pass
Fail
101.2
2H
4H

55C
2.5
2.69
746
Incosol
MIBK
Pass
Pass
32.3
<B
HB

57C
1.65
2.69
746
Incosol
MPK
Pass
Pass
21
<B
B

61C
5.5
1.43
746
Incosol
t-Butyl Acetate
Pass
Fail
38.5
F
H

63C
1.25
1.48
746
Incosol
Acetone
Pass
Pass
24.4
F
F

64C
3.7
1.63
746/TMPTA
Mole Sieve
Acetone
Pass
Slight Failure
99.2
2H
4H

65C
2.25
2.7
748
Incosol
MIBK
Pass
Pass
16.9
H
B

67C
1.4
2.7
748
Incosol
MPK
Pass
Pass
15.3
<B
B

71C
4.7
1.36
748
Incosol
t-Butyl Acetate
Pass
Pass
22.8
<B
F

73C
0.65
1.41
748
Incosol
Acetone
Pass
Pass
36.9
<B
<B

74C
3.7
1.62
748/TMPTA
Mole Sieve
Acetone
Pass
Pass
91
H
4H

83C
2.5
1.68
757
Incosol
Acetone
Pass
Slight Failure
49.6
F
F

84C
5.5
1.63
757/TMPTA
Mole Sieve
Acetone
Pass
Pass
95.1
H
4H

85C
0.5
3.05
None
Mole Sieve
MIBK/Oxsol
Pass
Very Slight
76.5
H
2H

100

Fail

[0072] The effect of different solvents was also evaluated. Table 11 shows the effect of various solvents using two different blocked amines: DETA blocked with MIBK, and xylylenediamine blocked with MIBK. The solvents from best to worst, regardless of reactive modifier or water scavenger, with respect to hindering gelation were: acetone, MPK, MIBK, t-butyl acetate, and p-chlorobenzotrifluoride. The inability of t-butyl acetate to hinder gelation could be due to the presence of 0.5-1.0% t-butyl alcohol, an impurity that could react with the epoxy resin.

[0073] A mixed solvent system comprised of equal parts p-chlorobenzotrifluoride/MIBK was evaluated (Sample 85C). The formulation showed no increase in viscosity after 30 day of accelerated aging. The calculated VOC level of the formulation was 3.05 lbs/gal, which is slightly higher than the target value of 2.8 lbs/gal. Other physical property values were good. Sample 85C displayed no viscosity increase although p-chlorobenzotrifluoride alone is the least effective solvent at retarding gelation.

[0074] Although not wishing to be bound by theory, we believe that these results are a function of the polarity and hydrogen bonding of the solvents. Table 12 shows a ranking of solvents and their polarity solubility parameters and hydrogen bonding solubility parameters. Oxygen containing solvent systems having both intermediate to high polarity (äP of 6-14) and high hydrogen bonding (äH of 9-14) are unacceptable for stable coating formulations. Systems with both low polarity (äP of 1-2) and low to intermediate hydrogen bonding capabilities (äH of 2-7) have poor capacity to stabilize a blocked amine epoxy coating precursor. Oxygenated solvents with intermediate polarity (äP of 5-10) and intermediate hydrogen bonding (äH of 4-7) are acceptable for stable single component epoxy coating precursors.

[0075] Thus, single component epoxy coating precursors made from blocked amines having an extended shelf life have been demonstrated. Coatings can made from these precursors having VOC levels of less than 3 lbs/gal.

[0076] Coating formulations made according to the present invention may contain additional components, including, but not limited to, pigments, such as titanium dioxide, fillers, such as silica, and other formulation aids, such as wetting agents, defoamers, flow aids, leveling agents, and the like.

11TABLE 11Effect of Solvent System on High TemperatureStorage Stability and Solution ViscosityKetimine +Stability at 55° C.Epoxy ResinSolvent(Viscosity) (Stokes)DETA-MIBKTolueneNoneMIBKSprayable after15 days50/50 Toluene/MIBKNoneXylylenediamine-MIBK (a)19 after 30 daysMIBKMIBK (b)5.5 after 30 daysMPK (c)3.2 after 30 daysp-chlorobenzotri-gelled after 30 daysfluoride (d)50/50 MIBK/p-0.5 after 30 dayschlorobenzotri-fluoride (e)t-butyl acetate (f)13 after 30 daysacetone (g)0.85 after 30 days(a) contains mole sieves but no reactive diluent (b) contains monofunctional reactive diluent (Epodil ™ 742) but no scavenger (c) contains monofunctional reactive diluent (Epodil ™ 742) but no scavenger (d) contains monofunctional reactive diluent (Epodil ™ 742) but no scavenger (e) contains moles sieves but no reactive diluent (f) contains Incosol-2 ™ and monofunctional reactive diluent (Epodil ™ 742) (g) contains Incosol-2 ™ and monofunctional reactive diluent (Epodil ™ 742)

[0077]

12

TABLE 12

Ranking of Solvents for Stability of

Xylylenediamine-MIBK Epoxy Coatings

Hydrogen

Polarity
Bonding

Solvents
Ranking
(äP)
(äH)

Acetone
Good
10.4
7

MIBK
″
6.1
4.1

MPK
″
—
—

Ethyl Acetate
″
5.3
7.2

Dioxane
Poor
1.8
7.4

T-butyl acetate
″
—
—

Toluene
″
1.4
2

P-chlorobenzo
Unacceptable
—
—

trifluoride

Dimethylformamide
″
13.7
11.3

Benzyl Alcohol
″
6.3
13.7

äP - Polar solubility parameter (MPa½)

äH - Hydrogen bonding solubility parameter (MPa½)

[0078] While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the compositions and methods disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.

	Number	Date	Country
Parent	09776489	Feb 2001	US
Child	10627958	Jul 2003	US

Method for making a blocked amine

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