JPS5819356B2 - Black plate article and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a black plate material for manufacturing articles such as cans by cold-open molding.
The idea is to use plare 5tock material to form containers after applying an organic polymeric coating to a sheet material.

"Black plate material" is sheet steel, of the usual thicknesses used in containers, and is a common substrate to which a tin coating is applied for the manufacture of tin cans.

Manufacturing cans from pre-coated blackplate material requires that the coating have significant flexibility and adhesion.

As a result, the coated material is formed into a cup without the coating being crushed or peeled off, and then drawn and formed to obtain a deep-drawn can.

Furthermore, the coating must have good corrosion resistance after the can is formed.

Numerous attempts have been made to provide flexible organic coatings that can meet all the above-mentioned requirements to be suitable for the manufacture of cones.

One such example is U.S. Pat.
No. 428 states the following:

That is, a mixture of 5 to 50 wt hexafluoropropylene and 95 to 50 wt of tetrafluoroethylene is copolymerized and suspended in an aqueous medium at a pH of about 10 using a mixture of wetting agents. .

The sheet material coated with this aqueous suspension is then heated to approximately 57°C.
5°F (301,6°C) to approximately 625°F (329,
Baking at 4° C.) melts the copolymer onto the surface of the sheet.

This coated sheet is then formed into a container.

US Pat. No. 3,206,848 proposes coating sheets with vinyl organosols, solution vinyls or epoxy phenols.

In this method, the sheet is coated and heated to 350°F (
Cured at a temperature of 176,7°C (176,7°C) or higher, formed into a cup, and then cured at a temperature of about 275°F (135°C) to 380'F
After reheating at (193.3° C.), it is cooled and redrawn into cones.

US Pat. No. 3,268,620 proposes the following method.

That is, mixtures of various organic polymers such as polyvinyl chloride, epoxidized polybutadiene, urea formaldehyde resin, vinyl chloride-vinyl acetate copolymer, etc. and various solvents were prepared and a coating was formed from this, which was then tin-plated. Burnt onto steel.

The end of the can can then be made from the coated plate.

Further, Patent No. 3,832,962 proposes the use of cross-linked or non-cross-linked vinyl or epoxy resins as a coating for pre-conversion coated aluminum sheets, and then drawing the coated sheets into cones. are doing.

However, all of these prior art patents suffer from - or more deficiencies.

For example, commonly used coatings, copolymers of vinyl chloride and vinyl acetate, such as those proposed in US Pat. No. 3,832,962, have very poor corrosion resistance and adhesion to bare metal.

Coatings based on high molecular weight epoxy resins or fully cured epoxy resins are usually too brittle to withstand the required molding operations.

The additional heating step, as in U.S. Pat. No. 3,206,848, would substantially increase the cost of can manufacturing, and the fluorinated copolymer of U.S. Pat. No. 3,194,428 is completely cost-effective. The polymer must then be melted onto the plate at elevated temperatures prior to forming the cones.

Due to the difficulty of applying coatings prior to forming, cans are currently manufactured by applying a lubricant to black plate material, forming the coated plate material into a container, and then removing the lubricant coating. It is manufactured by applying a conventional multi-step conversion coating to provide further adhesion and corrosion resistance, and finally applying an organic coating and then curing it onto the finished container.

Clearly, the numerous and complex manufacturing steps are costly and, as a result, there has been some reluctance to use containers made from black plate material.

The present invention provides a method for manufacturing molded articles from blackplate material, in which the blackplate material is coated with a composition comprising an epoxy resin or an aqueous, acidic emulsion of an epoxy-based resin; The black plate material is sufficiently heated to remove the organic solvent of the emulsion and partially cure the resin film, and then the resin is coated with or without conventional external water-soluble lubricants during the molding operation. The coated black plate material is formed into the desired shape using conventional equipment.

This method is particularly useful in can manufacturing.

If desired, pigments may be incorporated into the resin coating or the molded article may be coated with a conventional finish,
It may be cured at the end.

The epoxy or epoxy-based resin used is either an ordinary epoxy resin or a chemically modified epoxy resin, such as an epoxy resin esterified with stearic acid, an aminoplast crosslinking component modified epoxy resin, or a phenoplast crosslinked epoxy resin. .

Essentially, the water-insoluble epoxy base resin and other coating components are dissolved or dispersed in an essentially water-immiscible organic solvent, and this mixture is then emulsified in water to approximately 20% non-volatility.

Surprisingly, it has been discovered that this technique allows for the formation of an acidic coating mixture by isolating or separating the epoxy-based resin from the surrounding acidic water and applying the mixture to a black plate substrate.

As mentioned above, the coating must be flexible in nature and must survive the formation of the black plate sheet into the container body.

It has also been discovered that low molecular weight epoxy-based resins, preferably resins with a molecular weight of about 2,000 or less, provide flexible coatings useful in the present invention.

High molecular weight resins can also be used, but as the molecular weight increases, the coating becomes less flexible.

The acid used in the composition promotes adhesion between the organic film and the metal substrate.

A sufficient amount of acid is added to maintain the pH below 7, preferably in the range 2-7.

If desired, oxidizing agents such as hydrogen peroxide can also be included in the composition.

Coating can be done in one of two different ways.

That is, if the coating contains an oxidizing agent,
Coating is carried out by dipping the black plate material in or flowing the acid emulsion over the plate material for a time sufficient to form an organic-inorganic coating.

Excess material is then rinsed off with water from the black plate sheet.

Alternatively, if no oxidizing agent is included, the composition can be applied by any conventional or desired method, such as forward or backward roll coating, electrostatic spraying, curtain coating, and the like.

And in this case, a final rinse is not necessary.

Following application, the coating is thoroughly heated and dried to remove organic solvents and moisture.

Overcuring should be avoided, as anything that could compromise the flexibility of the coating during the molding process should be avoided.

After drying or prebaking the coated sheet, it is formed into containers using conventional equipment.

If desired, added lubricant or water can be used to improve the squeezing action.

After squeezing, the container is cleaned to remove lubricant if used, and then dry heated to completely cure the organic coating.

If the coated and shaped containers are further provided with an internal sanitary lacquer or an external decorative coating, these post-coatings are carried out prior to the final curing of the preliminary organic coating.

The final curing process therefore cures both the decorative coating as well as the preliminary coating.

Of course, if desired, a decorative coating can be applied after the preliminary coating has hardened.

One of the objects of the present invention is to provide an organic polymerizable coating which is applied to black plate material and partially applied to the coated sheet prior to forming the coated sheet into an article of desired shape. It is cured into a flexible coating.

Another important object of the present invention is to provide a method of manufacturing a container, the method comprising: applying an organic flexible, polymeric coating to a black plate iron substrate; The coated substrate is then shaped into a cone without damaging its peel or flexible, polymerizable coating, and the coating is finally cured in situ on the cone.

One of the further important objects of the present invention is to provide a coating composition in the form of an aqueous, acidic emulsion of an epoxy-based resin that can be applied to a black plate substrate as a flexible film. , the flexible film remains in close contact with the plate during the subsequent cone forming operation.

Another and also important object of the present invention is to provide a method for manufacturing cones from sheets of iron black plate, in which the black plate is coated with an aqueous, acidic emulsion of an epoxy-based resin; The coating is only partially cured, the coated black plate is then shaped into a cone, and the coating is finally cured only after the cone has been shaped.

The present invention is directed to the production of molded articles by cold open molding of black plate material.

Such black plate material is an inexpensive and easily formed steel material, and is available in the form of sl-IJ tubes or sheets.

Typically, such black plate material forms the substrate for the tin coating material used in the molding of conventional tin cans.

As tin becomes increasingly expensive and increasingly difficult to obtain, much effort has been devoted to using black plate material pre-applied with an organic polymeric coating to form cones. Ta.

The invention proposes a detailed and different method for arriving at the coating of tin plate material to produce cones as described above.

The black plate material used is preferably one specified by ASTM standards, with ASTM designation A650-71 being a two-step drawn black plate material suitable for the present invention.

Optionally, single draw black plate material having ASTM designation A625-68 is also available.

Pre-coatings are known to be obtained from epoxy-based resins, which have sufficient coating-forming ability, adhesion and corrosion resistance to remain after the coated blackplate material is formed into a cone.

These organic resins known to be useful include epichlorohydrin/bisphenol A-type epoxy resins, or chemically modified epoxy resins such as esterified resins, amineplast resins, crosslinked epoxy resins, or phenolic resins. Resin crosslinked epoxy resins and the like are included.

Of course, mixtures of various types of resins can also be used.

More specifically, if utilized, crosslinking resins of the urea-formaldehyde, melamine-formaldehyde, penduguanamine-formaldehyde or phenol-formaldehyde type can be used.

Melamine-formaldehyde resins have been found to be particularly useful as crosslinking agents, resulting in crosslinked cured resins with improved corrosion resistance.

Generally the ratio of epoxy resin to crosslinker is about 70:30
to about 90:30, and excellent results can be obtained with a ratio of 80:20.

Preferred acids used in the composition are phosphoric acid or hydrofluoric acid, or a mixture of phosphoric acid and hydrofluoric acid.

Excellent results are obtained with a total acid concentration of about 1 to about 5 gr/d, and preferably enough acid is always present to maintain the pH in the range of about 2 to about 7.

Oxidizing agents such as hydrogen peroxide can also be included in the composition, preferably in the range of about 1 to about 5 g r /l.

As mentioned above, the organic resins are first dispersed in a non-aqueous solvent.

There are many types of non-aqueous solvents used to dissolve solid resins, and preferred solvents include di-inamyl ketone and toluene.

These solvents are preferred because they appear to provide more stable emulsions and the resulting final coating is glossy and non-granular.

Satisfactory emulsions and coatings can also be obtained using other solvents such as cyclohexanone and di-isobutyl ketone.

Of course, mixtures of the various solvents mentioned above can also be used.

Clearly, the use of water-immiscible organic solvents serves the purpose of separating the epoxy resin from the surrounding acidic water in the final coating composition.

By dissolving the water-insoluble resin and other coating materials in the above-mentioned water-insoluble organic solvents and then emulsifying this mixture in water, the following was found.

That is, such emulsions or latexes are more stable against precipitation or gelation when other materials are combined in the composition.

As far as is currently known, the use of the above-mentioned solvents and the preparation of Todoroki epoxy-containing solutions for subsequent emulsification in water are important in order to obtain stable coating compositions and to maintain the normalization of epoxide groups and cross-linking agents. This is necessary to offset the reactivity.

The solvent must be miscible with the epoxy resin and crosslinking resin to form a single stable phase at reasonable solids levels.

Furthermore, the solvent must be non-reactive with the solid resin.

It is also preferred that the solvent is not more than 10% soluble in order to prevent appreciable dispersion of the solvent into the aqueous coating bath, which would make the resin unstable in the emulsion.

On the other hand, water. It is desirable not to dissolve more than 20% of the solvent in order to prevent any ingress of water-borne acids into the resin which undergoes reactions prior to formation of the coating in the coating bath.

The use of "Alipol EP-110'" and EP-120 has been found to be particularly useful.

These raw materials are ammonium salts of sulfuric esters of alkylphenoxy poly(ethyleneoxy)ethanols.

Such raw materials function as emulsifiers for the epoxy resin in the composition, while also acting as catalysts for the aminoplast or phenoplast crosslinker.

Relatively small amounts of emulsifier are required, usually in the range of about 2% to about 10%.

Other emulsifiers can also be used, such as polyoxyethylene-polyoxypropylene block copolymers.

Although the initial emulsion can be prepared in several different ways, the commonly used method involves initial mixing of the epoxy resin and crosslinking resin in a water-immiscible solvent at a slightly elevated temperature, i.e. 100°C. (37,8°C) to 150°
The emulsifier is then added gradually over a period of time without additional heating and with sufficient stirring to keep the materials agitated and suspended.

The addition of emulsifiers increases the viscosity of the composition to approximately the consistency of a jelly.

Water, preferably deionized, is then added very slowly at first and then rapidly.

During the addition of water, the emulsion "converts", ie the viscosity of the emulsion first increases and then decreases.

The amount of water added is usually sufficient to reduce the non-volatile content of the emulsion to a value within the range of about 15% to about 50%, and the amount of water and the ratio of water to organic solvent is about 9515%. It is possible to range from about 75/25 to about 75/25.

After preparing the emulsion, the coating bath is prepared by diluting with deionized water and adding acid and optionally hydrogen peroxide as an oxidizing agent.

The amount of dilution water added will of course be determined by the desired solid resin content of the final bath, but the desired solid resin content is about 5
500 gr/l, more preferably about 1
It is included in the range of 00 to 300 gr/12.

As far as the application of the coating to the black plate substrate is concerned, this is preferably done as follows.

That is, the black plate material is immersed in an acidified emulsion long enough or the emulsion is allowed to flow through the black plate material long enough to form an organic-inorganic coating, and excess material is then drained from the black plate material. Rinse it off.

This technique is necessary if an oxidizing agent is present in the composition.

If no oxidizing agent is included, the composition can be applied by any conventional means, such as forward or backward roll coating, electrostatic spraying, curtain coating, etc., and rinsing is no longer necessary.

After the first application, the coating is thoroughly dry heated to remove organic solvents and moisture.

This baking, partial hardening, or drying is performed in a drying oven at peak metal temperatures of approximately 220°F (104,4°C) to 240°C.
It is desirable to carry out the process under conditions such that the temperature reaches F (115.6°C).

In a circulating air oven at a temperature of 300°F (148,9'
A 1 minute cure in C) is sufficient to obtain the peak metal temperature and to sufficiently dry, bake, or partially cure the coating for subsequent molding operations.

These curing conditions are substantially variable; the curing temperature can be increased and the curing time can be extended as long as the coachin remains sufficiently flexible.

Following drying, the coated sheet is formed into a container using conventional equipment, typically first with a cupping operation, the formed cup is squeezed, and then formed into the desired specimen.

A water-soluble lubricant may optionally be used to facilitate molding operations.

Such lubricants are commercially available, and external water-soluble lubricants of this type are discussed in more detail below.

What was surprising was that in some cases it was found that the use of a lubricant containing 1% solids gave better results than that with 5% solids.

As can be appreciated from the foregoing, the coatings, coating methods, and coating compositions of the present invention pertain essentially to aqueous dispersions of epoxy resins.

The several ingredients in the coating composition are all commercially available under various trademarks or trade names, and these ingredients are specifically listed below to the best of applicant's current knowledge.

Epon resin is a product of Shell Chemical Company and is an epichlorohydrin/bisphenol A-type solid epoxy resin having the following chemical structure:

Epon Resin 1001 has an average molecular weight (about) 900, an epoxide equivalent weight of 450-550, and a melting point of 65-75°C, and Epon 1001-T-75 is a 75% weight solution of Epon 1001 in toluene.

Epon resin 1007 has an average molecular weight (approx.) of 2900, an epoxide equivalent of 2000-2500, and a melting point of 125-13.
5℃, and Epon 1007 to CT-55 are Epon 10
07 in a 1:1 (by weight) mixture of methyl isobutyl ketone.

Epon resin 1001/1007 solution is a mixture of equal weight parts of Epon epoxy resins 1001 and 1007, 81 fb nonvolatile content in methyl isobutyl ketone and toluene 4:1 (by volume).

Cymel resin is a product of American Cyanamid Co., Ltd., which sells new chassis. Cymel 1156 is a clear liquid butylated melamine-formaldehyde resin with a solid content of 98 parts ± 2 parts and a Gardner-Holdt viscosity. is Z2 to Z4 at 25°C, and the water solubility is 1% or less.

Cymel 1123 is a benzoguanamine-formaldehyde resin.

Beetle resin is also a product of American Cyanamid Company; Beetle 80 is a butylated urea-formaldehyde resin.

Kneeformite resin is a product of Rohm and Bath Company.
Nieformite F-24ON is a urea-formaldehyde resin with a solid content of 60 parts ± 2 parts, a Gardner-Holdt viscosity of Z, ~ Z5 at 25°C, and an acid value of 2 to 5.
It is.

Cymel, Neeformite and Beetle resins are all aminoplastics and are present in the composition as crosslinking agents.

A phenoplast crosslinker can also be used if desired.

A preferred phenol formaldehyde resin is Methylone 75
108, a product of General Electric Company.

Aripol EP-110 and E'P-120 are ammonium salts of sulfate esters of alkylphenoxypoly(ethyleneoxy)ethanol.

This material is a product of GAF and serves as an emulsifier for the epoxy resin in the composition and also acts as a catalyst for the crosslinking agent.

Pro-Zuru 522 is a commercially available external water-soluble lubricant manufactured by Mopil Oil.

Hydrofall 1895 is a market grade stearic acid manufactured by Ashland Chemical Company.

In all examples below, the coatings were applied as aqueous emulsions and applied as specified in the examples.

Unless otherwise noted, all coatings were performed using a grooved neorene advance roll coater, with the emulsions removed from a 400-500 ml tray mounted directly below the bottom roll.

By sufficiently varying the roll pressure and the non-volatile content of the emulsion, dry film thicknesses of 0.03 to 0.2
5 mil (Microtest Magnetic Gauge) could be applied.

After application, the coating is thoroughly dried to remove organic solvents and moisture.

This drying or curing step was performed with the panels held horizontally in a circulating air oven.

In each example, the actual drying times and temperatures are indicated.

Peak metal temperatures were determined using a thermopaper-temperature tape manufactured by Haaser Seven Meter Co., Nat., Massachusetts.

Following drying, the coated sheets were typically finished by either System 'A' or System 'B'.

System "A" used Acme Orange "Deco" ink, which was applied with a roller to give the desired color.

Clement force Valor P- while the panel is still wet
550-G, over varnished with T-bar varnish,
350°F (176,7°C) for 5 minutes, then 410°C
Bake for 3 minutes at 210°C.

In the system Bu, Mobil Chemical S-6839-
Use 009 thermoset vinyl sanitary lacquer and apply this #
It was applied using a 20 dr awdown bar and then baked for 3 minutes at 410°F (210'c).

JoyTest on panels finished with either System A or System B
)” was performed.

This test tested the panel for 30 minutes at a temperature of 200° (93,3
After soaking in a Part 1 solution of Joy Cleaner at 98,9°G) to 210'F (98,9°G) and rinsing off, the ink or lacquered surface of the panel can be scratched while the panel is still wet. , dry the panel with a forced air jet, apply Scotch tape tightly to the scratched area, and rapidly pull the tape away from the panel surface and observe the amount of ink or lacquer that comes off with it. The idea is to do so.

Because of this test result. , the degree of paint adhesion is 0
Ratings range from (completely bad, all paint peeling) to 10 (good, no paint peeling).

In all of the following examples, a Taignes-Olsen test machine was used to form the cups.

This hydraulically operated press can be fitted with several different combinations of rams and dies, depending on the required throttling.

Usually 66m in diameter from 0.14" black plate material
m disks are punched out and cups with a diameter of 33 mm are molded from them.

Dice and ram size can be changed, 33m
The 71L cup is re-squeezed to make a 26L cup.

Finally, change the dice once more and set the side wall of the cup to 0.
．． It was molded from 0.014" to 0.009".

The machine has a gauge to measure the pressure exerted by the ram during throttling, and generally the lower the pressure required, the better the throttling.

In some of the examples below, a topical water-soluble lubricant such as Mopil Oil's commercially available product Prosol 522 or an experimental lubricant having the following composition was used.

(1) - Shell Oil Company's product (2) When using GAF's product, the solid content percentage of the lubricant is 0.6 to 5.0
%! Although the level varies over time, a level of 1.0% has been found to be most useful.

Example 1 An emulsion was prepared with the following composition and had the following properties.

Compound 2 Epon resin 1001/1007 solution 33.37 Euphormite F-24ON 11.26 Aripol E
P-1205,96 Demineralized water - 1st addition 12.32 Demineralized water - 2nd addition 37.09100.00 Emulsion properties: Nonvolatile content: Weight ratio 35.7 Viscosity Ae
c, #4 Ford Cup 12 Water/Organic Solvent (Volume) 80/20 pH 5,75 Epon Resin/Nieformai I-80/20F24ON
(solids basis) Epon resin solution (preheated to 130°F (54,4°C))
and Neeformai) F24ON with Hoekmeier (
1/2" to 1" from the bottom of the hook (myer)
A 2-gallon can with a 6" impeller located at the location was filled.

The materials were mixed for 5 minutes at 2.80 ORPM.

Alipol EP-120 was added during mixing and mixing continued for 5 minutes.

The first addition of water was carried out slowly over a period of 3 minutes until the 2.80%
Mixing was continued in the ORPM.

The mixer was stopped, and the raw material adhering to the sides and bottom of the can was completely scraped off.

Mixing was continued for an additional 10 minutes at 2.80 ORPM.

The mixer speed was reduced to 1.20 ORPM and approximately 1/4 of the second addition of water was added.

Before conversion occurred, the mixer was stopped and the sides and bottom of the can were scraped.

The mixing speed was reduced to 80 ORPM and the remainder of the second addition of water was added fairly rapidly.

Mixing was then continued for 1 minute to obtain a bath. A coating bath was prepared by diluting the above emulsion to a non-volatile content of 9.6%.

Add enough 50φ hydrofluoric acid and 35% hydrogen peroxide to give 2.9grF/l and 2.0grH
Obtained 20 Jl.

The bath was kept at room temperature. Two 4" x 4" sections of a 0.014" black plate were coated by dipping them into the above solution for 90 seconds.

Following a 30 second rinse with deionized water, the panel
Dry for 0 minutes at a temperature of 400°F (204,4°C).

without applying any external lubricant to the panel.
33 mm diameter cups were formed at maximum ram pressures of 3200 psi and 3600 psi, respectively.

The appearance of both cups was excellent, the coating remained even, shiny, and did not break or crack.

Example ■ A commercially available oil-based reactive lubricant was applied beforehand.

Several 4" x 6" 1010 cold rolled steel panels were cleaned with a commercially available alkaline de-metal cleaner, rinsed with water,
Forced air dry, recleaned in alkaline soak IJ-Chi, hot water rinse, and treated with the coating composition of Example 1 for 30 seconds.

Following this, the panels were rinsed with deionized water for 20 seconds and dried in an oven for 10 minutes at a temperature of 400°F (204.4°C).

In this example, the nonvolatile content of the emulsion was approximately 8
．． 0%, H2O2 level is about 2.2gr/l, and pH
was in the range of 2, 8 and 3.1 adjusted with 50% HF.

Two panels of the group treated as described above were finished by system A, the other two by system B.
So, two more pieces were left unfinished.

The aforementioned joy test was conducted on all these panels.

With the exception of only a small area of damage on one panel finished with System B, these panels finished with either System "A" or B" showed excellent adhesion (10).

Although the unfinished panels were not criss-crossed or taped, no defects were noted in the coating and the panels had an excellent appearance.

Examples ■ The following two emulsions were prepared as described in Example I.

Each acidic emulsion was coated onto several 4" x 6" black plate panels using a roll coater.

Among these coated panels, those coated with Emulsion ■-1 were tested at a temperature of 230°F (110°C).
) (peak metal temperature: 170°F (76,7°G)) for 60-65 seconds, while those coated with emulsion lll-2 dried at a temperature of 2300°F (110°C) for approximately 75 seconds.
Dry for seconds.

For both of these bases, the dry film thickness is 0.0
It was 7-0.10 mil.

A cup was molded from several panels as shown in the table below.

For each cup, the maximum pressure recorded for each squeeze, external lubricant, and cup condition were recorded.

The coatings with emulsion 111-2 fractured and flaked, so no further squeezing was done on them.

The data clearly show that Emulsion 1-1 (Epon 1001) resin provides better results than Emulsion II-2 (Epon 1007) resin.

Examples ■ The following two emulsions were prepared as described in Example I.

The emulsion was applied using a roll coater.

Panels coated with emulsion ■-1 have a temperature of 230°F.
(110℃) for about 1 minute, and the film thickness is 0.05.
A range of 0.07 to 0.07 mils was obtained.

On the other hand, those coated with Emulsion 1V-2 had a temperature of 40
0°F (204,4°C) (Peak Metal Temperature: 300'F
(148,9°G)) for 1 minute until the film thickness was 0.
．． A range of 16 to 0.25 mils was obtained.

Other numbers of 4 // x 6 // black plate panels should be cleaned at a temperature of 16
Clean by spraying for 1 minute at 0'F (71.1C), rinse with warm water for 1/2 minute, and apply conversion coating using commercially available coatings of approximately 1.0 pos, - and 0.5 cc. Temperature 1 using iron phosphate coating solution containing 0.03
Spray at 60°F (71,1°C) for 1 minute,
1/2 minute cold water rinse, post-treatment for 1/2 minute in a reduced chromate-containing solution prepared according to the teachings of U.S. Pat. No. 3,279,958, 1/2 minute rinse with deionized water; and dried in p.

These control panels had a dark brown-purple surface, which is typical of those produced by iron phosphate conversion solutions.

One panel in the group coated with acidified emulsion ■-1 and one panel in the group coated with the non-acidified emulsion of Example ■-2 were placed in a deep dish containing several hundred TLl of methylene chloride. The resin film was removed by leaving it to stand for about 2 minutes at a time.

Upon removal and air drying, the panels coated with the non-acidified emulsion of Example IV-2 showed very slight darkening (compared to the bare black plate) and an almost unaffected surface. It was recognized that the

However, the panels coated with the acidified emulsion of Example 1'%r-1 had a uniform brown-purple surface, which one skilled in the art would recognize as a conversion coating treatment with added phosphoric acid. It is clear that this means that

Example ■ The following emulsion was prepared.

Each emulsion was applied to several 4//X6/' black plate panels using a roll coater,
Dry for 1 minute at a temperature of 230°F (110°C).

Several other panels were similarly coated with each emulsion and dried at a temperature of 420°F (215,6°C) for 9 minutes (5 minutes at a peak metal temperature of 400°F (204,4°G)).

A third set of panels was again coated with each emulsion.

However, the temperature of this panel was 420°F (215.6°).
C) for 19 minutes (peak metal temperature 400'F (204,
4° C.) for 15 minutes).

Emulsion 1-i was also used to coat another set of panels.

These were dried at the same temperature and for the same time as described above.

Film thickness averaged 0.07 mil in all cases.

Several other black plate panels were coated with a commercially available oil-based reactive lubricant.

Examples of these panels as well as bare black plate panels and treated with conventional iron phosphate conversion coatings
Some of the panels were used as control panels.

Cups were punched from all panels processed above at a speed of 2.
Molding was performed at 91 inches/min.

Some were aided by external lubricants (Prozuru 522, solids content: 5 parts).

Other panels from each set are system ++A11 described above.
Finishing treatment was carried out, and a joy test was conducted.

The test results are summarized in the table below. Temperature 420°F (215,
Panels cured for 9 and 19 minutes at 6° C.) failed and delaminated during the cupping, redrawing and molding steps.

In these cases, the redrawn cup was not intentionally applied to the ram for shaping purposes.

However, panels cured for 1 minute at a temperature of 230°F (1,10°C) had good gloss and uniformity as a result of molding with the aid of external lubricants, and commercially available oil-based reactive lubricants. The squeezing pressure was lower than that in the cup treated with.

Additionally, the redrawn cups were easier to ram for the forming process than the redrawn cups using commercially available lubricants, which encountered some difficulty.

Temperature 230°F (110°C) without application of external lubricant
Cups made from panels that were cured for 1 minute at 1000 ml showed higher cupping and redraw pressures than control panels with commercially available lubricants.

However, these cups produced cosmetically superior coatings with both gloss and uniformity.

When we conducted the Joy test, the panels coated with Emulsion V-2 resin showed the best results (
i.e. the highest degree of adhesion at the least severe drying conditions)
showed that.

However, no set of curing conditions in this experiment resulted in both excellent drawing properties and excellent paint adhesion properties.

In the following two examples, moderate curing conditions (i.e.
Temperature 230'F (1100C) for 1 minute and temperature 42
0°F (215,6°C) for 9 minutes) gave excellent paint adhesion and drawing performance results.

Example ■ In this example, emulsion lll-1, IV
-1, V-1 and V-2 were used to coat a group of 4'' x 6'' black plate panels.

For each emulsion, one group of panels has a temperature of 2
30°F (110°G) (peak metal temperature 170°F (
76,7 °C) for 1 min, and the other groups at 30 °C.
0°F (148,9°C) (peak metal temperature 220°F
(104,4°G)) for 1 minute.

Selected panels were finished with systems "A" and "Bn" and subsequently joy tested.

The grades are shown in Table 3 below. *During the Joy test, the non-painted side turned into a dry, powdery film.

All other coatings were unaffected on their unpainted side.

As evident in the table above, the best paint adhesion was achieved using Emulsion V-2 resin system and at a temperature of 300°F (14°F).
8,9°G) (peak metal temperature 220'F (104,4
C)) for 1 minute.

Example 1 An emulsion very similar to the emulsion of Example V-2 was prepared.

Component Weight % Epon 1001-T-7520.0 Cymel 1156 3.8 Aripol E
P-1203,8 Deionized water 71.9 H3P04 0.5 Emulsion characteristics Non-volatile content: 20.0% by weight pH: 1.8-2.0 Epon], 001 / Cynor 1156 (solid content basis): 80/20 Several 4" x 6" black plate panels coated with the emulsion described above were cured for 1 minute at a temperature of 3.00'F (148,9°C) and different concentrations of the experimental lubricants described above were used. Then, the cup was squeezed and shaped.

Control drawn and formed cups were also made from panels treated with a commercially available oil-based reactive lubricant.

The results are summarized in the table below. *Ram speed: 11.5 inches/min The cup molded from the emulsion coated panel in this example had a glossy and uniform interior and exterior surface.

A cup molded using an external lubricant with a solid content of 1% has a higher gloss than a cup made with a lubricant with a solid content of 5 parts.
It could be applied more easily to the ram during the molding process.

As can be seen from the foregoing description, panels coated with the emulsion of this example, which were coated at a temperature of 300°F (14
8.9°C) for 1 minute.

As previously mentioned, these conditions are what yielded excellent paint adhesion in very similar emulsions). This was good compared to the throttling pressures recorded during operation.

Examples ■ Epon 1004 (epoxy resin manufactured by Shell Chemical Co., Ltd., epoxide equivalent: 875-1000, melting point: 95-105)
°G) 350 gr and Hydrofol 1895 (Ashland Chemical, market grade stearic acid)
277 gr was mixed in a stainless steel beaker.

The dried mixture was heated at 450° C. for 3 hours and slowly stirred to convert the acid and epoxy resin to epoxy ester.

When the temperature of the esterified epoxy resin drops to 250°C, sufficient amounts of MIBK and l.luene (1:1,
(by weight) to yield a viscous, dark brown solution containing approximately 55 parts by weight of esterified epoxy resin.

The following two types of emulsions were prepared.

Several 4" x 6" black plate panels were coated with each emulsion using a roll coater.

All panels were dried at 400°F (204,4°C) for 1 minute.

Cups were molded from several panels as shown in Table 5 below.

In some instances, a topical lubricant similar in composition to the experimental lubricant described above was used at a solids level of 5 parts.

Ram pressure was better when external lubricants were used compared to when commercially available reactive lubricants were used.

Claims (1)

[Claims] 1. (a) The iron black plate material has an average molecular weight of 2.
At least one type of epichlorohydrin less than 000/
coating with an aqueous emulsion of pH 2 to 7 containing a bisphenol 8-type epoxy-based resin;
(c) forming the at least partially cured plate material into a desired shape; and (c) forming the at least partially cured plate material into a desired shape. In step (b), only if the curing of the resin is incomplete, a step of finally curing the resin at a temperature of 300°F (148,9°C) to 500°F (260°C); A method of manufacturing a black plate article by cold-open molding, characterized in that: 2. The method of claim 1, wherein step (b) is carried out at a peak metal temperature of 220°F (104,4°C) to 240°F (115,6°C) or less. 3 The aqueous emulsion is sufficiently acidic and step (a)
2. A method as claimed in claim 1, characterized in that a chemical conversion coating is formed on the surface of said plate material during said step. 4. The method according to claim 1, wherein the molecular weight of at least one epoxy resin component in the emulsion is 2,000 or less. 5. The method according to claim 1, characterized in that an external water-soluble lubricant is applied to the coated plate material during the performance of step (c). 6. The method of claim 1, wherein the aqueous emulsion consists essentially of an esterified epoxy resin and has a pH in the range 2-7. 7. Process according to claim 1, characterized in that the emulsion additionally contains a water-insoluble lubricant.