JPS59226070A - Water base permanent paint compositon and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on (RI-6142) registered on May 3, 1982.
) U.S. Patent Application Serial Number 374.467゜(RI-6141) U.S. Patent Application Serial Number A374,466, filed May 3, 1982, and (RI-6173) U.S. Patent Application Serial Number 4374, filed May 3, 1982 ,4
Discloses compositions and techniques related to No. 65.

BACKGROUND OF THE INVENTION (1) Field of the Invention: The present invention relates specifically to organic coating compositions and methods of use thereof, and is applicable to class 106, particularly subclass 270,
271, and 272; classified into class 252, especially subclasses 51.5R, 70, 77°392.403 i and class 206, especially subclasses 45.8N, 308B, and 814.

(2) Description of the prior art: U.S. Patent No. 3,434,987 to Dhein et al.
No. 3,474,060 teaches the use of modified alkyd resins modified with talamino/formaldehyde and baked at 150°C.

U.S. Patent No. 3,346,5 to 5chustes et al.
No. 22 teaches that acrylic resins and sucrose form milky dispersions with good storage stability, which together with chromates make good varnishes.

U.S. Pat. No. 3,896 to Turbler et al.
, 072 teaches the use of various monomers that produce good performance coatings, such as those for automotive applications, when baked at 160'C.

Bealbcamp U.S. Patent No. 2,662,865
No. 1, which teaches the use of amides and phenol-formaldehyde resins in two-component systems for producing lacquers and varnishes.

The protection of metal surfaces using varnish-type paints has several advantages, such as the visibility of letters and figures below the painted surface and decorative properties. Historically, metal varnishes have required organic-based solvents, with attendant operator exposure and environmental disadvantages. In addition, traditional organic-based systems include chromates, nitriles, borates,
Many additives such as molybdates and triazoles could not be solubilized.

On the other hand, the reported water-based systems had other deficiencies. Water-based types have poor rust and corrosion resistance and are essentially limited to cosmetic functions.

In contrast, the present invention provides coatings with substantial longevity even in corrosive environments, possibly through the use of co-solvents that tend to form azeotropes that rapidly enhance water resistance during curing. Without wishing to be bound by any theory or mechanism, it is believed that these cosolvents act as dispersants and further enhance the stability of the liquid composition at low temperatures.

For a quick overview, other prior U.S. patents of interest include: U.S. Pat. No. 3,660,128 C3heldahl
): Relating to reversal wax for artwork: U.S. Patent No. 2,862,825 (We st l
uncl et al.), No. 2,943,945 (Saywel et al.), No. 2,943,945 (Saywel
), and No. 3.565,843 (Kassin
ger): all related to soluble oils and not hard wax paints; U.S. Patent No. 3,434,851 <M
U.S. Pat. No. 3,446,764 (Phllips
), No. 3.699,065 ((:1ark), No. 3,
No. 379,548 (CJen), No. 4,039,496 (Hunsucker), No. 4,051,089 (T
abins), and No. 4.081,411 (H
U.S. Patent No. 3,49): All related to the base resin formulation and not the finished paint; U.S. Patent No. 3,49
No. 4,882 (Andrews): Concerns high gloss emulsified polyester emulsions.

U.S. Patent No. 4. , No. 187.204 (Hcrwat-d
): Relating to water-based paints containing less than 10 ml of water; U.S. Pat. No. 4,2259,477 (Vosishth
No. 4,148,948 (Wil ia
ms): relates to a leveling agent for water-dispersible beynod; US Pat. No. 43,413,227 (Howar
d and Rnavys-11): Concerning substituted benzotriazoles.

Other patents considered in preparing this application are as follows: 3, 081.238 Gwrry, R,A.

2, 900.262 Green, H, A.

2. 669,862 'Beauchamp,
'D, N.

3, 804.920 Cunningham, A.
, L. et al. 3.814,709 Meissner,
H, J, et al. 4, 137. 132 Ward,
J, J, B.

3, 720.616 Randetl, D.
,R.

3.210.351 D'Alello,' G
,F.

3.597.353 Ranclell, D.R.
, et al. 3, 972.845 N1kaiclo, et al. 3
, 282.744 Goldsmith, F.
,C.

4, 169.741 Lampatzer, K.
3.346,522 5huster, L, K
.

3.615,740 Goltz, K.

3.840,483 Guldenpfenni
g, R.

3,932.285 Cepr, ini, M,
Q.

3, 484.343 Kitamura, Y, et al. 3, 953.344 Narushimn, U
.

3,993.510 Be1a? Iiu, P
,N.

3.879,335 5torck, et al. 2, 695.
910 Aseff, P.A., et al. 3.5 6 5
．． 6 7' 8 Johnson, et al.
: 4,239,648 Mars
hall, et al. 4, 059.452 N15hi j
ima, et al. 3, 653.931 Bwrchart
, et al., none of the above cited patents teach the combination of the ingredients of the present invention to form a bright color formulatable water-based permanent non-corrosive film, especially without the addition of inhibitors.

SUMMARY The present invention relates to high temperature (e.g. 52° C.) storage stable water-based coating compositions that are hard, flexible, permanent and odor free when applied to a substrate and can be formulated in light colors. It forms a corrosion-resistant film with low corrosion resistance. More specifically, the coating compositions of the present invention are capable of being applied and flowed onto solid substrates and include (1) one or more water-dilutable resins, (2) one or more water-dilutable resins, and (2) one or more water-dilutable resins. (3) one or more surfactants, (4) one or more than one, many of which result in a final dispersion that is stable at relatively high temperatures. (5) one or more inorganic rust inhibitors, and (6) water, to provide greatly improved corrosion resistance, especially when used with long-term metal preservatives. Form a water-paced dispersion for use.

(2) Utilities of the present invention: The present invention provides valuable coating formulations with excellent corrosion protection, air curing properties, and storage stability.

Starting Material Resin: Preferably, the compositions of the present invention include an alkyd resin derived from isophthalic acid, terephthalic acid, or phthalic anhydride that has been modified to include ester groups that promote water dispersibility. These resins can be short, medium, or long oil alkyds.

Preferably, the average molecular weight of the resin component is in the range of about 150 to 450, more preferably 250 to 450, and most preferably 300 to 400.

Also, the degree of branching in the resin molecule should be chosen such that after esterification, the average molecular chain contains a sufficient amount of hydrophilic endpoints to achieve ease of water dispersion. Based on the information given below, this quantity will be obvious to those skilled in the art.

The average acid number of the resins useful in the present invention preferably ranges from 15 to 100, more preferably from 20 to 80, and most preferably from 30 to 55.

When used in the present invention, the amount of resin used ranges from 27 to 40, more preferably from 28 to 33, most preferably from 29 to 33% by weight, based on the weight of the composition.

Commercially available resins useful in the present invention include Kelsol resin from Svensa Kellogg, Buffalo, NY, and specifically Kelsol 3907, a water-dispersible air-drying resin from Cargill Corp., Minneapolis, MN, and Pa. The resin is from the Matsuku Crosskey Baynote and Varnish Company of Philadelphia, State.

Surfactant': A surfactant useful in connection with the present invention is Surf Inol 1, available from Airbrotakuts, Allentown, Benosylvania.
04A, and alcohol-derived surfactants such as Raybow 62 from Raybow Chemical Co., Huntington, West Virginia.

These surfactants act as leveling agents and in some cases as antifoaming agents. When used in the present invention, the amount of surfactant used is from 0.05 to 3, more preferably from 0.1 to 2.5, based on the weight of the composition.
Most preferably it is in the range of 0.2 to 1.0 hereditary.

However, this will vary depending on the selection and amounts of other ingredients used.

The use of coupling agents is a special feature of the invention.

Several types of coupling agents can be used in connection with the present invention, including ethylene glycol ethers, preferably butyl ether and propyl ether; hydroxy ethers (ether alcohols) examples: evabutyl cellosolve, diethylene glycol monoethyl ether, monoglobil ether , Flovir Cellosolve, Ethyl Cellosolve; as well as other coupling agents that will be apparent to those skilled in the art for use in specialized formulations according to the present invention.

Coupling agents are selected according to physical tests; any that do not interfere with the composition of the invention and render its components mutually soluble in the water base are generally acceptable.

For example, alcohols such as ethanol, impropatol, and imbutanol are generally useful as coupling agents for the present invention.

Commercial coupling agents useful with the compositions of the present invention include Etaxolv EP, manufactured by Eastman Kodak of New York, NY, and Propasol P%, manufactured by UNOFF Carbide of Washington, CT.

Coupling agents of the present invention generally range from about 1% to about 15% or more, more preferably from about 3% to about 12%, and most preferably from about 4% to about 10%, based on the weight of the formulation. used in amounts of

In addition to their Karapurinob function, coupling agents are typically useful during the drying and curing steps after application of the coating composition to the substrate. For example, when carefully selected, the coupling agent will form an azeotrope with the water present in the composition, thus increasing volatility, speeding curing, and providing a more permanent coating. Some coupling agents aid the final coating by, for example, providing leveling of the final paint, avoiding pinholes and providing a more continuous and better quality dry film.

Book: It is preferred to use deionized water with the compositions of the present invention to prevent chlorine, calcium, magnesium, and other components of tap water from interfering with the compositions of the present invention or their curing ability. Of course, distilled water can be used, but is generally avoided for economic reasons.

Compositions of the present invention generally contain a minimum of about 45%, more preferably 50 inches, and most preferably 60 inches or even more, based on the total weight of the formulation.

Because the compositions of the present invention can generally be classified as oil-in-water emulsions with special properties, amounts of water greater than about 92% result in swelling and reduced wettability in most compositions of the present invention. may cause However,
Specialized compositions utilizing carefully selected non-aqueous ingredients may tolerate up to about 97 inches of water by weight, based on total composition weight.

pH: The pH of the system is preferably in the range 7.0-1.0, preferably 8.0-9.0, most preferably 8.2-
It is in the range of 8.5. The system should be slightly overbased (alkaline) to obtain a maximum surface activity of 8.2-8.5. The residual acid remaining from the end point of a normal titration is removed by an alkaline substance (e.g. amine, triethanolamine,
The system should be slightly overbased (made alkaline) to obtain maximum surface activity of the resin ester groups by reacting with morpholine (or ammonia hydroxide) to form a soap. Excess amounts of base should be avoided as they form extremely "hard" salts that are immiscible with water and thus cause separation of the aqueous and non-aqueous phases.

Dryer: The composition of the present invention includes a metallic dryer that is oxidizing in nature and reacts with the free ester sites of the dried resin film to form a harder, more impermeable protective film.

Preferred dryers useful in the present invention are cobalt dryers, particularly 6% cobalt dryers such as Cobalt HydroCure II from Mooney Chemical Co., Cleveland, Ohio, and 12% cobalt dryers from Seven Engineering Co., Bedford, Pennsylvania. ,including. Manganese dryers are also useful in the present invention and are available from the companies listed above. Although any concentration of cobalt and manganese is useful, it is preferred to use both 6% cobalt drier and 6% manganese drier in the compositions of the present invention.

The range of use of dryers in the composition of the present invention is based on the metal content in the dryer, and the metal content is approximately 0.1
It is in the range of about 5 times maximum.

Chelating Agents: May also require faster oxidation of the dryer if desired. This can be achieved through the use of chelating agents.

One chelating agent that is particularly useful in connection with the present invention is sold under the trade name Active-8 and is manufactured by R.T. Vanta'-Bilt, Inc. of Norwalk, CT. 1,1.1-Fuenanthra.

It's phosphorus.

The amount of chelating agent to be used can be calculated as about one-tenth of the total metal weight present from the dryer.

Inhibitors: It may be desirable to provide additional protection to the compositions of the present invention through the use of inorganic water-soluble inhibitors, which is another embodiment of the present invention. Selection is made by one skilled in the art based on the desired finished composition and its intended application.

Inhibitors that are particularly useful in the long-term protection of iron alloys are the ammonium salts of dicumic acid or molybdic acid. These salts, when added in sufficient amounts, not only provide corrosion protection to the resulting dry film, but also increase viscosity and impart hesicyclotropic properties to the composition in solution. This aids the application of this embodiment of the invention in that it provides very high film forming properties at very low solids contents.

These inhibitors are manufactured commercially by Allied Chemical Company, a subsidiary of Allied Company, Morristown, New Chassis.

Another inhibitor found in the present invention to be particularly useful when considering the protection of non-ferrous alloys of aluminum is the sodium salt of tolyltriazole. This product is commercially available from Sherwin-Williams, Chicago, Illinois.

These inhibitors act as metal passivators. The amount of inhibitor used depends on the severity of the application, but in the present invention ranges from 0.01 inch to about 1%, more preferably from 0.05% to 0.07 inch, and most preferably from 0.05 inch to about 1%, based on the total weight of the formulation. It was found that the levels ranged from .1% to .6%. However, this will vary depending on the selection and amounts of other ingredients used.

Amine = Amines useful in the present invention include morpholino, 26-28
% ammonium hydroxide (hereinafter referred to as concentrated ammonium hydroxide), triethanolamine, jetanolamine, ethanolamine, and mixtures thereof.

When used in the present invention, the amount of amine used is about 0.
．． 1 to about 3.5% by weight, preferably 0.5 to 3.0%
, most preferably in the range of 0.5 to about 2.5% by weight.

Mixing method: Equipment - The equipment for the present invention is that customarily used for the production of coating compositions; e.g. flowmeters and measuring devices and stirring means, e.g. a pump mounted on the transverse arm connecting the main tank; Cauldrons and mixing vessels with internal stirrers, counter-rotating shearing devices, and any other available equipment known for Chinese cabbage.

Temperature Two Typically, the water is about 70°F (21°C) and the non-aqueous ingredients are transferred and mixed at that temperature.

However, these temperatures are not narrowly limited and may be varied to provide faster mixing or better compatibility of the ingredients according to the observations of Chinese cabbage experts.

Mixing Procedure 2 Although the formulations of the present invention may be prepared in a continuous manner if desired, batch methods are more commonly used. For example, the total amount of free water desired in the finished composition (e.g. 17
00 gallons, 6,562 J) into a mixing vessel large enough to hold the entire batch of ingredients. To this is added, with stirring, half of the coupling agent used, the amine, and, if desired, the inhibitor. The water-dispersible resin is then added to the mixing vessel and the mixture can be stirred while the dryer is prepared in a separate vessel.

Thoroughly mix the dryer and remaining coupling agent in a separate container and add the mixture to the mixing container. The composition is then mixed until homogeneous, after which the composition is discharged into a shipping container, such as a tank car, tank truck, drum, or container.

Quality Control: Finished compositions are generally pH controlled before packaging.
, solids content, freeze-thaw stability, corrosion protection under accelerated conditions, and other test parameters using techniques well known in the paint industry.

Application Rates The formulations of the invention may be applied to the substrate to be protected by conventional application techniques such as spraying, brushing, rotor coating, dipping, flow coating, or electrostatic spraying. Coating thickness can be varied by changing the formulation, number of coats, or - amount applied per coat, but generally ranges from about 0.5 to about 3 mils per coat after drying. .07
5 dishes).

Examples: The invention is not limited to the following examples, which are merely illustrative of the invention, and the invention is susceptible to a wide variety of modifications and changes without departing from its spirit. What can be done is understood by Chinese cabbage experts. For example, the compositions of the present invention can be shipped as a concentrate to which a substantial amount of water can later be added to avoid shipping water, especially for international or other long distance shipments.

The compositions may also contain other useful ingredients well known in the coatings industry, such as disinfectants, defoamers, pigments, dyes or leveling agents.

Example 1 The ingredients that make up this composition are as follows.

29.0% by weight Kelsol 3907 i57.8% by weight
water; 10, O7 weight ratio of butyl cellosolve; 2.5% by weight of concentrated ammonium hydroxide; 0.2% by weight
cobalt dryer (6% cobalt dryer); 0.1 wt.% manganese dryer (6% manganese dryer); 0.04 wt. 70°
Load with F). 5% by weight of butyl cellosolve and ammonium hydroxide are then charged to the kettle.

After stirring, Kelsol 3907 is added. This solution is left stirring while the dryer solution is prepared in a separate container.

Add the remaining butyl cellosolve to the second smaller container, mix together with Active-8, and stir the solution well. A cobalt dryer and a manganese dryer are then added to this second vessel.

After further stirring, the mixture is transferred to the main mixing vessel and further stirred until the composition becomes homogeneous.

If necessary, the pH is adjusted by addition of less than 1 part of concentrated ammonium hydroxide. Solid content is 22
%±1%.

The compositions are then tested for corrosion resistance by application to cold rolled 101O steel panels.

After drying for 72 hours, the test panel was tested to ASTM Test B-117.
Exposure to a spray of 5% sodium chloride CNaC1) at a temperature of 35°C (95°F) according to the method. This test panel resists breakage (corrosion) for 100 hours.

A similar test panel coated with the composition of this example was A'ST.
M test D-2247 at 49°C (120°
F) withstands 500 hours of exposure to ioo% relative humidity.

Samples of the compositions of this example were each prepared at 118°C (0°F).
), followed by 8 hours at 25°C (77°F);
Does not show separation or other obvious deterioration effects. Samples of the compositions of this example were tested at 49% without separation or other observable deterioration effects.
Withstands 144 hours at 120°F (°C).

When the same panels as above are immersed in the composition of this example and dried at room temperature and relative humidity of approximately 50%, the paint cures and is dry to the touch in 30 minutes.

The thickness of the composition on the test panel is approximately 0.7 mil (approximately 18 microns or O, 18 mm).

Example■ The ingredients of this composition are as follows.

30.3% by weight Kelsol 3907; 50.0% by weight
water; 17.0% by weight of butyl cellosolve; 2.3% by weight of concentrated ammonium hydroxide; 0.2% by weight
Cobalt Dryer (6% Cobalt Dryer); 0.2 wt% Active-8 water at 21°C (70°F
) to load. 8.5 wt. of butyl cellosolve and ammonium hydroxide are then charged to the vessel.

After stirring, Kelsol 3907 is added. This solution is left stirring while the dryer solution is prepared in a separate container.

To a second smaller container, add the remaining butyl cellosolve and mix with Active-8, stirring the solution well.

A cobalt dryer is then added to this second container. After further stirring, the mixture is transferred to the main mixing vessel and the entire composition is further stirred until homogeneous.

It can be seen that the solids content is 23%±1%.

The pH is then checked and is between 7.0-10, preferably 8.
．． Make sure it is between 2-8.5.

The composition is then tested for corrosion resistance by application to cold rolled 1010vIA panels. After drying for 72 hours, the panels were sprayed with 5% NaCl (CNaCl) at 35°C (
AST IVI Test B- at a temperature of 95°F
117. Panels can withstand breakage for 100 hours.

Similar panels were painted with the composition of the present composition and heated to 49°C (120°C) according to the ASTM Test D-224717) method.
F) is found to withstand 500 hours of exposure to 100% relative humidity.

The composition survived five consecutive freeze-thaw cycles, each consisting of 16 hours at 118°C (0°F) followed by 8 hours at 25°C (77°F), resulting in separation and other There were no observable effects or deterioration effects.

When said panel is immersed in the composition of this example and dried at room temperature and a relative humidity of 50%, the coating is 3.
It cured in 5 minutes and was dry to the touch.

The thickness of the composition on the above test panel was o, r mils (approximately 18
micron or 0.18 mm).

Example 1 The ingredients for this composition are as follows.

29.3% by weight of Kelsol 3907 58.98% by weight of water - 10% by weight of Qi butyl cellosolve 1.5% by weight of concentrated ammonium hydroxide 0.02% by weight
cobalt dryer (6% cobalt dryer); 0.2% by weight Active-8 The composition was prepared as in Examples I and 2;
Its solids content was found to be 22%±1%.

However, when this composition is tested for corrosion resistance by applying it to cold rolled 1010 steel panels and drying for 72 hours, ASTM Test B-117 shows that the test panels are 40
It has been shown that only time can withstand damage.

It is believed that the problems with the example amounts were caused by the film not curing well due to insufficient dryer presence.

Example■ The ingredients of this composition are as follows.

55.97 liters of water 0.24% by weight Ammonium dichromate 1.78% by weight n-butyl alcohol 32.68% by weight Kelsol 3907 076% by weight Cobalt Hydrocure o,i % by weight Active -8 4.46% by weight of butyl cellosolve 2.08% by weight of Ecthanelube EP 0.32% by weight of Surf-Inol 104A 1.61% by weight of concentrated ammonium hydroxide water into a conventional mixing pot equipped with a rotary stirrer at about 218C (70% by weight) °F). While stirring, ammonium dichromate is then added, followed by butyl alcohol, 1.04% by weight Ectasolve E.
P and ammonium hydroxide were added. After stirring, Kelsol 3907 is added and the solution is stirred vigorously until homogeneous. This solution is placed under stirring while the dryer is prepared in the second container.

To a second, smaller container, the remaining 1.04% by weight Ektasorb EP and Active-8 were added.

After vigorous stirring, cobalt hydrocure was added.

After further stirring, this mixture was added to the mixing pot and stirred until it became homogeneous.

The pH was then adjusted to approximately 8.2 by addition of less than 1 part ammonium hydroxide. Solid content is 25 cm ± 1%
It turned out to be.

The composition is then tested for corrosion resistance by application to cold rolled 1010 steel panels. After drying for 72 hours, test panels were sprayed with 5% saline at a temperature of 35°C (ASTM).
Exposed according to test B-117. 300 test panels
Withstood time damage.

A similar test panel coated with the composition of this example was
49°C (120°F) according to the method of Test D-2247.
) withstood 1500 hours of exposure to 100% relative humidity.

The composition survived five consecutive freeze-thaw cycles, each consisting of 16 hours at 118 °G (0 °F) followed by 8 hours at 25 °C (77 °F), and was able to survive separation and other It showed no observable effects or adverse effects.

When the same panel as above was immersed in the composition of this example and dried at room temperature and relative humidity of approximately 50q6, the coating cured within 30 minutes and was dry to the touch.

Example V The ingredients for this composition are as follows.

32.70% by weight Kelsol 3907 i58.9
75% by weight water; 2.0% by weight n-butyl alcohol; 3, OM
N% butyl cellosolve; 2.4 heavy hereditary concentrated ammonium hydroxide; 0.4
0.025% by weight Active-8; 0.5% by weight ammonium dichromate water into a conventional kettle with a stirrer at a temperature of about 21°C (70°F). Loaded. Add ammonium dichromate while stirring. With further stirring, 1.5% by weight of butyl cellosolve and n-butyl alcohol are added together with ammonium hydroxide.

The solution is left stirring while the dryer is formed in a separate container.

In a second, smaller container, add the remaining butyl cellosolve followed by the Cobalt Dryer and Active-8 with stirring. After stirring, this mixture was added to the main mixing vessel and the entire composition was stirred until homogeneous.

The pH is then adjusted to approximately 8.0-8.5. The solids content was then found to be 27%±1%.

The composition was tested in ASTM Test B-1 as described in Example ■.
Tested according to No. 17, the test panel resisted failure at 300 hours.

A similar test panel coated with the composition of this example was tested at 100° C. (1206 F.) according to ASTM Test D-2247.
% relative humidity exposure for 600 hours.

Samples of the compositions of this example survived five consecutive freeze-thaw cycles, each consisting of 16 hours at 118°C (0°F) followed by 8 hours at 25°C, with no apparent separation or It showed no deterioration effect. The sample was heated to 49°G (120°F
) showed no separation or other observable deterioration effects.

The same panel as above was immersed in the composition of this example and kept at room temperature. When dried at a relative humidity of about 50%, the coating cured in 30 minutes and was dry to the touch.

The thickness of the composition of this example on the above test panel was about 1.25
mil (approximately 37 microns or 0.37 mm).

However, the composition of this example was very cloudy at low temperatures, which is believed to be caused by the use of less coupling agent.

Example■ The ingredients of this formulation are as follows.

30.0 wt.% Kelsol 3907 i58.28 wt.% water; 1010% butyl cellosolve; 1.0 wt.% concentrated ammonium hydroxide; 0.5
fUi% triethanolamine; 0.02 wt-(6% cobalt dryer) cobalt dryer; 0.2 wt% Active-8 This composition was made as in Example I-1.

The solids content was found to be 23 ± 1%.

ASTM Test B-1 conducted as shown in Example I-1
A score of 17 indicates that this test panel resists breakage for 24 hours. ASTM Test D- conducted as per Example I-■
No. 2247 showed that the composition of this example withstood 72 hours of exposure. The thickness of the composition on this test panel is O,
It was S mil (about 13 microns or 0.13 mm).

The film of the composition of this example cured poorly, which may be due to the composition not having a sufficient dryer.

Patent Applicant Ashland Oil Incorporated Procedural Amendment August 7, 1980 Commissioner of the Patent Office Manabu Shiga 2 Title of Invention Water-based Permanent Coating Composition and Process for Manufacturing the Same 3 Case of Person Making Amendment Relationship with Patent Applicant Address Name Assurant 8 Oil Incorporated 84, Agent 5, [Claims] and [Detailed Description of the Invention] columns (attachment) of the specification subject to amendment (11 patents) The scope of claims is amended as follows.

Fl, (a) from about 27 to about 40% by weight water dilutable dispersible alkyd resin; (b) from about 0.05 to about 6% by weight surfactant;
c) about 1 to about 15% by weight coupling agent; (d) about 0.5 to about 3.5% by weight amine; (e) a metal component in the range of about 0.1 to about 5% by weight. , one or more metal-containing dryers; (f) a chelating agent in an amount of about 0.1% of the total metal weight present in the dryer; fg) about 45
97% by weight deionized water from 15
average molecular weight ranging from 0 to about 450 and from about 15 to about 10
further characterized in that the coupling agent is selected from the group consisting of ether, ethanol, isopropanol, isobutanol, and mixtures thereof; (2) A cobalt dryer, a manganese dryer, and a mixture thereof, wherein the chelating agent is 1.1.1-phenanthralin and the amine is morpholine, concentrated ammonium hydroxide, triethanolamine, jetanol. a water dilutable dispersible coating composition selected from the group consisting of amines, ethanolamines, and mixtures thereof; and adjusting the pH of the composition to a range of about 7 to about 10.

2. (an Select the amount of coupling agent; (b
) mixing half of this coupling agent with water, amine and water-dispersible alkyd resin at about 21r in a mixing apparatus equipped with stirring means; (c) stirring the mixture of (b); (d) separately. (e) mixing the remaining amount of the coupling agent, one or more dryers, and the chelating agent in a mixing device;
(e) adding the mixture of (c) to form a composition; (g) stirring the composition until it is homogeneous;
and (h) adjusting the pH of the composition to a range of from about 7 to about 10 by addition of less than 1% by weight of concentrated ammonium hydroxide; Method of manufacturing the composition.

3. (a) The alkyd resin, the surfactant, half of the coupling agent, the amine, and the deionized water are combined in a conventional mixing kettle equipped with stirring means for about 2 IC
(70F); (b) mixing the dryer with the remaining amount of the coupling agent in another container; to) thoroughly mixing the dryer-coupling agent mixture and then adding the (d) mixing the composition thoroughly until homogeneous; Method of manufacturing the composition.

4. The alkyd resin consists of Kelsol 3907;
the surfactant comprises Aynol 104A; the coupling agent comprises butyl cellosolve; the amine comprises concentrated ammonium hydroxide; the dryer comprises a 6% cobalt dryer and a 6% manganese dryer, and the chelate The composition according to claim 1, wherein the curing agent consists of 1.1.1-phenanthralin.

5. The above alkyd resin and the above surfactant are Kelsol 6
907; the coupling agent is b) 'Iz Cello'/Lup; the dryer is a cobalt dryer; the chelating agent is Active-8; and the pH is less than 1%. Adjusted to 8.2 by use of ammonium hydroxide; Claim 1
The composition described in Section.

6. The resin and the surfactant are Kelsin 6907; the trier is a 6% cobalt trier; the chelating agent is 1.1.1-phenanthralin; and the pH is 8. .5: The composition according to claim 1.

Z the resin is in the range of about 28 to about 36% by weight;
the coupling agent is in the range of about 6 to about 12% by weight; the surfactant is in the range of about 0.2 to about 1.0% by weight; and the dryer is a cobalt dryer and a manganese dryer. The composition according to claim 1.

8. The composition may additionally contain from about 0.01 to about 1% by weight.
and the metal inhibitor is selected from the group consisting of ammonium dichromate, ammonium molinodate, sodium tolyltriazole, and mixtures thereof; .

9 The above composition additionally comprises about 0.01 to about 1% by weight.
wherein the metal inhibitor M is selected from the group consisting of ammonium dichromate, ammonium molypdate, sodium tolyltriazole, and mixtures thereof; The method according to claim 3, which is added in step (a) of claim 3.

10, comprising the additional step of adding in step (b) a metal forbidding agent in the range of about 0.001 to about 1% by weight;
3. The method of claim 2, wherein the metal inhibitor is selected from the group consisting of ammonium dichromate, ammonium dicumate, sodium tolyltriazole, and mixtures thereof.

and the composition comprises: about 60% by weight deionized water; about 0.0% by weight deionized water;
2% by weight ammonium dichromate; about 1.7% by weight
about 32% by weight of Kelsol 3907; about 0.7% by weight of Cobalt Hyde 80 Cure; about 0.1% by weight of Active-8; about 4% by weight of butyl cellosolve; about 2% by weight of Ekta Sorno EP: Approximately 0.
3% by weight of Surfynol 104A; and about 1.6% by weight of concentrated ammonium hydroxide;
11. A process according to claim 10, wherein H is adjusted to 8 by addition of less than 1% by weight of concentrated ammonium hydroxide.

12. Kelsol 39 in which the above composition is about 32.70% by weight
07; 59.00% water; approx. 2.0% n
-7'methylalcohol; about 3.0% by weight
Sorno; about 2.4% by weight concentrated ammonium hydroxide; about 0.4 to 6% by weight cobalt dryer; about 0.0
and about 0.5% ammonium dichromate; and the pH is adjusted to about 8.0-8.5. Method.

16. The alkyd resin is comprised of Kelsol 39o7; the surfactant is comprised of Surfynol 104A; the coupling agent is comprised of butyl cellosolve; the amine is comprised of concentrated ammonium hydroxide; the dryer is a 6% cobalt dryer; 7. The method of claim 6, wherein the chelating agent consists of 6% manganese dryer and the chelating agent consists of 1.1.1-7 enanthralin.

14. The alkyd resin consists of Kelsol 6907; the surfactant consists of Surfynol 104A;
the coupling agent comprises butyl cellosolve; the amine comprises concentrated ammonium hydroxide; the dryer comprises a 6% cobalt dryer and a 6% manganese dryer; and the chelating agent comprises 1.1.1-phenanthralin. A method according to claim 2, comprising:

15. The alkyd resin and the surfactant are Kelsol 6907; the coupling agent is butyl cellosolve; the dryer is a cobalt dryer; the chelating agent is Active-8; and the pH is 8.2 by the use of less than 1% by weight of concentrated ammonium hydroxide.
The method described in section.

16. The alkyd resin and the surfactant are Kernol 6907; the coupling agent is butyl cellosolve; the dryer is a Cobalt 8 dryer; the chelating agent is Active-8; and the pH is 1. 7. The method of claim 6, adjusted to 8.2 by the use of less than % by weight concentrated ammonium hydroxide.

1Z The above resin and the above surfactant are Kelsol 390
7, the coupling agent is methyl cellosolve; the dryer is a cobalt 9 layer;
7. The method of claim 6, wherein the chelating agent is 1.1.1-phenanthralin; and the pH is adjusted to 8.5.

18. The composition of claim 1, wherein said composition additionally comprises colored particles.

19. The method of claim 6, comprising the additional step of adding colored particles to the composition after adjusting the pH.

20. The method of claim 2, comprising the additional step of adding a colored pigment to the composition after adjusting the pH of the composition.

21. The composition of claim 1, wherein said composition additionally comprises a water-dispersible dye.

22. The method of claim 6 comprising the additional step of adding a water-dispersible dye compound to said composition after said pH adjustment.

23. The method of claim 2, comprising the additional step of adding a water-dispersible dye compound to said composition after said pH adjustment.

24. The method of claim 10, comprising the additional step of adding colored particles to said composition after said pH adjustment.

25. The method of claim 10, comprising the additional step of adding a water-dispersible dye to the composition after adjusting the pH. (2) The bottom line of page 26 of the specification to the second line of page 24 of the same document are amended as follows.

lr is in the range of 8.2-8.5. The normal titration end point is
(3) Page 21, line 10 of the specification is amended as follows.

"Alkyd 8 resin and surfactant are preferably Tirusol 39o7." (4) The specification is amended as follows.

Page Line Before correction After correction 25
7 from the bottom This is sharp - This is a variety of sharper
Up

Claims (1)

[Claims] 1. (α) a dispersible alkyd resin dilutable with about 27 to about 40% by weight of water; (b) about 0.05 to about 3% by weight of a surfactant; (
C) from about 1 to about 15% by weight of a coupling agent; (f) from about 0.5 to about 3.5% by weight of an amine; (g) from about 0.1 to about 5% by weight of a metal component; a dryer containing one or more metals; (g) about 0 of the total weight of metals present in the dryer;
, 1% of a chelating agent; (g) deionized water in an amount of about 45 to 97% by weight; isophthalic acid, terephthalic acid, or derived from phthalic anhydride, and the alkyd resin is further characterized by an average molecular weight in the range of about 150 to about 450 and an acid number in the range of about 15 to about 100; The coupling agent is ether, ethanol, isopropylene, imbutanol, and mixtures thereof, and the dryer is a cobalt dryer such as Cobalt Hydrocure, a manganese dryer, and a mixture thereof, wherein the chelating agent is 1.1.1-phenanthralin and the amine is a group consisting of morpholine, concentrated ammonium hydroxide, triethanolamine, jetanolamine, ethanolamine, and mixtures thereof. and 7) adjusting the H of the composition from about 7 to about 10; a water-dilutable dispersible coating composition; 2. selecting an amount of (α) a coupling agent; (b) mixing half of this coupling agent with water, amine and water-dispersible alkyd resin at about 21°C in a mixing apparatus equipped with stirring means; (c) stirring the mixture of (b); F. In a separate mixing device, the remaining amount of the coupling agent,
one or more dryers, and mixing with a chelating agent; (e) (stir the mixture of J thoroughly; (f) (e)
(c) to form a composition; (g) stir this composition until it is homogeneous; and (h) adjust the pH of said composition to 1% by weight. A method for producing a water-dilutable, dispersible, permanent coating composition comprising the steps of adjusting the range from about 7 to about 10 by adding less concentrated ammonium hydroxide. 3. (a) The alkyd resin, the surfactant, half of the coupling agent, the amine, and the deionized water are heated at about 21° C. in a conventional mixing kettle equipped with stirring means.
(b) Mixing the dryer with the remaining amount of the coupling agent in a separate container; (c) Thoroughly mixing the dryer-coupling agent mixture and then Adding this mixture to the mixing kettle of (α) to form the above composition; and thoroughly mixing the composition with (α) until it is homogeneous. A method for producing the composition of item 1. 4. The alkyd resin consists of Kelsol 3907;
the surfactant consists of Surfynol 104A; the coupling agent consists of butyl cellosolve; the amine consists of concentrated ammonium hydroxide; the dryer consists of a 6% cobalt dryer and a 6% titanium dryer; and a chelating agent 1. Composition according to claim 1, wherein 1.1.1-phenanthralin consists of 1.1.1-phenanthralin. 5. The above alkyd resin and the above surfactant are Kelsol 3
907; the coupling agent is butyl cellosolve; the dryer is a cobalt dryer;
the chelating agent is active-8; and the pH
2. A composition according to claim 1, in which . 6. The resin and the surfactant are Kelsol 39o7; the coupling agent is butyl cellosolve; the dryer is a 6% cobalt dryer; the chelating agent is 1.1. l-phenanothralin;
A composition according to claim 1, wherein the pH is adjusted to 8.5. 7. The resin ranges from about 28 to about 33 times;
The coupling agent is in the range of about 3 to about 12% by weight; the surfactant is in the range of about 0.2 to about 1.0%; the coupling agent is in the range of about 3 to about 12% by weight.
in the range of about 0.2 to about 1.0;
% by weight; and the dryer is a cobalt dryer and a manganese dryer. 8. The composition additionally comprises a metal inhibitor ranging from about 0.01 to about 1 fold; and the metal inhibitor is ammonium dichromate, ammonium molypdate, sodium tolyltriazole, and mixtures thereof. A composition according to claim 1 selected from the group consisting of; 9. The composition additionally comprises a metal inhibitor ranging from about 0.01 to about 1 hereditary; the metal inhibitors include ammonium dichromate, ammonium molybdate, sodium tolyltriazole, and mixtures thereof. and wherein said metal inhibitor is added in step (α) of claim 3. 10, about 0. an additional step of adding a metal inhibitor in step (b) in the range of about 1% by weight from OI; a method according to claim 2; 11. The composition comprises; about 60% by weight deionized water;
about 0.24% by weight ammonium dichromate; about 1.
78% by weight n-butyl alcohol; approximately 32.7% by weight
About 0.76% by weight of Kelsol 3907i cobalt powder.
Hydrocure ■; Approximately 0.1 weight - Active-8; Approximately 4
．． 46% by weight of butyl cellosolve; about 2.08% by weight of Ectasolve EP; about 0.32% by weight of Surfynol 104Ai and about 1.61% by weight of concentrated ammonium hydroxide 1, and the pH is less than 1% by weight. 11. A process according to claim 10, adjusted to 82 by adding less concentrated ammonium hydroxide. 12. Kelsol 39 in which the above composition is about 32.70% by weight
07; 59.00% by weight water; about 2.0% by weight n-butyl alcohol; about 3.9% by weight butyl cellosolve;
about 2.4% by weight of concentrated ammonium hydroxide; about 0.4 to 6% by weight of cobalt dryer; about 0.02525% by weight of Cutib-8; and about 0.5% by weight of ammonium dichromate; The above pH is about 8.0-8
．． 11. The method of claim 10, wherein the method is adjusted to 5. 13. The alkyd resin consists of Kelsol 3907; the surfactant consists of Surfynol 104A; the coupling agent consists of butyl cellosolve;
Claim 3, wherein the amine comprises concentrated ammonium hydroxide; the dryer comprises a 6% cobalt dryer and a 6% manganese dryer; and the chelating agent comprises 1.1.1-phenanthralin. The method described in. 14. The alkyd resin consists of Kelsol 3907; the surfactant consists of Surfynol 104A;
the coupling agent consists of butyl cellosolve; the amine consists of concentrated ammonium hydroxide; the dryer consists of a 6-ticobalt dryer and a 6-manganese dryer; and the chelating agent consists of 1.1.1-phenanthralino. A method according to claim 2. 15. The alkyd resin and the surfactant are Kelsol 3907; the coupling agent is butyl cellosolve; the dryer is a cobalt dryer; the chelating agent is Active-8; and the pH is 1. 8.2 by using less than % by weight of concentrated ammonium hydroxide. 16. The alkyd resin and the surfactant are Kelsol 3907; the coupling agent is butyl cellosolve; the dryer is a cobalt dryer; the chelating agent is Active-8; and the pH is 1 wt. - adjusted to 8,2 by using less concentrated ammonium hydroxide, claim 3
The method described in section. 17, j: The resin and the surfactant are Kelsol 3907; the coupling agent is butyl cellosolve; the dryer is a cobalt dryer; the chelating agent is 1.1.1-phenanthralin. and the pH is adjusted to 8.5. 18. The composition of claim 1, wherein the composition additionally comprises colored particles. 19. The method of claim 3 comprising the additional step of adding colored particles to said composition after said pH adjustment. 20. The method of claim 2, comprising the additional step of adding a colored pigment to the composition after adjusting the pH of the composition. 21. The composition of claim 1, wherein said composition additionally comprises a water-dispersible dye. 22. Claim 3 comprising the additional step of adding a water-dispersible dye compound to said composition after said pH adjustment.
The method described in section. 23. The method of claim 2, comprising the additional step of adding a water-dispersible dye compound to said composition after said pH adjustment. 11. The method of claim 10, comprising the additional step of adding colored particles to said composition after said pH adjustment. 25. The method of claim 10, comprising the additional step of adding a water-dispersible dye to the composition after adjusting the pH.