DE2424887A1 - AQUATIC DISPERSION AND METHOD FOR MANUFACTURING IT - Google Patents

Description

The invention relates to an aqueous dispersion and a process for its preparation.

With the current attention being paid to controlling emissions, the coatings industry is seeking resources to find in order to reduce the use of organic solvents in coating compositions and the like or to eliminate.

The invention now provides preformed solid substances in aqueous dispersions, e.g. solid epoxy resins in aqueous dispersion, curing agents for solid epoxy resins in aqueous dispersions and mixtures

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of that. The invention is a spray-on, by Rollers, which can be applied or brushed on, are provided with a liquid coating or coating compound that is used in the Hardening only releases water vapor, which is essentially free of organic solvents, into the atmosphere.

In the process for the preparation of aqueous dispersions of heat-flowable or in organic solvents Soluble preformed solid water-insoluble substances according to the present invention is so proceeded that man

1. a first stream in a Hochscher mixing device, containing water and a suitable dispersant, with a second stream being a pre-formed Contains solid substance which liquefies by heating or dissolving in an organic solvent has been mixed,

2. the resulting stream, the water, dispersant, organic solvent (if any) and contains the solid substance, and circulates the second stream through the high shear mixer until the concentration the dispersed solid water-insoluble substance reaches the desired value, and that one

3. separates the organic solvent, if it is present, therefrom,

whereby an aqueous dispersion of the solid substance is formed, consisting essentially of an organic solvent free is.

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The invention also contemplates an aqueous dispersion of a preformed solid substance that thereby is marked that it contains the following:

1.2 to 75% by weight, preferably 10 to 70% by weight, most preferably 15 to 60% by weight, of a solid substance with an average particle size of less than 10u, suitably less than 5 η , preferably 0 , 1 to 3 », most preferably from 0.1 to 2 u, with the proviso that - if the mean particle size is above 5 η - then not more than 25% by weight of the particles are greater than 15 U,

2. 98 to 25% by weight, preferably 90 to 30% by weight, most preferably 85 to 40% by weight, water and

3. a suitable dispersant.

As used herein, the term "solid epoxy resin" is intended to also include the meaning that the solid epoxy resin is a mixture of a liquid epoxy resin and a solid Epoxy resin is as long as the resulting mixture is under standard conditions is firm. Such resins are described, for example, in U.S. Patent 3,772,228.

As used herein, the term "mean particle size" is intended to mean that 50% by weight of the particles have a size above and 50% by weight have a size below the specified value.

The terms "preformed solid substance, solid epoxy resin and solid curing agent for the epoxy resins" mean that the solid substance, the epoxy resin or the hardening

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medium under standard conditions of temperature and temperature Pressure, i.e. at 25 ° C and 1 at, are solid substances and that they have been produced or preformed before dispersion are.

Suitable epoxy resins which can be used in the invention are, for example, those resins which essentially are insoluble in water. Examples of these resins are those having the following formulas:

I.

CHa-CH-CHa-

OH _, CH ₂ -CH-CHa

rf- Ο-ι η

XXXX

II.

-CHa-CH-CHa

wherein each A is independently a divalent hydrocarbon group with 1 to 6 carbon atoms, -S, -S-S-, 0 0 0

Ii i! η

-S-, -S-, -0- or -C-, each R is independently hydrogen

0
or an alkyl group with 1 to 4 carbon atoms,

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each X is independently hydrogen, an alkyl group of 1 "to 6 carbon atoms, chlorine or bromine, m has a value of 0 or 1 and each η has such an average value Has the value that the epoxy resin is a solid at 25 ° C. and 1 atm.

Epoxy resins on a cycloaliphatic basis

III.

CHa-CH-CHa

(A)

O-CHa-CH-CHa
ι

OH

(A)

O-CHa-CH-CHa

HaC-CH-CHa

0 -

0 0

n m

CHa-CH-CHa-O-C-Q-C-O-CHa-CH-ι

OH

OH

CHa-CH-CHa -

0-CHa - ^1st

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ν.

0-CH ₂ -CH-CHa

in which A, X, R, m and η have the meaning according to the formulas I. and II and each Q independently have the residue of a dibasic aliphatic or aromatic carboxylic acid or means an anhydride thereof which would result upon removal of the hydroxyl groups therefrom.

Solid epoxy resins modified with qxazolidinone

VI.

Ha-C-C-Z -

t H

C ι

H t

H ι

C-C ι ι

OH H

■ Ν H-C-Z 'I

C-CHa t

wherein Z is the divalent organic radical of a polyglycidyl ether denotes a compound with several hydroxyl groups, X denotes oxygen or sulfur and η denotes one Has a value of 1 to 10.

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H-

V / O - C - ^ X * ^ O _n -

(A - C j TzM tCH-CH *)

-C-. ι

where Z is the residue of an organic polyisocyanate or an organic polyisothiocyanate, Z ^{1 is} the residue of a polyglycidyl ether of a compound with several hydroxyl groups, A is oxygen or sulfur and m has an average value of 1 to 5.

Figure 1 is a schematic diagram of one method of application of the method of the present invention to produce aqueous dispersions of solid epoxy resins or solid To prepare curing agents for the epoxy resin or mixtures thereof or another pre-formed solid substance.

In the following description of a typical method according to the present invention, the solid substance, to be dispersed is called an epoxy resin. However, the method of the invention is just as good on others preformed solid water-insoluble substances soluble in organic solvents or flowable with heat applicable.

A mixture of water and a suitable dispersing agent is from the reservoir 4 through the line 7 to the suction side of the pump 1 and then to the discharge side of a Centrifugal pump 2 passed through line 8 from the delivery side of pump 1. This is where the mixture comes from

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the suction side of the centrifugal pump 2 through line 9 into a heat exchanger 5 and into a container 4 through line 10. After this return of water and a dispersant has been stabilized, a solution of a solid epoxy resin in a suitable organic solvent is then removed from the vessel 6 passed through the line 10 into the suction side of a pump 3 and from the discharge side of the pump 3 into the housing of the centrifugal pump 2 through the line 11, whereupon the solution of the epoxy resin in the organic solvent and the mixture of water and the dispersant under a high Shear force due to the operation of the centrifugal pump 2 are brought into contact with each other, whereby solid particles of epoxy resin in water and organic solvent are formed and passed from the centrifugal pump 9 through the line 10 into the heat exchanger 5 and into the reservoir 4 through the line 10. The solution of the solid epoxy resin in the organic solvent is continuously fed into the housing of the centrifugal pump 2 - as described above - until the desired ratio between solid epoxy resin and water is obtained, whereby an aqueous dispersion of the epoxy resin with a particle size of less than about 10 ii, suitably less than about 5 η and usually from about 0.1 to about 3 watts. Then, by appropriate measures not shown, such as distillation, flash evaporation and the like, the organic solvent is removed, leaving a dispersion of a solid epoxy resin in water. If a higher solids content is desired, then some of the water can be removed by suitable measures. The purpose of the heat exchanger 5 or other suitable heating means is to control the temperature of the water

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and controlling the dispersant to a desired value by cooling or heating.

Figure 2 shows an alternative mode of operation in which the solution in the organic solvent into the centrifugal pump 2 is introduced through the line 11, which is smaller than the output of the pump 2 and in which the mixture is passed with the water and the dispersant through line 8 into a T-piece which is attached to the The delivery side of the pump 2 is arranged.

In another method of preparing the aqueous dispersions of the solid epoxy resins, solid curing agents for epoxy resins and mixtures thereof or other preformed solid substances or mixtures of water, a suitable dispersing agent and a solid substance which are made flowable by heat and / or are soluble in organic solvents are used in a mixed at such a temperature that a highly viscous homogeneous mixture is obtained. The temperature is generally kept at 20 ^° C. below to 50 ^° C. above the Durran softening point, the melting point or the heat distortion temperature, depending on which point is suitable for the solid to be dispersed. After stirring this viscous homogeneous mixture for a period of about 30 minutes to about 12 hours or more, depending on the mass used, and while maintaining this temperature, further water is slowly stirred into the mixture until the desired solids content is obtained, whereby an aqueous dispersion of the solid substance is obtained.

The designation "highly viscous ¹¹ means that the viscosity is such that the desired particle size during the process

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mixing or stirring is obtained and that the However, viscosity is sufficiently below that at which agglomeration of the mixture and rise would take place on the shaft of the stirrer.

Any suitable organic solvent can be used as long as the solid or mixture the solids to be dispersed is soluble therein. Suitable organic solvents are e.g. ketones, Alcohols, amides, cyclic amides, glycol ethers, chlorinated hydrocarbons, esters and aromatic hydrocarbons, such as acetone, methanol, ethanol, butanol, isopropanol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, Propylene glycol phenyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, methyl ketone, Methyl isobutyl ketone, tetrahydrofuran, benzene, toluene, methylene chloride, dichloroethane, ethyl acetate, ethylene glycol butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol phenyl ether, Ethylene glycol monoethyl ether acetate, diozane, dimethylformamide, N-methyl-2-pyrrolidone, mixtures thereof, and the like.

Examples of suitable water-soluble or dispersible dispersants are synthetic gums made by Cellulose, hydroxyalkyl guar, polyvinyl alcohols with acetate groups that do not hydrolyze, and those water-soluble or dispersible wetting agents or binding colloids, the pendant and / or terminal ester, 1- to 4-C-alkyl ether, aralkyl ether, phenoxy resin, amide or have amine groups such as Elvinol 52-22; Methocel 90 Hg, 100; Methocel 60 Hg, 50; Methocel 60 Hg, 4000; Elvinol 5-42; Elvinol 51-05; Elvinol 46-22; Elvinol 71-24;

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Igepal CO-430; Igepal CO-970; Igepal CO-530; Gelvatol 20-60} Jaguar HP-1; Jaguar HE-1 and mixtures thereof and the like.

The dispersant is used in amounts that facilitate the dispersion of the solid substance or mixture of such substances are maintained in the water. The amount varies from substance to substance, but there are generally 0.5 to 25, preferably 1 to 10 parts by weight based on the solid resin which will be diapered should, suitable.

A suitable dispersant should be understood to mean one which disperses the majority of the solid particles is maintained in the water for a significant period of time, e.g., about 30 days, wherein those particles that settle readily into the water by a simple agitation or the like can be redispersed.

The foregoing shows that curable dispersions can be prepared by using separate aqueous Dispersions of a solid epoxy resin and a solid curing agent are prepared and mixed thereafter to achieve the desired epoxy resin to curing agent ratio. It can also be a single one Dispersion can be prepared by adding an organic solvent mixture of the epoxy resin and the curing agent is used in the preparation of the aqueous dispersions.

Suitable water-insoluble hardeners are, for example, conversion resins, such as urea formaldehyde resins, melamine form

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aldehyde resins, alkoxylated urea-formaldehyde resins, alkoxylated melamine-formaldehyde resins, phenol-formaldehyde resins, Polycarboxylic acids, mixtures thereof, and the like.

Water-soluble hardeners such as methylolated and partially methylolated urea-formaldehyde, methylolated and partially methylolated melamine-formaldehyde, dicyandiamide, methylolated phenol-formaldehyde, amines, Polycarboxylic acids, imidazoles such as 2-methylimidazole, and Lewis acids, which are subject to complex formation with ethers or amines, can be present in the aqueous epoxy resin dispersion be dissolved to form curable masses. These hardeners can be found in the water either upon formation of the aqueous epoxy resin dispersion or after formation of this dispersion.

Fire retardants, flow control agents, colorants, thixotropic agents, antifoam agents, wetting agents, pigments, Fungicides, UV stabilizers, fillers, accelerators, mixtures thereof and the like can be added, to improve or modify the aqueous dispersions according to the invention.

The aqueous dispersions of the solid epoxy resins, if mixed with a suitable curing agent for the Epoxy resin are mixed, used as coatings, laminates and the like.

In a process for the preparation of the aqueous dispersions of the solid epoxy resins or other heat-flowable ones or preformed solid substance soluble in an organic solvent can be the temperature

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at 0 to 15O ⁰ C are maintained. However, they are generally produced at from 5 to 25 ^° C. below the Durran softening point, the heat distortion temperature or the melting point, depending on the solid substance that is being dispersed. However, this depends somewhat on the concentration of the organic solvent in the water-solid system and the softening point of the resin that is being dispersed. Thus, for example with an epoxy resin having a Durran softening point of 113-125 ° C, the temperature during the dispersion about 95 amount to about 120 ⁰ C, until the concentration of the organic solvent in the water-solid system about 10 wt .-% However, at this point, should a higher concentration of solids be desired, some of the organic solvent must be removed. However, if an organic solvent is initially added to the water (prior to starting the addition of the epoxy resin or other solid to be dispersed) at a concentration of about 7-14%, then the temperature can be about 25 to about 45 ° C until the concentration of the organic solvent in the water-solid system reaches about 17 #. At this point, however, if a higher concentration of solids is desired, some of the organic solvent must be removed _β

When an epoxy resin as a further example having a Durran softening point of about 90 to 95 ⁰ C the temperature may be up to 85 ⁰ C during the dispersion about 70 until the concentration of the organic solvent in the water-solid system about 10 weight % achieved. At this point, if a higher concentration of solids is desired, some of the organic solvent must be removed.

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It can be seen that the concentration of the solvent in the water-solid system can be controlled by a measure or device for removal of the solvent is used in connection with the reservoir 4 of Figure 1, such as a falling film still, purging with an inert gas or the like. In the figure, however, is the recovery device Not shown.

From the foregoing it will be seen that once the desired solids content in the Dispersion is achieved - then the dispersing process can be carried out continuously by simultaneously applying the appropriate proportions of water, the dispersant and the solid substance are introduced while removing the dispersion product.

The method according to the present invention is readily applicable to all preformed solid substances, which are soluble in an organic solvent or which are at the temperature of the dispersion process form a flowable liquid. Particularly suitable solid substances are natural and synthetic resinous Substances such as solid epoxy resins, solid urea-formaldehyde resins, solid melamine-formaldehyde resins, solid Phenol-formaldehyde resins, solid polyvinyl acetate resins, solid nylon (polyamide) resins, solid polyester resins, solid vinyl ester resins, solid polyacetal resins, solid polyurethane resins, solid polyvinyl chloride resins and solid polyvinylidene resins, solid polycarbonate resins, solid acrylate copolymer resins, and mixtures thereof.

As one of the possible uses of the dispersions according to the invention is for covering purposes, the transport cases

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most for the manufacturer of the coating compounds due to the Increased water transport costs. However, it was surprisingly found that - once the aqueous dispersions according to the present invention with the exception of those containing liquid hardening agents have been prepared - then the water content to a value of less than about 10 wt .-%, preferably less than about 5% by weight can be reduced to give a dry or semi-wet particulate Product can be obtained that can be transported to other places. There can water up to the desired Amount can be added and the solids can be redispersed with a simple agitation. This results in favorable, economical transport costs. The dispersions can be prepared by suitable measures, such as air drying, vacuum drying, spray drying and the like, can be dried.

The following examples are intended to illustrate the invention in more detail.

example 1

Using the device according to FIG. 1, a solution of 7.0 g of polyvinyl alcohol (Elvanol 52-22. This is a product from DuPont with a molecular weight of 50,000 to 100,000, which is hydrolyzed to 88 mol #) was dissolved in 400 ml of water, in the reservoir 4 and the solution was circulated through the pumps 1 and 2, the heat exchanger 5 and back into the reservoir until the temperature of the solution had reached 100 ^° C. Then 204 g of an 85 wt .-% solution with 80 ⁰ C of an epoxy resin based on bisphenol A and

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Epichlorohydrin having an epoxide equivalent weight of about 1800 in acetone was added from vessel 6 over a period of 36 minutes. The resulting dispersion was cooled to room temperature and the acetone was removed at 3O ⁰ C (and 30 mm Hg pressure). The resulting dispersion contained 30 wt .-% of a solid epoxy resin having a particle size of <5 Ά and it had a viscosity of 12 cps at 25 ⁰ C. After 5 days of standing at room temperature had less than 1% by volume of the solid particles deposited on the ground. These particles could be easily redispersed by shaking the container.

Examples 2 to 17

The procedure of Example 1 was followed in these examples repeated. The reactants, the reaction conditions and the results obtained are as follows Table compiled:

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Table I.

Resin or curing agent, type / g 2 3 4th Examples
5 6 D / 370 7th 8th 9 Dispersant, type / g A ^1/194 D ^4/50 D / 71 D / 86 56 B / 10 H ^8/216 I ^9/216 D ^b / 55.3 Water, g B ^2/7 E ⁵ / 2.5 F ^6/3 , 13 G ^7/2 , 400 B / 7 B / 7 B / 1.4 kg Solvent for the resin or
the hardener, type / g 400 200 250 200 C / 70 400 400 45.4 kg Temperature of the dissolution
pergating agent, ⁰ C C ^3/49 C / 12.5 C / 17 , 8 C / 37 100 C / 38 C / 41 C / 21.5 O
co Temperature of the solution of the resin
or the curing agent, C 55 100 100 60 80 80 80 100 00 Feeding time of the resin vein
of the hardening agent, min 25th 80 80 80 36 + 36 ^a 80 80 110 CD Concentration of the resulting
Dispersion, wt .-% 28 17th 29 19th 48 28.5 26th \
205 pounds CJ Viscosity of the resulting
Dispersion, cps at 25 ° C 32.7 20th 22nd 30th NB ^C 35 ' 29.2 I.
55 Mean particle size of the dispersed
yawed solids, u 12.5 26th 30th 273 <5 ^e 15th 12.5 105 <5 ^e <5 ^e <5 ^e <5 ^e <5 ^e ₅ e <5 ^e ^ «

a) 240 g of the solution were introduced over a period of 36 minutes. Then there was 39 g of acetone removed from reservoir 4 by vacuum stripping. The loading was continued for another 30 minutes.

b) In this example, the device of Figure 2 was used and the reservoir 4 was continuously flushed with nitrogen to ensure continuous removal of the solvent to be carried out so that the solids content of the dispersion was increased. Pump 1 was one Centrifugal pump with sufficient delivery pressure that the delivery pressure of pump 2 is overcome became. The pump 3 was eliminated and the solution of the epoxy resin was poured into the pump 2

pressed into the vessel 6 under nitrogen pressure by means of a flow control valve, not shown.

c) N.B. = not determined -18-

Continuation of table I co

Examples 10 11 12 13 14 15 16 17

Resin or curing agent, type / g ^D4 / 45 D / 134 D / 200 D / 126 O ¹⁵ / 1O1 P ¹ ° / 202 Q ¹ '/ R ¹⁸ 203 / £ 192 Dispergierungsmlttel, T3rp / g K ¹¹ / 8.0 L ¹² / 7.0 M ¹³ / 7.0 N ^14/7 , OB / 7.0 B / 7, QB / 7.0 B / 7.0 water, g 250

Solvent for the resin or curing agent, type / g. C / 15

_o Temperature of the solution of the fluid

coring agent, ⁰ C 100

?? Temperature of the solution of the resin or _{o of} the curing agent, ⁰ C 80

*** ■ Feeding time of the resin or the

^ Hardener, min 15

* ° concentration of the resulting

^ω dispersion, wt. # 15.2

Viscosity of the resulting dispersion, cps at 25 C N.B.

Average particle size of the dispersed solids, u

d) In this example, the dispersion was prepared under a nitrogen pressure of 2.91 atm.

e) The mean particle size was determined microscopically with a magnification of 600 χ.

f) The mean particle size was determined using a Coulter Counter (Model TA) from Coulter Electronics, Inc. determined.

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400 400 400 400 400 400 400 C / 36.6 C / 36 C / 36 C / 18 C / 35.6 C / 35.8 C / 34 100 100 100 50-52 , 5 76 109 ^d 78 80 80 80 50 80 80 80 36 36 36 20th 36 36 37.5 i 25th 33.3 35 20.4 33.6 33.7 32, f. * N.B. N.B. N.B. N.B. N.B. N.B. N.B. <5 ^e <5 ^β <5 ^β 1.0 ^f <5 ^e <5 ^e <5 ^e

Footnotes to Table I.

1) The epoxy resin A was a diglycidyl ether epoxy resin of the bisphenol A type with a mean EEW value of about 525.

2) The dispersant B was (Elvinol 52-22) polyvinyl alcohol, average molecular weight 50,000 to 100,000, 88 moles-96 hydrolyzed, available from DuPont.

3) Solvent C was acetone.

4) The epoxy resin D was a diglycidyl ether epoxy resin of bisphenol A type with a middle one EEW value of around 1800.

5) The dispersant E was a Hydroxypropylmethylcellulosegummi having a gel point in a 2% aqueous solution of 90 ⁰ C and a viscosity of 100 cps at 25 ° C, available from The Dow Chemical Co. as Methocel 90 HG, 100th

6) The dispersant was a Hydroxypropylmethylcellulosegummi F with a gel point in a 2% aqueous solution of 60 ⁰ C and a viscosity of 50 cps at 25 ⁰ C, available from The Dow Chemical Co. as Methocel 60HG, 50th

7) The dispersant G was a hydroxypropylmethyl cellulose gum with a gel point in 2% aqueous solution of 60 ° C and a viscosity of 4000 cps at 25 ° C, available from The Dow Chemical Co. as Methocel 60HG, 4000.

8) The epoxy resin H was a bisphenol A type diglycidyl ether with an average EEW value of around 925,

9) The epoxy resin I was a vulcanized rubber modified epoxy resin with an epoxy content of

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5.5% and a softening point of 86 ° C, produced by reacting a diglycidyl ether of an epoxy resin of the bisphenol A type with an average EEW value of about 190 with 20 parts by weight, based on the epoxy resin of a carboxyl-containing 7h% butadiene - 2696 acrylonitrile Rubber with 36.6 parts of bisphenol A and 0.33 parts by weight of dicumyl peroxide as a vulcanizing agent which contained 0.5% by weight of a flow control agent (Modaflow, available from Monsanto Co.).

10) Curing agent J was a butylated urea-formaldehyde resin, available from Reichhold Chemicals Inc. as Beckamine P-196.

11) The dispersant K consisted of 4.5 g Igepal CO-970 and 3.5 g Igepal CO-630. That’s what it’s about are a class of non-ionic surfactants available from GAF Corporation.

12) The dispersant L was (Elvinol 50-42) polyvinyl alcohol, 88 mole percent hydrolyzed, available from DuPont.

13) The dispersant M was a mixture in equal parts by weight of Elvinol 52-22 and Elvinol 51-05, both 88 mole percent hydrolyzed, available from DuPont.

14) Dispersant N was an equal weight mixture of Elvinol 52-22 and Elvinol 50-42, both 88 mole percent hydrolyzed, available from DuPont.

15) The vinyl ester resin 0 was a vinyl ester resin which is the reaction product of a diglycidyl ether Bisphenol A-type epoxy resin with a medium

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Ren EEW value of 525 and methacrylic acid in one Molar ratio was about 1: 1. This vinyl ester resin had a Durran softening point of 70 ° C.

16) The epoxy resin P was the polyglycidyl ether of the reaction product of a low-function epoxy novolak resin (2.05 to 2.1f) "with a low-function Novolak resin (2.05 to 2.1f), making an epoxy novolak resin with a mean EEW of 802 and a Durran softening point of 89 ° C. This resin also contained 0.5% by weight of one Flow control agent available from Monsanto Chemical Co. as Modaflow.

17) The epoxy resin Q was an epoxy resin of the diglycidyl ether of bisphenol-A-type, which was partially blocked with t-butyl phenol and had an average EEW of 3553 and a Durran softening point of 125 ⁰ C.

18) The epoxy resin R was the diglycidyl ether of the reaction product of the diglycidyl ether of 2,2'-bis (4hydroxycyclohexyl) propane with a mixture of 20 mol% adipic acid and 80 mol-96 mol isophthalic acid. The resulting Epoxy resin had a mean EEW of 1344 and a Durran softening point of 84

to 89.

Examples 18 to 31

In these examples, the procedure of the example was repeated with the exception of the following modifications. The reservoir 4 of Example 1 was replaced by a glass cylinder with the dimensions 63.5 mm × 76.2 cm. One Nozzle was placed on the top of this cylinder in such a way

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installed that the circulating mixture from the line 10 as a continuous uniform film the walls of the Cylinder had to flow down. This device operated with a small stream of nitrogen flowing through the column flowed as a falling film still, causing the organic solvent to flow continuously during the dispersing process could be removed. The nitrogen purge and resin / solvent feed rate were generally adjusted so that the content of the organic solvent was at most about 1.0% by weight of the aqueous phase was maintained. The water which distilled off together with the organic solvent was separated off and sent back to the dispersing process. Once the desired amount of resin has been introduced into the system the resin supply was stopped and the resulting dispersion was passed through the falling film still circulated until the organic solvent was removed. This made a dispersion of the resin in water free from the organic solvent.

Table II shows the reactants, the reaction conditions and the results.

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- 23 Table II

ro * ■ *

18th

19th

20th

Examples
21 22

23

Η H750 / 300 A ^5/122 U ° / 212.8 ^V7 / 300 W ^8/300 Z ⁹ / 29.7

Β ^2/16 Β / 12 Β / 12 Β / 12 Β / 12 Β / 12 Β / 16

S ³ / 0.2 S / 0.03 S / 0.03 S / 0.03 S / 0; 03 S / 0.03 S / 0.03

400 300 300 300 300 300 300,

Resin or curing agent, type / g dispersant, type / g Wetting agent, type / g water, g solvent for the resin or curing agent, type / g

Dispersant solution temperature, C

Temperature of solution of resin or curing agent, C

Feed time of resin or curing agent, min

Concentration of the resulting dispersion,% by weight

Mean particle size of the dispersed solids, η ^a

a) The mean particle size was determined using a Coulter Counter (Model TA) from Coulter Electronics, Inc. determined.

b) In this example, the test temperature was such that a flowable liquid without the With the aid of an organic solvent was obtained.

C ¹ V 10.6 T * 733, 3 none ^w C / 23.6 C / 75 C / 33.3 Y / 29.7 100 9T0 65-95 80 65-70 82.5 100-105 80 100 100 100 25th 90 100 20th 70 100 90 190 75 20th 11.1 50.0 28.9 41.5 50.0 50.0 9.0 0.8 1.0 2.5 1.6 1.0 1.0 3.0

Table II continued

25th

26th

27

Examples
28 29

30th

Resin or curing agent, type / g D ^1O / 134 D / 174 D / 174 Z ₂ ¹ Vi5.8 D / 185 D / 400

W / 7.0 W / 7.0 W / 7.0 W / 12 W / 7. B / 16

** Dispersing agent, type / g to wetting agent, type / g
2J water, g

400

agent, C

Resin or curing agent solution temperature, C 86

Resin or curing agent feed time, min 32

Concentration of the resulting dispersion,% by weight 25

Average particle size of the dispersed solids, and ^a 1.25

H / 300 B / 16

none none none S / 0.03 Z ^ ¹⁶ / O, 05 S / O, 04 S / 0.03

400 400

° Solvent for the resin or the _{ΛΛ Λ0} ^ hardener, type / g Y ^M / 34 Z '^ / 43

~ »Temperature of the solution of the Dispergie-300 400 400 300 Z ₃ ¹⁵ / 36.8 C ¹⁷ / 30.6 C / 44.4 Zq ¹⁸ / 42.8

100 100 70-80 100 105-110 87.5-90 88 100 90 100 100 80 29 30th 60 36 65 66 ^ 30th 30th N.B. 31.7 50.0 50.0 ^% 0.8 <5 ^C 3.2 <5 ^C 1.1 1.0

c) The mean particle size was determined microscopically with a magnification of 600 χ.

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Footnotes to Table II

1) see epoxy resin H, described in footnote 8) of table I.

2) See dispersant C, described in footnote 2) of Table I.

3) The wetting agent S was 2,4,7,9-tetramethyl-5-decyn-4,7-diol, available from Air Chemicals Inc. as Surfynol 104. '

4) Solvent T was methyl isobutyl ketone.

5). See epoxy resin A, described in footnote 1) of Ta

belle I..

6) Resin U was a phenol / formaldehyde resin, obtained by reacting 2.5 / 1 equivalents of pt-butylphenol / formaldehyde. The resin had a Durran softening point of 96.0 ⁰ C and it is available from Union Carbide as UCC CKM 1734th

7) The epoxy resin V was an epoxy resin of diglycidyl ether of tetrabromobisphenol A with an average EEW value of 480, a Durran softening point of 76 ° C and a bromine content of 19%.

8) Resin W was a mixture of 1. 70% of the reaction product, obtained by converting 18% of a Polyglycidyl ethers based on phenol / formaldehyde with an average EEW value of 178 and 52% of a diglycidyl ether based on bisphenol A with an average EEW value of 188 with 30% bisphenol A, whereby a polyepoxide with an average EEW value of 900 was obtained, and 2. 30% of the reaction product of 2 equivalents

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Bisphenol A with 1 equivalent of a diglycidyl ether based on bisphenol A with a medium EEW value of 188.

9) Resin Zq was a copolymer of 70% ethylene and acrylic acid with a melt index of 30 g flow

per 10 min at 190 ⁰ C.

10) see epoxy resin D, described in footnote 4) of table I.

11) Solvent Y was tetrahydrofuran.

12) Solvent Z was ethyl acetate.

13) The solvent Z ^ was toluene.

14) The resin was Zg a polyamide resin with a Fisher-Johns melting point of 157 ⁰ C, erhäfclich from DuPont as Elvamide 8063rd

15 ") The solvent Z was ethanol.

16) The wetting agent Z ^ was a silicone defoamer, im Commercially available from Dow Corning as Antifoam A.

17) Solvent C was acetone.

18) The solvent Zg was methylene chloride.

Example 32

A 1-1 resin kettle equipped with a paddle stirrer and a reflux condenser, 10 g of polyvinyl alcohol (Elvanol 52-22, available from DuPont), 0.025 g of a wetting agent, Surfynol 104, available from Air Products and Chemicals, and 50 grams of water. To this solution 250 g of an epoxy resin based on the diglycidyl ether of bisphenol A and tetrabromobisphenol A were obtained

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with an epoxy equivalent weight of about 475 and a bromine content of 18-2096. The mixture was ^{heated to 90 °} C. with thorough stirring and held there for 30 to 45 minutes. The temperature was then allowed to drop to 80 ^° C. and held at this temperature while 255 g of water were slowly added at a rate of about 3 g / min. After the addition of the water, the mixture was cooled to ambient temperature and an aqueous epoxy dispersion having an average particle size of 1.0u and a non-volatile content of h5% was obtained.

Examples 33 and 34

The procedure of Example 32 was repeated in these examples. In Table III are the reactants, the reaction conditions and the results compiled.

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Table III

Example . Example 33 34

Resin or hardening agent, type / g Z = / 250 Zg γ80

Dispersant, type / g B ^ / 15 B / 6

Wetting agent, type / g S ³ / 0.025 Z _? ⁵ / 0.2

js water in the initial batch, g 75 25

^ Reaction ^{temperature, 0} C 80 95-100

<»Second addition of water, g / addition time, min 230/90 60/45

ο Concentration of the resulting dispersion, wt .- # 45 48.5 A ^

a **

mean particle size of the dispersed solids, μ 0.9 1.0 ο · ro

ω a) The mean particle size was determined using a Coulter counter (model TA) from

Coulter Electronics, Inc. determines.

Footnotes to Table III

1) The vinyl ester Z ₁ - was a vinyl ester resin which was the reaction product of a diglycidyl ether of a bisphenol epoxy resin of the Α-type with methacrylic acid and maleic acid. It had a Durran extension

ccfcation point of 71 ⁰ C.

2) See dispersant B, described in footnote 2) of Table I.

3) see wetting agent S, described in footnote 3) of table II.

r) Resin Zg was a thermosetting phenolic resin with

a capillary softening point of 65 to 75 ° C, available from Reichhold Chemicals, Inc. as Varcum 5416.

5) The wetting agent Z ₁ was a mixture of equal amounts by weight of the wetting agent S, described in footnote 3) of Table II, and a silicone product available from Dow Corning Corp. than DC-840.

Example 35

The aqueous epoxy dispersion, prepared according to Example 30, was poured into an aluminum foil pan until a layer of liquid about 3.175 mm thick had been formed. After air drying for 24 hours, the remaining solid became small flakes broken open with the approximate dimensions 6.35mm 6.35mm χ 3.175mm. Analysis showed that the particles had a non-volatile content of 98,696.

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These dried particles (10.0 g) were mixed with 10.0 g of water using a magnetic stirrer for approximately 2 to 3 hours. The particles could be easily redispersed, creating a stable dispersion with a average particle size of 1.1 µ was obtained

Example 36 .

Demonstrating a continuous process for the preparation of aqueous resin dispersions was the exact one Procedure with inclusion of the proportions of the reactants according to Example 19 of Table II used. However, when the concentration of the dispersion reached 50% the resin feed was not stopped as in the example. In this example water, which is 4 phr Elvanol 52-22 fed into the dispersion at the same rate as the resin feed, The aqueous dispersion with a concentration of 5096 was then continuously removed from the process as more water, elvanol, and resin were fed into the process. The removed dispersion was circulated through a falling film still to remove the residual organic Remove solvent. In this way, an aqueous resin dispersion made from the organic solvent was free, received. This process was allowed to proceed until 2286 g of the dispersion was obtained.

Resin H, g 1142.8

Dispersant B, g 45.7

Wetting agent, g 0.03

Water, g 1142.8

Solvent C, g 127

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Resin loading time, min 200

Concentration of non-volatile substances in the resulting dispersion, Wt% 50

mean particle size of the dispersed solids, u 0.8

Example 57

The procedure of Example 1 was followed except that two streams were introduced into the centrifugal pump 2 housing. One stream was an 8596% solution of Epoxy Resin D in acetone and the other stream was a 90% solution of Curing Agent J in ethanol. The ratio of the two streams was such that a curing agent ratio for the epoxy resin: epoxy resin of 30: was achieved. The resin-hardener charges were added over a period of 28 minutes at temperatures of 80 and 25 ^° C. to a recirculating solution of 10 g of dispersant B in 400 ml of water which had been heated ^{to a temperature of 100 ° C.} . After the acetone and the ethanol had been removed, the joint resin-hardening agent dispersion had an average particle size of <5 η , a viscosity at 25 ° C. of 22.5 cps and a solids-in-water concentration of 38% by weight.

Example 38

It was used the procedure of Example 1, except that 6.8 g of dicyandiamide, a water-soluble curing agent, were added to the solution of water and the dispersing agent, which has been recirculated and heated to 8O ⁰ C before 182 g of a 80% solution of epoxy resin I in acetone with a temperature

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door was added of 8O ⁰ C over a period of 27 min. The resulting product after removal of the acetone was a dispersion of a solid epoxy resin in water which also contained therein a water-soluble epoxy resin curing agent and which contained 27.5% epoxy resin plus dicyandiamide. The mean particle size of the solid epoxy resin was about <5 ».

Example 59

The procedure of Example 1 was followed except that reservoir 4 contained 12 grams of Dispersant B, 72 grams of a methylolated urea formaldehyde available from American Cyanamid Co. as Beetle 65, a water soluble epoxy curing agent. After the temperature of the circulating water solution had reached 10O ⁰ C was added 255 g of a 84.5% solution of 8O ⁰ C of epoxy resin D in acetone over a period of 37 min added at 8O ⁰ C. The resulting product was a dispersion of a solid epoxy resin in water containing a water-soluble epoxy resin curing agent. The mean particle size of the epoxy resin was <5 »and the concentration of the epoxy resin plus curing agent was 38% by weight.

Example 40

The procedure of Example 1 was followed except that the solution of water and dispersant was circulated and heated to 75 ° C before a 90% solution of Hardener J in ethanol at 25 ° C was added over 42 minutes became. The resulting product was a dispersion of a solid epoxy curing agent in water and it had a solids concentration of 30% by weight and an average particle size of <5 η .

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Example 41

A coating composition which was free of organic solvents was prepared by using 33.3 g of the resin according to Example 1 in a thorough mixture with 4.3 g of Beetle 65. The resulting mass was applied to steel plates Q with a coating thickness of 2.54 to 12.70 η. The coating was ^{cured at 175 °} C. for 30 minutes. The coating was tested for solvent resistance, impact resistance and flexibility. The results obtained are shown in Table IV.

Example 42

A coating composition which was free of organic solvents was prepared from 33.3 g of the dispersion according to Example 1, by using it 2.0 g of a methylolated melamine-formaldehyde resin available from American Cyanamid Co. as Cymel 370. The mixture was on aluminum plates Q applied to a coating thickness of 2.54 to 12.70 U. The coatings were left at 175 ° C for 30 minutes hardened. The results obtained are summarized in Table IV.

Example 43

A coating composition, which was free of organic solvents was prepared by mixing 11.5 g of the dispersion according to Example 7 with 8 g of a solution were mixed, the 2.0 wt -.% Of dicyandiamide and 0.125 wt .-% benzyldimethylamine contained in water . This coating solution was applied to aluminum plates Q to a thickness of 2.54 to 12.70 μm and ^{cured at 200 °} C. for 30 minutes. The results obtained are shown in Table IV.

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Example 44

A coating composition which was free of organic solvents was prepared by mixing 13.7 g of the dispersion according to Example 8 with 8 g of a solution containing 2.0% by weight of dicyandiamide and 0.125% by weight of benzyldimethylamine in Contained water. The coating solution was applied to aluminum plates and Q having a thickness from 2.54 to 12.70 and to 5O ⁰ C for 5 to 10 minutes at 40 and then cured 30 min at 200 ⁰ C. The results obtained are shown in Table IV.

Example 45

A coating composition which was free from organic solvents was prepared by mixing 12.3 g of a dispersion according to Example 2 with 8 g of a solution which contained 20% by weight of dicyandiamide and 0.125% by weight of benzyldimethylamine in water. The coating solution was si .gebracht on-Q on aluminum plates having a thickness from 2.54 to 12.70 and up to 10 min at 40 to 50 ⁰ C 5 and then cured for 30 minutes at 200 ° C. The results obtained are shown in Table IV.

Example 46

Q aluminum plates were coated with the curable composition of Example 38 having a thickness from 2.54 to 12.70 u and cured for 5 to 10 minutes at 40 to 50 ⁰ C and then 30 minutes at 200 ° C. The results obtained are shown in Table IV.

Example 47

Aluminum plates Q were mixed with the hardenable mass according to

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game 37 coated with a thickness of 2.54 to 12.70 u and ^{cured at 175 0} C for 30 min. The results obtained are shown in Table IV.

Example 48

Steel plates Q were coated with the curable dispersion according to Example 39 with a thickness of 2.54 to 12.70 μm and ^{cured at 175 °} C. for 30 minutes. The results obtained are shown in Table IV.

Table IV

Example solvent reverse twist mandrel flexibility No. resistance strength- * mm

In-lbs

41 ¹ moderate->10> 16O 38.1

42 ² good - 40 40 38.1

43 ² good -> 50 40 12.7

44 ² good -> 60 40 12.7

45 ² good -> 50 40 12.7

46 ² good - /> 50 40 6.35

47 excellent

..-> 50 40 38.1

48 ¹ moderate ->10> 16O 38.1

1) The plate to which the coating compound was applied was made of cold rolled steel.

2) The panel to which the coating was applied was untreated aluminum.

3) Number of rubs with a solvent-saturated Cotton rag under hand pressure until the coating fails.

4) bad: no adhesion, tarnishing

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moderate: some loss of adhesion, tarnishing, good: no loss of adhesion, some tarnishing, excellent: no loss of adhesion, no tarnishing.

5) Impact strength as determined in accordance with Gardner Bulletin IG-1100 using a Gardner Mandrel Impact Impact strength tester No. IG-1125.

6) Mandrel Flexibility Test according to Gardner Bulletin IG-1100 using a Gardner Mandrel Impact Tester No. IG-1125.

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Claims (18)

Claims 1. Aqueous dispersion of a solid substance, characterized in that it contains the following: (1) 2 to 75 parts by weight of a solid substance having an average particle size of less than 10µ with the proviso that when the average particle size is greater than 5 », not more than 25% by weight of the particles have an average size of more than have 15 Ji , (2) 98 to 25 parts by weight of water and (3) a suitable dispersant. 2. Dispersion according to claim 1, characterized in that the dispersion has 10 to 70 parts by weight of component (1) with an average particle size of less than 5 W and 90 to 30 parts by weight of component (2). 3. Dispersion according to claim 1, characterized in that the dispersion 15 to 60 parts by weight of component (1) and 85 to AO parts by weight of the Contains component (2) and that component (1) has an average particle size of less than 5 ». 4. Dispersion according to one of claims 1 to 3, characterized characterized in that component (1) is a solid epoxy resin, a solid epoxy resin curing agent or is a mixture of these. -38- 409850/1193 5. Dispersion according to one of claims 1 to 3, characterized in that the component (1) is a solid diglycidyl ether of bisphenol A. 6. Dispersion according to one of claims 1 to 3, characterized in that the component (1) is a is solid epoxy novolak resin. 7. Dispersion according to one of claims 1 to 3, characterized in that the component (1) is a solid epoxy resin of the formula: B ₁ C-CH-CH - -CHa-CH-CHa-OCQC- (MJHa-CH- ι ι "- OH OH CHa-CH-CHa 0-CHa ' is where each A is independently a divalent hydrocarbon group bit 1 to 6 carbon atoms, -S-, -S-S-, 0 0 0 NNN -S-, -S-, -C- or -0- means, each X is independently for Is hydrogen, an alkyl group with 1 to 6 carbon atoms, chlorine or bromine, each Q independently of the remainder a dibasic aliphatic or aromatic carboxylic acid or anhydride thereof which would be obtained by removing the hydroxyl groups therefrom is m one Has a value of 0 or 1 and η has such an average value -39- 409850/1193 has that the epoxy resin is a solid at 25 ° C and 1 atm. 8. Dispersion according to one of claims 1 to 3, characterized characterized in that component (1) is a solid water-insoluble alkylated urea-formaldehyde resin is. 9. Dispersion according to one of claims 1 to 3, characterized in that the component (1) is a solid water-insoluble alkylated melamine-formaldehyde resin is. 10. Dispersion according to one of claims 1 to 3, characterized in that the component (1) is a is solid, water-insoluble phenol-formaldehyde resin. 11. Hardenable masses free of organic solvents, characterized in that it uses the aqueous dispersion according to claim 1, wherein the component (1) is a solid epoxy resin containing dissolved therein a water-soluble epoxy curing agent. 12. Curable composition according to claim 11, characterized in that the epoxy resin curing agent is a dicyandiamide. 13. Water-dispersible solid substance, characterized in that it contains less than 10% by weight Contains water and that it has been obtained by removing water from the composition according to claim 1 or 4. 14. Process for the preparation of aqueous dispersions of soluble in organic solvents or by -40- 409850/1193 Preformed solid substances which can be made flowable, characterized in that one (1) a first in a high shear mixer Stream containing water and a suitable dispersant with a second stream being one Contains pre-formed solid substance which can be obtained by heating or dissolving in an organic solvent has been liquefied, mixed, (2) the resulting stream, the water, dispersant, organic solvent (if any) and the solid substance, and the second stream circulated through the high shear mixer until the concentration of the dispersed solid water-insoluble Substance reaches the desired value, and that one (3) separating the organic solvent, if present, therefrom, whereby an aqueous dispersion of the solid substance is formed, consisting essentially of an organic solvent free is. 15. The method according to claim 14, characterized in that there is a centrifugal pump as the mixing device is used and that the flow through the pump is in a direction opposite to that provided Direction of movement of the impeller of the pump is, and that the impeller in the intended direction turns. -41- 409850/1 193 16. Process for the preparation of aqueous dispersions of preformed, heat-flowable or solid substances soluble in organic solvents with an average particle size of less than 10 li, characterized in that one (1) a mixture containing water, a suitable dispersant and the solid substance contains, mixed at a temperature that a highly viscous homogeneous mixture is obtained, (2) hold the resulting highly viscous homogeneous mixture at such a temperature for 30 minutes to 12 hours and that one (3) slowly add water to the mixture until the desired one Solids content is obtained, whereby an aqueous dispersion of the solid substance is obtained will. 17. The method according to claim 16, characterized in that g e k e η η - πι _ shows that the temperature is 20 C below to 50 ⁰ C above the Durran softening point, the melting point or the heat distortion temperature. 18. The method according to claim 14 or 16, characterized ge ^ indicates that a solid epoxy resin, a solid epoxy resin curing agent or a mixture thereof is used as the solid substance. 409850/1193 Blank page