JPS5817162A - Aqueous polymer dispersion, manufacture, coating agent composition containing same and electrodeposition painting method - 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 relates to aqueous polymer dispersions suitable for use in coating compositions, processes for making aqueous polymer dispersions, and uses of coating dispersions in coating methods. It is known from British Patent No. 11E 1,51!5,723 to produce stable aqueous dispersions of thermoplastic polymer particles consisting of a mixture of at least 211 different large aggregates useful as pharmaceutical compositions. ing. The preparation of this dispersion involves dissolving a thermoplastic polymer such as nitrocellulose in at least III polymerizable monomers with low solubility in water and dissolving this solution in the presence of a surfactant. This is accomplished by dispersing in water and polymerizing the monomers to form a stable dispersion of polymer particles. The polymer obtained from the above monomer is substantially bulky and not significantly crosslinked. However, for the purpose of multi(), the substrate KI!!
It is desirable to use coating compositions that can be heat cured after coating. The above objectives include the use of metallic kTI & paints to obtain good corrosion resistance.

Currently, metals are coated with an undercoat paint by an electrodeposition coating method. One of the potential drawbacks of such a method is that the individual parts of the various materials contained in the composition are applied by rounding and electrodeposition to form the final coating with nine vk1+. The particles are deposited on the substrate in a proportion different from that present in the coating l1iIiL-, for example due to differences in electrical behavior. We have now demonstrated that for a special type of thermosetting Il coating, a useful thermosetting coating can be obtained if all the components are contained in the same particle. , also squirting snu+i
It has now been discovered that it can be formed by other AM methods, such as. Another advantage of using such particles is the dispersion of the co-reactive materials in the coating composition (as opposed to dispersions where the various co-reactive materials present as separate particles are deposited non-uniformly on the substrate). The components should be intimately interlocked, for example during subsequent heating operations.

Therefore, according to the present invention, the dispersed polymer particles are cationically, anionically or nonionically stabilized in an aqueous medium, and each of the polymer particles contains (a) a polymer having a reactive group; Coalescent modifier-) An addition polymer having a reactive group chemically similar to the reactive group in the above polymeric modifier, and (book) presence in (a) and (b) above. There is provided an aqueous polymer dispersion characterized in that the crosslinking agent also has complementary reactive groups to the reactive groups of the crosslinking agent.

The dispersions described above are cationically, anionically and nonionically stabilized particles, each of which has (:) a reactive group, a preformed, heavily modified particle. (-) One or more polymerizable α,/-ethylenically unsaturated monomers, at least one of which has reactive groups identical to and similar to the reactive groups in the polymeric modified network. Quantity:
and (to) a crosslinking agent having complementary reactive groups to the reactive groups in (+) and (-) above: producing a dispersion of particles in an aqueous medium;
At that time, the above-mentioned preformed large-sized coalescent modifier (1) is dissolved in the at I-ethylenically unsaturated monomer (-) and polymerized, and α,! - The ethylenically unsaturated monomer is preferably produced by in situ polymerization to form an addition polymer.

The polymerization is preferably carried out under conditions such that no significant mutual reaction between the (■) and (-) reactive groups occurs, for example at a temperature close to -ambient temperature. Under such conditions, grafting of the addition polymer onto the preformed polymeric modified network is not expected to occur much or even significantly, and the non-grafted components ( Preference is given to using a) and (b).

It can be manufactured from k.

According to Motogi@, furthermore, an aqueous coating composition containing a polymer dispersion, a coating method using the above coating composition, and an electrodeposition method in which the article is used as an electrode in an electric circuit 111jK A method of coating an article is provided.

A dispersion of cationically, anionically or non-ionically stabilized particles in an aqueous medium, in which the stability of the dispersed particles in an aqueous medium is substantially 1, each of the bacterial species of the component of the particles. 0 means that the cationic groups present in or associated with these components are previously anionic groups and the counterions of these groups are based on nonionic groups. Thus - for example, a separate cation, anion or non-ionic surfactant may be present in the dispersed particles or in association with the constituent before the dispersed particles; One or more of the components of the particle can have stabilizing groups present in it. Generally, one and the same cationic group is an anionic group and nine are the same nonionic groups. , the stability of the dispersed particles in the aqueous polymer dispersions of the invention as well as during the preferred method of manufacturing the polymer dispersions described, i.e. during the in situ polymerization of ethylenically unsaturated monomers. The intermediate particles will contribute to the stability of the dispersion.The stability of the dispersion should be determined primarily by the blindness of the 93 stabilizing groups mentioned above.The stability of the 2. Although chemical groups may be present in small amounts in the dispersed particles or may be associated with the dispersed particles - such groups do not play a vital role in stabilizing the dispersed particles.

Composition t containing cationically stabilized dispersed particles
- In one embodiment of the coating method of the present invention, the particles are electrodeposited onto an article as a cathode, which particles are stabilized in an aqueous medium of about 6' or less - cathode 0III! It is necessary to destabilize it under conditions of, for example -10-II. Therefore, the key to achieving satisfactory deposition at the cathode using the polymer dispersions of the present invention is that the stability of the monodispersion is enhanced by the presence of nonionic groups, such as the /v (ethylene oxide) group. It should be noted that it is necessary not to increase it excessively. The same applies when dispersions that are anionically stabilized and destabilized at about -4 are electrodeposited at about -70 poles.

Suitable ingredients, i.e. polymeric modifiers, addition polymers.
The polymer is derived from a variety of monomers which are polymerized in the preferred method of the invention described above to give an in situ formed addition polymer and the selection of the crosslinking agent is as follows. The effective film forming temperature required for the mixture of polymeric modifiers, addition polymers and crosslinking agents before crosslinking is carried out; properties of the crosslinked film,
For example, the hardness or flexibility; the presence of suitable complementary reactive groups to enable crosslinking; the conditions under which crosslinking should take place are the compatibility of the components.

Reactive groups that can be present in the polymeric modifier and addition polymer component include
human-xyl, as described in No. 463;
Azuno, Cal? Nakasil, alkoxymethyl, engineering f
Mention may be made of oxide, and, blocked or capped (Cspea) incyanate groups or β-hydroxy ester groups.

A starting combination of a reactive group and a complementary reactive group capable of cross-linking is used, for example, an Ipa* sil group and a methylol reactive therewith, methylol in alkyl, methane! - and a droxyester group; a human EldP syl group with a nixyl group, a car-xyl group reactive with this; and a hydroxyl group or a d7 electrogroup, and an isocyanate group reactive with this. Something will happen.

Generally, these groups, if present, will react under the conditions that produce a dispersion of polymeric particles from the desired components and the WAK polymerized to ethylenically unsaturated monomers by the method described above. Although 1 is preferred, this does not preclude the possibility that a small degree of useful crosslinking may occur if desired, eg under the addition conditions.

The term polymeric modifier 11#i, an essential property of the final crosslinked thermoset coating obtained from coated steel relatives by polymerization, usually contributes to the hardness of the resinous 11#i polymerization. means a polymer that has not been

Preferably, the polymeric modifier has a molecular weight of at least 4500, more preferably at least 4700, and contributes significantly to the desired chemical resistance of the coating. % Km suitable polymeric modifiers are human crossyl group-containing resins (e.g. those derived from evitalolhydrin and diphenylolzoro/mam) or their derivatives, such as The agent contains a hydroxyl group (although the IΦ group has already been reacted) and an I4
11? It is possible to obtain an engineered resin having the characteristic desired polymer structure of the resin. Other polymeric modifiers include, for example, alkyl resins and certain monoester-free addition polymers such as stele//adal alcohol copolymers. Reactive groups that may be present in these polymers and that are reactive with reactive groups contained in typical crosslinking agents include -hydroxyl, amino, -hydroxyl, amino, and carboxyl groups. . More than one polymeric modifier may be used.

Preferred polymeric modifiers for use in the above process are preferably completely soluble in the ethylenically unsaturated monomer, although it is usually preferred to combine the preformed polymer with
Because of the phase concentration with the polymerized and good monomers, the preformed large aggregates may not be completely dissolved into the monomers. Mixtures of polymeric properties may also be used, including those with nine modified polymers containing no reactive groups.

Suitable ethylenically unsaturated monomers containing reactive groups such as hydroxyl, ζ-do and carxyl groups include hydroxy-isoflovir methacrylate;
Hydroxyethyl arylate, and PC! *Diptyl acrylate, acrylic acrylate, etc. These monomers can be used to prepare the addition polymer component of the dispersed particles, and are highly active monomers for use in the method of the present invention. It is a quantity.

Examples of ethylenically unsaturated monomers that can be copolymerized with monomers containing reactive groups such as those mentioned above include methyl methalyl and ethyl acrylate.

Mention may be made of phthyl magelylate, ethyl acrylate, 2-ethylhexyl ataryl and styrene. These monomers have a maximum solubility in water of 25″ ac of 1
Preferably, the weight is 0.

When the dispersion of polymer particles is prepared by the method described above, the crosslinking agent is an ethylenically unsaturated monomer, taking into account that it should not give rise to a significant degree of crosslinking at the temperature of the polymerization process. The selection is made depending on the relationship between the polymerization initiator system and the polymerization initiator system.

Polymer particles t) mmK Suitable crosslinking agents for use include urea-9-melamine and pencidanone-formaldehyde resins and phenol-formaldehyde resins; polyfunctional inocyanates or blocked or sequestered incyanates. Incyanate; and Parapatent Application III 0040.8
Examples include β-hydroΦ diester-containing materials such as those described in the 6ff specification. In the above-mentioned method, it is preferable that the frame A steel is dissolved in the ethylenically unsaturated monomer together with the polymeric modifier.

In one aspect of the invention, the cationic stabilization of the dispersed particles substantially depends on the cationic groups contained in or associated with one or more of the components of the polymeric particles. It is based on In order to ionize the #1 radicals, additional components such as acids such as acetic acid or phosphoric acid may also be present in the dispersion. In some cases, cationic lows, i! The formation is based on the presence of conventional cationic surfactants such as lower alkyl salts of fatty acids, such as lower alkyl salts of fatty monomers, which engage the particles and provide a distinct surface active material.
I'm going to try it. Suitable examples of such salts include the acetate salts of tallow and oleyl fat. Some snow-discrete polymeric cationic surfactants contain basic nitrogen atoms, such as copolymers of acrylic WI2-ethyl/methyl methacrylate/hydroxyethyl methacrylate/dimetyl ethyl methacrylate. Addition copolymers may also be used.

Alternatively, at least a portion of the cationically stabilized Butterfly 1 modifier may be modified so that the modifier contains a cationic group that stabilizes or is responsible for stabilizing KIF4. For example, if the polymeric modifier is an epoxy resin containing oxide groups and hydroxyl groups, at least a portion, e.g.
In some cases, the basic group may be introduced by reacting with an azun containing up to 10 (l) oxide groups. A suitable amine is, for example, jetanolamine, but a wide range of other azuns may also be used. The basic groups are then ionized using an acid such as acetic acid or phosphoric acid.

Furthermore, at least some, preferably all, of the residual unreacted neoxid groups, e.g. to prevent such groups from reacting during storage of the dispersion! It is desirable to react with a skinning agent, such as phenol. Addition polymers may also contain stabilizing groups as described above.

It is advantageous for at least a portion of the polymeric properties to contain stabilizing groups because, when used in coating compositions, these groups are substantially present in the final crosslinked coating. This is because it disappears (bmry). This may not apply if the stabilization is provided in the final coating by separate monomeric or low molecular weight surfactants, which can cause lI in the final coating, for example under acidic conditions.

In another embodiment of the invention, the stability of the dispersed particles is based on anionic groups contained in or associated with one or more of the components of the particles. In some cases, wing-on stabilization involves the addition of a separate anionic surfactant associated with the particles, e.g. amines of fatty acids, such as oleic acid and stearic acid, and an alkali metal salt, preferably triethanolic acid. salt; delkylaryl sulfonate, e.g. F! r Decylpenzenesulfonic acid again d? ? ! 7-alcohol/ethyleneoxy-FII compounds; 9 is based on the presence of conventional anionic surfactants such as sodium sialyl sulfosatacinate;

It is highly preferred that the anionic stabilization of the dispersed particles is by a polymeric surfactant containing substantially one sil group in the carousel. In order to effect the ionization of the carxyl groups, it is also necessary to have additional components in the dispersion, for example a water-soluble amine such as a triethanol luer 7 before the inorganic base. Such surfactants include, for example, acrylic WR1, methacrylic acid, lower alkyl CC+~.) acrylates or methacrylates, such as methyl methacrylate, and detel acrylate (9 monomers selected from ethyl acrylate). Examples include copolymers and copolymers with styrene.

One suitable copolymer is a 20/4G/40 copolymer of acrylic acid/methyl methacrylate/acrylate. A typical example of a polymeric surfactant is maleated (m@t 1 ml d) f-tazine polymer. Aqueous dispersions may contain, for example, d2 to 20 weight bags of polymeric modified disintegrating agents of this type, based on the total weight of the dispersed particles. Hydroxyl group-containing monomers may be used.

The polymeric surfactant may be derived, at least in part, from a substance that also acts as a polymeric modifier component, e.g. may be included. When the polymeric modified I11 is, for example, a nixy resin containing a heptopoxyl group and a cyto group in the I! A portion of the oxide groups, e.g. 25 to 50 moss, may be reacted with rounding reagents known to those skilled in the art to introduce karyl groups. Residual unreacted I #P xyl groups in the Nixy resin as a polymeric modifier can be reduced to % for rounding the reaction of such groups during storage of the dispersion, for example! It is desirable to react with a skin type compound such as benzoic acid. Addition polymers may contain 4 stabilizing groups ◎As mentioned above, it is advantageous for at least a portion of the polymeric modifier to contain xyl stabilizing groups; the reason is that This is because Cal substantially disappears in the final crosslinked film produced by Xyl Group Co., Ltd. However, this also does not apply to 1-IIA, where the anionic stabilization is provided by a separate monomeric, previously low molecular weight anionic surfactant. In another embodiment of the invention, the stabilization of the dispersed particles is based on nonionic groups contained in or associated with one or more of the components of the particles. . The stability of the dispersion also requires the presence of additional components in the dispersion, which affect its method of use. In some cases, non-ionic stabilization involves the use of discrete non-ionic surfactants that are associated with the particles, such as condensates of ethylene oxide with chain fatty acids and alcohols, such as FXSS moles of ethylene oxide and oleic acid. Oleyl alcohol; t
or the presence of a conventional nonionic surfactant, such as a reaction product with bisphenol A; Addition copolymers containing 4 may be used.

Alternatively, non-ionic stabilization involves modifying at least a portion of the polymeric modifier, such that at least a portion of the polymeric modifier is free from stabilization or contributing to stabilization. It is possible to incorporate an ionic group from K. For example, if the polymeric modifier is a polyoxy resin containing dioxyde groups and (Maesha) and droxyl groups, at least some of the polyoxyde groups, e.g. can be reacted with. The residual unreacted nyxide groups may also contain stabilizing groups, which may be reacted with masking agents, e.g. phenol, to prevent reaction of such groups, e.g. during storage of the dispersion. - The dispersed polymer particles may contain a high proportion of polymeric modifier, for example up to 75% by weight based on a total of 88 minutes.

The dispersed polymer itself, or the aqueous medium in which it is dispersed, contains conventional ingredients, such as those used in coating compositions. Such ingredients include pigments,
Before the glidant is the fusion solvent (**al@a@1+ag
5olvent) ・Dispersed particles are 0-
05 to 5 mμ, more preferably 0.1 to 1μ OW*.

The stabilization of the dispersed particles is achieved by a separate cationic, anionic or nonionic surface-active substance, i.e. component (a) of the dispersed particles.
* If it is based on a surfactant distinct and qualitatively different from (b) and (e), the proportion of this surfactant may be, for example, between 2 and 10% by weight, based on the weight of the dispersed particles. I'll get more. Stabilization may be based on separate surfactants and stabilizing groups present in other components of the well-dispersed particles.

The proportions of polymeric modifiers, addition polymers and crosslinkers present in the dispersed particles can be varied within wide limits, depending, for example, on the desired properties of the final coating.

Typical proportions of these ingredients are 5 to 10 parts by weight polymeric shavings, 20 to 95 parts by weight addition polymer, and 5 to 40 parts by weight crosslinking agent, based on the total weight of these ingredients. .

The polymeric dispersions of this invention, optionally containing pigments and other ingredients, can be used in coating compositions applied by a variety of methods, such as by roller application. obtain.

Examples of arguments for the present invention are shown below. The @＞ and regrets that occur when animals are left behind are due to their weight.

The phlegm theory example is based on an aqueous polymer dispersion as shown below, i.e., when a large polymeric modifier is formed as a reactive group.
A resin containing an oxide group, a 7P group, and a sil group: The addition polymer has a reactive group that is chemically similar to the reactive group in the resin described above. -f toxymether group! The crosslinking agent is a urea-formaldehyde resin containing an alkylated methylol resin that is co-reactive with the hydroxyl group and the hydroxyl group and the 1-butoxymethyl group. and the preparation of cationically stabilized large aqueous polymeric dispersants in the presence of separate cationic surfactants and their electrodeposition at 1kllK
An example of the use of &.

Knee life resin with a roaring amount of 900 [i.e. 0 drops]
0 JF resin contains 1 g of oxide groups; commercially available as 0 Ebicoat P ('Σν!ni・t@-) 1004; 1 Epicoat is 11 Cm・ml・−
80 parts of Descendants of Al Company, 66 parts of methyl metatallylate, 44 parts of tutyl acrylate and 10 parts of 1
- Heat the monomeric mixture consisting of butoxymethylacrylamide to form a mixture. Add 22 parts of formaldehyde resin to this solution [9 beetles 0 ('B...ti@'
) UFR80: Iil type part 96;ls*tl@”
ld Cyamamlde company's descendant mark].

12 parts of Lua electric fluidized steel in alcohol [“Etmin” It
h@msam ” CI7 ' Kthom@em ”
12 parts of cationic surfactant [1 Dw@ ma@”〒；1IDIl@臘・“
was emulsified using a high shear stirrer in 460 parts of water containing C. Then, a solution consisting of 0.4 parts of ascoric acid and 40 parts of water was added to the emulsion solution obtained above, and 5N* was added in the presence of the above-mentioned redotus catalyst.
h Addition polymerization reaction (25-50 @ Ct) @ fllt) @ heat) was carried out.

The polymerization product was dialyzed to remove ionic species with less mtb and then seeded with water to obtain a solids dispersion of 15110 ml.
I.

A steel cathode (pretreated with zinc phosphate and in good condition) was immersed in the -60 diluted dispersion, and a current of 200 Il was applied between the cathode and the steel anode, which had also been immersed in the dispersion. Once passed, the composition of the dispersed particles deposited on the cathode should be the same as the composition of the dispersed particles in the original coating composition.

After cleaning the cathode and heating it at 11106C for 0.5 hours,
For example, coatings with good protection of metals were obtained in the Mu8TM salt spray test.

Lol m example 2 books! I! The koji example is an aqueous polymer dispersion as follows: A pre-formed polymer with a basicity that modifies the A/A-cyto groups and contributes to the stability of the dispersed particles in the aqueous phase. The cross-linking agent is a polymeric resin having a reactive hydroxyl group; the in situ addition polymer contains a reactive hydroxyl group; and the crosslinking agent is a co-reactive alkaline polymer. Thirteenth element containing methylated methylol group
The preparation and use of an aqueous polymer dispersion containing dtk maldehyde is illustrated.

(aj 3 g O@(Dxsl*shiresin(' Xk
'* -) '828), 164s of phenol and 26.5 parts of jetanolamine in 16 g -18
First prepare an adduct of engineered poxy resin by reacting for 2 hours at 0'C. After cooling the adduct to about 80"lcK, it was dissolved in a mixture consisting of 470 parts of methyl methacrylate, 314 parts of acrylic hydrazole, and 71 parts of hydroxyisopropyl methacrylate. 42 parts of N-formaldehyde resin (° Pitre” UFR80L + 211
Alkyl azun fluidization cutting (1 etine” Cl2) 1
A solution was obtained by mixing with 2 parts of tamene hydroperoxide and 2.1 parts of acetic acid. This solution was added to 200 parts of water with high shear stirring for 5 minutes and then an additional 30 parts of water.
An emulsion was obtained by adding 0 parts of water with high shear stirring.

A solution of 0.4 parts of ascorbic acid dissolved in 4.0 parts of water was added to this emulsion with gentle stirring.
Polymerization was carried out under exothermic conditions. Once cooled down, add another 20
0 parts of water was obtained and added to the product and subjected to dialysis,
A product with a solid content of 23 ml was obtained.

This product was diluted with 11 liters of 15% solids and deposited on a steel cathode pretreated with zinc phosphate for 2 minutes at 1°C.
A smooth, glossy coating with a thickness of 221 chrome was obtained.

(bl) The dispersion prepared above was colored, pretreated with zinc phosphate and coated on a round steel cathode in an electrodeposited amount!!! to obtain a coating showing good protective action against gold-11.

The coloring of the dispersion was achieved by replacing 42 parts of urea-formaldehyde resin with lupine prepared by the following method, i.e.
11,111 parts of urea-formaldehyde resin, 163 parts of urea-formaldehyde resin, 20.3,111 parts of titanium diIIide [0
Tlpure''' (= Tlpure ” R・90Q
Tlpwr@''' is a trademark of Tlpwr@'''] and 4 parts of black pigment [°Pkllblae''
The mixture obtained by diluting the mixture with KTM-formaldehyde resin with 194 ml of formaldehyde resin was prepared by using the prepared paste.

(c) The dispersion prepared in (a) was pretreated with zinc phosphate and applied by spraying onto a fine steel channel to obtain a smooth and glossy coating.

Example 3 This actual residue demonstrates the preparation and use of a non-ionically stabilized dispersion using a ester as the modifying polymer.

Part tamene hydropero Φshir O, 25 (B
) Deionized water 5.66 (
C) Deionized water 54.30
(2) Neointyldalicol, azobic acid, isophthalic acid, terephthalic acid and trimellitic anhydride (currency ratio 1.11:0・42:0.30:o,
o 5:0-11) and 9 liters polyester resin (
1) was mixed with a mixture of methyl methacrylate and acrylic acid K111m in a weight ratio of 1:I to obtain an 80.5-molecular solution.

The ingredients were mixed and heated to dissolve the stabilizer. Component 1 was added and the mixture was dispersed with component (QK) by rapid heating. The resulting emulsion was diluted with component 0 and aO was added and polymerized at a temperature slightly below ambient temperature 9. A white stable emulzolone is obtained as the final product; this emulzolone is sprayed onto a metal substrate.
It can be applied more easily than K, and a smooth and glossy film can be obtained.

Example 4 This example demonstrates the preparation and use of a non-ionically stabilized dispersion using a modified polymer and a synthetic resin.

-Epicoat "10G? (City J['s, sil group-containing resin) was dissolved in methyl methacrylate and butyl acrylate, and 55-1Epicoat 01009.
A solution containing 29 methyl methacrylate and 16 butyl acrylate was obtained.

The components of this engineering foxy/monomer solution 29-@KTle were then added: (a) 6.6 parts methyl methacrylate, 2.7 parts butyl acrylate, 2.1 lll hydroxypropyl methacrylate; , 0.4 parts of methacrylic acid, 4 parts of water-incurable urethane-formaldehyde resin ("UFR" go) and 0.7 parts of t-f-tyl perbenzoate) used in Example 3. 40 mole ethylene oxide nonionic surfactant.

The resulting liquid was added to 9.5 parts of deionized water under high speed stirring, and the resulting dispersion was diluted with 32.61 parts of deionized water to form small droplets of large diameter 15'mμ. Get a dispersion. A solution of 0.311 parts of ascorbic acid and 5.0 parts of deionized water was added to initiate the polymerization of the 0 dispersion, which was heated to give a white stable emulzolone as the final product, which was sprayed. It can be applied to the substrate depending on the condition.

Example 5 One bottle! The example demonstrates the preparation and use of non-ionically stabilized aqueous polymer dispersions stabilized with salts of long chain fatty acids.

5 equivalents of I oxide pre-reacted with 2 equivalents of benzoic acid
00 engineering 1111 (-epicote 21001) 4
0 parts to 30 parts of methyl methacrylate.

A monomer mixture consisting of +511 butyl acrylate and +51S human a-dimethyl methacrylate was heated to dissolve and 25 parts of pen 1. Zoguanine-formaldehyde resin (1 ml + 125 ml) was added in 2 m of cumenehydroyl, along with 7.5 parts of oleic acid and 4 parts of triethanolic acid. g for the whole
Emulsify in 200 ml of deionized water and dilute with 200 ml of deionized water.

5 parts of 0.6 parts of ascorbic acid and 0.3 parts of iron sulfate
A solution of 11 l of 0 parts of water was added to Emulzolone, and in the presence of the above redotus catalyst, the radical IIJml was added.
e-reaction: 2 s ~ s oac o @ IK threat. A stable aqueous dispersion of large, anionically stabilized particles is obtained which, when applied by spraying to a metal substrate, yields a smooth, glossy coating.

II! Koji Example 6 This example demonstrates the use of an anionically stabilized woody polymer dispersion of the present invention using a car-xyl group-containing addition copolymer as the stabilizer.

Poly/I411 cytoequivalent weight 500 poly/oxy resin (1 epi=r-, )-fool ) 4 G1 with cyto-groups protected in pxi by pre-reaction with 2 parts of benzoic acid
1 g was dissolved by heating in a monomer mixture consisting of 30 parts of methyl methacrylate, 15 parts of butyl acrylate and 15 parts of hydroxyethermethacrylate. 2
Copolymer (acrylic acid/methyl methacrylate/decyl acrylate) as a 50-part solution in 5 parts cumene hydroperoxide and butyl cellosolve After adding 20/40/30), the whole was emulsified in 10IIe of deionized water with 5 parts of triethanolamine. 9th grade! Lusolone was diluted with 20 parts deionized water.

Ascorbic acid of this emulsilon KO-6It is 0
．． 3 parts of 1 iron sulfur were dissolved in 50 parts of water, 9 drops were added and a radical initiated polymerization reaction was carried out in the presence of this Vyttas catalyst: exothermic to a temperature of 25-500C.

A stable aqueous dispersion of anionically stabilized particles is obtained, and this dispersion, after a suitable K11 solution, is
The cathode metal substrate KIlk cloth can be coated by electrocoating or the metal substrate can be applied by spraying @VC.

Example 7 This example demonstrates the preparation of an anionically stabilized aqueous polymer dispersion of the present invention using a single hydroxyl group-containing addition polymer as a stabilizer.

828.40 parts of commercially available die-4dP cyto, 1 Epicote, which had been modified, 33 parts of methyl metatalate, 2
It was dissolved in a monomer mixture consisting of 2 parts butyl acrylate and 5s hydroxyisozolol methacrylate. 20 parts of melamine-formaldehyde resin, 'Suimel' 1141.29 as a 50 weight solution in 1 part of cumene hydroperoxide and butyl cellosolve.
part of a surfactant copolymer (acrylic acid/methyl methacrylate/butyl acrylate/hydroxyisopropyl methacrylate 20/30/30/30), and then the whole was mixed with 16 parts of potassium hydroxide. Good emulsification in deionized water. 2'0 of this emulsion
Diluted with 0 parts deionized water.

Polymerization was initiated by adding to the above emulsion a solution of 0.6 parts of Asc, pinic acid and O-3 of sulfuric acid and 50 parts of deionized water.

A stable aqueous dispersion with a particle size of 0.2 g (Kron) was used to deposit a coating on the cathode in an electrocoating bath; It shows good corrosion resistance and there is no undercut (
No peeling (mmd@rvwttimg) or blistering occurred.

II Theory Example 8 The same method as in Example 5 was repeated except that oleic acid and triethanolamine were used (6 parts of dodecylbenzenesulfonic acid and 3 parts of triethanolazine). As in the case of run fI15, a stable surface dispersion of anionically stabilized polymer particles was obtained.

Continued from page 1 Priority claim ■July 6, 1981■United States (US)■2
80310 @ July 6, 1981 ■ United States (US) ■ 280311 @ July 6, 1981 ■ United States (US) ■ 280312 1- Akira August Louis Lucien Paruel United Kingdom Berkshire Slough Wex Ham・Road (No address or other indication) 0 Inventor Richard Paul Redman Ham Road, Berkshire Slough, Wex, United Kingdom (No address or other indication) (jf) Applicant Imperial Chemical Industries PLC UK Milbank Imperial Chemical House, Nis d'Afrille 1P3, London (no street address)

Claims (1)

[Scope of Claims] 1. Dispersed polymer particles are cationically, anionically or nonionically stabilized in an aqueous medium, and each of the polymer particles (a) has a reactive group; An aqueous polymer dispersion characterized in that it also contains a polymer additive and a crosslinking agent having complementary reactive groups to the reactive groups present in (a) and (b) above. body. 2. The reactive group and the complementary reactive group are a hydroxyl group, an azeta group, a calyl group, an alkoxy group, a methyl group9. qIi selected from I-oxides, groups, 1c1-blocked or blocked isocyanate groups and I-hydroxyester groups! Dispersion according to clause 1c. 8. Combinations of reactive groups and complementary reactive groups include k-crossyl groups and methylol groups; The combination of a group and -; and the droxyl group O9 is a combination of an azuno group and an isocyanate group -j? The dispersion according to claim 2, wherein the dispersion is selected from the group consisting of a hydroxyl group and a β-hydrocarbon diester group. 4. Claim 11, wherein the polymeric texturing agent is a hydroxyl-based polymer and a conductor thereof.
The dispersion according to any one of Items 1 to 3. Claims 1 to 3 include polyfunctional isocyanates and polyfunctional β- and droxyesters selected from b. 4. The dispersion according to any one of Item 4. 6. Stabilization of the polymer particles - carried out with a separate active agent of the conventional ms, as claimed in claim I! The dispersion according to any one of Items 1 to 6. ? Dispersion according to any one of claims 1 to 115, in which the stabilization of the polymer particles is carried out by at least a portion of the polymeric modifier which acts as a stabilizing group. 8. The cationic and anionic particles are nonionically stabilized particles, each of which has 0) a preformed polymeric modifier having a reactive group: (1) at least Reactivity similar to Oka-teFi and the reactive groups in the above-mentioned polymer from Company III! 1It-, +site is a further polymerizable a, β-ethylenically unsaturated monomer: and (to) a crosslinking having complementary reactive groups to the reactive groups above and in (1). producing a dispersion of particles in an aqueous medium comprising:
At that time, the above preformed polymeric modifier 0) was added to α
,! - The polymerization is carried out by dissolving it in an ethylenically unsaturated monomer (■), and the a, β-ethylenically unsaturated monomer is polymerized in situ to form an addition polymer. , the dispersed polymer particles are cationically, anionically or nonionically stabilized in an aqueous medium,
and each of the polymer particles (a) has a polymeric modifier having a reactive group (b)
Addition polymers having reactive groups that are chemically identical or similar to the reactive groups in the above polymeric modifier and (・) Complementary reactions to the reactive groups present in the above (- and 伽) A method for producing an aqueous polymer dispersion using a crosslinking agent having a functional group. 9. The dispersed polymer particles are cationically, anionically or non-ionically stabilized in an aqueous medium, and
Each of the polymer particles comprises (a) a polymeric modifier having reactive groups; -) an addition polymer having reactive groups chemically identical or similar to the reactive groups in the polymeric modifier; and (C) A coating composition containing an aqueous polymer dispersion comprising a crosslinking agent having complementary reactive groups to the reactive groups present in (a) and (b) above. . 10. The cathode article is the anode article (the dispersed polymer particles are cationically, anionically or non-ionically stabilized in an aqueous medium, and each of the polymer particles has (龜) reactivity. polymeric modifier having groups (b)
An addition polymer having a reactive group chemically the same as or similar to the reactive group in the above polymeric modifier and CI! 1 immersed in an aqueous polymer dispersion which may also be a cross-linking agent having a complementary reactive group to one reactive group present in (1) and (b) above, and the relationship between the material and the counter electrode. 11161M method by electrodeposition of cathode articles and anode articles, characterized in that they conduct electric current.