DE1209685B - Heat-curable coating agent in the form of aqueous, optionally pigmented emulsions - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Ο .:

C09d

German KL: 22 g -10/01

Number: 1209 685

File number: R25816IVc / 22g

Filing date: June 27, 1959

Opening day: January 27, 1966

The invention relates to coating agents in the form of aqueous, optionally pigmented dispersions, which are to be used for the production of thermoplastic or thermosetting coatings. the Coatings are resistant to ultraviolet light and have excellent mechanical properties Resistance. Permanent coatings are obtained in particular in connection with crosslinking resins. The dispersions are characterized in that they are better without loss of stability Pigments can be incorporated.

The coating compositions according to the invention contain an aqueous dispersion of a copolymer as a binder from a mixture of monoethylenically unsaturated, copolymerizable compounds. This mixture consists of 2 to 20 percent by weight of the 3-chloro-2-oxypropyl ester of acrylic or methacrylic acid, 25 to 54 weight percent ethyl acrylate and / or methyl acrylate and 40 to 73% at least of another ester of acrylic acid with an aliphatic alcohol containing 3 to 8 carbon atoms. Small amounts of up to 10 percent by weight of other neutral, monoethylenically unsaturated, copolymerizable ones Monomers such as acrylonitrile, vinyl acetate, styrene, vinyl toluene or methyl methacrylate, can be added.

The aqueous dispersions are preferably prepared in such a way that a mixture of mentioned monomers in the specified ratio with the aid of a polymerization initiator or catalyst emulsified with free radicals and copolymerized thereon. By using an anionic, nonionic or cationic emulsifier the emulsification and the polymerization can be supported. Such a means also serves to make the dispersion of the copolymer stable after the completion of the polymerization. Of the The proportion of the emulsifier can be between about 1 to 6%, based on the total weight of the monomers, lie. The proportion of initiator can be 0.1 to 3 percent by weight, based on the weight of the monomers, be. The molecular weight of the interpolymer can be between about 10,000 and several Millions, e.g. B. 5,000,000. The solids content of the dispersions can be 1 to 60 percent by weight be. However, preferred is the preparation of dispersions that contain about 30 to 50 percent by weight Contain resin solids.

The production of the copolymer is not the subject of the patent.

The copolymer dispersion obtained in this way can be directly, with or without dilution, heat-curable coating agent in the form
aqueous, optionally pigmented
Emulsions

Applicant:

Rohm & Haas Company, Philadelphia, Pa.

(V. St. A.)

Representative:

Dipl.-Chem. Dr. jur. W. Beil and A. Hoeppener,

Lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

Benjamin Berryl Kine, Levittown, Pa .;

John Kucsan, Philadelphia, Pa. (V. St. A.)

Claimed priority:

V. St. v. America July 3, 1958 (746 320) -

with water, for coating materials such as paper, leather, textiles and metals, which either untreated or pretreated with known commercially available primers. It can also be used for covering stones, cement, concrete, bricks, asbestos-cement shingles, Cinder blocks and other masonry surfaces that are usually exposed to moisture are used to achieve waterproof coatings. Such coatings serve to leach out to prevent calcium, magnesium, or other salts normally found in cementitious products are present and usually bloom, i. H. the formation of a white deformation or cause discoloration on wetting on the surface of the products.

In general, the aqueous dispersions of the copolymer can be used as a colorless composition be used that have a thin, light, glossy, transparent and very decorative coating deliver. If necessary, however, dyes, fillers or pigments can also be added, with the amount will vary depending on the particular purpose being pursued with the composition. To the water-insoluble pigments that can be used include e.g. B. Azo pigments and lacquers, Phthalocyanine pigments, tan dyes in their water-

509 780/407

3 4

insoluble form and inorganic pigments, such as diol, tris - (oxymethyl) - aminomethane, 2 - phenyl

Soot, iron oxides, chrome yellow, titanium dioxide and litho-2-amino-1-propanol, 2-methyl-2-amino-1-pentanol,

pone. Powdered or flocked metals, such as aluminum-2-amino-butanol, triethanolamine, 2-amino-2-ethyl-

minium, bronze, brass, chromium or gold, 1-butanol, also ammonium chloride, pyridine hydro-

also be included. If necessary, 5 chloride and benzyldimethylaminooxalate can also be used. The amine

Mixtures are used. The amount of salt salts are latent, water-soluble catalysts that contribute to

The pigment used can be essentially neutral between about 5 and 100 ordinary temperature,

percent by weight, based on the weight of the mixture, but which decompose into volatile constituents,

polymers, lie. of which the one at the elevated for burn-in

The dispersions can be used as a binder for the temperatures used and hardening, so fibers of non-woven fabrics and as backward on- that the catalyst, after it has exerted its accelerated coatings on various fabric-area effects, during the types of heating, e.g. B. dimpled fabric that results in carpets or the curing stage is automatically removed,
should be used. In addition to the other components, the aqueous

The dispersions are particularly suitable for producing a water-soluble thickener of pigment compositions to hold, such as gum tragacanth, water-soluble cellulose prints or dyeing textile fabrics. It gave ether, polyvinyl alcohol or partially saponified poly, that the foregoing for each vinyl acetate. The aqueous dispersions can be a Constituents of the mixed polymer specified men- contain weak alkali, z. B. Sodium Acetate, gene ratios when printing or dyeing 20 sodium carbonate, chalk, morpholine or ammonia, Textiles are very essential to be made in the end product if appropriate including a mixture a suitable combination of properties to water-soluble substances, which a conventional, achieve. The 3-chloro-2-oxypropyl ester must form the weakly alkaline buffering agent. That Acrylic or methacrylic acid in an amount of the proportions of the various components of the at least 2% of the copolymer can be used within a wide range of aqueous dispersions the to fluctuate in an appropriately insoluble and insoluble manner and appropriately fortified Resistant to light and resistance, so that the dispersions or pastes capable of successive exposure to light one for the application of a and to do washing. On the other hand, condass appropriate to speaking specific technique emerged the use of more than 20 percent by weight have 30 sistance.

this ester leads to unacceptable rigidity and brittleness due to the above-mentioned copolymer dispersions

of the coating, so that this aqueous coating agent can be given with normal formation.

application that includes repeated bending, possibly also by adding a small amount

borrowed can stay on the fabric. Preferably certain water soluble or self dispersible ones

no more than 12% of this ester is used, 35 urea formaldehyde, N, N '- ethylene urea

if flexibility is more important than stiffness, formaldehyde and aminotriazine-formaldehyde

is laying. It is essential that the higher acrylate be modified into densates. Penta-

which the alkyl group contains 3 to 8 carbon atoms, in the methylol or hexamethylolmelamine or a methy-

indicated amount is used in order to counteract the pentamethylol or hexamethylol melamine

to maintain resistance to ultraviolet light. 40 condensate produced by etherification with methyl alcohol

It is surprising and unexpected that these higher levels can be obtained. The aminotriazine

Acrylates of this mark more than the ethyl condensate is used in an amount of one seventh

improve acrylate. up to one third of the weight of the copolymer

For what purpose the polymer coatings of the invention are used. Preferably the aminotriazine

can be used in any case, you can 45 condensate in an amount of about 20 weight

always insoluble and thus made very durable percent, based on the mixed polymer, used,

by leaving them at atmospheric conditions for a longer period of time.

Shem pressure exposed to high temperatures, or obtained by the fact that the formaldehyde condensate

which one with the polymer coatings described in the aqueous dispersion of the copolymer

coated or impregnated objects to 50 dissolves. In addition, preferably in the aqueous

a temperature of 93 to 389 ° C or more some dispersion of the copolymer and the condensate

Seconds (at the higher temperature range) until an acidic catalyst is also dissolved,

one hour or more (at the lower temperature).

area) heated. Temperatures from 143 to 154 ° C curable coating or the impregnated additive

10 to 20 minutes will produce satisfactory compositions on any substrate

Results. applied or impregnated material dried,

A small proportion of the aqueous dispersion can be obtained by simply adding it to the air or temperature.

between about 0.1 and 2 percent by weight, based on temperatures of 60 to 82 ° C. Afterward

on the aqueous dispersion, an acidic catalyst, the coating is cured by adding a

contain to prevent the condensation of the coating, which is exposed to temperatures between about 116 to 390 ° C,

makes it insoluble and infusible, accelerating it for a time that reverses the temperature

At this point, "insoluble" does not just mean that is proportional. For example, the lower

Insolubility in water, but generally in organic temperature range, the time span between a

see solvents. Examples of the acid P / ₄ hour and a little over an hour, e.g. B.

catalyst are ammonium phosphate, ammonium 65 I ¹ Z ₄ hours, while they are in the upper part of the

thiocyanate, hydrogen chloride or other acid salts temperature range between 10 seconds and 5 mi

an oxyaliphatic amine, including 2-methyl grooves. A preferred middle range is for

2-amino-1-propanol, 2-methyl-2-amino-1,3-propane about 143 to 154 ° C for about 10 to 20 minutes.

This heating serves to make the coating insoluble and in organic liquids as well as in water also to make infusible. The upper temperature limit and the duration of the temperature exposure should be selected and adjusted to one another that the coated or impregnated object will not be decomposed or damaged in any other way.

The modified dispersions can include any of those mentioned in connection with the thermosetting coating Substrates are applied, such as wood, leather, paper, metals (untreated or primed), Textiles, masonry surfaces of the type mentioned and plastic surfaces that are used for the Do not deform or decompose when baking or hardening at the required temperature.

The dispersions can be applied to the substrates in any suitable manner, e.g. B. by Spraying, applying with a brush or roller, by dipping, by applying with a knife etc. The material applied too much can be squeezed out by a suitable squeezing process, e.g. B. between pressure rollers, can be removed by air squeezing or with a knife or doctor blade. Thereon the coating can be dried as indicated. Except for simple air drying it can be used for this purpose also heated air, e.g. B. in an oven or tunnel dryer, irradiation, e.g. B. by infrared lamps or electrical induction by either electromagnetic or electrostatic induction fields high frequency. If the coating, as mentioned, is baked or hardened, so can this by using suitable heating devices, such as infrared lamps or devices for Generation of electromagnetic or electrostatic induction of high frequency can be achieved.

Are the dispersions applied to substrates with reactive groups, such as cellulosic or proteinaceous Textiles or paper made from fibers, this is how the substrate takes on during the baking and curing process participate in the reaction, so that the copolymer (and the formaldehyde condensate, if present) and the substrate are chemically bonded, creating the exceptional adhesion, Durability and resistance to water and solvents when washing and cleaning, including those used in dry cleaning.

In the following examples, parts and percentages relate to weight, if not is particularly indicated otherwise.

example 1

At a temperature of 6O ⁰ C in the presence of 1% ammonium persulfate and 0.5% sodium hydrosulfite an aqueous dispersion of a -oxypropylmethacrylat Emulsionsmischpolymerisats of 10 parts of S-chloro ^, 50 parts of ethyl acrylate and 40 parts of n-butyl acrylate produced. From 5 percent by weight of this copolymer, 0.5% of a blue copper phthalocyanine pigment, 0.11% ammonia, 0.05% of an ethylene oxide condensate of t-octylphenol, which contains about 10 oxyethylene units, 0.075% sodium alginate and 0.20% hydrochloride of 2-methyl -2-aminopropanol-1 an aqueous dispersion is produced. Ammonium hydroxide is added to this in order to adjust the pH to about 8.5.
An 80 x 80 piece of cotton fabric was passed through the pigment dispersion and then through a pair of pressure rollers separating the excess mass. It was placed in a tenter and air dried for 5 minutes and then - yet

ίο located on the frame - hardened for 10 minutes at 150 ⁰ C. The fabric remained soft and pliable. It showed good resistance to washing and cleaning (tested by washing for 40 minutes in 0.1% strength sodium stearate at 82 ^° C. with spinning and then rinsing in water several times for 10 minutes); it proved to be resistant to dry cleaning using perchlorethylene; it practically did not wear out, and its resistance to washing remained essentially unaffected even after irradiation with ultraviolet light (this was checked by a so-called cyclic aging test in which the sample was irradiated with ultraviolet light in a fade-ometer for 50 hours and then already was subjected to the washing test described).

Example 2

The method of Example 2 is carried out using a copolymer of 10% 3-chloro-2-oxypropyl acrylate, 40% ethyl acrylate and 50% 2-ethylhexyl acrylate repeated. The one colored with pigment Fabric is similar to that of Example 2 and is characterized by being exceptionally soft and has good fabric properties.

Example 3

The method of Example 2 is carried out using a copolymer of 3% S-chloro-2-oxypropyl acrylate, 40% ethyl acrylate, 7% acrylonitrile and 50% n-butyl acrylate repeated. The one colored with pigment Fabric is similar to that of Example 2 and is characterized by being exceptionally soft and has good fabric properties.

Claims (2)

Patent claims: 1. Thermosetting coating agent in the form of aqueous, optionally pigmented dispersions, containing as a binder a water-insoluble linear copolymer of 2 to 20 percent by weight of the 3-chloro-2-oxypropyl ester of acrylic or methacrylic acid, 25 to 54 percent by weight Ethyl acrylate and / or methyl acrylate and 40 to 73% of at least one ester of acrylic acid with an aliphatic alcohol with 3 to 8 carbon atoms. 2. Coating agent according to claim 1, containing 0.1 to 2 percent by weight of an acidic catalyst. Considered publications:
German Auslegeschrift No. 1011548;
French patent specification No. 1105 357. 509 780/407 1.66 © Bundesdruckerei Berlin