DE1669294A1 - Paints based on vinyl chloride-butyl maleate copolymers - Google Patents

Description

Dr. R. Koenigsberger DipKPh _V sRHo! Zbauer

Pot larwolves

Monks % Bräuhausstralje

se 3058

RHONE-POULENC S.A. β Paris »France

Paints based on vinyl chloride eutyl

röaleate copolymers

The present invention relates to paints on the Based on aqueous dispersions of vinyl chloride-butyl maleate copolymers «

Aqueous dispersions of vinyl polymers are in the art of paints for masonry because of their ease of use «their good behavior towards water and their strength on alkaline substrates under normal climatic conditions. The construction industry Now, however, needs paints with improved Elgensohaftentdie at the same time great stability to sunlight, very good resistance to liquids Water and a vapor permeability that avoid the

109832/1271

- 2 formation of dry blisters »naögliohfc, possess.

These coatings generally ought to have sufficient resistance to alkaline substrates Aisfimise the reaction evoked yersole punishment «inf directly on the turned-off cement or raw concrete »on the outside is located on the building, i.e. is exposed to the weather " as well as fresh! Qips can be applied · Bs is P also required that these paints in moist condition are abrasion resistant *

For this purpose it has already been proposed to use paints the basis of aqueous dispersions of Aory! polymeric »polyvinyl propionate or VinylaoetÄt-Mtylaaleat-Copolyiaeren see below. These compositions have valuable properties, but these are clearly not sufficient for the above to meet the specified requirements

"Ss new paints for masonry have now been found that have a combination of properties »which are sufficient * to meet the above requirements.

The paints according to the invention are additional sets, ■ except for the usual pigments, fillers and adjuvants an aqueous dispersion of vinyl chloride-butyl maleate copolymers contain "in which these copolymers" contain 45 to £ 0 by weight, preferably 50 to 57 percent by weight, butyl maleate and a reduced Viscosity, measured at 25 ° C for a solution with

109832/1271 "bad ORIGINAL

■■ - 3 - ■.

5 g / l in cyclohexanone «between 10 and 69 ml / g, preferably between 15 and 45 ml / g» and have a particle size in suspension below 5 μ / preferably below 2 μ ·

The vinyl chloride-butyl raleate copolymers in general are known Products for which a type of manufacture is described in French patent 814 093. .

These aqueous dispersions are prepared according to any known procedure, but it is more advantageous to work by copolymerizing the monomers in emulsion The process * which is carried out in an autoclave under autogenous pressure is generally carried out in the following way: The vinyl chloride and the eutyltnaleet are dissolved in water in the presence of an emulsifying agent, such as a wetting agent of the alkali alkylaryl sulfonate or alkali alkyl sulfate type, preferably together with a Protective colloid "such as hydroxyalkyl celluloses or polyvinyl alcohol" and a polymerisatlonalnitlator * such as potassium or ammonium persulfate. The emulsion is then polymerized by heating at a temperature of preferably about 60 ^° C «

An aqueous dispersion of copolymers is then obtained

one in general to a pH of 7 to 3 by adding

109832/1271

of, for example, ammonium carbonate. This neutralization can also be carried out during the polymerization stage.

For later use it is preferable that the aqueous Dispersion of the copolyraers up to 8% by weight, preferably between 4 and 6 wt .- #, based on the copolyraeren, of non-polymerized Contains butyl maleate. That amount of butyl maleate _ can be added after the polymerization »but you can Polymerization can also be carried out in such a way that the desired excess remains of free butyl maleate.

It is possible to use the selected amount of non-polymeric tertiary butyl maleate in whole or in part by the same amount of one Replace plasticizer for polyvinyl chloride. In this regard, one can use the alkyl phthalates, adipates, sebacates and phosphates as call it particularly advantageous.

The above-mentioned aqueous dispersions, which preferably contain about 30% by weight of vinylchlorld-butyl maleate copolymers, are used with various pigments and fillers, their use is known, added to obtain the desired paints.

Depending on the case, white pigments such as titanium oxide or lithopone, or organic or inorganic® colored pigments are used. As for the fillers © * the most commonly used calcium carbonate, dolomite ₉ barium sulphate

1Q-9832 / -1-271

fat, silicas »talc, kaolin or mica.

One advantage of the paints according to the invention is that that they contain a very considerable amount of pigments and Can introduce fillers, in the resulting film after drying the grus ate tall solner properties, such as For example, the abrasion resistance when wet, completely is retained. To express this due date, one determines

the ratio £, in which P is the weight of the pigments and fillers and L is the weight of the polymers. The concentration of the pigments in volumes or CPV can also be determined in the following way: i

CPV

^ Volume (pigments + fillers)

Volume (pigments + fillers} + volume of the polymer

ρ
The ratio τ of the paints according to the invention can reach values as considerable as 6: 1 and the CPV can be up to 70 # «

In addition to the pigments and fillers, various types of additives are also introduced, which are intended for the To give paints special properties. These additives are mainly ionic or non-ionic Wetting agents, dispersants, such as polyphosphates, thickeners, e.g. of the hydroxyethyl cellulose type, corrosion protection agents, such as sodium benzoate or nitrite, Preservatives against mold and bacteria, such as organic tin derivatives, or defoaming agents middle. The compositions according to the invention require each

109832/1271

However, the use of coalescing agents (solvents to promote the VerachweiSung of the particles) does not work.

To produce these paints, "an all" of the components of the composition, i.e. the aqueous dispersion of the Vinyl chloride-butyl aleate copolymers, pigments, fillers and mix the various additives directly.

However, one preferably works in the following ways: One brings in a mixer cd ^ r equipped with a turbine oil shear » the water and the anti-gelling, Mets-, Diapergier- and anti-show agents "then add the pigments and fillers while mixing and keep mixing until a homogeneous paste is obtained is. The dispersion is then added to this paste while mixing the copolymers as well as the anti-corrosive agents and preservatives.

The paints thus produced can be used directly or diluted with water before use. You let apply according to the usual methods »i.e. by painting, Roller application or spraying

The following examples illustrate the invention without restricting it.

In these examples, the films obtained after the application of the paint were then tested as defined below subjected to show the properties of the paints according to the invention.

1098312/1271

1869294

1. Resistance to alkaline substrates

The paint is applied with a brush in 2 layers on a plate made of Flbrozement. After more drying at about 20-25 ° C, this plate is immersed in water to which 5 dew .- $ sodium hydroxide is added in order to accelerate the decomposition process. To set the time period determined "until the paint is completely would be gone from the bottom * to the end"

This attempt at alkaline degradation is carried out under severe conditions carried out·

2. "Chalk ^{5 strength}

The chalking means the tendency of the pigments out of the dry Coating leakage under the effect of climatic influences · To measure this strength, the paint is applied Fibroceraeate plates, as described above, and put on Then these panels are exposed to climatic influences · After a period of time from one year it is determined ν whether the pigments have the tendency have to go off by rubbing

3 «Resistance to blistering in the presence of moisture , _____

A plasterboard is coated on all of its surfaces provided and dried for 3 weeks at 25 ° C ». The so produced

109832/1271

Test specimens are then half immersed in water for 2k hours, after making a notch at the bottom of each plate * to allow "the plaster of paris to soak up with water * After this period of time it is determined" whether the immersed veil of the plaque Has bubbles "

4 »Abrasion resistance when wet

Is in this test the paint) is tat-vinyl using a blade coater onto a rigid backing of VAnylaoe chlorrid Copolymer as applied "that a film of about 200 thickness is formed * After a drying time of 3 Woohen at 25 * C to test this Film for wet abrasion "by exposing it to the action of a brush made of nylon. The plate is constantly rinsed with water to which 0 * 2% by weight of a wetting agent has been added". The number of back and forth movements is determined after which the base is rubbed bare.

5 «permeability for water vapor

This attempt is made after the. French standard T 30 * 018 carried out. In this experiment, a container is used "which contains water and is sealed by a film of the paint to be tested." This container is placed in an extractable door that contains calcium chloride "and its weights are measured" decreases as a function Grams of water J «m ^£ substance J« day off »

109832 / 12-7t

1689294

The following examples explain the invention without it being described below restrict.

example 1

In a cylindrical vessel with a chamfer of 2 1, which is equipped with a turbine mixer »you bring them following components one

Water Λ7 # 5 β ™

niohtioniaohes fetsmittel »that from the Condensation of ethylene oxide "it" ifira aromatic radical originates from and from the Societe IQfOIiB-FOUSSlIC is put on the market {Handelana »·" Sourol C ") 2g

aqueous solution with 2 dew.-Jf Hjrdroxy-

Ethyl cellulose nite in viscosity

of 25,000 oP at 25 * C * that of the

Sooiete Heroulee Powder in the ribbon

is brought (trade name "üatrosol

250 HR ") 100 g

aqueous · solution «it to Q« w »-Jl MatriuohexajMtaphoephat 18 g

echauiaverhatendes agent based on i

of paraffin oils (trade name "Beva- ^

loid 67? " » which is marketed by Sooilte * Bevaloid) 2 g

The turbine is started. Then ax the following Powdered products bui

Titanium oxide (rutile) 200 g Talcum (grain size below

20 μ) 100 g

Caloiu carbonate 100 g Barluma sulfate * 5Ö g

109832/1271 _BAD

When the paste is homogeneous, add 560 g of an aqueous one Dispersion with 50 ow * - £ vinyl chloride-butylaaleate copolymers one, in which the copolymer 45 parts by weight of vinyl chloride each Contains 55 parts of butyl maleate and has a reduced viscosity of 22 ml / g · The size of the copolymer parts in suspension is less than 2 µ, and the dispersion contains 5% by weight, based on the copolymer, of unpolymerized butyl maleate.

P 0.5 g of bexabutyldistannoxane (C ₄ H ₉ J ₃ Sn - 0 - ao (C ₄ H ₉ J ₃ ) and

20 g of an aqueous solution old 20 % bat oil benzoate and continue to mix until a fineness of 5 to 6 is reached by Mossanzelger according to Horth.

The paint produced in this way has the following characteristics «

Density »1.48

Trooken extract contenti 63 %

* "Brookf Leid" viscosity, determined at 25 ⁹ C for a speed of 50 rpm of the body no. 4t 2800 oP

Ratio P / L · (as defined above) 2.5 t 1

Ratio CPV (as defined above) 54 Ji

The film obtained after applying the paint and drying at 15 ° C. is impermeable to liquid water and has the following properties »

109832/1271

1689294

- ti -

1. Resistance on alkaline carriers

This resistance is shown in the table below. In this table, for comparison purposes, are given the results "obtained with paints * which are generally believed to be" already remarkable Show resistance on alkaline carrier

Type of paint Tent span before disappearing
de? Color film Aqueous dispersion on the
Vinyl acetate-butyl base
maleate copolymer (70/50) 1 day Aqueous dispersion on the
Based on polyvinylpropio-
nat 7 days Aqueous dispersion on the
Based on polyalkylaeryla-
th 7 days Aqueous dispersion on the
Based on vinyl chloride-Bu-
tyl maleate copolymer, ge
according to the present case
game made No attack after 6
Months

These experiments show that. Clear superiority of paints based on vinyl chloride-butyl maleate copolymers according to the present invention »compared to alkaline Removal concerned ·.

109832/1271

- 12 2 «Resistance to chalk

After exposure to climatic influences, the paint in this example shows only a very faint chalk on «during this for a paint on the base of polyalkyl acrylates is very considerable.

3. Resistance to blistering in the presence of moisture __.

The immersed part of the plate has kerlne bubbles & uf _£ ,, while the same starting from a paint on the basis of a dispersion of. Polyvlny.1 propionate experiment carried out in a film gives _f is deteriorated by the presence of numerous bubbles.

Example 2

Mix according to the one in Bolispiej. 1, the specified work ψ following ingredients:

Wasuer 5.5 g

aqueous solution with 2 % "Natrosol 250 HiT

"Scurol C"

aqueous solutions with 10 % sodium hexa-phosphate

Shaumverhi? fcunßsraifctel "ßevaloi d 677 "

BAD O 109837/1271

IOC G 2 G 15th β 2 β

The following products are then added in powder form while stirring:

Titanium Oxide (Rutile) 235 g

Talc (grain size below 20 μ) 30 g Calcium carbonate 20 g

Finally, after homogenization, 570 g of an aqueous dispersion of vinyl chloride-butyl maleate copolymer which is identical to that of Example 1, as well as 0.5 g of hexabutyldistannoxane and 20 g of an aqueous solution containing 20 % sodium nitrite are added.

The paint thus obtained has the following physical properties:

Dry extract content: 57 %

Density: 1.29

"Broakfteld" - viscosity at 25 ^e C for

a speed of 50 rpm of the body No.

4: 2300 cps

P / L: 1/1

CPV: 25 %

This paint is practically impermeable to liquid water Coatings * which have a permeability for water vapor

of 155 g / m day. This number shows that even a A paint containing very little filler has sufficient permeability to prevent the formation of dry rushes.

109832M271

- 14 - Example 3

In a container with a capacity of 2 1, which with is equipped with a turbine mixer, the following ingredients are added while mixing:

Aqueous solution with 2 # "Natrosol 250 HR" 125 g aqueous solution with 10 % sodium hexameta-

phosphate 25 g

"Scurol C" 2.5 g

Hexabutyl distannoxane 0.5 g

aqueous solution with 20 % sodium benzoate 20 g

Water 90 g

The following products are then brought into powder form with mixing a:

Talc (grain size below 20 μ) 90 g

Titanium oxide (rutile) 30 g

Lithopone with 30 % zinc sulfide 350 g

Calcium carbonate 55 g

SohllesalAch you are concerned with mixing the following ingredients a:

Foam preservative "Bsvaloid 677" 2 g

aqueous dispersion of vinyl chloride-butyl maleate copolymers according to example 1 210 g

A paint is obtained which has the following physical properties Features:

109837/1771

63 * 1 , 61 3300 cP 5/1 65 *

Dry extract: density ί

"Brookfield" viscosity at 35 ^e C for a speed of 50 UiMn of the body no * 5 P / L:
CPV:

This paint «which has a significant content of fillers owns «is used to form a film» the ™ the abrasion test is carried out in a moist state. You then find out «that this film does not show any wear and tear Has 30,000 reciprocations. When you get the same Carries out an experiment with paints based on polyalkyl acrylates or vinyl acetate-butyl maleate copolymers, one observes that the pad moves: l 5G00 back and forth is rubbed bare.

It is also identical with the paint of this example paint with a vinyl chloride -Eutylmaleat-copolymer having a weight ratio of 60 '40 "that is outside the invention limits, here," of 15 g of butyl phthalate are added. To obtain a film-forming composition. After application as described in the aforementioned test, it is found that the color film has disappeared after 2CD back and forth passes.

Example 4

The procedure is as in Example 1 with 53.5 g of water and 348 g of one

109837/1271

an aqueous dispersion rait; 50 wt -. $ Vinyl chloride-butyl maleate copolymer * 50 wherein the introducing of a weight ratio of a reduced viscosity of 50 * j> 5 ml / g "in diti Dispersion 6 g Eutylphthalat. The partial double size of the copolymer in the suspension is below 2 _μ Ρ and the dispersion contains 2 Qew. ~ #, Based on copolymer "to nlchtpolymerlslertem butyl maleate.

The paint obtained has the properties of each nigen "dl" in Example 1 is described.

109832/1271

Claims (4)

Claims 1. Paints for masonry »characterized by a content of an aqueous dispersion of vinyl chloride-butyl maleate copolymers in which the copolymers contain 45 to 60 wt .- ^ butyl maleate» a reduced viscosity , measured at 25 ⁹ C for a solution of 5 g / l in cyclohexanone have between and 60 ml / g and have a particle size in suspension below 5 μ * as well as pigments, fillers and auxiliaries. 2. Coating materials according to claim 1 »characterized * that the vinyl chloride-butyl maleate copolymer contains 55 0ew .- # butyl maleate» a reduced viscosity »measured at 25 ⁶ C for a solution with 5 g / l in cyclohexanone ^ of 22 ml / g and has a particle size in suspension below 2 μ. 3. Coating materials according to claim 1 »characterized» that the vinyl chloride-butyl maleate copolymer contains 50 wt .- ^ butyl maleate »a reduced viscosity» measured at 25 ⁸ C for a solution with 5 g / l in cyclohexanone, of 35 ml / g and has a partial size in suspension below 2 μ. 4. Paints »obtained from paints according to any one of claims 1 to 3. 109832/127 '.