DE1494499C3 - Coating composition based on a binder composed of a mixed polymer of an unsaturated carboxamide with at least one other polymerizable athylenically unsaturated monomer and an organopolysiloxane resin - Google Patents

Description

according to the coating compositions contained binders when used in pigmented, heat-curable Ability to chalk stoving enamels in the same color as the actual pigmented film. It is this surprising and unexpected property that makes these compositions special as exterior paints and as coatings for z. B. aluminum switches suitable. When used in this way, they have the advantage of chalking coatings on the one hand, such as z. B. Soil repellency, but do not have the bad appearance of conventional chalking coatings.

Another advantage of the compositions according to the invention is their improved heat resistance in comparison to coating compounds which only consist of unsaturated carboxamide copolymers.

The amide polymer component of the invention Masses can be made from any aldehyde-modified polymer of an unsaturated carboxamide exist; the aldehyde-modified one. Copolymer is preferably at least partially etherified. Aldehyde-modified amide polymers can be polymerized by an unsaturated Represent amide with at least one ethylenically unsaturated monomer and reaction of the polymerization product with an aldehyde. The Ver- etherification is achieved through further implementation of the aldehyde-modified Copolymer carried out with an alcohol. Another possibility is to aldehyde-modified copolymers by copolymerization of an aldehyde-modified amide, such as z. B. an alkylolamide, which is then etherified, or by using an N-alkoxyalkylamide.

In each case the aldehyde-modified one contains the etherified one Amide polymer Amide groups in which one hydrogen atom has been replaced by the following groups,

- CHOIR ₁

40

where R is hydrogen or an alkyl radical and R _{1 is} hydrogen or an organic radical.

Process for the preparation of N-alkoxyalkyl-substituted unsaturated carboxamides, such as. B. N-butoxymethylacrylamide, which are quite useful for the preparation of the amide polymers used here, are described in US Pat. No. 3,079,434. If these and similarly substituted unsaturated carboxamides are polymerized, the reaction product obtained contains the abovementioned structural group without further treatment. However, if the unsaturated carboxamide does not contain such a group, that is, if an unsubstituted amide is used, the resulting amide polymer should be reacted with an aldehyde, structures in which R ₁ denotes hydrogen by reacting the aldehyde with an amido hydrogen atom to form a hydroxyorgano group can be obtained. If the aldehyde-modified product is reacted further with an alcohol, which is preferred, the hydroxyorgano groups are etherified by the alcohol.

Although it is not critical to the usefulness of the compositions, at least some of the hydroxyofgano groups should these amide copolymers produced from unsubstituted or alkylolamides to be ethereal.

After the etherification, the amide polymer contains amido groups with one hydrogen atom through the group

- CHOIR ₁

where R is hydrogen if the aldehyde used is formaldehyde, or an alkyl radical if other aliphatic aldehydes are used. R ₁ is the radical which is obtained by removing a hydroxyl group from the etherifying alcohol, ie an organic radical. The radical R ₁ in the non-etherified groups is hydrogen. R ₁ in the etherified groups can e.g. B. alkyl or aryl. The terms used here should be interpreted broadly; the groups represented by R ₁ may contain other substituents and functional groups which do not affect the properties of the product. R ₁ can e.g. B. unsaturated bonds, ether bonds, halogen and other substituents or it can be cyclic.

In some cases, satisfactory products can be etherified with no or only a very small proportion Organic hydroxy groups, in some cases 5% or less. Usually, however, should at least about 50% of the hydroxyorgano groups are etherified, since many masses with less than about 50% etherified groups tend to be less persistent and to gel. Butanol is used for etherification is preferred, but any other monohydric alcohol, such as z. B. methanol, Ethanol, propanol, pentanol, octanol, decanol, and other alkanols with up to about 20 or more carbon atoms can be used, as well as aromatic alcohols, such as. B. benzyl alcohol or cyclic Alcohols such as B. cyclohexanol; or the monoethers of. Glycols or diglycols; or substituted Alcohols such as B. 3-chloropropanol.

Acrylamide or methacrylamide are preferred in the production of the copolymer component, however, any other unsaturated carboxamide can also be used. Such others Amides are itaconic acid diamide, a-ethyl acrylamide, Crotonamide, fumaric acid amide, maleic acid diamide and other amides of a, /? - ethylenically unsaturated Carboxylic acids with up to about 10 carbon atoms. Maleic acid carbamide and its esters and imide derivatives such as B. N-carbamyl maleimide can also be used.

To prepare the amide polymer is at least one other unsaturated monomer with the unsaturated carboxamide copolymerized; any polymerizable ethylenically unsaturated monomer can be used for this. Such monomers are monoolefinic and diolefinic Hydrocarbons, halogenated monoolefinic and diolefinic hydrocarbons, unsaturated esters of organic and inorganic acids, esters of unsaturated acids, nitriles, unsaturated acids and the like. The copolymers described in US Pat. No. 3,037,963 are excellent examples of the type of amide polymers preferred in the present invention, and those described therein Compounds are examples of the numerous monomers that will copolymerize with the amide leave.

Preferably, about 2 to 50 percent by weight of the unsaturated carboxamide content should be used in the amide polymer and the remainder are derived from the other ethylenically unsaturated monomers.

The amide and the other or the others are best used to prepare the amide polymer Monomers with a common catalyst and a chain modifying agent (if any is used) mixed in the solvent and the resulting solution heated under the reflux condenser for sufficient time to achieve the desired conversion achieve. Usually the polymerization is complete in about 1 to 16 hours. It is often useful to add the catalyst in batches as the polymerization proceeds, and because of the very high Reaction rate and the highly exothermic nature of the reaction is good agitation and careful Temperature regulation required.

To achieve the desired structures, the carboxamide with an aldehyde is preferably in the presence of an alcohol. Formaldehyde in aqueous solution (formalin) or in an alkane pl such. B. butanol, or a formaldehyde-supplying substance, such as. B. paraformaldehyde, Tiioxymethylene or hexamethylene tetramine are preferred. However, other aldehydes can also be used, such as B. acetaldehyde, butyraldehyde and furfural, preferably those containing only carbon, hydrogen and containing oxygen can be used. Usually a ratio of about two will be used Equivalents of aldehyde are preferred for each amide group of the copolymer, but this ratio can may be considerably increased or decreased. For example, the ratio can 3.0 equivalents or only about 0.2 equivalent of aldehyde per amide group in the copolymer.

The reaction is preferably carried out in such a way that the aldehyde and the polymer are present in the presence a mild acidic catalyst, such as. B. maleic anhydride, heated at the reflux condenser. Other acidic catalysts, such as. B. oxalic acid, hydrochloric acid or sulfuric acid can also be used, however, gelation can occur if the catalyst is too acidic. The amount of catalyst used can vary widely; the more acidic the reaction medium, the greater the scope of the ensuing etherification.

As already mentioned above, similar polymeric substances can also be made by polymerizing one modified amides, such as. B. achieve an alkylolamide or an N-alkoxyalkylamide. The polymerization of an alkylolamide or an N-alkoxyalkylamide is used in essentially the same manner as the copolymerization of the unmodified amide carried out.

In addition to the amide polymer described above, the other essential component is that of the invention Binder an organopolysiloxane resin. Such organosiloxane resins are well known to those skilled in the art, and those used in the present invention conform to the general formula:

R "Si (OR ') mO ₄ _" - _m

where R denotes a monovalent organic radical which is bonded to silicon by a carbon-silicon bond, and R 'denotes hydrogen, an alkyl radical, an aryl radical or an acyl radical. The value of η in the above formula is between about 0.5 and 1.9 and the value of m between 0.01 and 2.5; the value of m + η must be between 0.51 and 3.

The substituents represented by R in the above formula are e.g. B. monovalent hydrocarbon radicals, such as B. methyl, ethyl, propyl, hexyloctadecyl and similar alkyl radicals, monovalent

ίο cycloaliphatic radicals, such as. B. cyclohexyl, cyclobutyl, cyclopentyl radicals; Aryl radicals including alkaryl and aralkyl, e.g. B. phenyl, methylphenyl, benzyl ¹ , phenylethyl radicals; Alkenyl, e.g. B. vinyl, allyl, 3-butenyl, oleyl and linoleyl radicals; Cycloalkenyl radicals, such as ζ. B. Cyclopentadienyl and 2-cyclobutenyl radicals; and alkenylaryl groups, such as ζ. Β. the vinylphenyl radical. R can also be a substituted hydrocarbon radical, e.g. B. a halogen-substituted organic radical, such as. B. pentachlorophenyl, l-bromo-3-trifiourpropyl, and perfluoroalkyl radicals, e.g. B. y-Trifluorpropyl, δ-Trifiuor-y-difluorobutyl, or it can be an amino-substituted hydrocarbon , Γ group of substances, such as. B. an aminomethyl, 3-amino- * propyl or 4-aminobutyl radical. Other substituted hydrocarbon radicals which are within the range of the substituent R are cyano-substituted hydrocarbon radicals such as e.g. B. a 3-cyanopropyl radical, carboxyl-substituted radicals, such as. B. 3-carboxylpropyl radical and sulfur-substituted radicals including

Hch 3-mercaptopropyl, ethylthioethyl, ethyldithiopropyl, Äthylsulfinylpropyl, Äthylsulfonylpropylreste and hydroxy-substituted radicals, such as. B. Hydroxypropyl or hydroxybutyl radicals. Close the groups represented by R ' Hydrogen, where the OR 'group is a hydroxyl radical, and alkyl groups with 1 to 20 carbon atoms, such as B. methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl and octyl groups. R 'can also an aryl radical, such as. B a phenyl, toluyl or a halogen or other substituted phenyl radical or an acyl radical, such as. B. acetyl, propionyl, butyryl or other similar acyl radical with in general

Be 1 to 8 carbon atoms.

The organosiloxane resins used in the present invention can be prepared by conventional methods produce; often an organoxysiloxane is partially hydrolyzed with some of the alkoxy substituents be replaced by hydroxyl groups, and the hydrolyzate is used to achieve the desired Condensed siloxane resin. If the hydrolyzate is not fully condensed, residual Remaining OH groups. The organosiloxane resin can also be made using an organosilicon halide be manufactured as an intermediate product.

These methods are well known, as are the utility of the organosiloxane resins of the above Formula in the coating compositions according to the invention does not depend on the method by which they are made.

Examples of organosiloxane resins and processes for their preparation can be found in various publications as well as in patents such. See, for example, U.S. Patents 2,258,218; 2,258,219;

2,258,222; 2,371,050; 2,389,477; 2,584,341; 2,663,694; 2,746,942; 2 768 149 and 3 015 637.

Of the organosiloxane resins, those commercially available are preferred, which are usually phenyl and / or contain methyl substituents.

7 8

The compositions of the present invention may also contain various types of alkyd resin as described above, either as a constituent using any of the above, in addition to the other resinous materials, or as organopolysiloxane resins. For example, a simultaneous reaction product of the organosiloxane can be the so-called intermediate siloxane resins, which are resin, ie an organosiloxane-modified alkyd resin. The alkyd resin can be any saturated or borrowed for the production of siloxane-modified alkyd-unsaturated, oil-modified or non-oil-modified resins, by incorporation into the decorated alkyd resin, as used for coatings or in amide polymer the alkyd resin in these and it can use any polybasic coating compositions. However, they can also be used in acid or a polyfunctional alcohol prepared in cold mixed masses. For example, the polyfunctional alkyd, which the components can simply be tional acids at room temperature, such as. B. phthalic acid, maleic acid, can be mixed. Since these are relatively low in fumaric acid, isophthalic acid, succinic acid, adipic-condensed types of siloxane resins, usually acid, azelaic acid, sebacic acid, linoleic acid or cheaper than the more strongly condensed resins, ethylhexanecarboxylic acid, as well as anhydrides of these 15 result when using these organopoly- Acids. The polyfunctional alcohol siloxane types in the various types of the above can e.g. B. glycerol, trimethyloethane, pentaerythritol, said coating compounds cost advantages.
Sorbitol, mannitol, ethylene glycol, diethylene glycol or, in addition to the essential ingredients described, be 2,3-butylene glycol. In general, other substances, modified alkyd resins, can also be used in the coating composition. 20 in particular epoxy resins, such as. B. Polyglycidyl ether Among the oils which the alkyd for the invention of polyvalent compounds, epoxidized poly

- ^ j may modify according to use, include the olefin and epoxidized aromatic compounds,

drying, semi-drying and non-drying can be added. The mass can also, for. B.

Oils, including soybean oil, perilla oil, tung oil, oiticica oil, phenol-formaldehyde condensation products or other

Saffron oil, poppy seed oil, sunflower oil, coconut 25 phenolic resins, aminaldehyde resins, such as. B. Form

nut oil, babassu oil, tallow oil, walnut oil, fish oils and aldehyde condensates of melamine or ^: urea,

similar oils. The alkyd resin should preferably contain some nitrocellulose and similar resinous materials.

Retain functions, e.g. unreacted hy- In addition, the binding agent or the over-

droxyl groups. . tensile mass, if necessary, additives that are usually in

The alkyd resin can be used with any of the known 30 coatings, e.g. plasticizers,

Manufacture processes that are added to the manufacture of alkyds antifoam and anti-skinning agents.

> find application for use in coatings. The masses described can be used as such If the siloxane resin is to be used in conjunction with the alkyd component, the alkyd will usually be found, but usually as a binder in bulk Process prepared, with the exception that one 35 uses to which a pigment has been added, the organosiloxane resin is derived from the reaction mixture Any conventional pigment can be used, neither some time after the start of the implementation or such. B. titanium dioxide, carbon black, talc, barytes, zinc butters before heating the mixture together with sulfate, strontium chromate, barium chromate, ferric iron added to other constituents of the alkyd. oxide and other color pigments, such as B. cadmium, The quantitative ratio of the constituents of the mass is 40 yellow, cadmium red, phthaloxyanine blue, and chrome yellow not particularly critical. It has been found that toluidine red or hydrated iron oxide. The already only 1 percent by weight of organopolysiloxane resin firing varnishes or coating compounds are thereby produced

l \ for the formation of binders with advantageous in-house produced that one the binder and the pigments

ψ stocks leads. For economic reasons, it is mixed with one another by known methods.

usually undesirable, more than about 40 weight percentages will add the invention percentages of siloxane resin in normal use. In the usual conventional coating compositions on the coating compositions according to the invention to be coated, the objects contain z. For example, between 1 and 40% organopoly process is applied by spraying or similar customary binders and an alkyd resin is then added to the composition to form a siloxane resin. hard, sticky film. The firing, so it is usually used in an amount of 50 temperatures, 150 ° C for 30 minutes to about 5 to 40 percent by weight. The rest of 26O ⁰ C for 1 minute.

Part of the binder consists of the amide polymer, the following examples serve to further develop

that therefore in an amount of about 20 to 99 clarifications of the invention,
weight percentage is present. .

The binders according to the invention can be 55 Example 1
by first preparing the amide polymer, the organopolysiloxane resin and the alkyd A reaction vessel was made with the following resin, if one is used. These parts are sent:
Ingredients can then be parts by weight at room temperature

mix to form the binder. The siloxane-60 acrylamide .. 75.0

Resin and the amide resin can optionally be added to methacrylic acid 37.5

are implemented together; Similarly, styrene 412.5

the alkyd resin and the siloxane resin before their incorporation Ethylacrylat 975.0

leibung can be implemented together in the mass. Cumene hydroperoxide 15.0

Usually a solvent or mixture 65 t-dodecyl mercaptan 15.0

of solvents used to prevent the mixing of the high-boiling aromatic solution

to facilitate resinous substances. medium 375.0

Surprisingly, the masses of n-butanol 375.0

The mixture was refluxed for 8 hours at 109 to 125 ° C., a further 7.5 parts of cumene hydroperoxide being added after the 2nd, 4th and 6th hour. Then 500 parts of a phenyl substituted siloxane intermediate resin was added; this resin had an average molecular weight of about 1,600 with an average of about four hydroxyl groups per molecule. Together with the siloxane resin 157.5 parts of a 40 ° / ₀ solution of formaldehyde in butanol, 2.0 parts of maleic anhydride, 7.5 parts of cumene hydroperoxide and 250 parts of a high boiling aromatic solvent was added. This mixture was refluxed for 3 hours while azeotropically removing water. After cooling, 125 parts of butanol and 875 parts of a high-boiling aromatic solvent were added. The resulting product had a solids content of 49.9 ° / _0, an acid value of 7.89, and its Gardner-Holdt viscosity was P to Q.

B e i s ρ i e 1 2

An aldehyde-modified, etherified amide polymer was prepared in the same way as in Example 1 except that no organopolysiloxane resin was added. The amide polymer had a solids content of 50% in a solvent mixture of 29% butanol and 71% of one high-boiling aromatic solvent. A number of binders have been made by that parts of this amide polymer at room temperature with that used in Example 1 Siloxane intermediate resin mixed, with the proportion of the siloxane resin up to 50 percent by weight, based on the resin solids, varied.

B e i s ρ i e 1 3

a) Preparation of the amide polymer A A reaction vessel was charged with the following:

Parts by weight

Acrylamide 10

Styrene 25

Ethyl acrylate ■. 65

n-butanol 50

High boiling aromatic solvent 50

Cumene hydroperoxide 1

t-dodecyl mercaptan 1

The mixture was refluxed for 4 hours, ₂ parts of cumene hydroperoxide being added after 2 hours and again after 4 hours. The reflux condenser continued

Continued for 2 hours, then ¹ liter of ₂ parts of cumene hydroperoxide, 0.27 part of maleic anhydride and 21 parts of a 40% strength solution of formaldehyde in butanol were added. This. Mixture was then

Heated at the reflux condenser for 3 hours and at the same time water was removed azeotropically. Thereafter, 5.5 parts of an epoxy resin consisting of the reaction product of bisphenol A and epichlorohydrin having an epoxy equivalent of 600 to 700 and 5.5 parts of a high-boiling aromatic solvent were added. After half an hour of refluxing and cooling, the solution (50% solids) had a Gardner-Holdt viscosity of U to V.

b) Preparation of the amide polymer B

Using the procedure used to make Amide Polymer A, a Polymer made from the following components:

Parts by weight

Acrylamide 15.0

Methacrylic acid 2.5

Styrene 38.5

Ethyl acrylate 34.0

Cumene hydroperoxide 3.5

Partial dodecyl mercaptan 1.5

n-butanol 50.0

High-boiling aromatic solution

medium 61.1

Butyl-Formcel 31.5

Epoxy resin 11.1

Maleic anhydride 0.4

The 50% solids solution obtained had a Gardner-Holdt viscosity of U to V and an acid number of 6 to 8.

c) Preparation of the binder

A binder was produced by mixing the above-mentioned amide polymers Room temperature with an organosiloxane resin addition of mono- and di-substituted methylsiloxane units and phenylsiloxane units, in which the OR 'groups according to the general formula are hydroxyl groups goods, in the following proportions:

percent

Amide polymer A 73

Amide polymer B 9

Siloxane resin 15

Epoxidized Soybean Oil Softener 3

Example 4

Another binder was made in the same manner as in Example 3 but using another organosiloxane resin and other proportions. The organosiloxane was a highly condensed additive resin and contained both methyl and phenyl groups in which the OR 'groups of the general formula were hydroxyl groups. The individual components were in the following proportions are used:

percent

Amide polymer A 66

Amide polymer B 8

Organosiloxane 25

Plasticizers. .. ·. 1

Example5

a) Production of siloxane alkyd modified resin A reaction vessel was charged with the following:

Parts by weight

2-ethylhexanecarboxylic acid 117.0

Trimethylol ethane 157.0

p-tertiary butylbenzoic acid 11.7

Isophthalic acid 164.7

Silicone antifoam agent 7.0

Xylene, 15.9.

11 12

The mixture was slowly heated to 235 ° C. and trimethylolpropane and 90 parts of xylene were added. The

'kept at 235 to 238 ° C until the Gardner reaction mixture was then at 227 ° C on the back

Holdt viscosity of a 50% solids solution heated in 'fiußkühler until the Gardner-Holdt viscosity

a high-boiling aromatic naphtha Lo-Z3 to Z4 when the concentration of the health agent was U to V. To 231 parts of this 5 mix by means of a high-boiling aromatic

Wise prepared alkyd resin (50% solids) solvent has been reduced to 60% solids,

346.6 parts of naphtha were added and the acid number on solids was 9.

Mixture was heated to 93 ° C. Then the above-mentioned alkyd resin (2010 parts, 60%

346.6 parts of the low molecular weight phenyl-substituted solids) was ^{heated to 93 0} C, and 1206 parts of the siloxane intermediate resin of Example 1 was added, and io phenyl-substituted siloxane resin with low mol

the mixture was heated with stirring to 216 ⁰ C, kulargewicht of Example 1 were added. This

until the Gardher-Holdt viscosity at 25.6 ⁰ C U to V mixture was heated to'177 ⁰ C and _{IV for 2 hours}

fraud. at the same time slightly flushed with inert gas. After

b) Production of the binder, ^an _u ^er sufficient amount of a high-boiling additive

i5 aromatic solvent to reduce the

A binder was made by mixing the following solids content to 60% if the resin had a Gardner ingredient at room temperature. Holdt viscosity from W to X and an acid number of

7 on a solids basis.

. The binding agents produced in the above examples

Amide polymer A ... 75 _{20 miUe} , _{were used for the} production of coating compounds

_{prepared as} described above using various conventional pigments

tes siloxane-modified alkyd 20 is used. A typical pigment composition

■ U Polyester-We.chmacher 5 _{was produced in the following way: One}

Ball mill was made with 248 parts of rutile titanium dioxide,

Examples 25 14 parts of anatase titanium dioxide with low oil removal

sorption, 22 parts synthetic hydrated calci-

Another binder was made by the method of silicate, 2 parts of dimethyldioctadecylammonium Example 5 prepared according to the following recipe Bentonite, 112 parts of amide polymer A, 25 parts represents: isophorone and 97 parts of a high-boiling aro-

^Percent 30 matic solvent charged. This mixture

Amide polymer A 60 was given a fineness of 4 ¹ /, according to Hegman

Siloxane-modified alkyd resin from additional grinders, and 112 parts of amide polymer A,

game 5 a) 33 2 parts of a connection preventing settling

Plasticizer 7 _and 95 parts of talc added. This mixture was

35 ground for a further 4 hours, the pigment

Example 7 composition had a solids content of 59%

Coating masses from the

a) Production of a siloxane-modified alkyd resin play binders described and the above

pigment compositions mentioned were on

An alkyd resin was applied from 2-ethylhexanecarboxylic acid, ₄₀ steel plates and using

Burned trimethylolethane, p-tertiary butylbenzoic acid and other processes. It has been found that they

Isophthalic acid produced. A mixture of 634 parts after exposure to the weather for 6 months and longer

- a 50% solids solution of the alkyd and had been exposed to improved gloss and

jai 136 parts of naphtha was heated to 93 ° C, after which it showed discoloration resistance compared with similar ones

were 136 parts of the phenyl-substituted siloxane ₄₅ compositions that contain no siloxane resins. One

The low molecular weight resin of Example 1 also showed significant improvement in the

added. This mixture was stirred for resistance to chalk and also tended

163 ⁰ C heated until the viscosity was U to V. the siloxane-modified materials for comparison

b) Production of the binder ^{to the} modified compositions in the original

50 color to chalk.

A binder was made by mixing the following
Components produced: comparative example

^Percent To prove the technical progress of the

Amide polymer A 47.5 coating compositions according to the invention composed of an amide

in accordance with the above description and a specific copolymer

siloxane-modified alkyd .. 47.5 lying. Application described alkoxysubsti-

Plasticizer 5.0 compared organopolysiloxane to coating mats

Sen, using a US patent

In game 8 writing 2 258 220 described alkylpolysiloxane

60 had been made, became the following

Another siloxane-modified alkyd resin carried out for comparison tests.

Use in binders of the above-described By the procedure of Example 1 of

Art was made in the following way: present specification became resinous

A mixture of 1020 parts of coconut oil, 150 parts of binder produced, where for "binder A" len pentaerythritol and 78 parts of trimethylolpropane 65 was the organopoly described in the example mentioned Heated to 199 ° C until alcoholysis is completely siloxane and an alkylpolysiloxane for “Binder B” was coming. Then 1176 parts of phthalic acid were added according to the aforementioned United States patent anhydride, 76 parts of p-tertiary butylbenzoic acid, 651 parts was used.

The alkylpolysiloxane contained amyl groups and had the following properties:

Resin solids content 100 ° / ₀

specific density (25 ⁰ C) ... 1.06 to 1.08
Viscosity .., 1200 to 2000 cSt

Binder A was used to prepare a blue one Gloss paint, as is customary for covering building boards, is used. There was also a second Paint produced with the same composition, but with binder A instead of binder B has been used. Each color was applied to aluminum plates with a dry film thickness of about 23μ applied and hardened at a metal temperature of 232 ° C.

The coating made with Binder A was hard and shiny and looked excellent. The coating made with Binder B was very soft (too soft to be for any use to be sold) and had only a mediocre gloss. Besides, he saw badly and fades due to the prevention of color development caused by the alkylsiloxane.

The coating made with Binder also had poor durability as indicated by loss of gloss during the accelerated weathering test.
The coatings had the following properties:

coating Hardness*) beginning Shine**)
End***) loss 10 Binder A
Binder B HB
fewer
than 4 B 87
71 49
27 42%
63%

*) Pencil hardness, using Eagle Turquoise pencils with increasing hardness from 4B to 3B, 2B, B and HB.

**) Measured with a 60 ° Gardner gloss meter.
***) After 632 hours in the short-term weathering apparatus (Atlas-Weather-O-Meter).

In summary, the experiments show that alkylpolysiloxanes Provide coatings for the trade

are intolerable, while the coating agents with the organopolysiloxanes used according to the invention deliver high quality coatings.

Claims (6)

1 2 nically unsaturated monomers, the poly-patent claims containing amide groups in which a water atom is replaced by the remainder 1. Coating compound based on a 5 R binder made from a copolymer of a | unsaturated carboxamides with at least CHORO ₁ another polymerizable, ethylenically unsaturated monomer, the polymer being replaced in which R contains a hydrogen atom or an amide group in which a hydrogen atom is an alkyl radical and R _{1 is} a hydrogen atom or an atom through the radical organic radical, and an organopoly- siloxane resin, where appropriate at least one R there is more resin, which is I draws that the binder is about 1 to about 40 CHORUS ₁ ¹ weight percent of an organopolysiloxane resin formula where R is a hydrogen atom or _R cj (r \ D '\ r \ is an alkyl radical and R _{1 is} a hydrogen atom or " ^{K) m} i = 2p- mean an organic residue, and one, Organopolysiloxane resin, optionally containing at least 20, in which R is a monovalent organic radical, At least one further resin is present, which is attached by a carbon-silicon compound du r ch geke η nzeichens that the binding silicon is bound and R 'is a hydrogen atom medium about 1 to about 40 percent by weight of an alkyl radical with 1 to 20 carbon atoms, a * ■ * Organopolysiloxane resin of the formula alkyl radical with 1 to 20 carbon atoms, an aryl 25 residue or an acyl residue with 1 to 8 carbon atoms, R _n Si (OR ') m0 -nm , where the value of η is between 0.5 and 1.9, —2— the value of m between 0.01 and 2.5 and the value of η + m is between 0.51 and 3, and where contains, wherein R is a monovalent organic optionally the polysiloxane resin, the amide mixture radical, the polymerizate by a carbon-silicon compound and / or the further resin with one another dung is bound to silicon and R 'a water have been implemented. Substance atom, an alkyl radical with 1 to 20 carbon copolymers of unsaturated carboxylic acid atoms, an aryl radical or an acyl radical with amides, in particular aldehyde-modified, etherified 1 to 8 carbon atoms, the copolymers of amides with other ethyl values of η between 0, 5 and 1.9, the value of m 35 nhch unsaturated monomers, such as. B. those described in the between 0.01 and 2.5 and the value of η + m USA. Patent 3,037,963, found to be between 0.51 and 3 and where given, previously extensive use in coating compositions, if the polysiloxane resin , the Amidmischpoly- For example, they were used as resin binders for one-component and / or the other resin, firing varnishes and other thermosetting compounds are used. 40 det. When used in this way, these mixed 2. Coating composition according to claim 1, characterized by polymerizate very tough and resistant films characterized as having an excellent chemical resistance as the third component. Contains alkyd resin. Organosiloxane polymers in 3. Coating composition according to Claim 2, characterized in that coating compositions are used and imparted to them characterized as having about 5 to about 40 Ge 45 specific properties. The production of organo weight percent Contains alkyd resin. However, siloxane-containing compositions prepared considerable 4. Coating mass according to claim or, 3, difficulties and was relatively expensive, characterized in that it is an alkyd resin. In addition, the compatibility was earlier with unreacted hydroxyl groups. Organopolysiloxanes with most of the resinous ones 5. Coating mass according to one of the above 50 coating agents extremely limited, and there were Claims, characterized in that they receive a film burned in use, the Contains pigment. were extremely hard and brittle, whereby the same the 6. Coating composition according to one of the preceding flexibility, which is a required property of claims, characterized in that it is an amide resin for its commercial use copolymer of an unsaturated carbon 55, was taken, so that the expert does not contain an acid amide in which at least 50 ° / ₀ was added incentive, organopolysiloxanes composed of the Rj groups represent an organic radical. to be used with other resins in coating agents, from which he expected certain qualities. It was all the more surprising that the inventive 60 according to coating compositions extremely compatible with Amide copolymers are and the films made from them in addition to sufficient flexibility possess numerous other surprising advantages. So z. B. these coating compositions easily The invention relates to a coating composition based on excellent chemical and solvent based films a binder made from a mixed polymer with good toughness and adhesiveness of an unsaturated carboxamide burn with sion in addition to the excellent flexibility, At least one other polymerizable ethyl also has been found that the in the invention