DE2142794A1 - Dimensions for protective covers * - Google Patents

Description

concerning
Compound for Sohu tz coatings

The invention relates to a mass for protective coatings, consisting of a mixture of

A. a curable film-forming preparation

(1) a silicone component with an average of 1-1.9 monovalent organic groups which are bonded to each silicon atom by carbon-silicon bonds and of which at least Are groups containing 25 mol $ aryl radicals,

(2) a polylactone component in which at least 40 mol $ of the monomeric Laoton units have the formula -zfCH ' ₂ J ^ -C00-, in which R ^{1 is} a hydrogen atom or a monovalent hydrocarbon group and

(3) an organic coating resin component, this preparation can be converted into a solid film during hardening,

B. a liquid diluent and optionally G. a crosslinking agent and customary additives.

According to one embodiment of the invention, the three are critical components of the curable film-forming preparation in the mixture according to the invention as separate polymers, i. the preparation can consist of a mixture of a silicone polymer,

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a polylaoton polymer and an organic coating resin ". According to a further embodiment of the invention, two of these critical components of the preparation can chemically as Segments or blocks of a copolymer are present, while the third component is present as a separate polymer, i.e. the preparation can consist of a mixture of a silicone-polylactone copolymer and an organic coating resin or they can be made from a mixture of a copolymer of the silicone and the organic coating resin and a polylactone polymer or it can consist of a mixture of a copolymer of a polylactone and an organic coating resin as well consist of a silicone polymer. According to a third embodiment, all three are critical components of the preparation chemically combined as segments or blocks of a terpolymer.

In all cases, the film-forming preparation can be hardened to form a solid film, since it is in the polymer, in the copolymer or in the Terpolymer reactive groups are present.

Therefore, if the curable film-forming preparation which is present in the mixture according to the invention contains separate polymers, each polymer contains reactive groups which allow the preparation to cure. If the preparation is an Oopolymerisat contains two of the components and the third component is in the form of a separate polymer, the polymer should and at least one of the segments or blocks of the copolymer contain reactive groups in order to harden the preparation allow. If the components are present in the preparation in the form of a terpolymer, only one of the segments or one has to be Block of the terpolymer contain reactive groups, preferably however, two or all three blocks contain reactive groups to allow curing.

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The silicone-polylactone copolymers are often more compatible with the organic coating resins (especially high molecular weight vinyl resins and cellulose-based resins) as simple Mixtures of the three separate polymers. Terpolymers, which are formed by reacting silicone-polylactone copolymers with organic coating resins form film-forming ones Preparations from which coatings with particularly excellent durability can be produced.

The silicone component in the curable film-forming preparations in the mixtures according to the invention has an average of 1-1.9 monovalent organic groups which are bonded to each silicon atom via carbon-silicon bonds. At least 25 Hol / b of these organic groups are groups containing aryl radicals, such as aryl groups, alkaryl groups or aralkyl groups, for example phenyl, naphthyl, tolyl, cresyl, benzyl and phenylethyl groups. The remaining monovalent organic groups in the silicone component can be other monovalent hydrocarbon groups, for example alkyl groups such as methyl, ethyl, butyl, propyl, pentyl, hexyl and cyclohexyl groups, or alkenyl groups such as vinyl, allyl, butenyl groups. and cyclohexenyl groups, organic epoxy groups such as β- (3,4-epoxycylohexyl) ethyl and / -glycidoxypropyl groups; Mercaptoalkyl groups such as β-mercaptopropyl and f-mercaptoalkyl groups; Organic amino groups, for example aminoalkyl groups such as / "- aminopropyl groups, aminoaryl groups, such as aminophenyl groups; H-aminoalkyl-aminoalkyl groups, such as the li-ß- (aminoethyl) - ^ - aminopropyl group; and the /" - methacryloxypropyl group. The silicone component can also contain groups which are bonded to silicon via oxygen atoms, for example the hydroxyl group, acyloxy groups such as the acetoxy group, or hydrocarbyl oxy groups such as the methoxy, ethoxy, propoxy and phenoxy groups and hydrocarbyl oxyether groups such as the methoxyethoxy group. The presence of. groups containing at least 25, preferably at least 30 lAol-fo aryl radicals in the silicone component is essential, as this

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makes it more solid, while the ratio of organic groups to silicon atoms makes the preparation good film-forming properties confers. Preferably, 25-90 moles are silicon-bonded monovalent organic groups are phenyl groups and the remaining monovalent organic groups are alkyl groups, the Contains 1-10 carbon atoms inclusive.

At least 40 mole-76 of the lactone units of the polylactone should be units of -oaprolactone or hydrocarbon- substituted ί- caprolactone in order to impart the desired property of good flexibility and solvent resistance to the coatings. Such lactone units can be represented by the formula

--GR

000-

in which R is a hydrogen atom or a monovalent hydrocarbon group (e.g. an aryl or alkyl group) is. Me polylactone component in the curable film-forming Preparations in the mixture according to the invention preferably have a molecular weight of 200-1500. It has been found that Polylactones within the specified molecular weight limits have the desired properties by being more reactive with the other components and form coatings that have particularly good flexibility and solvent resistance. All lactone units in the * polylaotone component can be units of formula I. Is can also be up to 60 MoI- ^ from other lactone units.

Representative monomeric cyclic esters (lactones), which are used as starting materials for the production of the lactone component in the film-forming preparations used in the composition according to the invention are e.g. ß-Propiolacton, / - Valerolaoton, i-Caprolactone, 7-Hydroxyheptan ^ acid lactone, 8-Hydroxyootanoic acid-r laoton, ^ -hydroxydodecanoic acid lactone, 13-hydroxytrideoanic acid-

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laoton, H-hydroxytetradecanoic acid lactone, 15-hydroxypentadeoanoic acid lactone, lo-hydroxyhexadeoanoic acid lactone, 17-hydroxyheptadecanoic acid lactone; the ^, <*, - dialkyl-ß-propiolactone, eg oCöw-dimethyl-ß-propiolaoton, ^, oC-diethyl-ß-propiolactone and oC ^ -dipropyl-ß-propiaoton; the monoalkyl - ^ - valerolaotones, for example monomethyl, monoethyl, monoisopropyl, monobutyl, honohexyl, monodeoyl and monododecyl - ^ - valerolaotones; the dialkyl- <i-valerolaotones in which the two alkyl groups are on the same carbon atom or on different carbon atoms of the cyclic ester ring, for example dimethyl, diethyl, diisopropyl, dipentyl and di-n-octyl-cPvalerolactones; the monoalkyl, dialkyl or trialkyl ε -oaprolaotones, for example monomethyl, monoethyl, monoisopropyl, monohexyl, mono-n-ootyl, dimethyl, diethyl, di-n-propyl, diisobutyl, di -n-hexyl-, trimethyl-, triethyl- and tri-n-propyl-f-caprolaetone; and the monoalkoxy- and dialkoxy-ci-valerolactones and -d-caprolactones, for example monomethoxy-, monoethoxy-, monoisopropoxy-, dimethoxy-, diethoxy- and dibutoxy- <f-valerolaotones and -fc-oaprolactones. Further examples of solo cyclic esters (lactones) are 3-ethyl-2-keto-1,4-dioxane, Vl 1-isopropyl-4-methylcyclohexyl) -i-caprolaoton, 3-bromo-2,3,4,5, -tetrahydrobenzoxepin-2-one, 2- (2'-Hydroxyphenyl) benzoloarbonsäurelaoton, 10-Hydroxyundecansäurelaoton, 2,5,6,7, -Tetrahydrobenzoxepin-2-one, 9-Oxabioyolo /F^.^undecan-e-one, 4-0xa-14-hydroxytetradeoanoic acid melon, o (., C (C-bis (chloromethyl) propiolaoton, 1,4-dioxan-2-one, 3-n-propyl-2-keto-1,4-dioxane, 3 - (2-Ethylhexyl) -2-keto-1,4-dioxane and the like. Examples of subgroups of cyclic esters which are suitable for the preparation of the polylactone component are unsubstituted lactones and the oxalactones which contain 6-8 atoms in the laotone ring, preferably d -Valerolaoton, ^ -Caprolaoton, the ketodioxanes; mono- and polyalkyl-eubstituted lactones and oxalaotones which contain 6-8 atoms in the Laotosrlng, preferably mono- and polyalkyl - / - Valerolaotone and - £ -caprolaotone and the corresponding oxalactones, where the alkyl substituents 1 - Contains 4 carbon atoms, as well as mono- and polyalkoxysubstitu-

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ated lactones and oxalaotones which contain 6-8 atoms in the Laoton ring, preferably the mono- and polyalkoxy- ^ valerolactones and I -caprolaotones and the corresponding oxalaotones, the alkoxy substituents containing 1-4 carbon atoms.

The polylactone components usually contain a residue derived from an initiator used in the manufacture of the polylactone. Such starters are glycols such as ethylene, propylene and butylene glycol, triols such as trimethylol ethane and propane and other polyols such as pentaerythritol. The polylactone component can be modified by the fact that other types of units are incorporated therein, for example polyoxyalkylene blocks such as polyoxyethylene and polyoxypropylene blocks, residues of dicarboxylic acids, maleic acid or fumaric acid of the formula -OGRGO-, in which R is an alkenylene group, as well as best of Polyisocyanates such as 1,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2-diisocyanatopropane, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, bis (3-isooyanatopropyl) ether, Bi3 (3 -isooyanatopropyl) sulfide, 1,7-diisocyanatoheptane, 1 ^ -diisocyanato ^ -dimethylpentane, 1,6-diisocyanato-3-methoxyhexane, 1,8-diisooyanatooctane, 1,5-diisocyanato-2,2,4-trimethylpentane, 1 , 9-diisocyanatononane, 1,10-diisocyanatodeoane, W 1, o-diisocyanato ^ -butoxyhexane, the bis (3-isocyanatopropyl) ether of 1,4-butylene glycol, 1,1t-diisocyanatoundecane, 1,12-diisocyanatododeoane, bis ( isocyanatohexyl) sulfide, 1,4-diisocyanatobenzene, 2,4-diisooyanatotoluene, 2,6-diisocyanatotolylene, 1 _f 3-diisocyanate nato- £ -xylene, 1,3-diisooyanate om-xylene, 1,3-diisooyanato-p-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitrobenzene, OGNG ₆ H ₄ CH ₂ G ₆ H ₄ NGO, OGNG ₆ H ₁₀ GH ₂ G ₆ H ₁₀ NGO and 2,5-diisocyanato-nitrobenzene. Such Polyisooyanatreste can be incorporated duroh reacting a Po lyi so cyanate with a Polylacton-Poljrol.

The organic coating resin component in the curable film-forming preparations which are in the mixture according to the invention

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present are polymeric organic substances that are commonly used can be used to form protective coatings. Suitable organic resin components are acrylic resins, vinyl halide resins, Alkyd resins, polyester resins and cellulosic resins. Good results are achieved when usually incompatible organic ones Coating resins having relatively high molecular weights, e.g., molecular weights of at least 20,000-30,000, are used will. Preferably the molecular weight is not higher than 80,000 because resins with higher molecular weights are difficult to take on Supports can be applied, which are to be coated by spraying.

Typical acrylic resins which can be used according to the invention are copolymers of (a) acrylic acid or methacrylic acid alkyl esters and (b) copolymerizable olefinically unsaturated compounds with a functional group such as a hydroxyl group, a epoxy group or an etherified methylol group. The acrylic resins can be prepared by copolymerizing, for example, methyl aylate or methyl methacrylate with comonomers such as acrylic acid, Methacrylic acid, itaconic acid and their esters, maleic acid and their esters, fumaric acid and their esters, vinyl acetate, methacrylonitrile, Hydroxyethyl acrylate or methaorylate, N-methylolacrylamide, Butoxymethylacrylamide, hydroxypropyl acrylate or methacrylate, Hydroxyethyl or hydroxypropyl maleate or fumarate and their half esters and glycidyl acrylate, methacrylate, maleate or fumarate. Other comonomers that are not functional Groups containing e.g. styrene or vinyl toluene can also be used. Suitable acrylic resins preferably contain at least 45% by weight of a polymerized alkyl ester of the Acrylic acid or methacrylic acid and 3-25 wt .- $, preferably 10-20 wt .- # of a polymerizable olefinically unsaturated Connection with a functional group.

Typical vinyl halide resins which can be used according to the invention are copolymers of a vinyl halide, in particular

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Vinyl chloride, and at least one copolymerizable olefinically unsaturated compound having a functional group, e.g. a hydroxyl group, an hydroxy group or a carboxy group. Suitable compounds of this last-mentioned group are mentioned above as suitable comonomers for alkyl esters of acrylic acid and methacrylic acid mentioned. Suitable vinyl resins preferably contain from 60 to 95% by weight of a polymerized vinyl halide, in particular Vinyl chloride, 0-40 wt .- ^ of a polymerize vinyl ester or -ether and 1-20 wt .- ^ one polymerize alcoholic Hydroxy group-containing olefinically unsaturated compound or a precursor of such a compound, such as vinyl acetate.

Alkyd resins which can be used according to the invention are described in the book of Alkyd Hesins by CR. Martins (Reinhold Publishing Corp. N.Y., 1961 /. Suitable alkyd resins are made from polyols and polycarboxylic acids manufactured. Suitable polyols are glycerine, ethylene glycol, diethylene glycol, 1,2,6-hexanetriol, trimethylolethane, Trimethylolpropane, pentaerythritol, dipentaerythritol, Sorbitol and mannitol. Suitable polycarboxylic acids or their anhydrides are adipic acid, succinic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, tetrachlorophthalic acid, trimellitic acid and similar acids. The alkyd resin can optionally also contain a proportion of unsaturated acids and / or monobasic acids contain, such as crotonic acid, sorbic acid, maleic acid or benzoic acid, as well as smaller amounts of other reactive modifiers, like allyl alcohol. The alkyd resin is modified with an oil or oleic acid, such as a conventional non-drying one or semi-drying oil or a fatty acid, such as ciccos oil, linseed oil, Tung oil, soybean oil, dehydrated castor oil or the like. Or their corresponding fatty acids and dine acids such as dimerized Linoleic acid.

The polyester resins which can be used according to the invention differ from the alkyd resins mentioned in that the polyester resins are not modified with oils or oleic acids.

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Typical cellulose-based resins which can be used according to the invention are cellulose acetate butyrate (e.g. the "half-second butyrate" sold as "EAB-381-2" and ^M EAB 551-0.2 ") and nitrocellulos (e.g. the quarter-second and half-second RS nitrocelluloses ).

The diluent present in the composition of the composition of the present invention can be any of a number of liquids be in which the film-forming preparations can either be dissolved or otherwise dispersed. Suitable liquid Diluents are water, aromatic hydrocarbons (such as benzene, toluene and xylene), alcohols such as isobutyl alcohol, Glycol ethers, such as methyl ethers of ethylene glycol, ketones, such as Methyl ethyl ketone, glycol ether esters, such as ethylene glycol monoethyl ether acetate and, usually in limited quantities, aliphatic hydrocarbons such as white spirits.

As the person skilled in the art is familiar with, the selection of a suitable solvent for a particular mixture depends according to the invention on factors such as the chemical composition of the particular curable film-forming composition.

As already mentioned, two or three of the components of the curable film-forming preparations can be used in the inventive Mixtures can be combined chemically in the form of a copolymer or a terpolymer. Preferred copolymers and Terpolymers are those that essentially consist of a silicone segment or block with units of the formula

^R a ^Si0 4-a ^ΐτ

in which R is a monovalent organic group attached to silicon is bound by a carbon-silicon bond or a Hydrocarbon oxy group, a hydroxyl group or a divalent one Atom or a divalent group that forms the silicone block with an organic block as defined below is connected and a has a value of 1-3 inclusive,

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The silicone block has an average of 1 - 1.9 monovalent organic groups R bonded to each silicon atom and Contains at least one such divalent atom or a divalent group R. The copolymer or terpolymer contains at least one organic segment or block of the following types: (1) a polylactone block having a molecular weight of 200-1500, in which at least 40 Mo 1- $ of the monomeric units Gaprolactone units are (2) an organic polymer Coating resin as defined above and (3) a copolymer of (1) and (2). If the organic segment or the block is a block from (1) or (2), the substance is a copolymer. If the organic segment or block consists of (3) ", represents the substance is a terpolymer. Such copolymers are curable, i.e. they contain reactive groups, namely at least two Groups per molecule on average. The reactive groups are preferably silicon-bonded hydroxyl groups and / or Hydroxyl groups in the silicone block, unblocking hydroxyl groups in the polylactontiack or hydroxyl groups in the block from the organic Coating resin.

The chemical bond between the siloxane block and the polylactone block or the block from the organic coating resin in the block copolyraerisates that form the preparation in the composition according to the invention can be created by any suitable divalent atom or a divalent group R in formula II, as by the following Atoms or groups: -0-, -S-, -NR-, -R ⁰⁰ O-, in which the valence on the left is bonded to a carbon atom of an oxyalkylene unit in the oxyalkylene block and the valence on the right is bonded to a silicon atom in the siloxane block and R is a monovalent hydrocarbon group or hydrogen and R represents a divalent hydrocarbon group. Examples of divalent hydrocarbon groups R in formula II and R are alkylene groups, such as methylene, ethylene, propylene, 1,2- or 1,3-propylon, butylene and arylene groups, such as ortho-, meta- and para Phenylene groups.

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In the above formulas "need the symbols representing the number and reflect the types of groups, not to have the same meaning every time they appear in the preparation. For example can, in the case of a block copolymer with groups of the formula II some of these groups may be dimethylailoxane groups, while others of these groups may be methylailoxane groups and / or trimethy1siloxane groups are.

The term "block copolymer" is used here to denote a substance in which at least one section or "block ^{11 of} the molecule is composed of recurring monomeric units of one type and at least one other section or" block ^{1 of} the molecule is composed of recurring monomeric units of another type is composed. The different sections or bltioke in the molecule can be arranged in any configuration, for example AB, ABA, branched or oyolisoh. Thus, the expression "blookopolymers ¹ · also includes graft copolymers. The block copolymers used according to the invention can represent individual chemical compounds. Usually, however, they are mixtures of different types of individual block copolymers. The block copolymers are usually mixtures because the siloxanes and polyoxyalkylenes used to produce the block copolymers are usually themselves." Represent mixtures.

As mentioned above, the silicone component, the polylaotone component and the organic resin component exist as separate polymers, each of which is a plurality of reactive ones Groups can contain. These reactive groups make different ones Ways of producing the copolymers and terpolymers mentioned by a reaction of these polymers. Not all reactive groups should be implemented in the formation of the copolymer or terpolymer, so that the copolymer or Terpolymer is still curable.

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When the silicone resin or the organic coating resin that is used to prepare the coating compositions according to the invention, contains hydroxyl groups, it can be used as a starter for formation the polylactone component can be used. In such cases, the polylactone component by reacting oaprolactone or a hydrocarbon-substituted caprolactone or a mixture of such lactones and another lactone with the Silicone or the organic coating resin to form a silicone polylaotone or a copolymer of the organic Coating resin and the polylactone of the above-mentioned type. A copolymer of the type mentioned can be carried out in a similar manner Reacting a silicone resin or a polylactone resin, the is olefinically unsaturated with an olefinically unsaturated one Monomer precursor implemented for an organic coating resin e.g., the monomer used to form a suitable acrylic resin or the vinyl halide resin specified above is used in the presence of a catalyst for vinyl polymerization to form the copolymer from the silicone and the organic coating resin or from the polylactone and the organic coating resin.

The invention envisages the use of a single silicone component, a single polylactone component, a single organic coating resin component, and a single Diluent in the new mixes for the mass. In fact, it is common to use two or more of these Fabrics preferred. In the case of the silicone, the polylactone and the organic coating resin, if two or more, these may be used These groups of substances are used, are present as separate types of substance or in chemical combination as copolymers. To the For example, the organic coating resin component can be an copolymer be made of an acrylic resin and an alkyd resin or, depending on the presumed compatibility, a mixture of these two Resins.

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The mixtures according to the invention can contain one or more crosslinking agents, as the curable film-forming preparation has reactive groups in the mixture, the active hydrogen atoms e.g., hydroxyl groups, carboxy groups, amino groups, or mercapto groups, are preferred crosslinking agents Formaldehyde resins, epoxy resins and organic polyisocyanates. Typical iOrmaldehyde crosslinking agents are hexamethoxymethylmelamine, butylated melamine-formaldehyde condensates, Urea-formaldehyde condensates and triazine-formaldehyde condensates. Typical epoxy resins as crosslinking agents are those with at least two spoxy groups, such as the alkanediol bis (3,4-epoxycyclohexanecarboxylates), the bis (3,4-epoxyeyclohexylmethyl ^ hydrocarbon dioarboxylates and the diglycidyl polyethers of dihydric phenols having the formula

GH ₂ -GH-CH ₂ -

CH-

I yy — OM ₂ OHOH ₂ -

GH.

OH

-il

CH ,,

-G- / 0 \ -0-OH ₀ -GH-GH

V ²

\ J

Typical polyisocyanate crosslinking agents are those mentioned above Polyisocyanates.

The mixtures according to the invention can furthermore be different Contain additives that are possibly contained in customary coating compositions, which are in the mixtures according to the invention organic additive resin components used. Typical additives of this type are smoothing agents, pigments such as titanium dioxide, Stabilizers, drying agents, plasticizers, anti-foaming agents and agents for preventing skin formation.

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Lent respect, the curable film-forming preparation is the Silicone component preferably in an amount of 4-60 parts by weight, in particular 8-50 parts by weight of the polylaetone component preferably in an amount of 0.5-35 parts by weight, in particular 5-25 parts by weight and the organic coating resin component preferably in an amount of 17-95 parts by weight, especially 43-90 parts by weight present, each based on 100 parts by weight of these three components. The curable film-forming preparation can with solvents up to of any desired viscosity, depending on the mode of application. Additives that are not pigments should not be more than Make up 30 wt .- ^ of the total mixture. Crosslinking agents, such as Amino-formaldehyde resins or epoxy resins should be preferred A range of 5-40 parts per 100 parts of the curable film-forming formulation can be used.

The mixtures according to the invention can be formed using all known procedures for mixing preparations for protective coatings. For example, the mixtures according to the invention can be formed by first forming a "carrier base material" from the curable film-forming preparation and a hardening agent, mixing part of the carrier base material with a pigment in a sand mill to produce "grinding pigment ¹¹ , the remainder of the Carrier base material and optionally other additives are added and the mass is filtered to remove the Sandea Instead of a sand mill, a ball mill or other suitable mixing device can be used.

The mixtures according to the invention can be used for the preparation of Sohutzüberzügen on a variety of Schiohttragern, including metals such as aluminum, tin-plated metals, copper and brass, at _w armhärtende organic plastics such as polyester, phenolic and Epojcydharz laminates, on paper, Wood and glass. The mixtures are particularly useful for dividing protective covers on ferrous metals such as steel. The inventive

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Corresponding mixtures can be applied to such substrates in the usual way, such as by spraying, dipping, rolling and "curtain-like ¹¹ coating. The mixtures are cured on the substrates with the formation of protective coatings. The curing is generally accomplished by applying the mixtures after When applied, the substrate must be kept at a temperature of 82-315 ° G. The curing temperature used depends on factors such as the chemistry of the curing reaction, the thickness of the coating formed, and so on.

Protective coatings formed with the aid of the mixtures according to the invention have excellent properties Flexibility over known protective coatings which have been formed from the same organic coating resin components. In addition, the components of the curable film-forming preparations in the Gemisohen according to the invention are with each other and compatible with the diluent, so that these mixtures can be stored without separation for a long time before use especially if they are kept in closed containers below ambient temperature. The Gemisohe form coatings with high gloss, low phase separation and good weathering properties as well as good flexibility.

The invention is illustrated in more detail by the following examples. The following abbreviations are used in the examples :

Abbreviation meaning

g grams

Weight weight

ml milliliters

cP Gentipoise (at 25 ⁰ C)

F / R front / back

h hours

min minutes

Ke CH, -

sec second

Polyol polycaprolactone polyol

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Furthermore, the following test procedures are used in the examples s carried out:

Non-volatile components

Ee a sample of 1 - 2 g in a weighed aluminum dish brought. The sample is heated to 135 ° C. for 2 hours in a forced air oven heated. The sohale is weighed again. The N.V. value represents the percentage of the sample remaining.

viscosity

a. Gardner (bladder tube), ASTH D154-58 PROC

"b. Brookfield (rotating disk), Brookfield Engineering Labs

c. Ford Cup (discharge measurement), ASTM D-1200-58

60 ° gloss

ASTM-D523, where the value reported is the percentage of represents reflected light.

Accelerated Weathering (Assessment of Dulling) Atlas Wheatherometer Model XW A3TM F-42-64. The reproduced Value ranges from 10 (no loss of gloss) to 0 (none Reflection).

Impact test

Gardner Impact Tester, see Physical & Chemical Examination Paints Varnishes Lacquers Colors Gardner-Sward 1962, p. 147

A weight is dropped a known distance to depress the support plate. The impression of the surface of a plate is the impact on the front side (F), while the impact on the back of the opposite plate is called Butt on the back (R) is called. The weight is increased until the coating fails. The F and R values

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T-bend

A test plate is bent through 180 ° until a U is formed. The distance between the legs of the U is in shape expressed in terms of the thickness of the original substrate. Thus, a T-bend would be a single thickness of a test panel the support that fits between the legs of the U-bend. A coating fails if on the bending edge Cracks appear or adhesion is lost.

Stain resistance against toluene

A drop of toluene is placed on a test sample, covered with a watch glass and left to stand for 5 minutes. A rating a rating of 10 indicates that the test sample does not swell, a rating of 5 means that the test sample softens, but does shrinks and a rating of 0 means that the test sample shrinks immediately.

Stain resistance against ethanol

The test is carried out in the same way as the pleoke strength carried out against toluene using ethanol instead of toluene.

Chalking off

An adhesive tape ("scotch tape") is applied to a test sample of the coating applied, removed and checked for losea pigment.

The following substances were used in the examples:

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Different

Silane A-174 if-methacryloxypropyltrimethoxysilane

Viscosity 350 cP at 25 ° 0.

Siloxane Me ₀ SiO (Me ₉ SiO) ^ (MeSiO) ₁₁ SiKe Oxyalkylene ^d ^ o π Copolymer A

Siloxane-Oxyalkylene- Me ₉ SiO (MeSiO) "(MeSiO), SiMe Copolymer B - / 55

Bsterdiol HIGH ₂ -C (CH ₃ ) ₂ ~ CH ₂ -O-CO-C (CH ₃ ) ₂ -CH ₂ OH

Hexamet ho xy-hexamet hylmelamin

"Cymel" 300 or 301. Hexamethylol derivative of melamine fully etherified _{with CM 3 OH.}

Hayta 3 silicone smoothing agent

Metal backing plates

Steel - "Bonderite 37" (24 GA) Aluminum- "Bonderite 721" fc (0.63 mm).

"Formcel ¹¹ : mixture of 40 wt .- ^ iormaldehyde and 60 wt .- $ n-butanol.

Silicone resins Silicone resin I.

Consisting of equimolar parts of dimethylsiloxane, diphsnylailoxane, monophenylsiloxane χιηά I-ionomethylsiloxane SiiUialten. The Harai'estatoxfe are 2.5 - 3 , 5 ^> OH χιηά are ait an HV-Werfc / on 6 ^Γ > ,. ί used in toluene. The Viskos it Ht ■ lov solution is 4ü - 70 υΡ <,

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Silicone resin II

A mixture of 75 moles $ phenyl, 12.5 moles $ amyl and 12.5 moles of ethyltriohlorosilane becomes a resin with the ideal formula

This resin comes with a U.V. of $ 75 in a Gemisoh of test "gasoline and butyl acetate. The hydroxyl group content of the solid resin is 4-5 wt .- ^, the content of isopropoxy groups 1-2% by weight and the viscosity of the solution is 150 - 500 cP. The molecular weight is 1200 - 1400.

Silicone resin III

This resin has the following general or average structure:

■ 1 ί Ύ?

H-CO-Si-O-Si-O-Si-OCH,

S β

where 0 = ^ ß ^ R * ^ ^{as resin} is used with a solids content of $ 100 and has a methoxy group content of $ 15 and a viscosity of 50 - 70 oP.

Silicone resin 2-6018

The resin has the same structure and the same properties as the silicone resin II made from 75 mol $ vinylsiloxane and 25 mole propylsiloxane units. It is used as a solid resin .

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Polyoaprolaotone polyols;

Average 1 mol wt.

Polyol I 530 Polyol II 830 Polyol III 540

i'functionality OH number

2 2 3

212 135 310

starter

Diethylene glycol diethylene glycol

Trimethylol propane

All Lao units are -O ₅ H ₁₀ GOO- units.

Acrylic resins Acrylic resin I (LKSA-0120)

An acrylic resin that contains hydroxyl groups and carboxyl groups and is dissolved in toluene and ethylene glycol monoethyl ether. N.V. value #

Acrylic resin II (LKSA-0121)

Corresponds to acrylic resin I, but is in ethylene glycol mono butyl ether and high-boiling aromatic solvents. N.V. value

Vinyl resins Vinyl resin I.

Terpolymer of 78 wt .- $ vinyl chloride, vinyl acetate and Gly.cidyl methaorylate (1 wt .- # oxirane oxygen). Molecular weight of the terpolymer about 8400.

Vinyl resin II

Terpolymer of 81 wt .- $ vinyl chloride, 16.9 wt .- # Vinyl acetate and 2.1% by weight maleic acid with a molecular weight from 8300.

Vinyl resin III

Terpolymer sat out 91 percent -. $> Vinyl chloride, 3 percent * - <fi vinyl acetate and 6 percent .-- £ vinyl alcohol (hydrolyzed vinyl acetate). The terpolymer has a molecular weight of about 23,100.

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Vinyl resin IV

Same as vinyl resin III except that the molecular weight of the terpolymer is about 15,500.

Vinyl resin V

Terpolymer seed of 83% by weight vinyl chloride, 16% by weight vinyl acetate and 0.9 wt .- ^ maleic acid with a molecular weight of about 14 800.

As can be seen from the above list, some of the resins used in the examples were in the form of solutions. When these resins have been further diluted, this is mentioned in the examples.

Unless otherwise stated, the percentages and ratios are based on weight.

example 1

Manufacture of an acrylic resin

In a 3 liter four-necked flask with a thermometer, one Stirrer, a dropping funnel, a nitrogen inlet tube, 400 g of xylene were added to a reflux condenser and heating mantle. The following mixture was added to the funnel:

Styrene 350 g Ethyl acrylate 540 g Hydroxypro pylmetic acrylate 110 g Xylene 140 g Benzoyl peroxide 12 g t-dodeoyl mercaptan 6 g

The mixture was poured into the reaction flask over 3 h 53 min at 110 - 118 metered ⁰ G 27 and maintained at 118 ⁰ G min. An additional initiator solution of 0.5 g benzoyl peroxide and 7 g xylene was added and the reaction was allowed to run for 30 minutes. This step was repeated twice and the reaction mixture was with the addition of 106 g of xylene and 110 g of ethylene glycol mono-

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ethyl ether acetate cooled. With this formed acrylic resin solution A, the percentage of non-volatile components was 52.7 $ This acrylic resin solution A containing hydroxyl groups was used in the later examples of thermosetting coatings made of silicone resin and acrylic resin is used.

Example 2

Production of a silicone-polyol copolymer

In a 1 liter four-neck flask with a thermometer, one The following materials were given to a stirrer, a water trap, a condenser and a heating mantle:

Silicone resin I 65> »N.V. 216 g Polyol (Polyol I) 60 g

"This mixture was heated to 137 ° 0 (start of reflux) and that Solvent in the trap was removed while the temperature rose to 151 G over a period of 1 hour 45 minutes. All in all UTU ... ^. Α 13.5 ml of solvent and 1.0 ml of water collected in the trap. 84 g of xylene was added with cooling. This was a ^ iiicon-polyol copolymer solution A with a solids content of 63.3 $ obtain. The solution was somewhat cloudy, but a sample dried completely clear on G-las.

Example 3

ICaItes mixture of stoving enamel and silicone acrylic resin The following stoving enamels have been put together:

Carrier base A. Parts by weight 8th σ , 2 151 B. 6th 121 Acrylic resin solution A - 8 121 - ,1 Silioonhara I - 24, 36 Silicone-polyol solution A 10 - - Xylene 16 19th 0 - , 5 Isobutyl alcohol 18 25th 19th He xamet ho xymet hy1me1amin 0 18,

2 0 9 8 10/1690 ^ w g ^

1A-39 913 Parts by weight A. B. C. 100 100 1 00 64 64 64

35 8th 35 8th 35 8th 35 2 35 2 35 2 0, 0, 0, ο, 0, ο,

- 23 grinding pigment

Carrier base material TiO ₂ , rutile additives Remainder of the carrier base material xylene

Ethylene glycol monoethyl ether acetate p-Toluenesulfonic acid monohydrate ($ 20 K.V. in isopropanol) Raybo 3.

The carrier base was mixed until a clear solution was observed. Part of the vehicle was used with sand to disperse the pigment. The remainder of the carrier and other ingredients were added with stirring until the laok preparation was complete. The lacquers were filtered in order to remove the sand and then sprayed onto aluminum sheets treated with chromate, dried in the air for 10 min and ^{baked at 176 °} C. for 20 min. Bs became the following properties

found:

AB C Gardner impact strength (cm. Kg) ff / R 34723 11.5 / 0 23 / 11.5

60 ° gloss 98 96 97 Accelerated weathering

Matters, evaluation (10 = best) 2-3 5-6 7

Chalk off no no no

Varnish A was a comparison, with no silicone resin was added. Varnish B explained that a silicone resin used in place of part of the acrylic resin was a coating showed better strength in the accelerated weathering test, but had a lower flexibility. Varnish C showed that when a silicone-polycaprolaotone-polyol copolymer was used part of the flexibility is restored and surprisingly an excellent and improved strength in the weathering

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attempt was achieved.

Example 4

Silicone-polyol copolymer

Using the apparatus of Example 2, the following substances mixed:

Silicone resin III 236 g

Polycaprolactone triol 90 g (Polyol III)

The mixture was ^{heated to 150 °} C. and held at this temperature for 2 hours. During this period, 13 ml of methanol distilled off. After cooling, a liquid product with 100% solids, which is referred to as silicone-polyol copolymer B, was obtained .

example 5

Cold mixed lacquers made from methoxy silicones and acrylic resins

became
The following lacquers / produced as in Example 3:

(Parts by weight) carrier base

Aoryl resin solution A silicone resin III Silicone-polyol copolymer hexamethoxymethylmelamine Xylene

Isobutyl alcohol

Hahl pigment carrier base material TiO ₂ , rutile

A. B. ,8th 121.8 121 16.0 - , 9 - 22nd , 0 18.0 19th , 0 17.0 25th 26.0 23 100 100 64 65

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(Parts by weight)

Remainder of the carrier base

Xylene 35 35

Ethylene glycol monoethyl ether acetate 35 20

p-Toluenesulfonic acid monohydrate _QQ q _q

(20 / o in isopropanol) * '

Kaybo 3 o, 2 o, 2

The paints were filtered and sprayed onto aluminum panels treated with Ghromat, 10 min in air dried and baked at 260 ⁰ 2 min G "were observed the following properties of the coatings.:

paint

Gardner impact strength (om.kg) ϊ / Β. 60 ° gloss
Ethanol stain resistance 5 min

Accelerated weathering, dulling,? _ ^ Ρ. Rating (10 = best) ^ o

The varnish A showed that cold mixtures of a kethoxy silicone are more flexible than the mixture with the hydroxy silicone according to Example 3, but the accelerated weathering in this example showed poor values. However, the paint 3 showed that a previously reacted methoxy-silicone-polyoaprolactone triol retained flexibility while accelerating strength Weathering test as well as chemical strength was better. The silicone resin of this example (silicone resin III) was also reacted with the acrylic resin solution A and made a similar one Baked enamel processed. This paint showed a slight improvement over the VA paint in terms of weathering tests, but was not as good as the varnish VB.

A. B. 34/23 34/3 4 93 96 satisfied satisfied gend - good gend - good

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Example 6

Production of a silicone-aoryl resin copolymer

Using the apparatus of Example 1, the flask was charged with 810 parts by weight of xylene. Through the dropping funnel the following mixture was added:

Parts by weight methyl methacrylate 375

Ethyl acrylate 375

2-ethylhexyl acrylate 375

Styrene 225

Hydroxyethyl methacrylate 150

Benzoyl peroxide 20

t-dodecyl mercaptan 14

Xylene 160

The feed mixture was stirred in the reaction baskets over a period of 1 at 132 - 140 metered ⁰ C and heated an additional hour at 133 ⁰ C under reflux conditions. A mixture of 0.8 parts by weight of benzoyl peroxide and 10 parts by weight of xylene was added and the mixture was kept at 134-135 ° C. for 30 minutes. The additional initiator addition was repeated twice and the reaction mixture was held at 135 ° C. for an additional hour, cooled and removed from the flask. The resulting acrylic resin had a solids content with an NV value of $ 57.8.

Another 277 parts by weight of the aoryl resin solution and 57 | 2 parts by weight of silicone resin II were added to the flask. The mixture was 2 h 5 min at 138 - 146 ⁰ G heated under reflux conditions. 1 ml v / water was removed by azeofcropic distillation. After cooling, the product obtained had a solids content of $ 63.4. This resin solution was referred to as silicone aoryl resin solution B in the following example.

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Example 7

Silicone aoryl resin laoke with cold-mixed polyol

Following the procedure of Example 3, the following were made Paints put together:

Parts by weight of carrier bulk material

Silicone-acrylic resin solution B Hexamethoxymethyl melamine Xylene

Isobutyl alcohol

Polyol I.

Grinding pigment
Carrier base TiO ₂ (rutile)

additions

Remaining carrier base material xylene

Ethylene glycol monoethyl ether acetate p-toluenesulfonic acid monohydrate (2O? 6 in isopropanol) Raybo 3

The paints were filtered and chromate _r be acted aluminum sheets sprayed. After drying in the air for 10 min, the metal sheets were ^{baked at 176 °} C. for 20 min. The following properties of the laoke were determined:

Lack AB

Gardner impact strength (om.kg) F / R 11.5 / 5.7 34/23 60 ° gloss 92 94

A. B. 126.1 126.1 18.0 18.0 24 24 28 28 - 9.0 100 100 64 69

35 8th 35 8th 35 2 35 2 O, O, O, O,

Accelerated weathering, dulling, evaluation

8-9

The lacquer B ₁ which had the addition of polyol showed better flexibility without a decrease in weather resistance.

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Example 8

Production of a silicone-polyol copolymer

Using the device according to Example 2, the following substances were converted:

Silicone resin I 153.8 g

Polyoaprolaotonpolyol _1nn (Polyol I) ¹⁰ ° ^g

The mixture was 2 h 50 min at 145 - 15O ⁰ G heated under Riickflußbedingungen while 1 ml of water was distilled off azeotropically. 100 g of xylene was added with cooling. The resin solution obtained contained 56.7% non-volatile substances and was referred to as silicone-polyol copolymer solution G.

Example 9

Production of a silicone-polyol copolymer

Using the device from Example 2, the following substances were converted:

Silicone resin I 230.8 g

Polycaprolactone _{polyol 1ΟΛ} (Polyol I) ^'10 ° ^g

The mixture was 4 h at 145 - 151 ⁰ G heated under reflux while 0.6 ml of water were removed azeotropically. 91 g of xylene was added with cooling. The resin solution obtained contained 60.3% non-volatile substances and was referred to as silicone-polyol copolymer solution D.

Example 10

Mixed paints made from silicone-polyol copolymers and acrylic resins

The following lacquers were produced according to Example 3:

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- 29 - Carrier land o ff 1A-39 913 A. , B. ο Acrylic resin I 1 G-ewioht st eile 33.0 0.2 100.0 1 22.0 Silicone resin I. 30.8 31 - ■ - Silicone-polyol copolymer solution G - 31 70.8 - Silicone-polyol copolymer solution D - 13th - 44.3 He xamet ho xymet hylmelamin 25.0 0.8 25.0 25.0 Xylene 33, 26.1 30.6 Xt hylene glycol mono at hylacet at 25th 25th 25th bald pigment Carrier base material 1 00 90 90 TiO ₂ (Hutil) 75 75 75 additions Heat carrier base llaybo 3 0.2 0.2 Xylene 31 31 Diaoetone alcohol 31 31 At hylenglykolmono ät hylät he racet at 13th 13th p-Toluolsulfoiisäure (20 / ό in isopropanol) 0.8 0.8

These paints were filtered and sprayed onto chromate-treated aluminum panels. After drying in the air for 10 minutes, the trays were ^{baked at 176 °} C. for 20 minutes. The following properties were determined:

Lacquer ABC

Gardner impact strength (cm.kg) F / R 11.5 / 0 34/23 23 / 5.7 60 ° gloss 89 93 93

Accelerated weathering,

Matters, evaluation (10 = best) 7-8 8 9

Varnish A represents a cold-mixed comparison of the silicone and acrylic resin. Varnishes B and G show that the silicone-polyol copolymers used according to the invention improve the flexibility of the varnish at different silicone / polyol ratios. In addition, the cousin resistance is not reduced _f but by adding the silicone-polyol

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Copolymers improved.

Example 11

Production of a silicone-polyol copolymer

It was a resin kettle of 500 ml with a heating mantle, Stirrer, thermometer, condenser and water trap are "charged" as follows :

silicone resin II 82.0 g

Polyeaprolactone Polyol 26.6 g (Polyol I)

The mixture was left over for 1 hour. 35 min at 150-177 ° G under reflux conditions heated. 0.8 ml of water were removed azeotropically during the reaction time together with 25 ml of solvent. After cooling, 30 ml of xylene was added to the reactor. A resin solution having an N.V. value of 72.5 '^ was obtained, which hereinafter referred to as silicone-polyol copolymer solution B.

Example 12

Production of a silicone-polyol copolymer

Using the device according to Example 2 were the following substances implemented:

Silicone resin II 200 g

^ -Oaprolactone (monomer) 120 g

Tin II ootoate 0.2 g

Xylene 10.0 g

The mixture was heated 15 min under reflux and 50 minutes at 159 - 163 ⁰ G kept. The mixture was cooled to 12O ⁰ C and another 200 g of silicone resin II were added. The mixture was heated to 155 ° C for an additional 40 minutes while azeotropically removing water. A total of 4.2 ml of water is collected. The mixture was cooled and discharged. The solids content was 70.1 #. The obtained silicone-polyol-gopoly-

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merisate solution F shows that £ -Oaprolaoton with a silicone resin can be polymerized and converted, whereby intermediate products are formed which are similar to those caused by condensation a polyol and a hydroxyl group-containing silicone resin (Examples 2 and 11).

Example 13

Paints made from silicone-polyol copolymer and acrylic resin

Stoving enamels were produced according to Example 3 using the silicone-polyol copolymers E and I and a commercially available acrylic resin. The following substances were used:

Parts by weight of carrier base

Acrylic resin II

Silicone-polyol copolymer solution E. Silicone-polyol copolymer solution F hexamethoxymethylolmelamine Xylene

Isobutyl alcohol

Grinding pigment
Carrier base
TiO ₂ rutile

additions

Remainder of the carrier base material

Xylene

Ethyl englykolmonoäthylätheracet at

p-Toluene sulphonic acid monohydrate (20- / 6 in isopropanol)

Raybo 3 0.2 0.2

These lacquers were filtered onto aluminum sheets treated with Ohromat " sprayed, air-dried for 10 min and baked at 260 ° C. for 2 min. The following properties were determined:

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39 35 35 35 0.8 0.8

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Lack AB

Gardner impact strength (om.kg) S / B 11.5 / 5.7 11.5 / 5.7 60 ° gloss 87 93

Accelerated weathering,

Get matted, evaluation (10 = best) 7 8

Xthanol spot resistance for 5 minutes is not easy

Change in crater formation

This example illustrates that different manufacturing processes result in intermediate products for the silicone-polyol copolymer, which show the same usefulness in paints. Similar ^ Examples will be given later with vinyl chloride copolymers.

Example 14

Manufacture of an acrylic resin

Using the apparatus of Example 1, 336 grams of xylene was added to a flask. Through the dropping funnel was the following mixture was added:

Styrene 150 g -

Met hylmet hylate 200 G Ethyl acrylate 300 G 2-ethylhexyl acrylate 240 G Hydroxypropyl metha- crylate 110 G t-dodecyl mercaptan 4th G

An initiator solution was prepared from 14 g of t-butyl perbenzoate and 150 g of xylene. 124 g of this solution was added to the feed mixture and the remainder was saved for later use. The Sinspeisungsgemisch was to the reaction flask over a period of 3 h 29 min under reflux conditions - metered (132 136 ⁰ C). The mixture was refluxed for 30 minutes and then one third of the excess initiator was added. After a further 30 minutes, a second batch of one third of the initiator was added. The remainder of the initiator solution was added 30 minutes later and the mixture was refluxed for 30 minutes

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and then diluted with 125 g of xylene with cooling. The received Resin solution contained $ 61.6 solids. It was called Acrylic Resin Solution G.

Example 15

Production of a silicone-polyol copolymer

Using the apparatus of Example 1 with the power on a Dean-Stark water separator, the following substances were implemented:

Silicone resin II 283 g

Polycaprolactone polyol (Polyol I) 91 g

The mixture was reacted at 140-150 ° C. for 1 hour 50 minutes. While After the reaction, 4.0 ml of water was removed azeotropically. After cooling and diluting with 110g of ethylene glycol monoethyl ether acetate a resin solution having a solids content of $ 63 was obtained. This resin solution was referred to as silicone-polyol copolymer E-2 because it was practically the same as E.

Example 16

Preparation of a solution from pre-converted silicone-polyol copolymer and acrylic resin

Using a device according to Example 15, the following substances were converted:

Acrylic resin solution 0 162.5 g

Silicone-polyol copolymer solution E-2 75.6 g

The mixture was heated under reflux conditions at 142-149 ° C. for 1 hour heated. 0.6 ml of water was removed azeotropically. After cooling down the solids content of the solution obtained was $ 63.4. This resin solution was referred to as solution D.

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Example 17

Production of a silicone-polyol copolymer with Acrylic resin

Using the device according to Example 15, the following substances were converted:

Acrylic resin solution C 162.5 g

Silicone resin II 44.4 g

Polycaprolactone (Polyol I) 14.4 g

The mixture was reacted for 1 hour 4 minutes at 145-150 ° C. Bs were 0.9 ml V / water removed azeotropically during the reaction. With cooling, 29 g of xylene was added. The resin solution obtained had $ 58.8 non-volatile components. This solution was called Solution E ".

Example 18

Manufacture of pre-converted silicone acrylic resin with cold mixed polyol

Using the apparatus of Example 15, the following substances implemented:

Aoryl resin solution G 162.5 g

Silicone resin I 44.4 g

The mixture was 40 minutes at 138 - 148 ⁰ G implemented, while 0.7 ml of water were removed azeotropically. While cooling, 14.4 g of polycaprolaotone polyol (polyol I) and 29 g of xylene were added. This resin solution contained $ 60.5 solids and was named Solution F.

Example 19

Stoving enamels made from resins of Examples 14-18

Paints were made from the following components:

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Trä gergrondst of f

Acrylic resin solution G

Silicone resin II

Polycaproole lactone polyol V (Polyol II) 10.7

Silicon-Polvol-Copolymer-Lo sung il-2

Solution D ■ -.

Solution yes

Solution j?

1-ielaminliarz (ßesiniin X-745-I-Ionsanto) Xylene

I3obutyl alcohol

Ethylene glycol monoethyl ether acetate

Lahl pigment

Carrier base (Rutile) TiO ₀ se Addition Tr ^ gergrundstο ff Remainder ^j Xylene

913 A. 1 B. ,8th C_ i7 1 D. .Ll (Parts by weight) 121.8 21st - - - 33.3 - - 5 1 - - 1A-39 10.7 - , 7 - 1 - - - 56 - 1 - - - - 174 1 - - - 11 88 - - , 5 - - 183 16.5 16 16, 6.5 16.5 30th 23 26th 8th 20th 26th 20th 20th 5 18th 16 1 16 16 6th 16 110 10 ! 10 0 1 10 77 77 77 77 77

1C1 101 101 101 101

(20.5 in isopropanol) ' ^f *' »

Haybo 3 0.2 0.2 0.2 0.2 0.2

These batches were produced according to Example 3, filtered and sprayed onto phosphate steel sheets. iTach .10 min After drying in air, the sheets were baked at 176 ° C. for 20 minutes. The average pilmiio'ce was 30.5 / im. The paints showed the following properties:

AB C DS

Umfkg) "| ^ ^agfe3ti S ^keit 81/46 103/57 103/69 92/81 61/34

60 ° (xlanz 86 85 91 90 90

60 ° jlanz after accelerated "" _{Qn Qn}

Weathering ^{77 80 89 84 85}

The paint 0 was a little more permanent than the other paints. Therefore is the vorumgesötirte silicone-polyol-Oopolynierisat, which in turn

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was pre-reacted with the organic resin, "regarding the Durability most preferred.

This example illustrates that various combinations of silicone resin, polyol, and acrylic resin can make useful coatings can be processed that have similar properties by reacting two or all three components beforehand and mixing them cold, this versatility does not always apply to all Resin systems is possible, as will be shown later, but it shows the broad scope of the invention. Later examples show that some organic coating resins are not compatible when they be mixed cold with silicone resins, but that silicone-polyol copolymers are more compatible and are therefore more useful.

Example 20

Manufacture of an acrylic resin

Using the apparatus of Example 1, 336 grams of xylene was added to the flask. In the dropping funnel was da3 the following feed-in device is given:

Styrene 150 g

Methyl methacrylate 250 g

Ethyl acrylate 300 g

2-ethylhexyl acrylate 180 g

Grlycidyl methacrylate 80 g

Hydroxyethyl methacrylate 40 g

t-butyl perbenzoate 14 g

Xylene 275 g

The mixture became at 129,131 over a period of 3 hours 35 minutes 0 metered into the reaction flask. The mixture was refluxed for 90 minutes, cooled and drained from the flask. Bs became a 62.9.0 non-volatile resin solution Ingredients obtained, hereinafter referred to as acrylic resin solution G- will.

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Jeigpial 21

Production of a silicone-polyol copolymer

Using the device according to Example 2 were the following substances implemented:

Silicone resin Z-6018 140 g

Polyoaprolaoton-polyol (Polyol I) 60 g xylene 85 g

The mixture was reacted at 144-152 ° C. for 2 hours 7 minutes. While 3 ml of water are removed azeotropically from the reaction. The received Resin solution contained 74.1 / β nonvolatiles and was referred to as silicone-polyol copolymer solution G-.

Example 22

Clear lacquers based on silicone-acrylic resins The following stoving clear lacquers were produced:

Parts by weight

■ acrylic resin solution G

Acrylic resin III

3 silicone resin Ζ-601Θ (75 ^ in Tol-Dow-G) Silicone-polyol copolymer solution G hexamethoxymethylolmelamine toluene

Cyclohexanone

Tin (II) octoate

Raybo 3

E3 films were cast from these approaches at Ohromat treated aluminum plates, dried and then baked minutes in air at 176 min 10 20 ⁰ O. The following paint properties were determined:

A. B. 56.4 56.4 24.0 24.0 16.7 - - 24.1 2.0 2.0 30th 30th 5 5 0.1 0.1 0.05 0.05

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A.

Gardner impact strength (cm.kg) F / R 5.7 / 11.5 öi / 69

T ~ bend 1ΐ =? 1 metal die failure '"better

tie Jl -as TT

Toluene stain resistance 5 min, - c-

(10 s best) _

This example shows better flexibility of the silicone-polyol oil polymer containing paints and paints that contain the silicone resin Z-6018, which are similar to the results Silicone resin; II is. The acrylic resin III is a commercially available one carboxyl group-containing acrylic resin, which with. the acrylic resin solution Qr "reacts. ■ _..._

Example 23

Vinyl-acrylic resin varnish, with silicone-polyol copolymer modified

To further explain the usefulness of the silicone-Pol ^ ol-Oopolymerisate the following vinyl acrylic resin varnish was produced;

Grinding pigment (sand) parts by weight

Vinyl resin II (25 # N.V. in 1: 1 toluene

Gyolohexanon) '- ^{> u}

TiO ₂ -RUtU 69.0

additions

Vinyl Resin II ($ 25 N.V.) 120.0

Acrylic resin solution G 70.5

Silicone-polyol copolymer B 11.4

Urea-formaldehyde resin ("Hesimene X-905 ¹¹ ) _{A n} (50/6 UV) ⁴ °

"Thermolite 31" (tin mercaptide, Vinylharz- _{n 0} stabilizer) ^{v 'd}

Tin (II) octoate 0.2

Toluene 30.0

After filtering, 125 g of the varnish was mixed with 40 g of one Mixture of toluene and cyclohexanone in a volume ratio of 2; 1

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diluted and sprayed onto chromate treated aluminum panels. Wax 10 min air-drying, the coatings were baked 20 min at 150 ⁰ O. The following properties were determined:

60 ° gloss 90

Gardner impact resistance

(cm.kg) F / R 23 / 5.7

'Γ-bend; 1T = 1 metal dioke better than 3T

If the starting silicone resin is used instead of the silicone-polyol copolymer III was used, no impact values were obtained for the backside. This example explains that the oilicon-polyol copolymer is useful, and not only with acrylic resins, but also in mixtures of acrylic resins with other compatible resin types.

Example 24

Manufacture of an acrylic resin

Using the apparatus of Example 1, the following ingredients were added to a flask:

Xylene 150 g Ιΐ-butyl alcohol 150 g Dropping funnel filling: Styrene 250 g Ilethacrylonitrile 150 g Ethyl acrylate 436 g Hydroxypropyl methacrylate 30 g Acrylamide 80 g Acrylic acid 20 g t-dodecyl mercaptan 4 g t-butyl perbenzoate 14 g n-But y 1 al ko ho 1 150 g

The mixture in the dropping funnel was stirred at 113 to the reaction flask over a period of 3 - 114, where ⁰ G and then heated for a further hour under Riickflußbedingungen. It was 50 g

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"Formcel" was added and the mixture was heated further for 4 h 30 min at 115-128 G under reflux conditions and the water was removed azeotropically. 100 g of xylene were added while cooling. The polymer solution obtained contained 68.9 / o non-volatile constituents and was designated as aoryl resin solution H.

Example 25

Clear lacquers made from self-crosslinking acrylic resins and Silicone intermediates

The following clear coats were used:

Parts by weight

Acrylic solution H Silicone resin I silicone-polyol solution A Diaoetone alcohol

Films treated with chromate were made from these approaches Cast aluminum sheets, which were baked at 260 ° C. for 2 minutes. The film thickness was over 28 µm and the flexibility of each coating was determined as follows:

AB fe Gardner impact strength (cm.kg) P / R 5 _f 7 / O 69/69

Here, too, increased use of the silicone-polyol copolymer with a different acrylic resin system the flexibility of the Coatings.

Acrylic resins as used in Example 24 are generally not as compatible with silicone resins as they are aforementioned acrylic resins. Acrylic resins that contain relatively large amounts of acrylonitrile, methacrylonitrile, acrylamide, or methacrylamide contain, show poor compatibility with silicone resins, such as the Siliconharzenll, III, Z-6018 or Z-6188 (cf. U.S. Patent 3,417,161). However, the silicone resin I and its polyol derivatives are compatible and useful. In the

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This patent is used to refer to silicone resins with acrylic resins compatible that first the silicone resin with a Silane (A-184) reacted and this intermediate with the Acrylic monomers is copolymerized. The following examples Aeigen that a modification of these systems with polycaprolactone also beneficial effects on the flexibility of the obtained has coatings.

Example 26

Self-crosslinking acrylic resin with copolymerized Silicone resin

A · Manufacture of an unsaturated silicone intermediate

Using the device from Example 2, the following substances were converted:

Silane A-174 8 g

Silicone resin II 209 g

The mixture was 43 minutes at 116 - 13O ⁰ G implemented. 5.2 ml of solvent were removed during the reaction period. On cooling, 15 ml of Äthylenglykolmonoäthylätheraeetat were added. After discharge, the solution obtained had a solids content of /) on 73.1 $.

B. Preparation of an acrylic resin-containing copolymerized Silicone resin (26a)

Using the apparatus of Example 2 with a dropping funnel, a flask containing 37.5 g of xylene and 37.5 g n-butyl alcohol charged. The following mixture was made and put in the dropping funnel:

Styrene 62, Sg

Methacrylonitrile 37.5 g

Ethyl acrylate 109.0 g

Hydroxypropyl methacrylate 7.5 g

Acrylamide 20.0 g

Acrylic acid 5.0 g

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t-dodecyl mercaptan 1.2 g

t-butyl perbenzoate 3.5 g

n-butyl alcohol 37.5 g

Silicone intermediate from A 86.4 g

The mixture was metered into the flask at 96-107 ° C. over a period of 1 hour 40 minutes. Ss were added 0.1 g of t-butyl perbenzoate and the mixture 40 min at 100 ⁰ C held! ■ laughing cooling to 96 ° ΰ were 20g "Fornicel" was added and the water trap was filled with xylene was attached as water was removed azeotropically for 2 h 10 min at 108-117 ° C. under reflux conditions. During this period, 145 g of n-butyl alcohol and 7IgXyIoI were added while 6 ml of v / water was removed. 30 g of ethylene glycol monoethyl ether acetate were added with cooling. The solution obtained had a solids content of 43.3? "" The resin solution was referred to as silicone-acrylic resin copolymer solution J.

Example 27 ^:

Self-crosslinking acrylic resin with copolymerized Silicone-polyol copolymer

A. Production of a copolymer from unsaturated Silicone polycaprolactone polyol.

Using the apparatus of Example 2, the following materials were added to a flask:

Silicone resin II 209 g

Polycaprolactone polyol r _o , -

(Polyol I) ^b ^ »5 g

The mixture was ^{kept at 150 °} C. for 2 h. 1 ml of water was removed azeotropically along with 13 ml of solvent. After cooling to 130 ⁰ C, 8 g of silane A-174 was added and the mixture maintained at 13O ⁰ C for 30 min, with 0.7 ml of methanol were removed. 45 g of ethylene glycol monoethyl ether acetate were added while cooling. A copolymer (27A) with a solids content of 68.3 · ^ was obtained.

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B. Manufacture of an acrylic resin with the silicone-polyol

Gopolymer from A. (27A)

Using the same device with exposed The following substances were drained into the reaction vessel given:

Xylene 37.5 g

n-butyl alcohol 27.5 g

A mixture of the following substances was placed in the funnel:

otyrol 62.5 g

Methacrylonitrile 37.5 g

Methyl acrylate 109.0 g

Hydro xypropylmetiiacryl at 7.5 g

Acrylamide 20.0 g

Acrylic acid 5.0 g

t-dodecyl mercaptan 1.2 g

t-butyl perbenzoate 3.5 g

n-3utyl alcohol 37.5 g

Silicone-polyol copolymer 1 ^ 9

) ¹ ^

ypy from A. (27A) ββ, ϊ.ο HV

The Gremisch was stirred in the reaction vessel over 1 at 100 - 107 ° C metered, iiach addition of 0.1 g t-butyl perbenzoate the Gremisch was 40 min at 107 - 110 held G, liach cooling to 8O ⁰ G 20 g Formcel and 5C g of η-butyl alcohol were added and the mixture was heated to 144 G. The water trap was connected and filled with xylene. Wasner azeotropic removal was ^{continued at 114-119 0} G for 1 hour 30 minutes. A total of 6 ml of water were removed, 100 g of xylene and 50 g of n-butyl alcohol being added. The mixture was cooled and 50 g of xylene and 30 g of ethylene glycol monoethyl ether were added. The polymer solution K with a solids content of 43.4 >> was obtained.

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Example 28

Self-crosslinking acrylic resin with a content of copolymerized Silicone-polyol-fumarate intermediate

A. Preparation of a polycaprolactone polyol fumarate copolymer

Using a device according to Example 2 with connection to a nitrogen gas inlet tube, 215 g of polyol I _1, 29 g of fumaric acid (2-0H / 1-COOH) and 14 ml of xylene were placed in a flask. The trap was filled with xylene and the reaction was carried out at 169-225 ° C. for 1 hour 50 minutes. 8 ml of water were azeotropically distilled from the mixture during the reaction. The mixture was cooled. A solution of $ 91.1 solids (Polyol 28A) was obtained.

B. Production of a silicone polyol fumarate polymer Using A.'s device, the following were made

Substances implemented:

Silicone resin III 262 g

Polyol 28A 110 g

The mixture was ^{kept at 155-158 0} O for 1 hour, 3 ml of methanol being stripped off. After cooling, the silicone-polyol-fumarate polymer (28B) obtained had a solids content of 91.73 *.

C. Production of a self-crosslinking acrylic polymer containing copolymerized silicone-polyol-fumarate polymer

Using the same device with a dropping funnel turned on, the following materials were added to the Reaction container given:

Xylene 37.5 g

n-butyl alcohol 37.5 g

The following mixture of substances was added to the drip tray:

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- 45 - Styrene 62.5 1A-39 913 G Methaoryl nitrile 37.5 G Ethyl acrylate 109.0 G Hydroxypropyl methaorylate 7.5 G Acrylamide 20.0 G Acrylic acid 5.0 G Silicone polyol fumarate 67 8 rf Polymer 2ΘΒ & t-dodecyl mercaptan 2.0 G t-butyl perbenzoate 3.5 G n-butyl alcohol 37.5 G

The mixture in the dropping funnel was metered into the reaction vessel over a period of 1 h 5 min at 98-106 ° C. The mixture was ^{kept at 108 0} O for a further 10 min. 0.1 g of t-butyl perbenzoate, 21 g of xylene, 21 g of n-butyl alcohol and 20 g of Formcel were added. The water trap has been connected and there has been a further 3 hours 30 minutes under reflux conditions at 108 - 117 ⁰ C heated. During this period, initially 7 ml of methanol and then 6 ml of water were removed by azeotropic distillation. As the resin dosed during this period, 75 grams of xylene and 125 grams of n-butyl alcohol were added. The obtained polymer solution L was cooled. It contained $ 48.8 non-volatile components.

Example 29

Coatings made from self-crosslinking acrylic resins with a Content of copolymerized silicone intermediates

The following clear coats were used:

A. Parts by weight σ 50 B. Silicone aoryl resin solution J Polishing solution K 50 44.2 Polymer solution L 25th 27.9 Xylene 25th 25th 27.9 Ethylene glycol monoethyl ether acetate 25th 209810/1690

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Films were applied to chromate-treated aluminum panels with a doctor blade. and phosphate ^ -ated steel sheets poured, dried in the air for 10 min and ^{baked at 260 0} G for 2 min. High gloss films averaging 18 Aim thick were obtained. The films had the following properties:

A BC

Sheet steel Gardner - - -

Impact resistance (cm.kg) F / R 11.5 / 5.7 46/23 115/115

Aluminum sheets - T-bend fails better better

at 3T as 1T as 1T

Coating A showed that the production of compatible copolymers from silicone and acrylic resins with a high nitrile content works according to the state of the art. However, the hard hydroxy silicone resin (silicone resin II) carries its bad ones Flexibility on the copolymer. The coating obtained -was not flexible enough to process after coating. Coating B, which modified that with the polycaprolactone Contained silicone resin, was fully compatible and much more flexible. Coating G showed that others were previously incompatible Silicone resins (silicone resin III) could be made compatible and flexible by similar other methods.

Example 50

Acrylic resin that can be diluted with water and contains Silicone-polyol copolymer

Usual silicone resins or silicone-polyol copolymers, as used in the present invention do not become readily apparent in water-dilutable or latex-type acrylic resin systems dispersed or mixed with it. Usually there will be an intolerance observed. The unsaturated silicone-polyol copolymers However, (27A) of Example 27 were copolymerized as follows and resulted in a stable, water-thinnable, compatible system that was useful for stoving enamels.

A. Preparation of an aoryl resin containing oopolymerized silicone-polyol copolymer

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Using the apparatus of Example 1, 75 g of ethylene glycol monoethyl ether was placed in a flask. In the A mixture of the following substances was added to the dropping funnel:

Methyl methacrylate 87.5 g

Ethyl acrylate ■ 137.5 g

Acrylic acid 25.0 g silicone-polyol copolymer 27A 105.0 g

Isopropanol 15.0 g

t-butyl perbenzoate 3.0 g

n-octyl mercaptan 0.6 g

Ethylene glycol monoethyl ether 67.0 g

The mixture in the dropping funnel was charged over 45 min at 100-112 ⁰ C in the reaction vessel is metered. 3s 0.1 g of t-butyl perbenzoate and 35 g of ethylene glycol monoethyl ether were added and the reaction mixture was 1 hour at 113 - 120 ⁰ C maintained. After cooling, a copolymer / aoryl resin solution M with 60.9 / l solids was obtained.

B. Production of a stoving enamel that can be diluted with water

The copolymer-acrylic resin solution H, prepared according to A. was processed into a varnish as follows:

Weight parts

Copolymer-acrylic resin solution M 71

Hexamethoxymethylmelamine 13

aqueous ammonia (28; / ό NE,) 4.5

V / ater 96

The mixture formed a cloudy solution to which 33.4 parts of titanium dioxide (rutile) were added. After grinding with sand to diaper the pigment, 0.3 part of a 50% solution of p-toluenesulfonic acid monohydrate in water and 0.1 part of silicone-oxyalkylene copolymer A (smoothing agent) were added. The color was filtered and applied to Ghromat treated aluminum sheets with a doctor blade 30 and baked at 150 ⁰ C min. Films averaging 25 µm in thickness were obtained

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obtained the 60 ° gloss of 89 and a G-ardner impact resistance (om.kg) of 34 pointed from the front and 23 from the back. A cold one Mixing the same silicone resin with a similar pure acrylic resin resulted in matt, brittle films and instaMle lacquers.

Example 31

Thermosetting silicone vinyl resin coatings

The following batches of topcoats were produced using the sand grinding process:

Vinyl resin I 20 # N.V. ^

Vinyl resin II 20 / $ UV ⁽¹⁾ silicone resin III

Silicone-polyol copolymer B - 6.3

Silicone-polyol copolymer solution A - - - 9.9

Diiaodecyl phthalate 4.4 - - -

Diglycidyl ether of bisphenol A ^ ₁₁

(iCRL-2774) ^> ° ¹ ^ '°

Stabilizer T-17-M 0.6 0.6 0.6 0.6

Rutile 48 48 48 48

1 Weight st e il e B. £ D. A. 1 50 150 150 150 4th 50 150 150 150 , 4 - - -

After the paints had been filtered off, a mixture of 0.2 part of tin (II) octoate and 20 parts of toluene was added to each batch with stirring. The paints were then sprayed onto aluminum panels treated with Ghromat, 10 min and air-dried for 20 minutes at 15O ⁰ C baked. The average film thickness was about 25 µm. The following film properties were determined:

60 ° gloss

Gardner Impact Resistance, Backward (cm.kg) (substrate breaks over 69) Accelerated weathering, dulling, rating (10 = best) 5 min toluene stain resistance

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A.
88 B.
88 G
89 D.
93 69 69 69 69 2 5 6th 6th very
Well Well very
Well Well -
3 very good

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This example shows that the addition of a silicone resin improves weather resistance. The silicone-polyol copolymer, which is based on the same silicone base resin, however, showed Surprisingly better weather resistance (paint 0) and a somewhat better chemical resistance. The paint D was from Interest, because the silicone base resin I with the vinyl resin system was incompatible, but the silicone-polycaprolactone polyol copolymer produced from this silicone resin I was usable and gave a coating with the highest gloss of this range.

A mixture of toluene and cyclohexanone in a weight ratio of 1: 1 was used as the solvent.

Example 32

Production of a silicone-polyol copolymer

Using the device according to Example 2, the following substances were converted;

Trimethylolpropane 51 og

£ -0aprolactone 55.0 g

Xylene 10.0 g stannous octoate 0.2 g

The mixture was 50 minutes at 140 - 161 ⁰ C implemented. Then 200 g of silicone resin II (70 ^ NV in butyl acetate white spirit) were added. The reaction was 1 h 30 min at 155 - 158 ⁰ C continued while 2.2 ml of water were removed azeotropically. 25 ml of ethylene glycol monoethyl ether acetate were added with cooling. A resin solution containing 71% non-volatile components was obtained. This solution / all silicone polyol copolymer solution N is called.

Example 33

Production of a silicone-polyol copolymer

Using the device according to Example 2, the following substances were converted:

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- 50 - Silicone resin III 220 1A-39 G 913 Polyoaprolaoton polyol
(Polyol III) 105 G

The mixture was heated for 2 h at 150 ⁰ C while 11.5 ml of methanol were removed. After cooling to room temperature, a liquid product remained, which is referred to as a silicone-polyol copolymer.

Example 34

Thermosetting vinyl resin silicone coatings

The copolymers of vinyl chloride and vinyl acetate containing hydroxyl groups, such as vinyl resins III and IV, were not really compatible with commercially available silicone resins such as silicone resins I ₁ II and III or other similar resins such as silicone resin Z-6018. Pigmented lacquers made from these mixtures were dull and, in the case of the methoxysilioone resins, like that. Silicone resin III, a slippery residue (bleeding) was noted on the surface of the coating. The previous reaction of a silicone resin with the vinyl resins mentioned was unsuitable because the vinyl resin solutions had a high viscosity and these are also less heat-stable than acrylic resins under the required reaction conditions. It was found, however, that previously reacted silicone-polyaprolaotone polyol copolymers according to the invention were compatible with the vinyl resins mentioned. The following thermosetting paints were prepared to demonstrate the utility of these materials.

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(Parts by weight) Laok approach ABODEF

Vinyl resin III (20 / o NV) ⁽¹⁾ 71.3 71.3 71.3 80.2 76.6 76.6 76.6

Vinyl Resin V (20 / * UV) ⁽¹ ^ 17.9 17.9 17.9 9.0 13.6 - 13.6 Vinyl Resin I (5> KV) ^ - 10.9

Urea-formaldehyde resin (»Uforinite F-200E" -55 /> N.V.) 5.2 5.2 5.2 5.2

Urea-formaldehyde resin ("Resimene X-9O5 ^H -5O / _O N.7.) 8.1 7.0 5.8 to

Silicone-polyol copolymer solution A 18.0 ------ j ^

^ Silicone-polyol copolymer solution F - 16.2 ----- ¹ ^

^ Sllicon polyol copolymer solution J --16.1 ----. CiD

- »Silicone-polyol-copolymer solution Ξ - - - 15.7- - - ^»

"vSilicon-Polyol-Oopolymerlösung K - - - - 13,9 - - ι

OiSilicon polyol copolymer solution 3 ----- 12.9-

oSilioon resin II ------ 12

Epoxy resin EBL-4221 0.2 0.2 0.2 0.2 0.2 - 0.2 "

Stabilizer "Thermolite 31" 1.01.01.01.01.0 0.5 1.0

TiO ₂ 15 15 15 15 16 16 16 antimony oxide 1.2 1.2 1.2 1.2 1.0 1.0 1,

Oycohexanone 13.0 13.0 13.0 13.0 15.0 15.0 15, silicone L-45, 2 ° i in xylene 1.0 1.0 1.0 1.0 1.0 1.0 1 ,

^N '"solvent: toluene: methyliso" butyl kentone, weight ratio 1: 1 *' solvent: toluene! Cyclohexanone, weight ratio 1: 1

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The paint preparations given in the table were produced by the sand grinding process, filtered and diluted to a sprayable viscosity with about 45 parts by weight of xylene: diacetone alcohol solvent in a ratio of 1: 1. Bs were sprayed with each coating with chromate-treated aluminum plates, for 10 minutes in air dried and baked at 15O ⁰ 20 G min. The coatings obtained were about 25 µm thick and had the following properties:

Varnish A B. G D. E. F. G 60 ° gloss 92 93. 86 77 98 89 62+ Accelerated
Weathering,
Atlas XW - 1000 h
Accelerated
Weathering, dulling,
Rating 8 8-9 8th 10 8th 9

^25/5 ' ^{7 25/23 46/46 46/46 57/46 46/46 5} ' ^{7 /} °

The lacquer G was a comparative lacquer, which was a silicone resin that was cold mixed with a vinyl resin system. Sine Incompatibility was observed, as evidenced by the low gloss and a sticky exudate on the surface of the coating showed. No weathering test was carried out because of this disadvantage. The other paints showed that different Silicone polyols were useful and in each case increased flexibility. The reviews at the accelerated Weathering was considered to be excellent compared to commercially available vinyl (75) alkyd (25) urea systems, which have a Evaluation of the fatigue of 3 after 1000 h of test duration showed.

Example 35

Silicone vinyl systems

The following mixtures were prepared in order to obtain a different one SiI icon-Poll vgI-Oopolymer j nat in another To examine fa-bensysteni;

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Yi / W ΤΓ (

Vinyl resin III 20? I N.V. Silicone resin II Silicone-polyol copolymer solution E HBH-GHÜN (2)

Urnst ο ff formaldehyde resin ("Resimene X-905") (50; on request)

toluene

Methyl isobutyl ketone xylene

L-45 silicone oil (2 / o solution in xylene)

(1) Solvent: methyl isobutyl ketone: toluene = 1: 1

(2) 25; ^ phthalic green and 75? ^ Vinyl resin III

The mixtures were poured onto chromate-treated "aluminum sheets and 20 min baked at 15O ⁰ C were obtained semi-transparent green films (thickness 30 microns) which had the following properties.:

1A-39 91 B. I3 30th Weight parts - A. 3.9 30th 2.6 2.7 2.8 - 4.7 2.6 4.7 2.8 15.0 4.7 0.05 4.7 15.0 0.05

paint

60 ° gloss

A. B. 60 95 5.7 / 0 69/57 satisfactory very - Well Well

Gardner impact resistance (cm.kg) F / R 5 min toluene stain resistance

Here, too, was the silicone-polyol copolymer with the vinyl system more tolerable, as indicated by the gloss measurements. The polyol also increased the flexibility of the system, while maintaining excellent chemical strength.

Example 36

Cellulose derivatives with silicone polyols

Methoxy silicone resins such as silicone resin III showed a limit value of the compatibility when mixing with cellulose derivatives, such as cellulose acetate butyrate (CAB) or nitro

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~ 54-1-39 913

cellulose (toilet). The hydroxysilicon resins, such as the silicone resin II, were compatible with GAB, embrittled jedcxb. the movies. These Resins were also incompatible with HC. However, it was found that the previously reacted silicone-polycaprolactone copolymers were compatible with both cellulose derivatives. Some of the approaches examined are presented below:

CAB approaches Y2 ascCAB (20th * NV) Flexol R-2H ⁺

Silicone-Polyol-Copolymer B Beetle 216-8 60 $ NV ⁺⁺

A. B. 200 178.5 10 - - 14.3 8.3 8.3 35 35

Polymer plasticizer (polyester)
, ⁺⁺ urea-formaldehyde crosslinker

The pigment was dispersed by grinding with sand. After this Each batch was filtered with a thinner composed of toluene, ethyl isobutyl ketone and isobutyl acetate in a weight ratio Diluted 1: 1: 1 to a viscosity of 16 s in Ford cup No. 4. The colors were then treated with Chroniat Sprayed aluminum sheets, air-dried for 10 minutes and baked at 150 ° C. for 20 minutes. The film properties were as follows obtain:

Lack AB

60 ° Slanz 83 86

liardner impact strength (cm.kg) P / H 23 / 11.5 23 / 11.5

Accelerated weathering, "η

Get matted, evaluation

The approaches showed that a silicone-polyol copolymer can replace the polymeric plasticizer used in lacquer A and result in a coating that has the same flexibility and a very good weather resistance at W3. Similar comparison results were made with liitrocellulose for flexibility obtain. The accelerated weathering gave "poorer values for nitrocellulose than expected for the same

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Silicone content.

Example 37

Silicone alkyd kin enamels

Alkyd resins or polyesters that contain excess hydroxyl groups can be cold-mixed or pre-reacted with oilicon resins are formed with the formation of useful coatings, which are im Trade known 3ind. As already mentioned, the addition of a weatherproof silicone resin leads to the flexibility or deformability such "coatings to deteriorate. The polycaprolactone-modified silicones can, however, be used to restore the desired flexibility and improve weather resistance. This is done through the following approaches explained:

! -. ahl pigment alkyd resin ^ ¹ '60 j NV

TiO ₂ (rutile) xylene

additions

Alkyd resin ^ 60, Ό ! IV

Kelamin-Foruaideiiydharz ^ "'9C. Ό IT.V.

DÜiconharz II

Silicone-polyol copolymer solution Isobutyl alcohol xylene

p-Toluenesulionic acid monohydrate

(20, 3 in isopropanol) 0.8 0.8

Parts by weight 3 A. 83.4 63.4 60.0 60.0 26.6 26.6 23.3 23.3 17, c, 17.8 - 21.3 31.6 - 25th 25th 2 ~ 25th

The Lacxce mentioned were filtered, sprayed onto phosphate fourth steel and 20 min b
following properties:

Trays sprayed and ^{baked at 176 0} O for 20 min. The paints had

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1A-39 913 90 A. B. 34/17 91 4 ⁺ 23 / 5.7 4th

- 56 -

paint

60 ° gloss
Gardner nominal bearing strength (oni.kg) P / R

Accelerated weathering, dulling, evaluation

^ 'Alkyd resin - "Duraplex ND-76" - short ooconut oil alkyd resin with low oil content

^M Resimene-740 "

The non-silicone alkyd resin had a matting rating of 2.

Example 36

Manufacture of a polyester

A polyester resin was prepared as follows: In a 190 liter stainless steel reactor, the following were added Substances given:

Trimethylolpropane 29 kg (63.8 lbs.)

Esterdiol 59.7 kg (131.5 lbs.)

Isophthalic acid 71.7 kg (158.1 lba.)

Ethylbenzene 8.17 kg (18.0 lbs.)

The mixture was heated to 210 ° C. under reflux conditions after 3.64 kg of ethylbenzene had first been boiled off. It has been further 12 h at 210 ⁰ G heated while 19.8 kg (43.7 lbs.) Of water were removed azeotropically. There were 4.53 kg (10 lbs.) Ethylbenzene gradually added during the esterification, in order to keep the reflux temperature at 21O ⁰ C. 1.77 kg (3.9 lbs.) Of ethylbenzene was collected in the trap and lines. After a reaction time of 12 hours, the polyester had an acid number of 8.13 mg KOH / g. The resin was cooled to 155 ° C. and 8.17 kg (18 lbs.) Of ethylbenzene were added. At 119 ° C, 45.6 kg (100.5 lbs.) Of isobutyl acetate was added. An additional 8.17 kg (18 lbs.) Of isobutyl acetate was added at room temperature. A polyester resin solution with a Brookfield viscosity of 28,600 oP and a solid content of 70.9 / o was obtained. The product was

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referred to as polyester solution A.

Example 39

Production of silicone-polyester copolymers

In a 3 L reaction flask with a stirrer, thermometer, heating mantle, one in grass inlet tube, one Dean-Stark trap and a condenser were filled with the following substances:

Polyester solution A 480 g

Silicone resin III 16G g

Xylene 160 g

The G-emisoh was kept at 135 ° 0 for 3 h, while methanol was in the Trap was collected. The reaction mixture was initially cloudy, but a clear solution was observed after 30 min at 135 ° C. The finished resin solution was clear, contained $ 63 solids and had a viscosity of 4200 cP (Brookfield). This resin solution was designated as silicone-polyester copolymer A.

Example 40

Production of a silicone-polyol copolymer

In a three-necked flask of 12 1 with a stirrer, heating mantle, thermometer, condenser and one The following substances were given to the solvent trap:

Silicone resin III 8230 g

Polyoaprolactone triol (Polyol III) 3000 g

Daa mixture was heated to 110 ⁰ G, and the first occurring distillate of methanol was collected. The reaction was continued at 129-145 ⁰ O for 5 hours 5 minutes while methanol was continuously removed. After a total of 426 ml of methanol was collected, the mixture was cooled. The resin obtained had a viscosity X (Gardner) and a color value of <1 (Gardner). This resin was referred to as silicone-polyol copolymer P in the following.

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Example 41

Production of a silicone-polyol-polyester terpolymer

Using the same device as in Example 39, the following substances were converted:

Polyester solution A 286 g

Silicone-polyol copolymer P 150 g

The mixture was reacted for 1 hour 10 minutes at 140-145 ° C., during which time 8.5 nil of methanol was removed. After the first 10 minutes of reaction, 50 ml of ethylene glycol monoethyl ether acetate were added. With cooling, 100 ml of the same solvent was added. The silicone-polyol-polyester terpolymer solution B obtained had a solids content of 64.0 / o and a viscosity of about Z (Gardner).

Example 42

Coatings made from silicone-polyester copolymers A and B

The following paint batches were produced using the sand grinding process:

Part by weight of grinding pigment

Silicone-Polyester-Gopolymer A
P silicone-polyol-polyester-ferpolymer B

Rutile TiO ₂ (GLKO)
At hylenglykolmono äthylät he rac et at

additions

Silicone-polyester-copolymer A 55.6

Silicone-polyol-polyester terpolymer B Hexamethoxymethylmelamine Toluenesulfonic acid monohydrate ($ 20 in isopropanol)

Thinner ^

L-45 silicone oil (2 # in xylene)

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A. 66 B. 70.3 10 - - 69.6 66 10

- , 0 54 , 2 13th , 2 13th , 0 0 0 »2 75 80 1 I. , 0

A. 7th B. 94 at 97 5,
O 57
69 fail
4T better than
3T

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- 59 - 1A-39 913

^ ' Thinner: weight st eile

Xylene. 20th

n-butyl alcohol 20

Methyl isobutyl ketone 10

Ethylene glycol monoethyl ether acetate 25

The paints obtained were filtered and heated to a viscosity of 19 s in a Ford cup Wr. 4 adjusted by small additions of xylene. After spraying onto aluminum sheets treated with chromate and drying in air for 15 min, the coatings were ^{baked for 2 min at 260 °} C. (oven temperature). The stoved paints had the following properties:

Lacquer 60 ° gloss Gardner impact resistance (cm.kg) on the front

back

T-bend (flexibility)

60 ° gloss after accelerated weathering 85 84

The example shows that a silicone-polyol-modified polyester results in a more flexible varnish than a conventional varnish with a Silicone-polyester copolymer *

Example 43

Manufacture of a polyester

Using the device of Example 39, the following substances were converted:

Trimethylol propane 398.8 g

Isophthalic acid 243.4 g

Adipic acid 134.2 g

The mixture was esterified at 165-217 ° C. for 8 h 30 min 85 ml of water were drawn off. While cooling, 300 g Ethylene glycol monoethyl ether added. It became a polyester solution with $ 68.5? This solution is in the hereinafter referred to as polyether solution B.

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Example 44

Production of a silicone-polyester copolymer

Using the apparatus of Example 39, the following substances implemented:

Polyester solution B 438 g

Silicone resin III 144 g

The mixture was for 2 hours at 148 - 150 held G ^0, while 18 ml of methanol were removed. 140 g of ethylene glycol monoethyl ether acetate were added with cooling. The resin solution contained 60.6% solids and is referred to below as silicone-polyester copolymer solution C ".

Example 43

Production of a silicone-polyol-polyester terpolymer

Using the device of Example 39, the following substances were converted:

Polyester solution B 438 g

Silicone-Polyol-Gopolymer P 183 g silicone resin III 27 g

The reaction mixture was for 2 hours at 135 - 150 ⁰ G held while 8.5 ml of methanol were removed. The clear solution was further diluted with 190 g of ethylene glycol monoethyl ether acetate on cooling. The resin solution obtained contained 60.9% solids and is referred to below as silicone-polyol-polyester terpolymer

Example 46

Coatings made from silicone polyester

Using the sand milling method, the following were made Paints made:

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B. 3 73.7 1A-39 913 55 G-ewioht parts 15th A. 74, - 55 15th

- 61 -

Mahlpigraent

Silicone-polyester-copolymer solution silicone-polyol-polyester-terpolymer D rutile TiO ₂ ethylene glycol monoethyl ether heraoet at

additions

Silicone-polyester-O-polymer solution G 57.8

Silicone-polyol-polyester-terpolymer D hexanieth xymethy! Melamine Xylene

Isobutyl alcohol p-toluenesulfonic acid (2Ο '/ ό in isopropanol) Siloxane-oxyalkylene copolymer, 10> £ in xylene

Initial viscosity, Ford cup No. 4 54 aec 54 see

The paints were filtered and diluted to a viscosity of 19 seconds (Ford cup no. 4) with a thinner made from xylene and ethylene glycol monoethyl ether acetate in a voltun ratio of 1: 1. Aluminum sheets treated with the chromate paints were sprayed, dried in air for 10 minutes and ^{baked at 260 °} C. (oven temperature) for 2 minutes. The following paint properties were found:

Laok 60 ° gloss Gardner impact resistance (om.kg) front

back

T-bend Ethanol strength 5 min

Toluene resistance 5 min 60 gloss after accelerated weathering

- CVi 57 , 5 10 5 10 30th 30th 20th 20th O, 0 , 2 0, 0 , 5

A. B. 97 98 te 23
23 57
46 fail
at 3T better
than 3T no
effect no
effect Well satisfactory 75 74

209810/1690

- 62 - 1A-39 913

Example 47

A. Manufacture of a silicone-alkyd-acrylic terpolymer Using the apparatus of Example 39,

the following substances implemented:

Phthalic anhydride 158.5 g

Trimethylol ethane 135.7 g

Goo-nut fatty acids 102.4 g

Dibutyl tin oxide 0.3 g

Xylene 25, above

The mixture was 3 h "at 195 - esterified 22O ⁰ C, while 26 ml of water azeotrope was removed, the mixture was cooled to 120 C were 215 g of silicone resin III and 230 g of xylene was added, the mixture was gradually increased to 140 ⁰ G... heated, while 21 ml of methanol were removed over a period of 1 h 45 min. The reaction ^{agemisoh was cooled to 100 0} G and the following mixture was added:

Hydroxyethyl methacrylate 11.4g

2-ethylhexyl acrylate 25.0 g

Methyl methacrylate 250.0 g

Styrene 79.0 g

Xylene 205.0 g

t-butyl peroctoate 4.8 g

The reaction mixture was then kept at 107-115 ° 0 for 45 minutes. There were 0.9 g of each of three portions of added t-butyl peroctoate every half hour and the reaction mixture was finally maintained at 112 1 ⁰ G h. After cooling, a clear resin with 64.8% non-volatile substances, which is referred to as terpolymer N in the following, was obtained.

B. Production of a silicone-alkyd-acrylic terpolymer with a polyoaprolaotone polyol

Using the device according to Example 39, the following substances were reacted;

209810/1890

2U279A

- 63 - 158 , 5 1A-39 913 Phthalic anhydride 96 , 0 G Trimethylol ethane 178 , 0 G Polyol III 102 A. G Oooosnut fatty acids O , 3 G Dibutyl tin dioxide 25th , 0 G Xylene G

The mixture was esterified for 3 hours at 195-219 ° C., while 26 ml of water were azeotropically distilled off. The mixture was cooled to 120 ° C., with 292 g of silicone resin III and 312 g of xylene being added. The mixture was gradually heated to .14O ⁰ C, During, "25 ml of methanol over 2 h were removed. The Heaktionsgemisoh became >
puts:

became. The mixture was gradually ^{heated to .14O 0} C while

)1
was cooled to 100 C and the following mixture was added

Hydroxyethyl methacrylate 15 | 0 g

2-ethylhexyl aorylate 34.0 g

Methyl methacrylate 340.0 g

Styrene 107.0 g

Xylene 278.0 g

t-butyl perootoate 6.5 g

The reaction mixture was held at 110-115 ° C. for 45 minutes. Three portions of 1.2 g of t-butyl peroctoate were added every half hour and the mixture was finally ^{kept at 112 °} C. for 1 hour. After cooling, a clear resin with 64.0% non-volatile constituents was obtained, which is referred to below as terpolymer P.

C. Production of coatings from the terpolymers P and N

Clear warui-hardening coatings were obtained as follows set:

203810/1690

1A-39 913 B. , 2 - , 5 Parts by weight 78 , 4 A. 7th , 0 77.2 0 - 30th 7.5 0.4 30.0

Terpolymer N Terpolymer P He xamet ho xymet hylmelamin

Toluenesulfonic acid monohydrate ($ 20 in isopropanol)

toluene

Films were made on phosphate steel plates, caliber 24, poured, air-dried for 10 min and then baked at 260 ° C. for 2 min. There were clear glossy coatings with the following Properties obtained:

Cover A B

Film thickness, around 30, -5 30.5

Gardner impact strength (cm.kg)

Front 23 46 Back 0 11.5

Mandrel bending better than

than 6.35mm 3.175mm

These coatings explain that the terpolymer modified with polycaprolactone (in the alkyd part) results in a more flexible thermosetting coating. The substitution of the polyol III was performed on a molar basis, ie the two terpolymers corresponds w kept the same ratio of the reactive groups (-COOH / OH).

The patent is not required

209810/1690

Claims (1)

Claims 1. Composition for protective covers, ventilating from a mixture from A. a curable film-forming preparation aua (1) a silicone component with an average of 1-1.9 monovalent organic groups which are bonded to each silicon atom by carbon-silicon bonds and of which at least Groups containing 25 moles # aryl create, (2) a polylaoton component in which at least 40 mol $ of the monomeric Laoton units have the formula -J-CR ¹ "-j-000- in which H ^{1 is} hydrogen or a monovalent hydrocarbon group and (3) an organic coating resin component, B. a liquid diluent and possibly O. a crosslinking agent and customary additives. 2. Composition according to claim 1, characterized daduroh, that in the silicone component 25-90 mol $ of the monovalent organic groups are vinyl groups and the remaining monovalent organic groups are alkyl groups with 1-10 Carbon atoms are inclusive. 3 »mass according to claim 1, daduroh characterized, that the polylaoton component mainly consists of caprolaoton units consists. 4 mass according to claim 1, characterized by that the organic coating resin component is an aoryl resin, a vinyl halide resin, an alkyd resin, an oelluloa resin or a Is polyester resin. 209810/1690 2H279A - CC- 1A-39 913 5. mass naoh claim 1-4, characterized in that the components (1), (2) and (3) of the film-forming Preparation as separate curable polymers. 6. Composition according to claim 1-4, characterized in that two of the components (1), (2) and (3) of the film-forming preparation chemically bonded as curable block copolymers are present and that the film-forming preparation has the block copolymer mixed with the third component, which is in the form of the separate curable polymer. 7 · Composition according to claims 1-4, characterized in that components (1), (2) and (3) are chemically present bound as a block of a hardenable perpolymer. 8. Composition according to claim 1-4, characterized in that the components (1) and (2) of the curable The film-forming preparation is chemically bound as a block in a curable Blockcupoljaerisat and the film-forming preparation consists of a mixture of this block copolymer and component (3), which is in the form of a curable polymer is present separately. 9. mass naoh claim 1-5, characterized in that the silicone component as a separate curable polymer is present. 10. Composition according to Anspruoh 1 -5 and 9, characterized in that the component (1) as a separate curable Polymer with an average of two hydroxyl groups bonded to silicon or at least silicon-bonded alkoxy groups is present per molecule. 11. Mass naoh one of claims 1, 4, 5 and 8, thereby gekennze is worthwhile that component (3) a 209810/1690 2H279A -tf- 1A-39 913 Has a molecular weight of at least 20,000. 12. Composition according to claim 11, characterized in that that component (3) has a molecular weight of at least 30,000. 13. Composition according to one of claims 1, 4, 51 8 and 11-12, characterized in that the component (3) is an acrylic resin mainly composed of a copolymerized one Alkyl aorylate or alkyl methaorylate and a copolymerized olefinically unsaturated compound with a hydroxyl group, an epoxy group or an etherified methylol group ". 14. Composition according to one of claims 1, 4, 5, 8 and 11-12, characterized in that component (3) is a Vinylhalogenioy xst, which mainly consists of 60-95 Grew .-> o of a polymerize vinyl chloride resin, 0-40 (Jew .- ^ one Polymerize vinyl esters or vinyl ethers and 1-20 wt .- $ one alcoholic hydroxyl-containing olefinically unsaturated Monomers "consists. 15 mass according to one of claims 1, 4, 5, 8 and 11-12, characterized in that component (3) is an alkyd resin. 16. Composition according to one of claims 1, 4, 5, 8 and 11-12, characterized in that component (3) is a cellulose acetate "butyrate". 17. Composition according to one of claims 1, 4, 5, 8 and 11-12, characterized in that component (3) is nitrocellulose. 209810/1690 2H2794 1A-39 913 18 «mass naali one of claims 1, 3 and 5, thereby characterized 'that the component (2) mainly from a main amount of caprolactone units and one minor amount of a residue of a glycol or trioist starter consists. 19. Composition according to one of claims 1,5,5 and 18, characterized gekennze rejects that component (2), a polylactone polyol which is mainly made up of recurring lactone units, which are end-blocked with hydroxyl groups. 20. Composition according to one of claims 1-19, characterized in that the curable film-forming preparation Has reactive groups that contain active hydrogen atoms contain and the mixture as an additional component a formaldehyde resin, an epoxy resin or an organic polyisocyanate as Contains crosslinking agents. 21. Composition according to one of claims 1, 3, 5 and 18-19 »thereby characterized in that the polylactone component has a molecular weight of 200-1500. '22Y Curable copolymer or terpolymer, consisting of I. a silicone block made of units of the formula R SiO. · « a 4-a in which R is a monovalent organic group attached to the Silicon atom is bonded by a carbon-silicon bond or a hydrocarbonoxy group, a hydroxyl group or a divalent atom or group which bonds the silicone block to an organic block, and a has a value of 1-3 inclusive and wherein the silicone block has an average of 1-1.9 monovalent organic groups, represented by R and on, each silicon atom are bonded and contain at least one divalent atom or group represented by R and 20981071690 2H2794 -6f- 1A-39 913 II. At least one organic block of the following types: (1) a polylactone block in which at least 40 mol of the monomeric units have the formula - ^ KJR'o ^^ fGOO - in which R ^{1 is} hydrogen or a monovalent hydrocarbon group, (2) an organic polymeric coating resin and (3) a block copolymer from (1) and (2). 23. A curable copolymer according to claim 22, wherein in the formula R is a methyl group, an alkoxy group, a hydroxyl group or an oxygen atom that connects the silicone block with the organic block connects, is, where each silicone block an average of at least two hydroxyl or alkoxy groups R and wherein each organic block is the polylactone block consisting mainly of caprolactone units and a Has a molecular weight of 200-1500. 78XXI 209810/1690