DE2858105C2 - Reactive lacquers and stoving lacquers based on copolymers containing hydroxyl groups and processes for the production of coatings - Google Patents

Description

(S) polyisocyanates,

(C) inert organic solvents and optionally (D) other additives commonly used in reactive lacquers,

characterized in that as component (A) a hydroxyl group-halliges Copolymo- ^ aI is used, which by heating with esterification in the presence of an epoxy-carboxycal analyzer and

^) is obtainable with simultaneous copolymerization by means of polymerization initiators in inert organic solvents and optionally chain terminators, with at least one alkali compound being used as the epoxy-carboxyalkalyser and the copolymer (A) in an amount of 60-95% by weight and the polyisocyanate (B ) is present in an amount of 5-40% by weight, (A) and (B) together must result in numerical values fc of 100% by weight.

2. Stoving enamels off

(A) hydroxyl group-bearing copolymers based on

(a) aromatic vinyl compounds,

JO (b) Acrylates or methacrylates with 1 to 12 carbon atoms in the alcohol residue, esters of the Croton

acid with saturated alcohols that contain 1 to 10 carbon atoms in the alcohol residue,

(c) Vinyls and hydroxyl-bearing uj? -alhylenically unsaturated compounds,

(d) ajü-unsaturated monocarboxylic acids and

(e) monoglycidyl compounds,

(BO aminoplast resins,

(C) organic solvents and optionally

(D) other additives commonly used in stoving enamels,

characterized in that as component (A) a hydroxyl group-hallous Copolynierisal, which by Heating with esterification with esterification in the presence of an epoxy-carboxy-analyzer and below simultaneous copolymerization using polymerization initiators in inert organic solvents and optionally chain terminators is obtainable, at least one being epoxy-carboxycal analyzer Alkali compound is used and duli the Copolymerisal (A) in an amount of 70-95 wt .-% and the

Aminoplast resins (B ') are present in an amount of 5-30% by weight, (A) and (B') together numerically

values of 100% by weight must result.

3. Reaction varnish according to claim I. characterized in that the copolymers (A) have a hydroxyl group content of 2 to 6 wt .-%, based on the weight of the starting monomers, and acid numbers of 2 to 12 have.

4. Reaction varnish according to claim I, characterized in that it also contains I to 10% by weight of reactive melamine resins.

5. A process for the production of coatings by applying a varnish based on copolymers containing hydroxyl groups, polyisocyanates, solvents and optionally customary additives to a carrier and curing at low temperature or by baking, characterized in that, that a lacquer according to one of claims 1, 3 or 4 is used.

6. Process for the production of coatings by applying a varnish based on copolymers containing hydroxyl groups ^ aminoplast resins, solvents and, if appropriate, customary Additions to a carrier and curing by baking, characterized in that a varnish is used according to claim 2 used.

The invention relates to reactive lacquers and stoving lacquers as well as processes for the production of coatings.

DE-PS 10 38 754 describes a process for the production of esterified polyhydroxy copolymers described. This known method is characterized in that simultaneously and in the presence of one Epoxy-Carboxykalysators and a catalyst for the Vinylpolymerisalion are reacted: (a) a

short-chain a-ji-unsaturated monocarboxylic acid, (b) a vinyl monomer with only one active terminal CH ₂ = C group capable of addition polymerization and (c) a monoepoxide, which is an optionally alkyl-substituted alkylene oxide, an ether or ester with only is a three-membered epoxy substituent, the monoepoxide otherwise having no reactive group. The reaction must always be carried out simultaneously in the presence of an epoxy catalyst and a catalyst for the vinyl polymerization. As reworking of the examples there has shown, these known copolymers give yellow to brownish colored solutions. The paint films produced therefrom show an undesirable yellow to brown coloration after the solvent has evaporated, so that these products can only be used to a very limited extent.

The object of the invention is to provide reactive lacquers and stoving lacquers which have significantly improved properties, namely:

1. The coating films should be "speck-free" or very "low in specks" and despite the presence of catalysts does not yellow.

2. The coating films are said to have high scratch and abrasion resistance, combined with good Resistance to solvents i <.ständigkeil, good resistance to water and chemicals.

3. In addition to air drying, the paints should be stovable over a wide temperature range; the films should be fully cured in 30 minutes at 130 ^{° C. on stoving.}

4. The coatings of the applied reaction lacquers, which have been cured at room temperature, should not be inferior to stoved films in terms of weather resistance.

5. The paints should have a surprisingly long pot life.

This object is achieved by the paints according to claims 1 to 4.

The copolymers used in the paints according to the invention, which according to DE-PS 28 51 615 are used as component Λ in the reactive varnishes together with a polyisocyanate component B and in the stoving varnishes component A is used together with an aminopia3 resin component B '.

The following polyisocyanates, for example, can be used as component B: Toluylene-diisocyanate, tolylene-o-diisocyanate, diphenylmethane-diisocyanal, naphthylene-1,5-diisocyanate, 4,4'-4,2-triphenylmethane triisocyanate, 1-isocyanatophenyl ethyl isocyanate or xylene diisocyanate, Fluorine-substituted diisocyanates, ethylene glycol diphynyl ether-diisocyanal, diethylene glycol diphenyl ether-2,2'-diisocyanate, 1'-dinaphthyl-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, benzophynone-3 , 3'-diisocyanate, fluoro-1-diisocyanate, anthraquinone-2,6-diisocyanate. Pyrn-SS-diisocyanate, Chrysn-2,8-cwi.socyanate, 1-methylbenzoi ^, 4,6-triisocyanate, naphthalene-1 ^ J-triisocyanate, biphenylmethane-2,4,4'-triisocyanate, triphenylmcthaπ-4, 4 ', 4 "-triisncyanal, 3'-methoxyhxane diisocyanate, octane diiso-ft ^ (^> - diisocyanate 1,4-dimethylnaphthalene, cyclohexane-1 ^ -diisocyanal, 1-isopropylbenzene ^ -diisocyanal, 1-chlorobenzene-2,4-diisocyanate, 1-fluorobenzene ^ -diisocyanate, 1-nitrobenzene ^ -diisocyanal, I-ChloM- methoxybenzene ^^ - diisocyanate, A / .obcnzoM ^ '- diisocyanal, Benzolazonaphthalin ^ / T-diisocyanal, Diphcnyläthcr ^ -diijiKyanat and Diphenyl ether M'-diisocyanate and polyisocyanates based on isophorone diisocyanate with socyanurate structures and a functionality between 3 and 4. tion products of polyhydric alcohols with polyisocyanates, for example the reaction product of 1 mol Trimethylolpropane with 3 moles of toluylenediisoeyanm, also called trimcrisicrtc or polymerized isocyanates.

In addition, there is also a reaction product containing biuret groups from 1 mol of water and 3 mol Hxamethylindiisocyanat with an NCO content of 16 to 17 Cicw .-% in question. That is particularly preferred the last-mentioned conversion principle from water and hydroxamethylcndiisocyanate. The NCO content of the reaction product applies to a 75% solution in xylene / ethyl glycol acetate.

Mixtures of solvent-containing, hydroxyl-containing copolymers A and Polyisocyanate B in the simplest possible way, for example after adding known auxiliary agents such as leveling agents. Pigments or dyes, by spraying, dipping, pouring, brushing or other suitable measures the appropriate documents and dry the fabric at room temperature; In special cases, the coatings can be stoved, which essentially depends on the documents used and the requirements placed on the coatings in practice. The use of reactive melamine resins can also be advantageous. You can use the reactive melamine resins in amounts from I up to 10% by weight, based on the weight of the binder components. add, as a result of which, in particular, an increase in gloss can be observed in the sheet-like structure.

In the reaction varnishes already explained, the conversion and the application of the surface structure to the substrate in solution (iccignetc solutions are / .. B. ethyl acetate, butyl ester, ether ester diethyl glycol diacelate and aromatics such as benzene, toluene or xylene. The concentration of the solutions can be in vary within wide limits and depends essentially on the solubility of the components. Solutions with a solids content of 20 to 80% by weight are preferably used. Components (A) and (B) are used in the following amounts in the reaction paints:

(A) from 50 to 95% by weight of copolymers containing hydroxyl groups,

(B) 5 to 40% by weight of organic polyisocyanate, where (A) and (B) together are numerical values of 100% by weight must surrender.

f A particularly preferred reaction varnish contains:

ΐ (A) 63 to 68% by weight of hydroxyl group-containing copolymers and

% (B) 32 to 37 wt .-% organic triisocyanate, which by reaction of 3 moles of 1 lexamethylene diisocyanate

? -; 5 and 1 mol of water was obtained, (A) and (B) having to give numerical values of 100% by weight.

The main areas of salt for the copolymers are - in combination with aliphatic and aromatic Polyisocyanates or their mixtures - air- and oven-drying metal, wood and plastic coatings. i. Such two-component paints are preferred if they are air-dried or force-dried

Lacquers are expected to have properties that are usually only offered by stoving lacquers.

These new reaction lacquers are used as binders especially for the exterior refinish lacquer sector as well as for the Bus and truck painting used.

f: In combination with aliphatic polyisocyanates, full, non-yellowing paints with mil

; excellent weather resistance and gloss retention.

U ^l5 When curing with aromatic polyisocyanates, a certain amount of yellowing is to be expected.

■ ^: Reaction lacquers based on the invention show, accordingly, their higher crosslinking density

^; comparable good hand products for the same purpose a high level of scratch and abrasion resistance, combined

, the one with good solvent resistance. The good resistance to water should also be emphasized

and chemicals.

2u In addition to air drying, such lacquers can be baked in a wide temperature range; so the films in 30 minutes at 130 ⁰ C for example, are fully cured.

The coatings cured at room temperature are in the weather resistance of unfired films not after.

: The copolymers have a high pigment absorption. For pigmentation, all are neutral pigments

:? and fillers are suitable. Strongly basic pigments as well as pigments with soluble metal compounds can

: exert a kaialytic effect on the crosslinking, reducing the processing time of the ready-mixed

Paint approaches is shortened.

^: The hydroxyl group-bearing copolymers which are obtainable by the process of DE-PS 28 51 614,

can instead of the polyisocyanates also with masked polyisocyanates for the production of stoving enamels be used as z. B. in DE-OS 26 23 081 is described. As a disguised polyisocyanate door this Purpose are those in DE-OS or -AS 26 12 786, those in DE-OS or -AS 26 12 785, those in DE-OS or AS 26 12 784, those described in DE-OS or -AS 26 12 781 and those described in DE-OS or -AS 26 12 638 suitable.

In stoving enamels, components (A) (B ') are used in the following amounts: Jj

(A) 70 to 95% by weight of hydroxyl-containing copolymers,
(B ') 5 to 30% by weight of aminoplast resins.

where the% by weight information must add up to 100% by weight. As aminoplasmic resins, all can be found here Aminoplast resins are used which are compatible with Acrylatcopolynierisatharzcn and in large numbers are on the market and are often based on urea and / or melamine-formaldehyde and with lower Alkanols are present in etherified form.

The solution of the finished Copoiymeren is cooled and introduced the aminoplast solution, wherein the Solvent content is adjusted so that the desired concentration is achieved. Then pigments can can be added.

The stoving enamels according to the invention, after stoving at 90 to 180 ^° C., produce films with excellent resistance properties to chemicals of all kinds, such as solvents, acids and alkalis, and also super fuels.
The baking enamels can be dried at room temperature. Hardening doesn't necessarily need to be

to be made at 120 to 140 ⁰ C in 30 minutes. At 16O ⁰ C z. B. the burn-in time is reduced to about 15 minutes.

Preferred aminoolaste are condensation products of formaldehyde and melamine, with melamine per mole Approximately 4 to 6 moles of formaldehyde are either weakly acidic or weakly basic and with butanol or isobutanol 80 to 100% should be diluted. The resulting implementation

products should have a molecular weight of 400 to 1200 and in organic solvents such as xylene and butanol or isobutanol and other alcohols may be soluble.

The mixed polymer and the aminoplast are in the ratio of 70 to 95 parts of the Copoiymeren and of 5 to 30 parts of the aminoplast dissolved in the organic solvent. The proportions of the copolymer and the alkylated aminoplast are to be chosen so that the two components are both in the

Coating solution tolerated as well as in the finished film. Any suitable concentration of the interpolymer can be used and of the aminoplast in the solvent of up to 50 percent by weight are used If pigment is present, the total content of the solids in the coating composition is between 5 and 75 percent by weight. The ratio of pigment to binder (mixed polymer plus aminoplast) can be between 1: 2ü and I: I lie.

i-5 The following solvents can be used: hydrocarbons such as benzene, toluene, xylenes and aromatic ones Naphthenes or mixtures of such solvents: lister, such as ethyl, butyl, amyl, Älhoxyäthyl or Methoxyethyl acetules, lactals or propionates; Ketones, such as acetone, methyl isopropyl ketone, methyl isobuiyl ketone, Dioxane, isophorone or cyclohexanone; Alcohols such as n-bulanol, l-butanol, isopropyl alcohol, n-propyl

alcohol, amyl alcohols and cyclohexanol; Ethers, such as diethyl ether, the monoethyl, monomethyl and monobiityl ether of ethyl glycol and various other solvents such as dimethylformamide, dimethyl acetamide. Acetonitrile, nilromethiine, nitroithane, nitropropane or nitrobutane, as well as mixtures of two or more solvents of the same kind (iruppc and of several or all of the groups listed above.

The following pigments can be added: inorganic pigments such as chrome yellow, Prussian blue, Brunswick green; Tilane pigments, / .. B. titanium dioxide, stretched tilane pigments (which are stretched either with precipitated or natural extenders, such as hard alkali sulphate, / .. H. calcium sulphate and barium sulphate); tinted tilan pigments, titanates, such as barium, zinc, lead and magncsium titanate. Other types of organic pigments can be used / .. as zinc sulfide pigments such as zinc sulfide. Lithopon, extended zinc sulphide pigments, such as lithium-based lithopon, zinc sulphide extended with natural extenders, zinc oxide or antimony oxide or organic pigments, ie organic dyes which are free from sulphonic acid, carboxylic acid or other water-solubilizing groups. The term "pigment" also includes other water-insoluble organic dyes, e.g. B. the calcium or barium lacquers of azo lacquer dyes.

The ring varnishes according to the invention can be applied to the substrates in any way, /. B. by brushing, spraying, F. immersion, rolling. They are then dried and hardened by heating.

Component A is a hydroxyl group-bearing copolymer Huf based on soluble in organic solvents

(a) aromatic vinyl compounds,

(h) Acrylates or methacrylates with 1 to 12 carbon atoms in the alcohol residue, containing crotonic acid with

saturated alcohols which contain I to ΙΩ carbon dioxide in the alcohol residue, (C) vinyl esters and ιτ, / y-ethylenically unsaturated compounds bearing hydroxyl groups, (d) «,, / ^ - unsaturated monocarboxylic acids and

(C) Monoglycidyl compounds, which are prepared by heating with esterification in the presence of an epoxy-carboxy catalyst and with simultaneous copolymerization by means of polymerization initiators in inert organic solvents and optionally chain terminators, with at least one alkali metal compound being used as epoxy-carboxy catalysts.

Esterification catalysts based on an alkali metal compound can be all sodium, lithium, potassium, rubidium and cesium compounds - individually or in a mixture - which are soluble in the reaction mixture of σ, // - unsaturated monocarboxylic acid, monoglycidyl compound and at least two other vinyl compounds are and proceed at least in the addition and / or while keeping the reaction mixture at the reaction temperature for the purpose of esterification by addition at the same / piece copolymerization in solution, a wherein the alkali used should however compound free of such ingredients to be that in the copolymerization of Additionsprodiiktes that represents an F.stcr, can have an unfavorable effect.

For example, the carbonates, bicarbonates, formates and the hydroxides of the above are useful called alkali metals. On a driving scale, lithium hydroxide and potassium hydroxide are best - individually or in a mixture - carried out. «To

When used on a mobile scale, potassium hydroxide is used particularly advantageously due to the low price and the excellent catalytic properties. This is expediently used Alkali hydroxide or the alkali bond or mixtures thereof in the unsaturated one to be esterified Dissolved monocarboxylic acid. But you can also from the alkali compound, z. B. alkali hydroxides, alkali carbonates or alkali bicarbonates ^ and the ", // - unsaturated monocarboxylic acid only its alkali salt as a catalyst and can then prepare the alkali metal of the "j-unsaturated carboxylic acid" in the reaction mixture dissolve or, when carrying out the esterification and copolymerization, bring them into solution by heating.

In general, it is sufficient to use from about 0.005% by weight to about 0.5% by weight alkali metal compound already mentioned type, based on the weight of the constituent components, for the addition reaction to add. However, an addition of about 0.01% by weight to about 0.3% by weight of alkali metal compound is preferred manure. :

The most preferred range for the addition is from about 0.02% by weight to about 0.1% by weight alkali metal compounds, with potassium and lithium compounds being very particularly among the alkali metal compounds find advantageous use.

Acrylic acid, methacrylic acid and / or crotonic acid, individually or as a mixture, are used as σ, ^ - ethylenically unsaturated monocarboxylic acids. This also includes half esters of maleic and fumaric acid with saturated alcohols that contain 1 to 10 carbon atoms.

The monoepoxydcn include substituted alkyl compounds as well as ethers and esters, provided that the one tripartite epoxy ring included.

Examples of alkyl-substituted monoepoxides are propylene oxide, butene-2-oxide, hexene-2-oxide, octene-2-oxide and styrene oxide.

Examples of substituted ether monoepoxides are butyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether and phenyl glycidyl ether.

Examples of ester monoepoxides are the glycidyl esters of the following acids: acetic acid, propionic acid, butyric acid. Caproic acid. Caprylic acid, 2-ethylhexanoic acid, isononanoic acid, "-, ff-dialkylalkane monocarboxylic acids, in which in -position to the carboxyl group the hydrogen atoms of the alkanemonocarboxylic acid are replaced by alkyl radicals are substituted such that a tertiary carbon atom is present, having the formula

R '

R ₂ -C-COOH I ·.!

L I

where R ', R-' and R ^{1 represent} alkyl groups and the total sum of the carbon atoms of all alkyl groups3 | J ₍

to 25. The glycidyl groups of aa-dialkylulcanic monocarboxylic acids with ¹ C- to 13 C- gjj are preferred

.Flomen in the alkyl group radical.

lü The most preferred glycidyl ester of aa-dialkylalkane monocarboxylic acid has the sum formula C ,, H _M 0 ,.

Examples of the aromatic vinyl compounds are styrene, vinyl toluene, o-methylstyrene and halosylrole which have no group capable of reacting with the carboxyl group other than the vinyl group.

Examples of the esters of acrylic, methacrylic and crotonic acid are methyl, ethyl, propyl, isupropyl, ι s η-butyl, isobutyl, sec-bulyl ·. tert-bulyl, amyl, mexyl, meptyl, octyl, nonyl and deeyl esters can be used individually or in a mixture.

The following can be used as vinyl esters, for example: vinyl esters of, among others, dialkyl sulphon monocarboxylic acid with the formula

R- C-COOH

R ¹

where R ', R' and R 'represent alkyl groups and the total sum of the carbon atoms of all alkyl groups 3 to 25, and of these, vinyl esters with the following formula CT "111" - CC) -O -CII = CII. preferred. Vinyl acetate and vinyl propionate can also be used as vinyl esters. Hydroxyethyl methacrylate can be used as hydroxyl-bearing α, / f-ethylenically unsaturated compounds.

M hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and butanediol monoacrylal and / or butanediol mono-methacrylate, individually or in a mixture, can be used. Furthermore, ether esters bearing hydroxyl groups, such as polypropylene glycol monomethacrylate and / or polyethylene glycol monomethacrylate with average molecular weights between about 175 to about 390, can also be used. In a preferred embodiment for the preparation of copolymers which are in the inventive Ben lacquers are used, with a deficiency of a. ^ F-unspecified monocarboxylic acid up to Worked equivalent, where the molar ratio Monoepuxy: t / Ji -unsäüigler monocarboxylic acid I :(), 95 to I amounts to. The copolymers should have acid numbers of 3 to 5. The hydroxyl numbers of the copolymers should be 40 to 2%. Another embodiment is characterized. that to implement

d) 11 to 0.5% by weight «, ^ unsaturated carboxylic acid,

e) 1.5 to 39% by weight of monoglyeid compound,

a + b) 50 to 98% by weight of other vinyl compounds are used.

A variant of the above Ausluhrungsform is characterized in that the implementation as other vinyl compounds (c) up to 30% by weight of one or more vinyl compounds having a hydroxyl group in the molecule can be used.

Another variant of the above process is characterized in that the other vinyl compounds a) styrene, b) acrylates and / or methacrylates with 1 to 12 carbon atoms in the alcohol residue are set.

One embodiment of the above process is characterized in that other vinyl compounds with a hydroxyl group in molecule (c) are hydroxyethyl acrylate, hydroxypropyl acrylate, butanediol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butanediol monomethacrylal. Polypropylene glycol monomethacrylate and / or polyethylene glycol monomethacrylate with average molecular weight weights between 175 to about 390 can be used.

One embodiment of the method is characterized in that d) acrylic acid and / or methacrylic acid, e) monoglycidyl esters or monoglycidyl ester mixtures of aliphatic saturated monocarboxylic acids with 2 to 19 carbon atoms, a) styrene, b) vinyl esters of saturated monocarboxylic acids or mixtures of such esters with 4 to 19 carbon atoms in the carboxylic acid molecule, ethyl acryl, n-, iso-, sck., tert-butyl acryl

N) lat, methyl acrylate. Ethyl methacrylal, n-, iso-, sec.-, lert.-bulyl methacrylal, methylniethacrylal and c) hydroxyethyl acrylal, hydroxypropyl acrylate, bulanediol monoacrylal. Hydroxyäthylmethacrylat, Hydroxypropylmethacrylat, Bulandiolmonomethacrylal are implemented.

One embodiment is characterized in that d) 6 to 12% by weight of acrylic acid with e) 18 to 44% by weight of glycidyl ester of a, u-dialkylalkane ^{monocarboxylic acid with the empirical formula C 1} LiH ₂₄ O.!, Its structure door about

R ¹ OO RCC -C-- CIl 'CII CH ²

R ¹

is equivalent to,

wherein R ¹ , R "and R ^{1 represent} radical alkyl groups, at least one of which is the methyl group, the molar ratio of glycidylic acid / acrylic acid I being 0.98 to I, and a) 15 to 30% by weight of styrene and / or vinyl toluene, b) 15 to 25% by weight of methyl methacrylate, c) 15 to 25% by weight of hydroxyethyl methacrylate, and the reaction takes place until an acid number of 3 to 5 has been reached and the stated% by weight is / u need to add 100% by weight.

One embodiment of the above process is characterized in that d) 5 to 7% by weight of acrylic acid with e) 17 to 25% by weight of glycidyl ester of a », w-dialkylalkane monocarboxylic acid with the empirical formula ChHj ₄ Oi, whose structure is approximately

R 'OOR ^J- C-C-O-CH, -CH CHj

i ·

is equivalent to,

wherein R ¹ , R ² and R are alkyl groups, at least one of which is the methyl group, the molar ratio of glycidyl ester to acrylic acid being 1: 0.98 to 1, and a) 25 to 30% by weight of styrene, b,) 15 to 20% by weight of methyl methacrylate, c,) 15 to 20% by weight of hydroxyethyl methacrylate. c?) 2 to 6 wt .-% Polypropylcnglykolmonomklhacrylat, whose structure approximately of the formula

H ₂ = C-COO- ^ CH ₁ CHO / ,, -H

is equivalent to,

where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387 and h>) 3 to 10 wt .-% vinyl ester of a, ff-dialkylalkanemonocarboxylic acid with approximately the formula

C, H "- CO- O - CH = CH,

where the grouping C., H,., largely the structure

CH,

C ₇ H, -C-

C, H ||

having,

where the weight% must add up to 100 weight%, are polymerized until acid numbers of 3 to 5 are present.

F.inc embodiment of the process is characterized in that the copolymerization with addition a Kctlcnrogler takes place. *O

F.inc embodiment is characterized in that copolymers from

; i) 20 to 32% by weight of styrene and / or vinyl toluene,

b) 16 to 26% by weight of methyl methacrylate.

c) 26 to 16% by weight of hydroxyethyl methacrylate, of which, if necessary, up to 7% by weight of hydroxyethyl methacrylate through polypropylene glycol monomethacrylate with the formula

CH,

CH, = C -COU

CH, CHjCHO

are replaced

where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387,

d) 6 to 9% by weight acrylic acid and / or methacrylic acid and (, 5

e) 20 to 30% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms are prepared, the components a, b, c, d and e being selected so that they become Add 100% by weight.

One embodiment is characterized in that it consists of copolymers

a) 10 to 29 wt .-% styrene and / or vinyl toluene,

b) 1h to 26% by weight methyl methacrylate!

^ c) 16 to 26% by weight hydroxyethyl methaaylal.

d) 7 to 12 wt .-% acrylic acid and / or methacrylic acid and

e) 36 to 20% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids with 9 to 15 carbon dioxide are prepared, the components a. b, c, d and e are selected so that ¹ Jiesc add up to 100% by weight.

One embodiment is characterized in that copolymers from

a) 27 to 32 wt .-% styrene and / or vinyl toluene,

b) 18 to wt .-% methyl methacrylate,

C |) 16 to 18% by weight hydroxyethyl methacrylal,

C ₂ ) 2 to 6% by weight of polypropylene glycol monomethacrylate with the formula

CH., / CH ₃

where η denotes numbers from S to 6 and the average molecular weight is about 350 to 387,

d) 6 to 7 wt .-% acrylic acid and / or methacrylic acid and

e) 23 to 25% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms be prepared, the components a, b, c, d and 3 are selected so that these add up to 100% by weight.

Another embodiment of the method is characterized in that copolymers from

3 to 40% by weight

a) styrene and / or vinyl toluene and / or b) methyl methacrylate.

10 to 40% by weight

b,) Acrylic acid esters and / or methacrylic acid esters of aliphatic saturated monoalcohols with 2 up to 12 carbon atoms,

10 to 30% by weight

c) hydroxyethyl acrylate and / or hydroxyethyl methacrylate. Polypropylene glycol monomethacrylate with • 40 of the formula

CH, / CH ₃ \

CH ₂ = C-COO-I ₁ CH ₂ CHOJ _n -H
where / ι numbers from 5 to 6 and the average molecular weight is about 350 to 387,

5 to 12% by weight

d) acrylic acid and / or methacrylic acid and

35 to 15% by weight

Glycidyl esters made from aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms be, where the components a, b, c, d and e are selected so that they are 100 wt .-% add to.

One embodiment of the above process is characterized in that for copolymers, which are intended for polyisocyanate crosslinking, the starting components are selected and implemented in this way that copolymers with a hydroxyl group content of about 2 to about 6 wt .-%, based on the Weight of the starting monomers and with acid numbers of 2 to 12, preferably 3 to 6, can be obtained.

One embodiment is characterized in that for copolymers which are crosslinked with aminoplast resins are determined, the starting components are selected and implemented so that copolymers with a hydroxyl group content of 2 to 4.5% by weight, based on the weight of the starting monomers, and with an acid number of 10-15.

Another preferred embodiment of the process provides that the organic solvent Xylene, monoglycol ether acetate or mixtures of xylene and mono ether acetates can be used, with as Polymerization initiator, 8 to 1.5% by weight of di.-lert.-butyiperoxide and optionally up to 1% by weight of iodecylrp.erfcaptar! can be used as Kstlsnabbrccher, whereby the weight isprozen (data for the polymerization initiator and the chain breaker on the sum of the weights of the cingesel / .th to be converted Refer to monomers.

The most preferred embodiment of the invention is characterized in that heating the solvent xylene orthe mixture of xylene and Atnylglykolacetatmitdem Glycidylesteraufl40bis 180 ⁰ C, another Gsmisch consisting of acrylic acid, in which the catalyst was dissolved, then Tu-terL- with the other vinyl monomers Butyl peroxide and dodecyl mercaptan were added uniformly in 2 to 5 hours and polymerized and condensed for a further 4 to 5 hours at the same temperature. s

Suitable solutions for the production of the new copolymers are those that are not active Contain hydrogen atoms such as xylene, Monogiykolätheracetate or mixtures of Monogly kolstheracetat and Xylene, methyl glycol acetate, ethyl glycol acetate, isopropyl glycol acetate or n-butyl glycol acetate being exemplified as monoglycol ether acetals.

As polymerization initiators, for example, diacyl peroxide, z. B. dibenzoyl peroxide, perester, ζ. Β. ίο tert-butyl peroctoate and dialkyl peroxides, e.g. Be used as Di.-tert-butyl peroxide, and all peroxides whose half-lives are in a temperature range of 50 to 150 ⁰ C.

The peroxide part is about 0.5 to 5 wt .-%, based on the total proportion of ar, jB-ethylenically unsaturated monomers including the esterified monoepoxides.

As chain regulators, for example, octyl mercaptan, decyl mercaptan, lauryl mercaptan is, if appropriate and the branched dodecyl mercaptan used. The proportion of chain regulators, based on the total The proportion of ethylenically unsaturated monomers including the esterified monoepoxides is 0 to 2.5 wt%.

Practical embodiments for the production of the copolymers are described below, which may be included in the paints of the present invention.

Production of the copolymers Coiolymerizate A 1

In a reaction vessel equipped with a stirrer, reflux condenser and thermometer, a mixture consisting of is refluxed at about 146.degree

294.0 g xylene,

150.0 g of ethyl glycol acetate,

144.5 g glycidyl ester of a ^, ff-Dialkylalkanmonocarbonsaure following empirical formula CuH ₂₄ O ₃ with an .'0 epoxy equivalent of 245 to 253 (boiling range 5 to 90% at 710 mmHG from 251 to 278 ° C = 0.59 epoxy equivalent, 21, 72 = wt%). (The glycidyl ester is described in the Technical Bulletin RES / CAX / 1 of Shell Chemicals with the title: "Shell Resin Intermediates Cardura E 10". Its structure can be represented by the following formula, which is based on a synthetic, saturated, highly branched monocarboxylic acid with 10 Carbon atoms

R 'O O

₂ I Il / \

R ² -C C -C O _{-CH 3} -CH CH ₂

I, R ³

in which R ¹ , R ² and R 'represent cracked alkyl groups, at least one of which is always the methyl group). The following mixture, which is in a dropping funnel at room temperature, is added to the mixture at 146 ° C. and consists of 26.2 g of vinyl ester of a -cr-dialkylalkanemonocarboxylic acid with the formula C ₁ H ₁₅ CO-O-CH - CH ₂ (3.94% by weight), with the remainder being CH ₁ , largely due to the structure

C ₂ H ^ - C - CH ι

C ^ Hii can be marked,

116.1 g of hydroxyethyl methacrylate (= 17.45% by weight),

26.0 g of polypropylene glycol monomethacrylate having an average molecular weight of 350 to 387 and a hydroxyl number from 145 to 160 (= 3.9 wt ⁰ / "). (The above product can be represented by the following formula:

CH,

CH ₂ = C-COO-

CH, CH ₂ -CHO

-H

where π the /, ahlcnwcrtc 5 to 6),

192.0g styrene (- 28.85% by weight), 118.0 g of methyl methacrylate (- 17.7% by weight), 6.4 g of di-tert-bulylproxide,

6.4 g dodscyl mercaptan,

42.0 g acrylic acid (= 6.388% by weight) and 0.583 acid equivalent), 0.3 g of potassium hydroxide, the potassium hydroxide being first dissolved in the acrylic acid, in 4 hours added drop by drop and then copolymerized for another 5 to 6 hours. the The copolymer solution has a solids content of 61.8%. The viscosity of the solution diluted to 50% with xylene gives a flow time of 115 seconds, measured in a Din beaker with 4 mm Jet. The acid number of the copolymer is 3.3.

The calculation of reaction batches for the production of copolymers with a certain hydroxyl group content is described in DE-AS 26 03 259 in columns 5 and 6 and in DE-AS 26 26 900 been.

Table I.
Copolymers A1 to A8 1 xylene A2 A3 A4 A 5 A6 A7 A8 B Copolymer 2 Athyigiykoiacetate 294 g 294 g 294 g 294 g 294 g 294 g 220 g xylene and I.
IllgSolvesso 100 Item 3 glycidyl esters
from example 1 i5ög 150 g 150 g 150 g 150 g 150 g IHg bulyl acetate Item 4 acrylic acid 160g 160 g 145 g 145 g 155 g 155 g 155 g Item 5 polypropylene glycol
monomethacrylate
from Example I. 46 g 46 g 42 g 42 g 45 g 45 g 45 g Item 6 styrene 19.6 g 19.6 g 26 g 26 g 33 g 33 g 33 g Item 7 methyl methacrylate 190.4 g 190.4 g 198 g 198 g 197.7 g 158.2 g 159.2 g Item 8 hydroxyethyl meth- 126 g 126 g II2g 100 g 118.6 g 158.2 g 158.2 g I. Item 116.2 g 116.2 g 116, Ig 116g 109.6 g HOg HOg I -Pos.

21g 26g

aerylat

Pos. 9 vinyl ester one α, α-dialkylalkanemonocarboxylic acid

Pos. 10 potassium hydroxide Pos. 11 lithium hydroxide Pos. 12 dodecyl mercaptan

Item 13 Tuesday to tertiary

Butyl peroxide Inflow time of items 4 to 13

Copolymerisalionszeit after Incoming end

Expiry time of 50% diluted solution

Acid number

Solids content Iodine color number according to DIN 6162 <l <1 <l <1 <

*) Diluted to 50% by weight of copolymers with ethylglycol acetate.

In the case of the copolymers A 2 to A 8, the solvent and the Ulycidyle.stor are as in the case of the copolymer A 1 described, heated to 144-148 ° C and the monomers and the dissolved catalyst, which can be stored at room temperature, added uniformly to the mixture kept at the boil and then copolymerized.

0.3 g - 7.4 g 0.1g - 0.1g - 0.1g 0.1g - 6.4 g 0.1g - 7.4 g 0.1g - 6.4 g 6.4 g 7.4 g 6.4 g 6.4 g OJg 2 hours. 6.4 g - 4 hours 4 SId. 6.4 g 6.4 g 6.4 g 5 hours 4 hours 5 SId 5 hours 4 hours 4 hours 4SId. 382 sec. 5 hours 192 sec 109 sec. 6 SId. 6 hours 4 hours Din 4 98 sec. Din 4 *) Din 4 98 sec. 95 sec. 98 sec. 4.8 Din 4 4.6 4.0 Din 4 Din 4 Din 4 62.8% 4.8 62.5% 62% 4.2 4.0 4.3 62.4% 61.3% 61.3% 60.8%

example 1

Preparation of a reactive varnish: 100 g of copolymer solution (according to Table I, copolymer A 2) and 20 g of a 75% solution of a xylene / ethyl glycol acetate »1: 1 dissolved, biuret group-containing aliphatic triisocyanate, which was obtained by reacting three moles of hexamethylene diisocyanate and one mole of water , with an NCO content of 21% by weight, are adjusted to the injection viscosity with a solvent mixture consisting of xylene / butyl acetate -1: 1 and steel sheets are coated with a dry film thickness of 45 ° and cured for 10 days at room temperature. The films had excellent gloss and good resistance to xylene.

Investigations of the reaction solution obtained according to Example 1 as proof of the technical progress achieved

I. Determination of the pot life, ie the shelf life of the two-component paint at 20 ^° C

20th

This result shows that these paints have a surprisingly long pot life. If one applies the processing conditions customary in practice - increase in viscosity by twice the initial viscosity, d. H. a maximum of 36 seconds flow time - this lacquer has a processing time of longer than 60 hours. In addition, paint residues that have been used for 96 hours can be added by adding freshly prepared Paint solutions are diluted and can still be processed well.

2. Determination of the curing time of the paint films

This two-component lacquer solution produced is drawn onto a glass plate so that a dry film thickness of c; i. 40 [xrs reserved. ; j

Run-out time in seconds (Outlet nozzle 4 mm) Beginning 18th after 24 hours 21 after 48 hours 25th after 50 stands 26th after 72 hours 46 after 96 hours 280 after 100 hours gelled

2a determine the Konig pendulum hardness at 20 ⁰ C

Pendulum hardness

after one day 40 seconds

after two days 92 seconds

after three days 170 seconds

after four days 201 seconds

What is surprising here is that the clearcoat is already complete after 4 days of curing at 20 ° C Film hardness has reached over 200 seconds. If you put this result in relation to four days of open pot life, d. H. The fact that the lacquer solution does not gel in time, this result was surprising and not predictable.

2 b determining the Pcndelhürtc Konig after baking at 8O ⁰ C and 30 minutes baking

Pendulum hardness

8O ⁰ C 30 minutes 85 seconds

after one day at 2O ⁰ C 125 seconds

after two days at 20 ^° C. for 168 seconds

After three days at 2O ⁰ C 200 seconds

The drying time of 30 minutes at 8O ⁰ C is obtained after two more days of drying at 2O ⁰ C, the almost complete film hardness of 168 second pendulum hardness.

The resulting lacquer films are very hard on the surface and cannot be damaged with a fingernail test. In addition, these coatings are characterized by poor lightfastness and resistance to solvents such as xylene, toluene or acetone. After 1 'Ajähriger Floridabewitterung at 5 ⁰ C to the south designed test sheets / intrinsically these paint films do not crack and only a 10% reduction in gloss compared with the Ausgangsglan /, of 110% - measured by Lange - is.

65

Il

Comparative studies to prove the technical progress achieved
compared to the best products on the market in terms of pot life

Copolymer A 2 - Analog reaction varnish, Analog reaction varnish,

Reaction varnish according to, however, copolymer according to, however, copolymer according to

Example 1 of the invention Example 2 of DE-PS 26 03 259 Example 1 of DE-PS 26 26 900

Determination of the pot life of the reactive lacquer by measuring the flow time in the DIN cup with a flow nozzle 4 mm in diameter at 20 ^° C. in seconds

10.

65

Time 18th Sec 18 sec at the beginning 18 sec 25th Sec 28 sec after 24 hours 21 sec 75 Sec 155 sec after 48 hours 25 sec 280 Sec not measurable, gelled after 56 hours 40 sec not measurable, gelled after 60 hours 90 sec

15th

after 60 hours

Comparative studies to prove the technical progress achieved
compared to the best products on the market in terms of pot life

20th

Pot to determine the "life" were been in the above table, he listed ^one ι paints .dungsgemäß produced compared to the best on the market Konkurrenzprodukren with the aliphatic triisocyanate which received durcii transfer out of 3 moles Hexamethylendiisoeyanal and 1 MoI water is mixed. The mixing ratios of the copolymers with the polyisocyanate, based on the solids content, were 70% by weight copolymer: 30% by weight polyisocyanate. The mixtures were diluted with a solvent mixture consisting of XyJol-Butylacelal in a weight ratio of 1: 1 to a viscosity of 18 seconds discharge / .ei I, measured in a DIN beaker with a 4 mm discharge opening, and the increase in viscosity was dependent on time at 20 ⁰ C determined. As can be seen from the table above, the varnishes produced according to the invention are clearly superior to the known reactive varnishes according to DE-PS 26 03 259 and DE-PS 26 26 900. The paints produced according to the invention have a more favorable pot life in relation to a slower increase in viscosity b / .w. Gelation. This suggests that the reactive lacquers will be processed more favorably.

Table IJ
Production of reactive paints

_w Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8

The production and use of the Realuiunslaeke takes place as described in Example I.

Copolymcrisal Polyjsocyanul I stated Al like in the example 1 specified A3 like in the example 1 specified A4 like in the example I stated A5 like in the example I stated A6 like in the example 1 specified A7 like in the example I stated Λ8 like in the example

Claims (1)

Patent claims: 1. Reaction varnish made by mixing (A) hydroxyl group-bearing copolymers based on (a) aromatic vinyl compounds, (b) Acrylates or methacrylates with 1 to 12 carbon atoms in the alcohol residue, esters of crotonic acid with saturated alcohols which contain 1 to 10 carbon atoms in the alcohol residue, (c) Vinyls and hydroxyl-containing aJJ-ethylemically unsaturated compounds, (d) aJJ-unsaturated monocarboxylic acids and (e) monoglycidyl compounds,