DE1669028B2 - THERMAL CURABLE BINDERS FOR COATING COMPOUNDS - Google Patents

Description

For the appropriate coating binders, there are also those that are

If the content of the free hydroxylesterification reaction in component a) is not at all or only slightly

groups the requirement for the combination and take, such as. B. aliphatic hydrocarbons,

Compatibility with aminotriazine formaldehyde resins ketones, esters, tertiary alcohols,

and for cross-linking reactions with the methylol 5 The viscosities of the solutions of the starting poly-

or methyl ether groups formed by the free carb- mers, measured in oO ^ iger solution at 20 ° C below

Oxyl groups are promoted. Use of the practical Gardner-Holdt scale,

In component a), instead of one, there can be in the entire range of this scale, pro-

polymerized maleic anhydride, other products with Gardner viscosities from A to D should also be used

«, ^ - unsaturated dicarboxylic acid anhydrides contain io as copolymers with low molecular weight,

be e.g. B. Itaconic anhydride. those with viscosities from E to Y as copolymers

For the use of the above-average molecular weight according to the invention and those with viscous binders, the structure or the compositions from Y to Z _{2 are} referred to as copolymers with a higher settlement of the starting polymers for the production of molecular weight,
of component a) is important. In addition to the 15 Since the production of component a) by Um-α, / 3-unsaturated dicarboxylic acid anhydrides, the copolymers in aromatic solution with the following monomers are possible: Ethylene, propylene, polyols at a higher temperature a longer time α-olefins of the formula H ₁ C = CHR, where R requires, with the content of free hydroxyl straight-chain or branched alkyl radical with 2 to groups, possibly as side reactions, meaning transesterification of 20 carbon atoms, acrylic acid esters, fumaric acid ao gen between these and the ester groups, the esters, which have 1 to 10 carbon atoms in the alcohol portion, for. B. of acrylic or methacrylic acid alkyl esters ufid methyl methacrylate. The selection of the comono- or fumaric acid dialkyl ester in the copolymer mixture depends on the particular one to be used. Methacrylic acid esters are less inclined to later use the binder and are directed towards transesterifications than acrylic acid and fumaric acid in adaptation to the nature of the over-ester. The extent to which transesterification takes place, depending on the rigid or flexible substrates, also depends on the type of alcohol that is bound in the ester with the desired properties, such as shape in the monomers. Methanol becomes hardness or elasticity. "-Olefins, e.g. B. Ethylene, Pro- more easily split off than ethanol and so on. Esterpylene, butylene, peutylene and hexylene, in groups with secondary or tertiary alcohols, give the copolymers the same degree as methyl methacrylate, and show only a subordinate or no tendency to merisates and thus also component a) to transesterify. These transesterification reactions are at the property of hardness. Acrylic acid esters with two and the choice of copolymers for the reaction with more carbon atoms in the alcohol content and trihydric alcohols are important. Copolymaric esters with four or more carbon atoms and higher molecular weights must not contain any groups tending to transesterify as comonomers in the alcohol content, meaning and elasticity in the copolymer. if the one-alcohol component in these estene monomers during the triol conversion cannot represent gelatinization before melamine resin compatibility has been established. A-olefins with six or more coals are also sufficient. The transesterifications must therefore bring about below material atoms in unbranched chains than remain within limits, above which it elasticizes the copolymer by means of comonomers. 40 innovation for the formation of insoluble or gelatinized

Acrylic reaction products, for example, act as comonomers before melamine compounds

acid estei with two or more carbon atoms in alcohol tolerance is achieved.

portion and fumaric acid dialkyl ester with a lot more and more The alkylated aminoplasts, which in the invention

C-atoms are contained in the alcohol content softness and elastic mixture as component b),

city in the copolymer, if the alcohol content in «can be made by alkylation of a condensate

these ester monomers is not branched. The one aldehyde and urea, N.N'-Ethylenur-

The softness of the Λ-olefin copolymers acts as a substance, dicyandiamide or aminotriazines with one

if necessary, the proportionate use of alkanol containing 1 to 6 carbon atoms

against ethyl methacrylate as a comonomer. have been holding. It can be alkylated aminoplasts

Which are used as starting basis for component a) 50, provided that they are soluble in the organic copolymers in a known manner niche solvent which is used for production at higher temperatures, preferably in aromatic coating composition. In general tables solvents, e.g. B. in xylene or a, the alkylated aminoplasts should be made at least 80% high-boiling aromatic mixture. Which contain and preferably 100% methylol groups. Reaction is carried out in the temperature range of 50 to 55, containing a 1 to 6 carbon atoms 25O ⁰ C, preferably at 90 to t70 ° C, are alkylated by free-radical alkanol. Alkylic polymerizations are preferred. For free-radical polymerization products used with 3 to 6 carbon ions, free-radical formers such as peroxides, e.g. B. atoms containing alkanols were obtained. The benzoyl peroxide, di-tert-butyl peroxide or azo-butylated products are used because of their larger compounds. The reaction can take place with a large number of polyols but also thermally at a higher temperature. Reaction products and solvents, especially when using low-boiling points or when using a room.

temperature of gaseous monomers is a work suitable for the production of the aminoplast under pressure. In general, the aminotriazines are: melamine, acetoguanamine, Ben-reaction with the polyols in the same solvent 65zoguanamine, formoguanamine, ammeline, 2'Chlor * means carried out in which the polymerization 4,6-diamino-1,3, 5 ⁱ triazine 2-phenyl-p-hydroxy-4,6-dider monomers is carried out. In addition to the pre-ainino-l, 3,5-triazine, _{6-methyl-2,4-diafflino-l) 3)} 5-trizugsweise used aromatic solvents azine, 2,4,6-Trihydrazin-1,3,5 ' triazine, 2) 4 _S 6-Triäth.yl-

: riamino-l, 3,5-triazine or N ₁ N-di- (C ₁ - QJ-alkyl- such as acetic acid, phthalic acid, benzoic acid, toluene-

nvlamine, such as Ν, Ν-dimethylmelaniin. As aldehyde sulfonic acid, naphthalenesulfonic acid or the mono-

Any aldehyde is suitable, such as the acetal salt of maleic acid with triethylamine

aldehyde, crotonaldehyde and acrolein, however, drying of the coatings can be increased

those with reversible polymers of formaldehyde, such as 5 temperatures, e.g. B. 60 to 104 ⁰ C, erfo.'jen. That

Paraformaldehyde, manufactured Kondtasate preferably hardening can be done at 80 to 230 ⁰ C,

The component a), consisting with polyols environmentally indifferent whether a catalyst has been used or is set copolymers, and component b), not the curing time can be in the ratio of area in obereu Temperaturnämlich the aminoplast of about 230 ⁰ C between Vs and 2 minutes 50 to 95 parts * component a) and dissolved 50-5 parts io and in the lower temperature range of about 8O ⁰ C component b) in the organic solvent are between 1 and 2 hours. Particularly expedient - the proportions of component a) and the moderate curing 15 to 30 minutes at 120 to component b) are to be chosen so that the two 130 ⁰ C are undertaken.
Components both in the overlay solution and

tolerated in the finished film. It can be any suitable 15 _. . . ₁

Concentration of component a) and the compost e 1 s ρ 1 e

nente b) in the solvent of z. B. 1 to 60 weight- A) Preparation of the thermosetting

[Percent apply. Is an allspice on- binding agent contained component a)
essential, the total solids content is in

of the coating mass between 5 and 75 percent by weight 20 in one with stirrer, thermometer and reflux

The ratio of pigment to binder [three-necked flasks equipped with a compo cooler will produce 560

nenieai plu * Kumpoucute b)] can contain between 1:20 parts by weight of 1-dodecene and 944 by weight of xylene

and 20: 1. heated to 130 to 140 ⁰ C and a mixture consisting

The following solvents can be used: carbon from 16 parts by weight of benzoyl peroxide, 700 parts by weight

Hydrogens such as benzene, toluene, xylenes and aromatic _a5 share methyl acrylate and 106 parts by weight male

matic naphthenes or mixtures of such solution acid anhydride added in 8 hours and more

middle; Esters, such as ethyl, butyl, amyl, ethoxyethyl, polymerized for 2 hours. The body content of the

or methoxyethyl acetates, lactates or propionates; solution is 42 percent by weight. After adding

Ketones, such as acetone, methyl isopropyl ketone, methyl another 16 g benzoyl peroxide in 6 hours and another

isobutyl ketone, dioxane, isophorone or cyclohexanone; 30 final polymerizing at 130 to 140 ⁰ C is

Alcohols, such as n-butanol, t-butanol, isopropyl alcohol, a body content of 50 percent by weight and a

n-propyl alcohol, anyl alcohol and cyclohexanol; Gardner-Holdt viscosity from C to D reached.

Ether, such as diethyl ether, the monoeth;! -, mono- The resin solution is clear at room temperature,

methyl and monobutyl ethers of ethylene glycol and 1000 parts by weight of the 50% resin solution

various other solvents such as dimethyl ₃₅ mixed with 62 parts by weight of trimethylol propane

formamide, dimethylacetamide, acetonitrile, nitrome- and below cycle temperature to about 168 to

than, Nitroäthafl, Nitropropane or Nitrobutane. Heated to 172 ° C (after a reaction time of 8 hours this is

and also mixtures of two or more solution reaction products with melamine-formaldehyde resins

agents of the same group as well as several or compatible after baking). The viscosity of the

from all of the groups listed above. 40 52 ° / _e solution according to Gardner-Holdt

The following pigments can be added: inorganic scale about T to U. while the acid number is 44 and ink pigments, i.e. organic dyes that freely have a hydroxyl number of about 50,
from sulfonic acid, carboxylic acid or other water-solubilizing groups. Under the term ","". _, .. "
"Pigments" also contain other water-insoluble oiga- ₄₅ ^B) Production of the warm dyes according to the invention, e.g. B. the calcium or barium hardenable binders
lacquers from azo lacquer dyes. (70 percent by weight component a): 30 weight

The coating compositions can be used in any way percent component b) melamine resin)
be applied to the substrates, e.g. B. by

To brush. Spraying on, dipping, rolling. They 50 700 parts by weight of component a), are then dried and cured by heating. according to example 1 A) are at room temperature In general, it is not necessary to add hardening 300 parts by weight of a 50 ° / ₀ solution of a isokatalysatoren. If necessary, however, butanol-etherified melamine-formaldehyde resin, including an acid catalyst, can be added. The amount provided according to the method described in the German Auslegeschrift such a catalyst can be between 0.1 and 55 1127 083 mixed.
1 percent by weight, based on the weight. The melamine resin used is according to that of the aminoplast. The use of a catalyst ^{described in Härtungs- German Auslegeschrift 112 7} 083 is advisable when low temperatures according to Example 1 have been produced in such a way that curing temperatures are necessary. When using a viscosity after hardening catalysts after water separation, the insoluble 60 Gardner vonAbisB has been present. The excess can be made simply by drying and aging with isobutanol was distilled off and xylene has reached room temperature. Hardening catalyst has been replaced. ^{The solids content should be 50 to 50 seconds at 20 0} C, which can be used for curing the 52 percent by weight according to the invention and the viscosity 50 to 70 DIN compositions,
all acid catalysts. For example, you can rub a 65 This mixture is _{rubbed with 340 parts by weight of TiO 2} catalytic amount of sulfuric or hydrochloric acid or (rutile) to a varnish and add their salts on spray, e.g. B. ammonium sulfate viscosity of 20 DIN seconds with butyl acetate or ammonium chloride or an organic acid, thin., And after application, on phosphated

r ⁰¹

m 8

Baked trays in 30 minutes at 130 ° C. The 1000 parts by weight of the 50% resin solution will be

Films show good gloss, good surface finish mixed with 62 parts by weight of trimethylolpropane hardness, excellent flexibility and good chemical and cycle temperature of around 168 to 172 ° C alkali resistance. heated. After a reaction time of 8 hours, the

5 Settlement product with melamine-formaldehyde resins according to Example 2 compatible with stoving. The viscosity of the

A) Manufacture of the thermosetting Ι] * ¹ ? * ™ ^L ° ^sun ? ^betr f # ⁿ *? ^{h de} ', ^ T' ¹ *? ¹ ^ "

Binder contained component a) Scale about B while the acid number at 42 and the

Hydroxyl number are about 70.
In the same way as in Example 1 A) io
has been described, 560 parts by weight B) Preparation of the thermosetting binder

} - ° o ° ^de T · ^And T- ^^ if Χ * ¹⁰¹ . ^to "J ^bis (60 percent by weight component a): 40 percent by weight heated to 140 C and a mixture consisting of 16 percent by weight component b) melamine resin)
parts by weight of benzoyl peroxide, 106 parts by weight of Ma- '
Oleic anhydride and 730 parts by weight of butyl acrylate 15,600 parts by weight of component a) according to Example 3 A) are added in 8 hours and 400 parts by weight of that in Example 1 are added for a further 2 hours. The body content of the solution is 48 overall Meiaminharzes applied in the form of a 50 ⁰ / _O strength weight percent. After adding a further 5 g of benzoyl solution, prepared as peroxide described in Example 1 B) and then polymerizing at 130, mixed and on deep-drawing sheets up to 140 ° C, a body content of 52% by weight is supported and at 130 ° C baked in 30 minutes, percent and a viscosity according to Gardner-Holdt of Films with good surface hardness and smaller than A were achieved. The resin solution is retained with spatial flexibility. In the binder temperature clear. can be a copolymer reacted with polyols

1000 parts by weight of the 52 ° / _o by weight resin solution will be included, which up to 23 percent by weight, vormit 62 parts by weight of trimethylolpropane mixed 25 preferably 6 to 12 weight percent itaconic acid and from circulatory temperature to about 168 to 172 ° C anhydride instead of maleic anhydride einerhitzt ( After a reaction time of 8 hours, the re-polymerized is present.

Settlement product as component a) with melamine- Advantageously, as component a), a stoving compatible with triformaldehyde resins as component b) after the hydric alcohols individually or in a mixture). The viscosity of the 54 ° / _o by weight 30 set used copolymer in which per mole of solution-Gardner Holdt scale anhydride is after about D, in the copolymer 0.8 to 1.8 Mo !, while the acid number and the hydroxyl at 40 preferably 0.8 to 1.2 mol, triol condensed in at about 60. are present.

In a preferred embodiment of the invention

B) Production of the thermosetting binder 35 according to the binder consists of the compo-

(70 percent by weight of component a): 30 wt ^nent _u ^ea> ^ ^us Umseöungsprodukten of polyols and

percent of component b) melamine resin) such copolymers ^ which are built up from 5 to

^vv '10 percent by weight maleic anhydride, 10 to 50

700 parts by weight of the 50 ° / _o solution of the compo- weight percent mono-olefins of the formula H ₂ C = CHR,

nents a) according to Example 2 A) are in Zimmer- 40 where R is a hydrogen atom or a straight chain

temperature with 340 parts by weight of TiO ₂ (rutile) and or branched alkyl radical with 1 to 20 carbon atoms

300 parts by weight of a 50 ° / ₀ solution of an iso- indicated, 40 to 85 weight percent acrylate

butanolverätherten 50 ° / _o solution of melamine-formaldehyde and / or fumaric acid esters, the alkyl radicals of 1 to

resin as component b), prepared as in the case of 10 carbon atoms, and 0 to 30 percent by weight

game 1 B) described, rubbed into a varnish and 45 methyl methacrylate.

to a spray viscosity of 20 DIN seconds with butyl In this preferred embodiment, as

acetate diluted and after application to phos component a) those products are used in which

Phated sheets are baked in at 120 ° C in 30 minutes. as Λ-mono-olefins the following compounds

The films show excellent flexibility. have been polymerized: 1-bulene, 1-pentene, 1-hexene,

50 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,

Example 3 1-dodecene, and in which the acrylic acid esters and / or

Ε ^ Afl ^ fi

y /

A) Manufacture of the thermosetting binding ΕΠΑ? *? ^ ende Afl ^ residues show: Me-

agent contained component a) * yl- Athyh Propyi-, Butyl-, Kexyl-, Octyi-, 2-Athyl-

* hexyt- and decyi-.

M in the same way as described in Example 1 A)

560 parts by weight of 1-dodecene and 944 Ge. Example 4

wichitstefle xylene heated to 13Θ to 14Ö ^C C and a

Mixture, consisting of 16 parts by weight of benzoyl- It was a solution in organic solvents

peroxide, 106 parts by weight of maleic anhydride and dear esterified copolymer according to Aa-730 Parts by weight of dibutyltumarate in 8 herbaceous plants are given in the German patent; 544326 added and polymerized for a further 2 hours. The posed and this was bait a drug triazine body content of the solution is 37 percent by weight. Formaldehyde resin in a binder combination After adding a further 20 g of benzoyl peroxide in combined.

6 Standen and then polymerizing with this comparative binder tyoTde it with a percentage compared »Ϊ30 to 140 ⁰ C wirdeinKöipergehall of 50 weight" 5 Sndungsgemäßen binder according Seispiel 1 and a viscosity according to Gardner-Holdt of the present Erfiaduag.
Mciaer than A) achieved. The resin solution is at room temperature

10

Information in German patent 544 326: it was according to Example 1 part A) [production of the in the Coating compound containing reaction product a)] of the present invention, the copolymer manufactured. In contrast to the present invention, 1260 g of methyl methacrylate and 106 g maleic anhydride are used.

The resulting copolymer was then, as in the same example 1 of the present invention, an-die Testing resulted in the following measured values:

Erichsen cupping

Gloss measured according to Lange at 45 ⁰ C .. given in the same manner with trimethylolpropane comparable io mandrel bend test

estert. The esterification product obtained then became a 6 mm mandrel

under the same conditions as in the example of the present invention part B) (preparation of thermosetting coating compound) combined to form a binder and, as indicated there, to form a stoving varnish processed.

Paint according to

example 1
the invention

mm

110%

no lacquer tear

the state of the art

2.0 mm

95%

45% of the paint surface is cracked

Claims (2)

1 * 2 Component b) are conventional urea or amino acid-formaldehyde resins, preferably Melamia-formaldehyde resins, etherified with an alcohol containing 1 to 6 carbon atoms. 1. Heat-hardenable binders for coating compositions, are compositions based on a mixture consisting of aminotriazine-formaldehyde resins and consisting of a) a component that plasticizes in organic solvents with hydroxyl and soluble reaction product of copolymer carboxyl groups known. The plasticizing seeds made from - unsaturated dicarboxylic components are low molecular weight consumer acid anhydrides, -olefins, methacrylic acid esters, ίο deasation resins or higher molecular weight polymers, acrylic acid esters and / or fumaric acid esters, with thermoplastic properties.
Polyoien, and b) etherified aminoplasts, because in German patent 544326 it is characterized by the fact that, as a grain production of mono- and polyoien mngeponente a) 50 to 95 percent by weight soluble polymers containing anhydride groups, reaction products from copolymers with less 15 described. Soluble copolymers containing anhydride groups and containing terminal anhydride and mono-OleSnea with mono- or di-alcohols as 20 mol% dicarbon-unsaturated dicarbons are not important as binders for coating compounds, especially unbranched double bonds, and acrylics for coating raw materials They also have acid esters and / or fumaric acid esters, which have 1 to 10 carbon atoms in the Al in combination with urea or aminotriazole alcohol and give formaldehyde resins that do not contain methyl methacrylate, with three to three solvents, water or Alkaline hexavalent alcohols, possibly below digkeit. Soluble copolymers containing anhydride groups, which are set only with the use of mono- or dialcohols, are not obtainable, however, the reaction products having acid numbers of 5 to 60 and hydroxyl numbers of 20 to 120,
sit, and as component b) 5 to 50 weight copolymers, as described in the examples of the cited percent alcohols having 1 to 6 carbon atoms, with a G content of etherified urea or aminotriazine form 30 and contain more weight percent maleic anhydride aldehyde resins. in copolymers, deliver when implemented with 2. Binder according to claim 1, characterized in that component a) is a product before compatibility with Hamsioff or settlement product, in which per mole of anhydride-aminotriazine-formaldehyde resins is achieved,
group in the copolymer 0.8 to 1.8 mol tri- It has now been found that ma *; are present condensed into products gemethylolpropane. that are suitable for coating compounds, if one 35 copolymers reacted with polyols as component aj, which are less than 20 mole percent », / 3-unsaturated Contain dicarboxylic anhydride, in combination with urea or aminotriazine-formaldehyde resins can be used. For the implementation of the copolymers, three-bi; polyols are used. hexavalent alcohols, optionally with the concomitant use of mono- and dialcohols. In addition, it was found that such products in a mixture with aminotriazine-formaldehyde resins as 45 binders are particularly suitable for coating compounds in which the copolymers with trivalent Alcohols without any significant use of The thermosetting binding mono- and dialcohols according to the invention are present. Hermittel consist of a) 50 to 95 percent by weight in such binders have excellent properties, organic solvents soluble conversion 50 in which as trihydric alcohols those used Products made from anhydride reacted with polyols, which are less polar than glycerine, contain groups Copolymers and b) 5 to 50, for example trimethylolalkanes or hexanetriol. from weight percent etherified urea or amino these trihydric alcohols that are less polar than triazine-formaldehyde resins, preferably melamine-glycerol, has been found for the Ge-formaldehyde resins according to the invention. To produce the composite, a reaction product with trimethylolpropane component a), copolymers are used which have proven to be the best, with per mole of anhydride im Solution polymerization of monomer mixtures consisting of 0.8 to 1.8 moles of trimethylolpropane copolymers from less than 20 mol percent of a <x, 0-preferably 0.8 to 1.2 mol of trimethylolpropane used saturated dicarboxylic anhydrides and normal have been. or branched α-olefins with 1 to 20 carbon atoms 60 in the partial reaction of the copolymers with and also acrylic acid alkyl esters and / or fumaric acid with a content of less than 20 mol percent, pre-dialkyl esters and optionally methacrylic acid, preferably from 5 to 10 mol percent, of a ", /? - unthyl ester, are obtained and with three- to six-saturated dicarboxylic anhydrides with three- to Valuable alcohols, preferably with triplets, and hexavalent alcohols, result in soluble reactions have been. The in this implementation obtained 65 settlement products as component a), in addition to a Tene component a) should number from 5 to 60, acid number from 5 to 60, preferably from 20 to 50, preferably from 20 to 50, and hydroxyl numbers from 20 to 120, preferably from 30 to 120, preferably from 30 to 90, have. As to 90, own.