EP3046980A1

EP3046980A1 - Room temperature-curing silicone-polyester binder

Info

Publication number: EP3046980A1
Application number: EP14758110.2A
Authority: EP
Inventors: Dirk Hinzmann; Bärbel WOLFF; Thomas KLOTZBACH; Jessica LEYERS; Sascha Herrwerth
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2013-09-20
Filing date: 2014-08-25
Publication date: 2016-07-27
Also published as: US9617390B2; JP2016536437A; US20160222169A1; DE102013218981A1; MX2016003467A; CN105722932A; WO2015039838A1

Abstract

The present invention relates to a room temperature-curing silicone-polyester binder having hydrolysable alkoxysilyl groups, method of production and use thereof.

Description

Room temperature curing silicone-polyester binder

The present invention relates to a room temperature-curing silicone-polyester binder having hydrolyzable alkoxysilyl groups, process for the same

Production and its use.

Binders for modern paint systems must meet a variety of requirements. Thus, on the one hand, they must have certain coating properties, such as scratch resistance, hiding power and weather resistance, on the other hand good processability, economic production and compliance with legal requirements must be guaranteed.

EP 02741 12 describes a silane-modified binder based on

Polyacrylate resins for the production of coating compositions. Disadvantage of the binders described there is that they often no longer have the desired property profile at sufficiently low VOC values (volatile organic compound), for example, no sufficient weather resistance and

Chemical resistance. The object of the present invention is to provide improved binders that can be used to provide durable coatings.

The above-mentioned complex object is achieved by binders according to the present invention.

A first object of the present invention are binders based on an alkoxy and / or silanol-functional polysiloxane A), one or more di- or polycarboxylic acids B) and one or more di- or polyols C), one or more di- or polyisocyanates and one or more aminosilanes D1) or one or more isocyanate silanes D2), wherein the constituents A) to D1) or D2) are condensed together in the binder.

The binders mentioned are obtainable by polycondensation and polyaddition of the abovementioned constituents A) to D1) or D2), so that

According to the invention, two alternatives result. When using component D1), the binders according to the invention consist of five constituents, with the use of component D2) of four constituents. From the aforementioned components the binder according to the invention is produced. The binder according to the invention is a silicone-polyester hybrid binder with

Alkoxysilyl functionality. The term silicone-polyester hybrid binder is defined as a composition of an alkoxy- or silanol-functional branched polysiloxane, which via Si-O-C or Si-C linkages with organic

Groups or resins is connected. The chemical attachment of organic building blocks such. B. monohydric or polyhydric alcohols / polyols on the alkoxy or silanol groups of the polysiloxane takes place to form a Si-O-C bond. The binders according to the invention have the advantage that binders

provided that overcome the disadvantages of the prior art.

In particular, the binders according to the invention are distinguished by low VOC values of less than 250 g / l in the paint. Continue to lead the

inventive binders used in coatings to increase the longevity, increased corrosion protection and increased chemical resistance of the coatings obtained.

Component A) are alkoxy- and / or silanol-functional polysiloxanes. Component A) is preferably nonlinear, branched, alkoxy-functional and / or silanol-functional polysiloxanes, preferably those of general formula 1,

Formula 1 wherein R ι is independently alkyl, aryl or alkoxy groups, hydroxy or - OSi (R ₃₎ ₃ groups, wherein R _{3 is} independently alkyl, aryl,

Alkoxy groups, hydroxy or -OSi (R ₃ ) 3 groups,

and wherein R ₂ independently of one another may be hydrogen, alkyl groups or aryl groups, preferably alkyl groups, very particularly preferably methyl groups or ethyl groups, and n> 1.

In particular, n in formula 1 is selected so that, depending on the nature of the selected groups R-1, R ₂ and optionally R ₃ , the molecular weight Mn of

alkoxy-functional and / or silanol-functional polysiloxane between 300 to 5100 g / mol, preferably 400 to 3000 g / mol, most preferably 450 to 1800 g / mol.

In the case of alkyl groups are preferably linear or branched alkyl groups having 1 to 18 carbon atoms, in particular it is

Methyl groups.

In the case of aryl groups are preferably aryl groups having 6 to 18 carbon atoms, in particular are phenyl groups. In the case of alkoxy groups, these are preferably linear or branched alkoxy groups having 1 to 18 C atoms, in particular they are methoxy groups or ethoxy groups.

In formula 1, n> 1, that is, the alkoxy-functional and / or silanol-functional polysiloxane has at least two -Si (Ri) ₂ -O units according to formula 1. In this case, the radicals Ri are both within and between the

individual -Si (Ri) ₂ -0 units independently selectable from the aforementioned groups, so can be combined in any way with each other.

Thus, the preferred alkoxy-functional and / or silanol-functional polysiloxanes according to formula 1 are (phenyl) -methylpolysiloxanes, with methoxy-functional or ethoxy-functional (phenyl) -methylpolysiloxanes being particularly preferred.

The alkoxy-functional and / or silanol-functional polysiloxanes according to formula 1 preferably contain about 4 to 70 silicon atoms.

The alkoxy-functional and / or silanol-functional polysiloxanes according to formula 1 can thus contain the following structural elements:

M, M ^OR , D, D ^OR , T, T ^OR and Q, where:

M = [(R ₄₎ ₃ Si0 _1/2]

D = [(R ₄₎ ₂ Si0 _2/2]

T = [(R ₄ ) SiO _3/2 ]

Q = [Si0 _4/2 ]

M ^OR = [(R ₅ ) _3-m (R ₄ ) _m Si0 _1/2 ]

D ^OR = [(R ₅ ) _2-p (R ₄ ) _p SiO _2/2 ]

T ^OR = [(R ₅ ) SiO _3/2 ] or [(R ₄ ) SiO _3/2 ], with R ₅ = aliphatic or aromatic alkoxy radical having up to 18 C atoms or hydroxy, preferably methoxy or ethoxy,

R ₄ = aliphatic or aromatic alkyl or aryl radical having up to 18 C atoms, preferably phenyl or methyl,

m = 0, 1, 2 or 3

and p = 0, 1 or 2.

The alkoxy and / or silanol content of the alkoxy- and / or silanol-functional polysiloxanes is between 5 and 30% by weight, preferably between 8 and 25% by weight, very particularly preferably between 10 and 20% by weight.

As component B) di- or polycarboxylic acids are used, in particular aromatic, aliphatic or cycloaliphatic di- or polycarboxylic acids and their derivatives, such as. Phthalic anhydride, isophthalic acid, terephthalic acid,

Adipic acid, maleic anhydride, fumaric acid, succinic anhydride,

Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride

Dimethyl terephthalate, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid,

Hexahydrophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, 1, 12-dodecanedicarboxylic acid and 1, 14-tetradecanedicarboxylic acid, and their diesters and anhydrides.

Preference is given to phthalic anhydride, isophthalic acid, terephthalic acid or

Dimethyl terephthalate, adipic acid, maleic anhydride, fumaric acid,

Succinic anhydride, hexahydrophthalic anhydride,

Methylhexahydrophthalsäureanhydrid used as component B).

As component C) are di- or polyols, especially aliphatic polyols such. For example, ethylene glycol, propanediols [1, 2 - and 1, 3], butanediol-1, 4, hexanediol-1, 6, neopentyl glycol and other neodiols (hydroxypivalate neopentyl glycol, trimethylphenol, polyether polyols). As polyhydric alcohols, for. As trimethylolpropane, pentaerythritol, di-trimethylolpropane and others are used. As an example of cycloaliphatic polyols, perhydrobisphenol A, dimethylolcyclohexane and 3 (4), 8 (9) -dihydroxymethyltricyclo [5.2.1 .02.6] decane (TCD-alcohol-DM) can be used.

In addition, as component B) and C) monocarboxylic acids and monoalcohols may be added to control the polycondensation. suitable Monocarboxylic acids are, for example, benzoic acid, isononanoic acid,

2-ethylhexanoic, Versatiesäure or saturated or unsaturated fatty acids, suitable monoalcohols are, for. 1-octanol, dodecanol, hexadecanol,

2-ethylhexanol, 2-octyldodecane-1-ol.

In one embodiment of the present invention, a binder of an alkoxy- and / or silanol-functional polysiloxane A), one or more di- or polycarboxylic acids B) and one or more di- or polyols C), and one or more di- or Polyisocyanates and one or more Aminosilanen D1) constructed. In this way, a silicone-polyester hybrid resin is provided which has hydrolyzable alkoxysilyl groups at room temperature. From components A) to C), an OH-functional silicone-polyester hybrid resin is formed which reacts with the likewise present di- or polyisocyanates and aminosilanes to form the binder according to the invention.

For example, the binder of the invention when using

Isophorone diisocyanate and N- (3-trialkoxysilylpropan-1-yl) -N-n-alkylamine as

Component D1) are described in simplified form with the general formula 2:

Formula 2

O

wherein R 1 denotes the linkage to the hydroxy-functional silicone-polyester hybrid resin, R 2 can independently of one another be alkyl, aryl or alkoxysilylalkyl and R 3 are alkyl groups, preferably methyl or ethyl groups.

Suitable di- and / or polyisocyanates as component D1) are preferably per se known substituted or unsubstituted aromatic, aliphatic, cycloaliphatic and / or heterocyclic polyisocyanates. Examples of preferred di- and / or polyisocyanates are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diphenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (Vestanat ^® IPDI),

Dicyclohexylmethyl diisocyanate (Vestanat ^® H ₁₂ MDI). Further preferred

Polyisocyanates are the biuret dimers and the isocyanurate trimers of

aforementioned diisocyanates.

Particularly preferred polyisocyanates are hexamethylene-1,6-diisocyanate,

Isophorone diisocyanate and dicyclohexylmethyl diisocyanate, their biuret dimers and / or isocyanurate trimers.

Preferred aminosilanes in components D1) are bis (3-propyltrimethoxysilyl) amine, bis (3-propyltriethoxysilyl) amine, aminopropyltrimethoxysilane,

Aminopropyltriethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane,

3-aminopropylmethyldiethoxysilane. Corresponding amino silanes are available for example under the name DYNASYLAN® ^® from Evonik Industries AG or Silquest ™ from Momentive.

In a further embodiment of the present invention, a binder of an alkoxy and / or silanol-functional polysiloxane A), one or more di- or polycarboxylic acids B) and one or more di- or polyols C) and one or more isocyanate silanes D2) built up. Also in this way is a silicone-polyester hybrid resin which is hydrolyzable at room temperature

Alkoxysilyl groups provided. From the components A) to C), an OH-functional silicone-polyester hybrid resin is again formed which reacts with the isocyanate silanes to form the binder according to the invention.

For example, when using 3-isocyanatepropyltrialkoxysilane as the component D2), the alternative binder according to the invention can be described in simplified form with the general formula 3:

Formula 3 wherein R1 describes the linkage to the hydroxy-functional silicone-polyester hybrid resin and R 2 are alkyl groups, preferably methyl or ethyl groups. Preferred isocyanatosilanes as component D2) are 3-

Isocyanatepropyltrimethoxysilane (Vestanat ^® EP-IPMS of Evonik Industries AG) or 3-lsocyanatpropyltriethoxysilan. With preferred use of such isocyanatosilanes, the modification to a silyltrialkoxyfunktionellem silicone polyester can be done directly.

The binder according to the invention is composed in sum of a siloxane component A) and a polyester component of B) and C) and of either an isocyanate component and an aminosilane component D1) or an isocyanate silane compound D2).

More preferably, the binder according to the invention is composed of 10 to 50 wt .-% of component A) and 50 to 90 wt .-% of a combination of the polyester component B) and C) and the isocyanate component of D1) or D2), based on the Solid content of the binder.

The weight ratio of component A) to the polyester constituent of components B) and C) is in particular from 1: 9 to 9: 1, preferably from 3: 7 to 7: 3. The proportion of a monoalcohol or a monocarboxylic acid is in particular from 2 to 20% by weight. -%, based on the total amount of all components. The stated proportions by weight amount to 100% by weight in total.

The weight ratios of the di- or polyisocyanate component and the

Aminosilanes in component D1) are in the di- or polyisocyanate between 10 - 50 wt .-%, based on polyester resin, preferably 20- 40 wt .-%, particularly preferably 25- 35 wt%. The proportion of aminosilanes in component D1) is calculated stoichiometrically on the free isocyanate groups present for the further reaction and is thus in a range of 20-80% by weight. The proportion of isocyanate silane component D2) is between 5 and 50% by weight, based on polyester solid resin, preferably 20 to 40% by weight, particularly preferably 25 to 35% by weight.

Another object of the present invention is a method for

Production of binders according to the present invention, wherein in a first step an alkoxy- and / or silanol-functional polysiloxane A), an or a plurality of di- or polycarboxylic acids B), and one or more di- or polyols C) are reacted with each other to form a silicone-polyester hybrid resin, and in a second step, the silicone-polyester hybrid resin obtained in the first step one or more di- or polyisocyanates and one or more

Aminosilanen D1) or one or more isocyanate silanes D2) is reacted.

In the first step of the process according to the invention, the formation of a silicone-polyester hybrid resin takes place. This process step preferably takes place in a so-called "one-pot synthesis" at temperatures of 80-260 ° C.,

preferably at 180-230 ° C, that is, the above-mentioned components A) to C) are reacted with each other at the temperatures mentioned.

In addition, in the polycondensation reaction of the components A) to C) an esterification catalyst, such as. As Lewis acids, acids or bases. Typical catalysts are organotitanium or tin compounds such as tetrabutyl titanate or dibutyltin oxide. Also conceivable are catalysts which are based on other metals such. As zinc or antimony based as well as metal-free

Esterification. The amount of catalyst added is generally from 0.01 to 1, 0 wt .-%, preferably 0.05 to 0.3 wt .-%, based on the total amount of components A) to C).

During the polycondensation reaction, the resulting water and the alcohol are completely distilled off. This can be done, for example, by azeotropic

Distillation take place. The polycondensation reaction according to the invention is carried out until the desired values for hydroxyl and acid number are reached. The solvent-free polycondensation product obtained is a highly viscous, sticky or solid mass which, depending on the composition, has different viscosities, hydroxyl numbers and acid numbers. The desired OH number for the silicone-polyester hybrid resin is in the range of 50 to 300 mg KOH / g, preferably in the range of 80 to 230 mg KOH / g. The determination of the OH number is carried out titrimetrically. The sample is acetylated with acetic anhydride in the presence of pyridine. One mole of acetic acid is formed per hydroxyl group; while the excess acetic anhydride provides two moles of acetic acid.

The consumption of acetic acid is determined titrimetrically from the difference between the main and a blank value to be carried out in parallel. Taking into account the consumed ml 0.5 n potassium hydroxide solution in the main and blank test and the acid number of the Sample and the weight, the hydroxyl value is calculated.

_{0HZ =} (b - a) x 28.05 _{+ sz}

a = consumed ml 0.5 n potassium hydroxide solution in the main experiment

b = spent ml of 0.5 n potassium hydroxide solution in a blank test

E = weight in g

The desired acid number for silicone-polyester hybrid resin is in the range of 0.1 to 20 mg KOH / g, preferably in the range of 1 to 10 mg KOH / g, most preferably 1, 5 to 7 mg KOH / g. The determination of the acid number is also carried out titrimetrically. The acid number indicates how much mg of KOH is necessary to neutralize the free fatty acids contained in 1 g of fatty acid. A suitable initial weight is weighed into a beaker, dissolved in about 100 ml of neutralized ethanol and titrated potentiometrically with sodium hydroxide solution to the end point. The evaluation of the acid number is determined as follows: r 1 Vx 56.1 x n x f

SZ [mgKOH lg] = ^J -

e

V = consumption of titrant (ml)

n = normality titrant

MW = Molar mass of the acid

E = sample weight (g)

f = Factor Titrant The polycondensation is carried out with or without solvent, preferably in the absence of solvents.

Depending on the viscosity, the solids content can be adjusted by means of suitable solvents, for example n-butyl acetate, aromatic or non-aromatic solvents or other solvents. Preferred solvents are in particular:

Glycol ethers such as ethylene glycol dimethyl ether, glycol ether esters, esters such as

Butyl glycol acetate, 3-methoxy-n-butyl acetate, butyl acetate, ethoxypropyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, aromatic hydrocarbons such as xylene, Solvesso 100 and Shellsol A. Particularly suitable is butyl acetate.

Preferably, a solids content of> 70 wt .-% is particularly preferably> 75 Wt .-%, most preferably> 85 wt .-%.

The molecular weights M _{n of} the silicone-polyester hybrid resin are between 700 to 8000 g / mol, preferably 800 to 4000 g / mol.

In a further inventive step, the reaction of the silicone-polyester hybrid resin with one or more di- or polyisocyanates and one or more aminosilanes D1) or one or more isocyanate silanes D2). The reaction of the silicone-polyester hybrid resin with a di- or

Polyisocyanate and an aminosilane D1) is preferably again in a two-stage process. In the first step, the reaction of the di- or polyisocyanate with the OH groups from the silicone-polyester hybrid resin, wherein the reaction conditions are chosen so that sufficient NCO groups remain for the further reaction with aminosilane. The reaction of the OH-functional silicone polyester with the di- or polyisocyanate can be carried out with suitable catalysts which are well known to the person skilled in the art

Reaction temperatures from room temperature to 80 ° C take place. In the following, some catalysts may be mentioned by way of example: tin compounds such as tin diacetate, tin dioctoate, dibutyltin laurate. Furthermore, bismuth catalysts, eg. As the so-called Borchi catalysts are used. In addition, are also suitable in structures such. DABCO (1,4-diazabicyclo [2,2,2] octane). The further reaction with the aminosilane to silylalkoxy-functional silicone polyester hybrid resin is carried out without further catalysis. When using isocyanate silanes D2), the polyaddition can be carried out directly with the above-exemplified catalysts in a temperature range of

Room temperature to 80 ° C to silylalkoxy-functional silicone-polyester hybrid resin. Another object of the present invention is the use of the binders of the invention in coatings. Coatings containing the binders according to the invention are likewise provided by the present invention. The alkoxysilyl-functional binder according to the invention is used in particular for the production of 1-component coatings, in particular for topcoats, anticorrosive coatings, in particular in shipbuilding or for general industrial coatings such as for agricultural machines and

Construction. Further suitable fields of use are protective coatings for offshore drilling rigs or bridges. In particular, the binders according to the invention are suitable for ultra-high-solid topcoats with high weather stability and higher

Chemical resistance to acids, bases, kerosene, gasoline, diesel or skydrol.

The curing of such binders takes place in the presence of atmospheric moisture with suitable catalysts, generally at room temperature with hydrolysis and condensation of the alkoxysilyl groups.

Catalysts that promote the curing of alkoxysilyl groups are the

Expert sufficiently well known. Examples which may be mentioned below are: tin compounds such as tin diacetate, tin dioctoate, dibutyltin diacetylacetonate, tin tetraacetate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate,

Dibutyltin dioleate, dimethoxydibutyltin, dimetyltin, dibutyltin benzylmaleate, bis (triethoxysiloxy) dibutyltin, diphenyltin diacetate, titanium compounds, such as

Tetraethoxy-titanium, tetra-n-propoxy-titanium, tetra-i-propoxy-titanium, tetra-n-butoxytitanium, tetra-i-butoxytitanium, tetrakis- (2-ethylhexoxy) -titanium, di-i-propoxy-bis

(ethylacetoacetate) titanium, dipropoxybis (acetylacetonate) titanium, di-i-propoxy-bis (acetylacetonate) titanium, dibutoxy-bis (acetylacetonate) titanium, tri-i-propoxyallylitic acid acetate, isopropoxyoctylene glycol or bis ( acetylacetonate) titanium oxide, metallo-aliphatic compounds such as lead diacetate, lead di-2-ethylhexanoate, lead dineodecanoate, lead tetraacetate, lead tetrapropionate, zinc acetylacetonate, zinc 2-ethylcaproate, zinc diacetate, bis (2-ethylhexanoic acid) zinc , Zinc dineodecanoate, zinc diundecenoate, zinc dimethacrylate, tetrakis (2-ethylhexanoic acid) zirconium dichloride, tetrakis (methacrylic acid) zirconium dichloride, cobalt diacetate. Furthermore, bismuth catalysts, eg. B. the so-called Borchi catalyst, iron (II) - and

Iron (III) compounds, e.g. As iron (III) acetylacetonate or iron diacetate,

Aluminum compounds, e.g. As aluminum acetylacetonate, calcium compounds, eg. Calcium ethylenediaminetetraacetate, magnesium compounds, e.g. B.

Magnesium ethylenediamine tetraacetate can be used as catalysts.

In addition, are also suitable in structures, for. Triethylamine, tributylamine, aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, tetramethylguanidine or 1, 8-diazabicyclo [5.4.O.] -7-undecene, 1, 4-diazabicyclo [2, 2, 2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, N, N-bis (N, N-dimethyl-2-) aminoethyl) -methylamine, Ν, Ν-dimethylcyclohexylamine, N, N-dimethylphenylamine or N-ethylmorpholine. Also catalytically active Tetraalkylammonium compounds, such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide, N, N, N-trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate or choline-2-ethylhexanoate. Also organic or inorganic Brönsted acids such as methanesulfonic acid, p-toluenesulfonic acid,

Dodecylbenzenesulfonic acid, 1-naphthalenesulfonic acid, camphorsulfonic acid,

Acetic acid, trifluoroacetic acid or benzoyl chloride, hydrochloric acid, phosphoric acid, their mono- and / or diesters, such as. B. butyl phosphate, (iso) propyl phosphate,

Dibutyl phosphate, etc., are suitable as catalysts. Also inorganic and organic Bronsted bases such. For example, sodium hydroxide,

Tetramethylammonium hydroxide, potassium hydroxide or tetrabutylammonium hydroxide are suitable as catalysts. Of course, combinations of several catalysts can be used.

Also, so-called photolatent bases are known as crosslinking catalysts, as described in WO 2005/100482. Among photolatent bases are preferably organic bases with one or more basic

To understand nitrogen atoms, which are initially in a blocked form and release the basic form only after irradiation with UV light, visible light or IR radiation by cleavage of the molecule.

Also catalytically active are catalysts which are sold by Du Pont under the trade name Tyzor®. The same applies to catalysts of the type Kenreact® (Kenrich), Borchi Kat® (Borchers) or K-Cure® / Nacure® (King Industries).

Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent. The preferred ones

Embodiments and examples are therefore to be considered as merely descriptive, in no way limiting, disclosure.

Hereinafter, the present invention will be explained in more detail by way of examples. Alternative embodiments of the present invention are obtainable in an analogous manner.

Examples:

In the context of the present invention, the following methods were used in addition to the measuring methods already mentioned above: a) Viscosity, determined with spindle viscometer Brookfield LV-DV-I + The viscosities were determined by means of a spindle viscometer type Brookfield LV-DV-I +. Brookfield viscometers are rotational viscometers with defined spindle sets as rotation bodies. In the used

Rotational bodies were an LV spindle set. Due to the

Temperature dependence of the viscosity, the temperatures of viscometer and measuring liquid was kept exactly constant during the measurement to +/- 0.5 ° C. Other materials used besides the LV spindle set were one

thermostattable water bath, a thermometer 0 - 100 ° C (scale divisions 1 ° C or smaller) and a timer (scale values not greater than 0.1 second). For measurement, 100 ml of the sample was filled in a wide-mouth bottle; tempered and bubble-free measured after a previous calibration was done. To determine the viscosity, the viscometer was positioned to the sample so that the spindle dips to the mark in the product. The measurement is triggered with the aid of the start button, whereby care was taken that the measurement took place in the favorable measuring range of 50% (+/- 20%) of the maximum measurable torque. The result of the measurement was shown on the display of the viscometer in mPas

The division by the density (g / ml) gives the viscosity in mm ² / s. b) Determination of the Nonvolatile Content (Solid State Determination) Nonvolatile content is determined in accordance with DIN EN ISO 3251: 2008, whereby for the determination of the solid in the context of the present invention the test is carried out at 125 ° C. for 60 minutes. c) dry time measurements

To assess the catalytic activity of catalysts in a binder, the determination of the drying time with a dry time recorder (Drying Recorder) is suitable. Such a test method describes the ASTM D5895. Dry time measurements were carried out analogously to this test method using a Drying Recorder Type BK3 (The Mickle Laboratory Engineering Co. Ltd., Goose Green, Gomshall,

Guildford, Surrey GU5 9LJ., U.K.). It was on

Standard glass strips (30 x 2.5 cm x 2 mm) were applied using a box wiper (Erichsen Model 360) thin binder films. The standard glass strips were previously cleaned with acetone and then an ethanol / deionized water mixture of dust, dirt and grease adhesions. It was then the slide by means of a lever on the back, moved to the left in start position. Then the scoring nails were folded down onto the sample glass plates. The test duration was 6, 12 and 24, respectively Hours set and the measurement started. At the end of the test period, the scribing nails were folded up and the glass plates were taken out for evaluation. The arrival and drying times were read on the basis of the attached time scale. d) pendulum hardness according to king

With pendulum hardness determination according to König (DIN 53157 or EN ISO 1522), the damping of a swinging pendulum serves as a measure. The pendulum with two

Stainless steel balls is placed on a paint film. There is a physical relationship between the duration of the pendulum oscillation, amplitude and the

geometric dimensions of the pendulum. The viscoelastic behavior of the coating is decisive for the hardness. When the pendulum is vibrated, the balls roll on the surface and thus exert pressure on them. The more or less strong springback depends on the elasticity. The lack of elastic forces causes a strong damping of the pendulum movement. High elastic forces, however, cause only a small attenuation.

Pendulum hardness according to "König": number of oscillations in ose.

1 oscillation = 1, 4 seconds e) Gloss measurement and gloss retention

The principle of gloss measurement is based on the measurement of directional reflection according to DIN EN ISO 2813. For this purpose, the intensity of the reflected light is measured in a narrow range of the reflection angle. The intensity of the reflected light depends on the material and the angle of incidence. For paints more light is reflected with increasing radiation. The rest of the incident light penetrates into the material and is there, depending on the color, partially absorbed or diffused. The measurement results of the glossmeter are not related to the amount of light emitted, but to a black, polished glass standard with a defined refractive index. For this standard, the measured value = 100

Gloss units set (calibration).

The gloss retention in% of a paint surface is calculated using the following formula:

B * 100

Gloss retention in%

B = gloss level after UV exposure

A = gloss level before UV exposure f) color difference ΔΕ

Delta E, often written as dE or ΔΕ, is a measure of the perceived

Color difference, which is as far as possible "evenly spaced" for all occurring colors, where the delta stands as a sign of difference, so that work dealing with colors can be quantified.

The color difference is usually specified as Delta E. In DIN 5033 Part 2, the term "color difference" is preferred over the term "color difference". Compared to color difference, he stands for the quantified form. Any color that actually occurs, including any color emitted or measured by a device, can be assigned a color location in a three-dimensional space. This possibility is based on Graßmann's law.

The value of Delta E between the color loci (L *, a *, b *) _p and (L *, a *, b *) _v is calculated as Euclidean distance according to ISO 12647 and ISO 13655:

Rating of ΔΕ

For color differences ΔΕ as the Euclidean distance of the L * a * b * values (or from the polar coordinates L * C * h *), the assessment named in the following table is usually stated.

ΔΕ rating

0.0 ... 0.5 no to almost no difference

0.5 ... 1, 0 difference may be noticeable to the trained eye

1, 0 ... 2.0 noticeable color difference

2.0 ... 4.0 perceived color difference

4.0 ... 5.0 significant color difference that is rarely tolerated

above 5.0 the difference is rated as a different color

In the CMC system, the value ΔΕ = 1, is noted as "still tolerable color deviation." Since color spaces, despite the improvements achieved only in the near

Environment of the color locus are sentimental, AE = 10 and higher is preferred to see as another color. g) QuV-A test The assessment of the weather resistance of coatings is simulated by means of a QUV rapid weathering device. With a UVA 340 lamp, the QUV provides the most realistic simulation of sunlight in the shortwave portion of the spectrum

[Sunlight in the critical shortwave range between 365 nm and the lower limit for sunlight (295 nm)]. The QUV provides excellent, relative

Predicting damage that outdoor materials suffer. The test is carried out according to the ASTM G 154 standard as a cycle test. One cycle includes: a) UV irradiation for 8 hours with a radiation intensity of 0.89 W / m ² at a temperature of 60 ° C

b) A condensation interval of 4 hours without UV irradiation at 50 ° C

The paint surfaces produced with those prepared from the examples

Binders were then loaded for a total of 1000 hours.

example 1

In a reaction vessel, 517 g Silres SY 231 (methoxy-functional methyl / phenyl silicone resin from Wacker), 180 g of neopentyl glycol, 180 g

Trimethylolpropane, 360 g Methylhexahydrophthalsäureanhydrid and 270 g of 2-Octyldodecan-1-ol filled and heated to 180 ° C under nitrogen with an attached column tower to separate the alcohol and water formed during the reaction. The temperature is continuously increased up to 230 ° C.

After about 8 to 13 hours, the polycondensation after reaching

Acid numbers <5 mg KOH / g ended. Here, the turnover is about 96%.

The obtained silicone-polyester hybrid resin is adjusted by means of n-butyl acetate to a solids content of 90 wt .-%. The following key figures were obtained:

Solids content: 90% by weight (1 h at 125 ° C)

Viscosity: 5500 mPa ^* s

Acid value: 3.6 mg KOH / g

Hydroxyl number: 1 19 mgKOH / g

Example 2

In a reaction vessel, 80 g of DC 3074 (methoxy-functional methyl / phenyl silicone resin from Dow Corning), 41 g of adipic acid, 98.7 g Methylhexahydrophthalsäureanhydrid, 106.3 g of neopentyl glycol, 23.8 g of ethylene glycol and charged to 180 ° C under nitrogen with an attached

Column attachment heated to deposit the resulting during the reaction of alcohol and water. The temperature is continuously increased up to 230 ° C.

After about 8 to 13 hours, the polycondensation after reaching

Acid numbers <5 mg KOH / g ended. Here, the turnover is about 96%.

The obtained silicone-polyester hybrid resin is adjusted by means of n-butyl acetate to a solids content of 80 wt .-%. The following key figures were obtained:

Solids content 80% by weight (1 h at 125 ° C.)

Viscosity: 480 mPa ^* s

Acid value: 2.0 mg KOH / g

Hydroxyl number: 1 10 mg KOH / g

Example 3 (Inventive)

120.7 g of DC 3074 (methoxy-functional methyl / phenyl silicone resin from Dow Corning), 7.7 g of succinic anhydride, 93.2 g of methylhexahydrophthalic anhydride and 128.3 g of neopentyl glycol are introduced into a reaction vessel and heated to 180 ° C. under nitrogen Column tower for

Deposition of the formed during the reaction of alcohol and water heated. The temperature is continuously increased up to 230 ° C.

After about 8 to 13 hours, the polycondensation after reaching

Acid numbers <5 mg KOH / g ended. Here, the turnover is about 96%.

Solids content: 90% by weight (1 h at 125 ° C)

Viscosity: 23,000 mPa ^* s

Acid value: 2.8 mg KOH / g

Hydroxyl number: 140 mg KOH / g

Example 4 (Inventive)

In a reaction vessel with reflux condenser and dropping funnel 350 g of the presented from Example 1 prepared hydroxy-functional silicone hybrid resin. At room temperature under nitrogen supply 100.3 g vestanate ^® IPDI

(Isophorone diisocyanate Evonik Industries AG) added dropwise, heated to 50 ° C and held for about 2 hours at the temperature until the theoretical NCO value of 4.8% (on solid resin) is reached. It is cooled to room temperature and in a separate dropping funnel 1 1 1, 4 g of N- (3-Trimethoxysilylpropan-1 yl -) - Nn-butylamine (Dynasylan ^® 1 189 Evonik Industries AG) was added dropwise, so that the temperature of 40 ° C is not exceeded.

After completion of the addition, the resulting binder with a

Solvent mixture of 2 parts of n-butyl acetate and 1 part of isobutanol adjusted to a solids content of 75 wt .-%.

Viscosity: 5000 mPa ^* s

Example 5 (Inventive)

In a reaction vessel with reflux condenser and dropping funnel 200 g of the hydroxy-functional silicone-hybrid resin prepared from Example 2 are presented. At room temperature, supply of nitrogen, 57.3 g vestanate ^® IPDI

(Isophorone diisocyanate Evonik Industries AG) added dropwise, heated to 50 ° C and held for about 2 hours at the temperature until the theoretical NCO value of 4.0% (on solid resin) is reached. It is cooled to room temperature and in a separate dropping funnel 84.5 g of bis (3-triethoxysilylpropyl) amine

(Dynasylan ^® 1 122 from Evonik Industries AG) was added dropwise, so that the

Temperature of 40 ° C is not exceeded.

After completion of the addition, the resulting binder with a

Solvent mixture of 2 parts of n-butyl acetate and 1 part of isobutanol adjusted to a solids content of 75 wt .-%. Viscosity: 1500 mPa ^* s

Example 6 (Inventive)

In a reaction vessel with reflux condenser and dropping funnel 200 g of the hydroxy-functional silicone-hybrid resin prepared from Example 1 are presented. At room temperature, 63.0 g Vestanat ^® EP-IPMS are added dropwise (3-isocyanatepropyltrimethoxysilane from Evonik Industries AG) under nitrogen flow at 50 ° C heated and kept at the temperature for about 3 hours until no free

Isocyanate groups are more present.

After completion of the reaction, the binder obtained is adjusted with n-butyl acetate to a solids content of 80 wt .-%.

Viscosity: 1000 mPa ^* s

Example 7 (Inventive)

In a reaction vessel with reflux condenser and dropping funnel 100 g of the hydroxy-functional silicone-hybrid resin prepared from Example 3 are presented. At room temperature, 59.5 g of Vestanat® H ₁₂ MDI (dicyclohexylmethyl diisocyanate from Evonik Industries AG) are added dropwise under nitrogen, the mixture is heated to 50 ° C. and kept at the temperature for about 2 hours until the theoretical NCO value of 5.0% ( on solid resin) is reached. It is cooled to room temperature and 85 g of bis (3-triethoxysilylpropyl) amine (Dynasylan® 1 122 from Evonik Industries AG) are added dropwise in a separate dropping funnel, so that the temperature of 40 ° C is not exceeded.

After completion of the addition, the resulting binder is adjusted with n-butyl acetate to a solids content of 80 wt .-%.

Viscosity: 6900 mPa ^* s

Preparation of a topcoat

From the corresponding binders from Examples 4 to 7, a white-pigmented topcoat (Table 1) and a clearcoat (Table 2) are prepared as described below.

Table 1

¹ Tego Airex 900 is a deaerator from Evonik Industries AG

2 Tego Dispers 670 is a dispersing additive from Evonik Industries AG 3 Thixatrol ST is a rheology additive from Elementis

⁴ Kronos 2315 is a titanium dioxide from Kronos

⁵ Blanc fixe micro is a micronized barium sulfate from Sachtleben

⁶ Dynasylan MTMS is methyltrimethoxysilane

7 Tib Kat 318 is a catalyst from Tib Chemicals

8 Salicylic acid is a catalyst Table 2

The clearcoats 1 to 4 were cured with the aid of the catalysts Tib Kat 318 or salicylic acid via hydrolysis / condensation reaction of Silyltrialkoxygruppen. The clearcoats were coated with almost the same dry film thickness of about 50μηι and 7 days at room temperature (about 20 to 25 ° C) dried. Afterwards king pendulum hardness, drying times by means of drying recorder, and UV stability after 1000 hours UV-A exposure were evaluated. Table 3 summarizes the test results.

Table 3: Clearcoat result

Of the white paints from Table 1, the chemical resistance was tested. The white paints 1 to 4 were cured with the aid of the catalysts Tib Cat 318 or salicylic acid via hydrolysis / condensation reaction of the silyltrialkoxy groups. The white paints were coated with almost the same dry film thickness of approx. 50μηι mounted and dried for 7 days at room temperature (about 20 to 25 ° C). Subsequently, the coatings were soaked for 8 hours with a

Cotton pad from the listed in Table 4 chemicals at room temperature (20 to 25 ° C) charged.

Table 4 Chemical resistance White lacquers

Ranking / Rating:

1 = no change in the paint surface

2 = slight attack of the paint surface

3 = strong attack of the paint surface

Claims

claims:

1 . Binders based on an alkoxy- and / or silanol-functional

Polysiloxane A), one or more di- or polycarboxylic acids B), one or more di- or polyols C), one or more di- or

Polyisocyanates and one or more aminosilanes D1) or one or more isocyanate silanes D2), wherein the constituents A) to D1) or D2) are condensed together in the binder.

2. A binder according to claim 1, characterized in that component A) is nonlinear, branched, alkoxy-functional and / or silanol-functional polysiloxanes of the general formula 1,

Formula 1 wherein R-ι independently of one another alkyl, aryl or alkoxy groups, hydroxy or -OSi (R ₃ ) ₃ groups, wherein R ₃ independently of one another alkyl, aryl, alkoxy, hydroxy or -OSi (R ₃ ) Can be 3-groups,

and wherein R _{2 is} independently hydrogen, alkyl groups or

May be aryl groups, and n> 1.

3. A binder according to claim 1 or 2, characterized in that as component B) aromatic, aliphatic or cycloaliphatic di- or polycarboxylic acids and their derivatives are used.

4. A binder according to one or more of claims 1 to 3, characterized in that as di- or polyols C) ethylene glycol, propanediols, butanediol-1, 4; Hexanediol-1, 6; Neopentyl glycol, trimethylolpropane;

pentaerythritol; Di-trimethylolpropane, perhydrobisphenol A;

Dimethylolcyclohexane and 3 (4), 8 (9) -dihydroxymethyl tricyclo [5.2.1 .02.6] decane (TCD-alcohol-DM) can be used.

5. A process for the preparation of binders according to claim 1, wherein in

a first step, an alkoxy- and / or silanol-functional polysiloxane A), one or more di- or polycarboxylic acids B), and one or more di- or polyols C) are reacted with each other to form a silicone-polyester hybrid resin, and in a second step, the silicone-polyester hybrid resin obtained in the first step several di- or polyisocyanates and one or more aminosilanes D1) or one or more isocyanate silanes D2) is reacted.

A method according to claim 5, characterized in that in the polycondensation reaction of the components A) to D1) or D2) an esterification catalyst is used.

Use of the binders according to one or more of claims 1 to 4 in coatings.

Coatings containing binders according to one or more of claims 1 to 4.

Coatings according to claim 8, characterized in that they are 1-component coatings.