Binding substances having high hydroxyl number and transparent lacquer compositions containing said substances, having good optical properties and good scratch resistance and chemical resistance

FIELD: chemistry.

SUBSTANCE: invention relates to a hydroxy-functional binding substance having a hydroxyl number ≥180, determined according to DIN 53240, and a solubility parameter SP ≤10. The present invention also relates to methods of producing said binding substance, a transparent lacquer composition containing said substance and to a substrate coated with such a transparent lacquer composition.

EFFECT: obtaining binding substances for transparent lacquer compositions having high content of solid substances, which lead to formation of coatings with high scratch resistance, chemical resistance and good optical properties.

18 cl, 1 tbl, 4 ex

 

This invention relates to hydroxyquinoline binding substances with a high hydroxyl number and the compositions of transparent varnish containing binder. Further, the invention relates to a method for hydroxyquinoline binders, to their use for obtaining the compositions of the coating with a transparent varnish for the serial coating of automobiles and to coated substrates them.

In coating systems, in particular for coating automobiles, transparent varnishes are the last layer to protect the underneath layers from mechanical damage and weather effects. In addition, they should give brilliance, saturation and gloss effects painted surface of the car.

Composition of clear lacquer, as a rule, are based on solvents. In order to provide lower emission of organic solvents in the drying process, for reasons of environmental protection and to reduce costs, the composition of transparent varnish usually have a high proportion of solids.

The usual 1K - and 2K-songs transparent varnishes for the serial coating of automobiles as binders contain the acrylate-polyol or a complex of the polyester-polyols, which otverzhdajutsja the diisocyanates or polyisocyanates. As hardeners to obtain permanent and almost the oil, weather universal varnishes used primarily use the hardeners hexamethylenediisocyanate (HDI) and isophoronediisocyanate (IPDI). Preferably applies HDI, which can be obtained by coating with good stitching and durability. Especially common are polymeric hardeners which due to their relatively low sensitizing potential and because of their good commercial availability. As the curing agent is particularly preferably used HDI-isocyanurate as the appropriate composition of coatings that contain this compound have a low viscosity and however well be recycled and show good filling.

Next, transparent lacquers for automotive industry advantageously have other positive properties, such as, for example, resistance to scratch and chemical resistance. In the prior art it is known that good resistance to scratching and chemical resistance can be achieved by using a polyol as one component with a high hydroxyl number.

As a polyol as one of the components in the automotive clears for batch coating in the prior art, first of all, use of the polyacrylate polyols (BASF Handbuch Lackiertechnik, A. Goldschmidt, H.-J.Streitberger, Vincentz Verlag, Hannover, 2002, str). Composition of clear lacquer on the Nove polyacrylate-polyols have good chemical resistance, as well as good hardness, because of the high hydroxyl numbers of polyacrylate polyols with low molecular weight binder. However, transparent varnishes based on polyacrylate-polyols, in particular with high hydroxyl values of the polyacrylate polyol and/or high proportions of solids of the composition of transparent varnish, do not have satisfactory optical properties (appearance).

Such a high hydroxyl number, as in polyacrylate polyols, can not be carried out for low molecular weights with the usual complex polyester-polyols (Polyester und Alkydharze, U. Poth, Vincentz Verlag, Hannover, 2005, page 44 and at the other SS.). Composition of clear lacquer, which contain the usual complex polyester-polyols, in dry condition have good optical properties, but have relatively poor resistance to scratching and chemical resistance compared with polyacrylate-polyols of the prior art, particularly in 2K-compositions of transparent varnish. Next is disadvantageous that in the usual complex polyester polyols breadth of molecular weight distribution of neblagopryatnye, i.e. becomes wider, the higher is installed hydroxyl number of complex polyester. From this broad molecular weight distribution can follow incompatibility in relevant is omposite transparent varnish. In addition, often already small fraction of high molecular weight resin components lead to extremely high viscosity, which greatly limits the subsequent processing. Moreover, in the synthesis of polyesters should take into account that essential is a low acid number of the resulting binders. This is passed through the catalytic activity of the acid group and the related effects on the storage stability and machinability of materials. Further, these conventional complex polyester-polyols with high hydroxyl values as adverse reactions may occur gilotinirovaniya polyesters.

Also complex mixture of conventional polyester-polyols and polyacrylate polyols in the compositions of transparent varnish lead not only to good optical properties, but also to a satisfactory resistance to scratch and chemical resistance, especially in 2K-compositions of transparent varnish.

Thus, the present invention is to provide binders for compositions of transparent varnish with a high proportion of solids, which provide coatings with high resistance to scratching, chemical resistance and good optical properties.

This problem is solved by using hydroxypurine inogo binders with a high hydroxyl number, characterized in that it has a hydroxyl number ≥180 mg KOH/g, determined according to DIN 53240, and the solubility parameter SP ≤10. The solubility parameter SP is determined by following the method described in Journal of Applied Polymer Science, volume 12, 1968, SS-2370. To do this, every 0.5 g of the binder is diluted with 5 g of acetone. Then titrated with n-hexane, respectively deionized water (DIW = Deionized Water)until it forms a haze.

The solubility parameter SP can be calculated as follows:

with

Vml=(Vacetone·Vn-hexane)/(φacetone·Vn-hexanen-hexane·Vacetone),

Vmh=(Vacetone·VDIW)/(φacetone·VDIWDIW·Vacetone),

δmlacetone·δacetonen-hexane·δn-hexane,

δmhacetone·δacetoneDIW·δDIW.

and

VacetoneVn-hexaneVDIW= molar volume of an appropriate solvent,

ϕacetoneϕn-hexaneϕDIW= volume fraction of the corresponding solvent and

δacetone, δn-hexane, δDIW= the solubility parameter SP of the respective solvent (δacetone= 9,75 (cal/cm3)1/2δn-hexane= 7,24 (cal/cm3)1/2δDIW=(LK 23 : 43 (cal/cm3)1/2).

The parameter RA is toremote SP may be set by selection of monomers with suitable polarity upon receipt of binders, respectively, by additional modifications of conventional binders substances with suitable polarity. Thus it is essential that the used monomers, respectively serving as a modification of substances that have a low polarity. So, for example, polar monomers, such as, for example, with hydroxyl compounds 4-hydroxyethylacrylate and hydroxyethylmethacrylate, are disadvantageous for use in, for example, acrylates, as they lead to high values of SP. Not so pronounced is the effect of aromatic compounds, for example styrene.

For additional modification of binders is essential to choose the appropriate substances with low polarity. Thus, for example, conventional hydroxyquinoline binders, in particular polyesters, can be tarifitsirovana by the esterification of monocarboxylic acids, in particular acyclic aliphatic monocarboxylic acids in order to keep low SP values.

However, it is essential that non-polar monomers, respectively substances for additional modifications not be long, as it leads to poor results in tests for resistance to scratching, chemical resistance and durability.

Suddenly binders according to the invention allows not only to solve the above problems, but CROs is e, can be used to obtain the compositions of transparent varnish with particularly high shares of solids.

Although application WO 97/22420 discloses a multilayer coating system with a transparent varnish, comprising a copolymer of 20 to 50 wt.% vinyl monomer with a cyclic structure and 80-50 wt.% other vinyl monomers, such as, for example, (meth)acrylates, which has TGvalue of 0-60°C, determined in accordance with the method of Fedors (Polymer Engineering and Science 14 (2), 1974) the solubility parameter in 9-11 and srednevekovym molecular weight in 4000-30000 g/mol. The cured varnish film is not prone to the formation of water spots due to acid rain and has good optical properties. However, as described in WO 97/22420 varnish film are not satisfactory with respect to their resistance to scratching.

Disclosed there binders have low hydroxyl number (EUR. examples), however, when you try to raise these hydroxyl number is also automatically get high SP values.

In contrast, the essence of the present invention is the use of binders with a high hydroxyl number and simultaneously low values of SP.

Particularly good optical properties are obtained if the binder according to the invention has a SP value of 8.8 to 10.0, suppose the equipment of 9.2 to 10.0.

Especially good chemical resistance and resistance to scratching are obtained if the binder has a hydroxyl number is determined according to DIN 53240 in ≥200 mg KOH/g, preferably 200 to 240 mg KOH/g

Good compatibility with other components of the lacquer compositions and good optical properties are obtained if the binder according to the invention has srednesemennyh molecular weight ≤4000 g/mol, preferably 1500-4000 g/mol, particularly preferably 2000-3500 g/mol, determined by gel chromatography (GPC) with polystyrene standards in THF with 0.1 wt.% acetic acid.

The preferred binder is a complex of the polyester-polyol, polyacrylate polyol, a polyurethane polyol, a simple polyester-polyol, polycarbonate polyol, or any mixture of these types of polyols. These binders are preferred polyols for polyurethane curing, because they can be obtained easily and have the necessary hydroxyl groups to the polyurethane curing. Particularly preferred binder is a complex of the polyester-polyol, a polyurethane polyol, a simple polyester-polyol, polycarbonate polyol, or any mixture of these polyols. In highly preferred binder is a complex of the polyester-polyol. Challenging the polyester-polyols have a good compatibility with isocyanate hardeners and then give the best filling ability and better covering power unevenness in coating compositions.

Especially preferably, at least one hydroxyphenyl complex polyester tarifitsiruetsya at least one acyclic aliphatic monocarboxylic acid. The above esterification of at least one acyclic aliphatic monocarboxylic acid is also synonymously referred to as "acid modification". Highly preferably, at least one hydroxyphenyl complex polyester tarifitsiruetsya at least one acid selected from the group isomeric With8-C9-monocarboxylic acids. Especially so you can achieve satisfactory compatibility and hence satisfactory gloss hardened transparent varnishes. Very particularly preferably, at least one hydroxyphenyl complex polyester tarifitsiruetsya octane acid or isononanoic acid, more preferably isononanoic acid.

To achieve a particularly high proportion of solids in the clear lacquers with good filling mainly use a binder with a polydispersity Mw/Mn<4. Especially good properties are obtained when the binder has a lower polydispersity, i.e. <2,5, particularly ≤2,0.

In highly preferred binder is g is perranuthnoe, dendritic connection. Hyperbranched, dendritic connections, i.e. hyperbranched, dendritic macromolecule and dendrimers, in General, can be described as three-dimensional, highly branched molecules with a tree structure. Dendrimers represent a high symmetry, while similar macromolecules, which are referred to as hyperbranched and/or dendritic, to a certain extent can be asymmetric and, nevertheless, to preserve the highly branched tree-like structure. The use of such compounds in the compositions of transparent varnish contributes to a particularly high proportions of solids with good filling properties.

Hyperbranched, dendritic connection is mostly monodisperse (Mw/Mn=1) or essentially monodisperse (Mw/Mn≈1).

Especially preferably the binder is monodisperse or substantially monodisperse, partially esterified acyclic aliphatic monocarboxylic acid, preferably isomeric With8-C9-monocarboxylic acid complex polyester, which can be obtained simply, reliably and reproducibly, and its properties and finite structures can be coordinated easily and conveniently. Such polyesters can be obtained by partial esterification of hydroxyphenyl the national complex of the polyester, which, in turn, can be obtained by the method for synthesis of dendritic polymeric polyhydric alcohol complex of the polyester-polyol) with reactive and optionally protected hydroxyl terminal groups according to EP 991690 B1,

and polymeric polyhydric alcohol is n dendritic branches, which come from a Monomeric or polymeric molecules initiator with n reactive groups (A), with each branch g enables generation of branching, with each generation includes at least one polymeric or Monomeric lengthening chain branching with three functional groups, of which at least two are reactive hydroxyl groups (b) and one is a carboxyl group (S), which reactive groups (a) and/or hydroxyl groups (C) is reactive, and when need at least one intermediate generation, which includes at least one intermediate chain extension with two functional groups, one of which is a protected hydroxyl group (B") and one group (D), which reaktsionnosposobnykh relative to the hydroxyl group, and n and g are integers and at least represent 1,

and (i) two hydroxyl groups (B) amend the constituent Monomeric or polymeric extender branching circuit are acetal-protected hydroxyl groups (B'), and protection through acetal is introduced by the reaction between the two hydroxyl groups (b) and one ecitalopram carbonyl compound; and

- (ii) the first generation of branching is added to the molecule to the initiator by the reaction between the reactive group (a) and carboxyl group (C) in a molar ratio of reactive groups (A) to carboxyl groups (C), at least 1, resulting in the obtained polymeric polyhydric alcohol with the acetal-protected hydroxyl groups (a') and n dendritic branches, which include one generation, with the acetal-protected hydroxyl groups (In') if necessary, you can remove the protection via cleavage of the acetal, allowing obtained polymeric polyhydric alcohol with reactive hydroxyl groups (B); and

(iii) other generation branching is added in g - 1 repeated stages by reaction between reactive hydroxyl groups (B), which is obtained by removing the protection by cleavage of the acetal, and carboxyl groups (C) in a molar ratio of hydroxyl groups (B) to carboxyl groups (C), at least 1, resulting in the obtained polymeric polyhydric alcohol with the acetal-protected hydroxyl groups (a') and n dendritic branches, which vklyuchayuthie or several generations, with the acetal-protected hydroxyl groups (In') if necessary, may be unsecured by using the acetal cleavage, resulting in the obtained polymeric polyhydric alcohol with a reactive hydroxyl groups (B), and

- if necessary, (iv) in the stage (ii) and/or each repetition of stage (iii) separately

(a) a partial protection, such as protection as acetal, Catala and/or a complex ester of available reactive hydroxyl groups (B), resulting in the obtained polymeric polyhydric alcohol with at least one reactive hydroxyl group (C) for use in stage (iii) or repeat stage (ii), and/or

(b) adding an optional intermediate chain extension, which after removal of the protected hydroxyl group (B") gives a polymeric polyhydric alcohol with a reactive hydroxyl groups (B) for use in stage (iii) or repeat stages (iii) and n dendritic branches which comprise one or more branching generations, and at least one intermediate generation represents at least one subgeneration.

Thus the composition of transparent varnish with binders according to the invention have good viability, mostly they have acid numbers defined with the according to DIN 53402 ≤10, preferably ≤8.

Further object of the present invention is a composition of transparent varnish comprising at least one binding substance according to the invention. Mainly the composition of transparent varnish further comprises at least one curing agent.

Especially good coverage with a particularly high resistance to scratch and chemical resistance and good optical properties are obtained if the difference is defined according to the above methods, the SP value of the binder and the hardener is a maximum of 1.0, preferably to 0.8, particularly preferably of 0.5.

As curing agents in the compositions of transparent varnish, first of all, can be used isocyanate hardeners, and other cross-linking agents, such as, for example, aminoplasts hardeners and tricarbocyanines (TACT), alone or in combination with each other. Preferably used aliphatic and/or cycloaliphatic isocyanates, optionally in combination with other crosslinking agents.

Preferably the compositions of clear lacquer to obtain permanent and weather resistant, used universal varnishes, first of all, use hexamethylen-diisocyanate (HDI) and isophorondiisocyanate hardeners (IPDI). Preferably used at the ore, one HDI-hardener than achieve coatings with good stitching and durability.

Preferably the compositions of transparent varnish according to the invention using a polymer which is hardeners because of their relatively low sensitizing potential and because of their good commercial availability. Especially preferred as the curing agent is used HDI-isocyanurate, as appropriate composition of coatings that contain this compound have a low viscosity and however well treated and demonstrate good filling.

Composition of clear lacquer predominantly contain from 35 to 65 wt.% binder and from 65 to 35 wt.% hardener, calculated on the solids fraction of clear lacquer, and share added up to 100%.

Composition of clear lacquer according to the invention are mostly 2K-compositions of transparent varnish. This ensures that the binder and the hardener can harden before applying.

Further object of the present invention is a method for hydroxyquinoline binders according to the invention, in which the first

- it turns out one complex dendritic polyester-polyol with reactive and optionally protected hydroxyl end group and, which has n dendritic branches, which come from a Monomeric or polymeric molecules initiator with n reactive groups (A), and each branch includes g of branching generations, with each generation includes at least one polymeric or Monomeric chain extension fork with three functional groups, of which at least two are reactive hydroxyl groups (b) and one is a carboxyl group (S), which reactive group (a) and/or hydroxyl groups (C) is reactive, and, if necessary, at least one separating generation, which includes at least one intermediate chain extension with two functional groups, one of which is a protected hydroxyl group (B") and the group (D), which is reactive towards hydroxyl group, and n and g are integers and at least 1;

and (i) two hydroxyl groups (B) applied Monomeric or polymeric extender branching circuit are acetaline hydroxyl groups ('), and protection through acetal is introduced by the reaction between the two hydroxyl groups (b) and one ecitalopram carbonyl compound;

and (ii) the first generations the branching adds to the molecule of initiator (core) by the reaction between the reactive group (a) and carboxyl group (C) in a molar ratio of reactive groups (A) to carboxyl groups (C), at least 1, as a result, you get a complex polyester-polyol with acetal-protected hydroxyl groups (a') and n dendritic branches, which include one generation, with acetylenic protected hydroxyl groups (In') if necessary, may be unsecured by using the cleavage of the acetal, as a result, you get a complex polyester-polyol with reactive hydroxyl groups (B); and

(iii) other generation branching are added to g - 1 repeated stages by reaction between reactive hydroxyl groups (B), which is obtained by removing the protection by cleavage of the acetal, and carboxyl groups (C) in a molar ratio of hydroxyl groups (B) to carboxyl groups (C) in at least 1, as a result, you get a complex polyester-polyol with acetaline protected hydroxyl groups (B') and n dendritic branches, which include two or more generations, with acetylenic protected hydroxyl groups (In') if necessary, may be unsecured by using the cleavage of the acetal, as a result, you get a complex polyester-polyol with reactive hydroxyl groups (B), and

- if necessary, (iv) at the stage (ii) and/or each repetition of stage (iii) separately

(a) a partial protection, as, for example, for the ITA as acetal, Catala and/or a complex ester of the available hydroxyl groups (B), as a result, you get a complex polyester-polyol with at least one reactive hydroxyl group (C) for use in stage (iii) or repeat stage (ii), and/or

(b) adding an optional intermediate chain extension, which after removal of the protected hydroxyl group (B") gives a complex polyester-polyol with reactive hydroxyl groups (B) for use in stage (iii) or repeat stages (iii) and n dendritic branches which comprise one or more branching generations, and at least one intermediate generation represents at least one subgeneral;

with subsequent partial esterification of a complex polyester-polyol acyclic aliphatic monocarboxylic acid, preferably isomeric With8-C9-monocarboxylic acid.

Further object of the invention is a method for hydroxyquinoline binders according to the invention, in which a hyperbranched, dendritic, hydroxyquinolines polyester partially tarifitsiruetsya at least one acyclic aliphatic monocarboxylic acid, preferably at least isomeric With8-C9-monocarboxylic acid.

Next objective is om of the invention is the use, at least one hydroxyquinoline binders according to the invention for obtaining the compositions of the coating with a transparent varnish for the serial coating of cars, for the coating of body parts for the coating of trucks and for repair painting. Mainly the composition of transparent varnish suitable for use in the method of "wet on wet". In this way, if necessary, pre-treated and optionally pre-coated cataphoretic immersion priming and filling the substrate in two stages, first apply the base paint and then clear lacquer. The "wet on wet" means that both of varnish is applied for a short period without hot drying base varnish, then together be subjected to a hot drying and crosslinking. Particularly preferred transparent lacquer according to the invention for use in the method of applying a lacquer, which is covered with dried hot drying cataphoretic coating the substrate is covered with a modified base varnish, after intermediate evaporation of the solvent (flash-off) is applied to the base lacquer, after another evaporation of the solvent is applied a transparent varnish and after, if necessary, subsequent evaporation of the solvent joint is hot drying component lacquer. is this method does not use any conventional filler.

Further object of the invention are substrates that are coated with composition of transparent varnish according to the invention. The substrates of this kind are, if necessary, pre-processed and, if necessary, pre-coated cataphoretic immersion priming and filling the substrates of steel, galvanized steel and aluminum, used in the production of automobile bodies.

Examples

Example according to the invention 1 is getting complicated polyester SP1

In a reactor equipped with a stirrer, reflux condenser and water separator, serves 1523 weight of isononanoic acid and mixed with 40 weight parts of xylene. The mixture is gently heated with stirring to 80°C. Then, to this is added slowly 4439 parts by weight of dendritic hydroxyquinoline complex polyester (Boltorn H-30, commercially available from Perstorp), in order to avoid agglomeration. After the addition the reaction mixture is heated to 200°C. To monitor the reaction together in the Protocol make the volume of condensate and from time to time take samples to determine the hydroxyl number. Once achieved previously calculated corresponding to full engagement of the amount of condensation, distillation removes the proportion of xylene. The reaction mixture was stirred at 200°C until the acid number reaches less than 5 mg KOH/g (determined according to DIN 53402). The mixture is cooled to 145°C and dissolved in 994 weight parts of pistillata.

The obtained polyester resin has a solids fraction 86.3 wt.% and viscosity in 15.1 DPA·s (determined according to DIN EN ISO 2884-1). Received a hydroxyl number of 220 mg KOH/g (determined according to DIN 53240).

Comparative example 1 - getting the polyacrylate polyol

The reactor was flushed with nitrogen and installed the cooler, put 720,86 weight parts of pistillata and with stirring is heated to 140°C. in Parallel, to prepare two separate flow. Tributary 1 consisted of 283,74 weight parts of styrene, 498,47 weight parts of ethylhexylacrylate, 728,53 weight parts of 4-hydroxyethylacrylate and 23,01 weight parts of acrylic acid. Tributary 2 consisted of 92,02 weight parts of pistillata and 153,37 weight parts of TURIN. After the temperature reached 140°C, slowly and evenly over a period of time in 285 minutes added inflow 2. 15 minutes after the start of inflow 2 slowly and evenly over a time period of 240 minutes in the reactor was added a tributary 1. After adding tributary 2 the reaction mixture was stirred for another 120 minutes at 140°C until postpolymerization. The solids content of the received product was determined to 65,20%, an acid number of up to 14.4 mg KOH/g and a hydroxyl number of up to 185,1 mg TO is/g (each time in terms of solid matter) and a viscosity of up to 20 DPA·s at 23°C.

Comparative example 2 - getting the polyacrylate polyol

The reactor was flushed with nitrogen and installed the cooler, put 865,03 weight parts of pistillata and with stirring is heated to 140°C. in Parallel, to prepare two separate flow. Tributary 1 consisted of 303,68 weight parts of styrene, 561,35 weight parts of ethylhexylacrylate, 947,85 weight parts of 4-hydroxyethylacrylate and 27,61 weight parts of acrylic acid. Tributary 2 consisted of 110,43 weight parts of pistillata and 184,05 weight parts of TURIN. After the temperature reached 140°C, slowly and evenly over a period of time in 285 minutes added inflow 2. 15 minutes after the start of inflow 2 slowly and evenly over a period of time 240 minutes tributary 1 were added to the reactor. After adding tributary 2 the reaction mixture was stirred for another 120 minutes at 140°C until postpolymerization. The solids content of the received product was determined 66,45%, an acid number up to 13,83 mg KOH/g and a hydroxyl number of up to 200,2 mg KOH/g (each time in terms of solid matter) and a viscosity of up to 18 DPA·s at 23°C.

Comparative example 3 - getting the polyacrylate polyol

A 5-liter Juvo laboratory reaction vessel with heating jacket, equipped with a thermometer, stirrer, water separator and obladatelnitsami, put 288,0 g pistillata and 455,0 Cadura E10. When mixing and coating with 3 m3/h of nitrogen heated to 150°C and using a metering pump evenly over 4.5 hours is added dropwise a mixture of 72,0 g of di-tert-butyl peroxide and 187,0 g pistillata. After 0.25 h after the start of flow through the metering pump over 4 h add a mixture of 61,0 g of methyl methacrylate, 38.0 g of styrene, 756,0 g hydroxyethylmethacrylate, 145,0 g of acrylic acid and 363,0 g of n-butyl methacrylate. After the end of the inflow temperature still hold approx. 2 hours then cooled to 120°C and by butyl acetate set up solid in 61%. Then the polymer solution is filtered through a 5 μm - GAF-bag. The resulting resin has an acid number in 12,97 mg KOH/g (DIN 53402), hydroxyl number in 260,1 mg KOH/g (each time in terms of solid matter), the solids content of 61%±1 (60 min 130°C) and a viscosity of 11.5 DPA·s - measured according to DIN ISO 2884.

Table 1
An overview of the properties of the resins according to the invention compared with the properties of comparative examples
ResinTypeHydroxyl numberSP Mn [g/mol] (GPC)Mw/Mn (GPC)
SP1Complex polyester, the original product2209,8826322,0
Comparative example 1Acrylate18510,1136763,7
Comparative example 2Acrylate20010,383988a 3.9
Comparative example 3Acrylate26010,5624942,8

The results of the investigated acrylate resins show that the polyols on acrylate basis with a high hydroxyl number clearly have a higher solubility parameter than the polyols on acrylate basis with low hydroxyl number.

Composition of clear lacquer

Using the above resins according to the following sub-samples in each case receive the first component 2-component the th of transparent varnish:

1234
SP192,26
The acrylate of comparative example 198,44
The acrylate of comparative example 295,30
The acrylate of comparative example 384,64
Butanol2,391,731,732,39
GB ester17,38are 5.36are 5.367,38
12 34
MPA212,419,019,0112,41
Pentalateralthe 14.9010,8210,82the 14.90
Butyl acetate016,3216,32the 14.90
BDGA3to 7.67to 5.57to 5.57to 7.67
Ethoxypropionate3,762,732,733,76
Xylene2,101,521,522,10
Byk 33140,140,110,110,14
Byk ES-8050,290,210,21 0,29
Tinuvin 29261,451,051,051,45
Tinuvin 384-271,741,261,261,74

To obtain 2K-coating of transparent varnish homogenized, and then immediately put obtained according to the above data, in each case, the first components with the following specified portions of the second component (polyisocyanate hardener Basonat H I190 BASF Aktiengesellschaft). Was used for this test sheets of iron, which in each case were covered by the conventional and known precipitated on the cathode, thermally utverzhdennym electrophoretic lacquering, conventional and well-known, thermally utverzhdennym varnishing filler and dried for 10 minutes at 80°C with a layer of standard, normal, basic black lacquer BASF Coatings AG. The base layer of lacquer and a layer of transparent varnish was utverjdali together for 22 minutes at 140°C. the Obtained base coating had a thickness of 7.5 μm, the resulting coating with a transparent varnish coating thickness 35 µm.

Basonat HI 1908 65,0245,6847,9555,35

The obtained coating of transparent varnish had the following properties:

1234
The proportion of solids of the mixture [wt.%]65,455,755,055,4
Microhardness
[N/mm2]9976170124
1glycolic acid - n-butyl ether (G - B - ester), commercially available under the trade name Polysoivan About company Celanese
2MPA = methoxypropylacetate
3BDGA = butyldiglycol
4modified simple ether polydimethylsiloxane, Byk-Chemie GmbH, Gozel
5additive, Byk-Chemie GmbH, Gozel
6the stabilizer based on sterically obstructed amines, Ciba Specialty Chemicals, Basel, Switzerland
7UV-absorber, Ciba Specialty Chemicals, Basel, Switzerland
8conventional binder, isocyanurate-HDI content of isocyanurate to 19.3-20.3 per cent, a SP value of 9.4 (90%solution in 1:1 mixture of n-butyl acetate and Solvesso® 100)
9determined according to DIN EN ISO 154577 using the measuring device Fischerscope by Fischer with maximum power 25.6 mn
Surface optics (appearance)10200-10
AMTES residual gloss after cleaning [%]87929079

The results of the experiments show that due to the low value of SP good optical properties ("EXT is th"). Resin with high SP value in the respective compositions of transparent varnish clearly show poor optical properties, than according to the invention resin-based complex polyester with a high hydroxyl number.

Moreover, the binders according to the invention, however, also exhibit good hardness and satisfactory residual gloss.

As an additional benefit of the resins according to the invention can be significantly achieved a higher proportion of solids, as compared with conventional compositions.

1. Hydroxyquinoline binder with a high hydroxyl number, characterized in that it has a hydroxyl number ≥180 mg KOH/g, determined according to DIN 53240, and the solubility parameter SP≤10.

2. The binder according to claim 1, characterized in that it has an SP value of 8.8 to 10.0, preferably of 9.2 to 10.0.

3. The binder according to claim 1 or 2, characterized in that it has a hydroxyl number is determined according to DIN 53240, ≥200 mg KOH/g, preferably 200 to 240 mg KOH/g

4. The binder according to claim 1, characterized in that it has srednecenovogo molecular weight determined using GPC with a polystyrene standard in THF with 0.1 wt.% acetic acid, ≤4000 g/mol, preferably 1500-4000 g/mol, particularly preferably 2000-3500 g/mol.

5. Connecting wishes is in according to claim 1, characterized in that it is a complex of the polyester-polyol, polyacrylate polyol, a polyurethane polyol, a simple polyester-polyol, polycarbonate polyol, or any mixture of these polyols.

6. The binder according to claim 5, characterized in that it is a complex of the polyester-polyol and at least one hydroxypoly complex polyester, esterified with at least one acyclic aliphatic monocarboxylic acid.

7. The binder according to claim 6, characterized in that at least one hydroxyphenyl complex polyester etherification at least one acid selected from the group isomeric With8-C9-monocarboxylic acids.

8. The binder according to claim 7, characterized in that at least one hydroxyphenyl complex polyester etherification octane acid or isononanoic acid, more preferably isononanoic acid.

9. The binder according to claim 1, characterized in that it has a polydispersity Mw/Mn<4, preferably <a 2.5, particularly preferably ≤2,0.

10. The binder according to claim 1, characterized in that it is a hyperbranched, dendritic connection.

11. The binder of claim 10, wherein the hyperbranched, dendritic connection is justiceiraxfilmhey acyclic aliphatic monocarboxylic acid, preferably the isomeric With8-C9-monocarboxylic acid, a complex of the polyester, which can be obtained by partial esterification hydroxyquinoline complex polyester, which in turn can be obtained by the method of synthesis of dendritic polymeric polyfunctional polyhydric alcohol complex of the polyester-polyol) with reactive and optionally protected hydroxyl terminal groups,
and polymeric polyhydric alcohol has n dendritic branches, which come from a Monomeric or polymeric molecules initiator with n reactive groups (A), and each branch includes g of branching generations, with each generation includes at least one polymeric or Monomeric chain extension fork with three functional groups, of which at least two hydroxyl groups (B) which are reactive and one is a carboxyl group (S), which reaktsionnosposobnykh in relation to the reactive group (A), and/or hydroxyl groups (B), and optionally at least one intermediate generation, which includes at least one intermediate chain extension with two functional groups, one of which is a protected hydroxyl group (B") and one group (D, which is reactive towards hydroxyl group, and n and g are integers and at least 1,
and (i) two hydroxyl groups (B) applied Monomeric or polymeric extender branching circuit are acetaline hydroxyl groups ('), and protection through acetal is introduced by the reaction between the two hydroxyl groups (b) and one ecitalopram carbonyl compound; and
- (ii) the first generation of branching is added to the molecule to the initiator by the reaction between the reactive group (a) and carboxyl group (C) in a molar ratio of reactive groups (A) to carboxyl groups (C) in at least 1, resulting in the obtained polymeric polyhydric alcohol with the acetal-protected hydroxyl groups (a') and n dendritic branches, which include one generation, with the acetal-protected hydroxyl groups (In') if necessary, may be unsecured by using the acetal cleavage, resulting in the obtained polymer polyhydric alcohol with a reactive hydroxyl groups (B); and
(iii) other generation branching are added to g - 1 repeated stages by reaction between reactive hydroxyl groups (B), which are obtained by removing protection from what omashu cleavage of the acetal, and carboxyl groups (C) in a molar ratio of hydroxyl groups (B) to carboxyl groups (C) in at least 1, resulting in the obtained polymeric polyhydric alcohol with the acetal-protected hydroxyl groups (a') and n dendritic branches, which include two or more generations, and with the acetal-protected hydroxyl groups (In') if necessary, may be unsecured by using the acetal cleavage, resulting in the obtained polymeric polyhydric alcohol with a reactive hydroxyl groups (B), and
- if necessary, (iv) at the stage (ii) and/or each repetition of stage (iii) separately
(a) a partial protection, such as protection as acetal, Catala and/or a complex ester of available reactive hydroxyl groups (B), resulting in the obtained polymeric polyhydric alcohol, at least one reactive hydroxyl group (C) for use in stage (iii) or repeat stage (ii), and/or
(b) adding an optional intermediate chain extension, which after removal of the protected hydroxyl group (B") gives a polymeric polyhydric alcohol with a reactive hydroxyl groups (B) for use in stage (iii) or repeat stages (ii) and n dendritic branches, which include one or several generations fu is tvline, and at least one intermediate generation is at least one subgenera.

12. The binder according to claim 1, characterized in that it has an acid number in ≤10, preferably ≤8.

13. Composition of clear varnish comprising at least one binder according to one of claims 1 to 12.

14. Composition of clear lacquer on item 13, characterized in that it further includes at least one hardener, and the difference of SP values of hardener and binder maximum is 1.0, preferably to 0.8, particularly preferably of 0.6.

15. Composition of clear lacquer on 14, characterized in that at least one curing agent is an isocyanate hardener, laminoplasty hardener or tricarboxylate aminotriazol (TACT).

16. The method of obtaining hydroxyquinoline binder according to one of claims 1 to 12, characterized in that the first get
- complex dendritic polyester-polyol with reactive and optionally protected hydroxyl terminal groups, which has n dendritic branches, which come from a Monomeric or polymeric molecules initiator with n reactive groups (A), with each branch g enables generation of branching, with each generation includes at least one polymer or monomer the th extension chain branching with three functional groups, of which at least two are reactive hydroxyl groups (b) and one carboxyl group (S), which reaktsionnosposobnykh in relation to the group (A), and/or hydroxyl groups (B), and optionally at least one intermediate generation, which includes at least one intermediate chain extension with two functional groups, one of which is a protected hydroxyl group (B") and the group (D), which is reactive towards hydroxyl group, and n and g are integers and at least 1,
and (i) two hydroxyl groups (B) applied Monomeric or polymeric extender branching circuit are acetaline hydroxyl groups ('), and protection through acetal is introduced by the reaction between the two hydroxyl groups (b) and one ecitalopram carbonyl compound;
and (ii) the first generation of branching is added to the molecule to the initiator by the reaction between the reactive group (a) and carboxyl group (C) in a molar ratio of reactive groups (A) to carboxyl groups (C) in at least 1, as a result, you get a complex polyester-polyol with acetal-protected hydroxyl groups (a') and n dendritic branches, which include the up per generation, with acetylenic protected hydroxyl groups (In') if necessary, may be unsecured by using the cleavage of the acetal, as a result, you get a complex polyester-polyol with reactive hydroxyl groups (B); and
(iii) other generation branching are added to g - 1 repeated stages by reaction between reactive hydroxyl groups (B), which is obtained by removing the protection by cleavage of the acetal, and carboxyl groups (C) in a molar ratio of hydroxyl groups (B) to carboxyl groups (C) in at least 1, as a result, you get a complex polyester-polyol with acetaline protected hydroxyl groups (a') and n dendritic branches, which include two or more generations, and with the acetal-protected hydroxyl groups ('if necessary can be removed through cleavage of the acetal, as a result, you get a complex polyester-polyol with reactive hydroxyl groups (B), and
- if necessary, (iv) after stage (ii) and/or each repetition of stage (iii) separately
(a) a partial protection, such as protection as acetal, Catala and/or a complex ester of available reactive hydroxyl groups (B), as a result, you get a complex polyester-polyol with at least one reacts onopolies hydroxyl group (C) for use in stage (iii) or repeat stage (ii), and/or
(b) adding an optional intermediate chain extension, which after removal of the protected hydroxyl group (B") gives a complex polyester-polyol with reactive hydroxyl groups (B) for use in stage (iii) or repeat stages (iii) and n dendritic branches, which include one or more branching generations, and at least one intermediate generation is at least partially generation;
with subsequent partial esterification of a complex polyester-polyol with an acyclic aliphatic monocarboxylic acid, preferably isomeric With8-C9-monocarboxylic acid.

17. The method of obtaining hydroxyquinoline binder according to one of claims 1 to 12, characterized in that the hyperbranched, dendritic, hydroxyquinolines polyester partially mixed, at least one acyclic aliphatic monocarboxylic acid, preferably at least one isomeric With8-C9-monocarboxylic acid.

18. The substrate coated with the composition of transparent varnish on one of p-15.



 

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FIELD: chemistry.

SUBSTANCE: aqueous coating composition contains at least one water-soluble film-forming polymer selected from polyurethanes, polyesters, polycarbonates and polymers obtained by polymerising olefinically unsaturated monomers and additionally contains solid particles of an amine resin based polymer. The coating is formed on a substrate by applying the aqueous composition to obtain a peelable temporary coating.

EFFECT: solid particles of an amine resin based polymer used in the aqueous composition improve peeling capacity of the temporary coating layer.

11 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a conformal coating applied on a substrate in form of an electronic block or an electronic circuit, containing a binding layer and a particulate, which enables to shield growth of the electroconductive crystalline structure. The invention also relates to a method of shielding formation an article with a conformal coating.

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23 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: polymer composition contains a first basic polymer (A) containing at least a thermoplastic polymer; a second basic polymer (B) containing at least a thermoplastic polymer and which is incompatible with the first basic polymer (A); and an additive (C) containing at least a substance which is incompatible with any of the first basic polymer (A) and the second basic polymer (B). The additive (C) is a liquid or suspension at temperature lower than the pyrolysis temperature of the first basic polymer (A) and the pyrolysis temperature of the second basic polymer (B). Components (A), (B) and (C) are separated from each other by a phase, and boundary surfaces, each lying between two phases (A), (B) and (C), are in contact with each other, forming spatially continuous parallel boundary surfaces. A moulded product, for example, is a filter or a spacer for refrigerators or capacitors. The polymer composition is used to produce an adhesive, ink, paint, films and fibre for a powdered catalyst.

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25 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: polyvinyl butyral, surfactant, plasticiser and water are fed into a screw extruder. The components are mixed in the first zone of the extruder to form a welding mass. The welding mass is moved to the second zone of the extruder. Water is added to the welding mass in the second zone and mixed, and water is injected to a zone with high pressure, temperature and shear.

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12 cl, 8 dwg, 7 tbl, 4 ex

FIELD: process engineering.

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18 cl, 1 tbl, 15 ex

FIELD: metallurgy.

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6 cl, 2 tbl, 17 ex

Dispersion paint // 2425077

FIELD: chemistry.

SUBSTANCE: dispersion paint contains the following in wt %: 2-40 dispersed polymers, 0.1-20 filler, 0.5-20 powdered synthetic material, 0.1-15 wax, 0.5-15 fibre, water.

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19 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an aqueous anti-corrosion agent for coating metal substrates. The aqueous anti-corrosion agent contains a water-dispersed and/or water-soluble polymerisation product P with covalently bonded ligands A, which form chelating compounds with metal ions freed during corrosion of the substrate and/or surface of the substrate, as well as with cross-linked functional groups B, which can form covalent bonds between themselves, other additional functional groups B' of the polymerisation product P and/or with other functional groups B and/or B' on cross-linking agents V. The polymerisation product P has a polymer base in form of one or more structural elements, selected from a group of polyesters, polyacrylates, polyurethanes, polyolefins, polyatomic alcohols, polyvinyl esters, polyvinylamides and polyalkylene amine. Groups B and B' are (meth)acrylate and ethylacrylate groups, ether and ester vinyl groups, crotonate and cinnamate groups, allyl groups etc. Ligands A are selected from a group comprising urea, amines, amides, imines, imides, pyridines, organosulphur compounds, organophosphorus compounds, organoboron compounds, oximes, acetylacetonates, polyatomic alcohols, acids, phytic acids, acetylenes and/or carbenes. The invention also describes a single- and a two-step method of treating metal substrates using the aqueous anti-corrosion agent described above.

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11 cl, 1 tbl, 6 ex

FIELD: medicine, pharmaceutics.

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EFFECT: obtaining antibacterial medication, which possesses high degree of dispersancy, transparency, whiteness and excellent antibacterial properties, especially ability to preserve its antibacterial activity after contact with water.

43 cl, 35 tbl, 21 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a coating compositions. The coating composition contains a thermally crosslinking film-forming resin binder or resin binders, a polymer or copolymer levelling agent having molecular weight between 1000 and 100000 g/mol (Da). The polymer or copolymer levelling agent is obtained through polymerisation in the presence of an alkoxyamine initiator/regulating compound or monomer. The monomer is selected from a group of acrylate or methacrylate compounds. The said copolymer levelling agent is obtained from a composition which contains an ethylene-unsaturated monomer. The polymer levelling agent used is poly-tert-butyl acrylate or poly-tert-butyl methacrylate. The coating is obtained by depositing the composition onto a substrate and applying heat energy or electromagnetic radiation.

EFFECT: use of the said polymer or copolymer as a levelling agent in coating compositions enables to obtain smooth coating for surfaces.

3 cl, 21 ex, 10 tbl

FIELD: chemistry.

SUBSTANCE: method of producing alkyd resin involves feeding and mixing in a reactor an oil-containing component, glycerine and LiOH, and heating the mixture to 230-260°C, followed by vinylation, polyesterification and bringing to the required characteristics by adding a solvent, wherein vinylation is preceded by alcoholysis, distillation of water without an azeotrope and an alcohol test; after the alcohol test the mixture is cooled to 150-160°C and then undergoes vinylation in the presence of vinyl toluene, xylene, phthalic anhydride and di-tertiary butyl peroxide.

EFFECT: high efficiency of the process and low power consumption owing to a shorter time for synthesis of the alkyd mixture; the obtained resin has improved colour characteristics and shorter drying time to 3rd degree.

7 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to making coatings from aqueous dispersions and an aqueous dispersion containing at least one alkyd resin and at least one polymerisate having at least one (meth)acrylate segment. The (meth)acrylate segment contains 1-30 wt % of structural units derived from (meth)acrylates which in the alkyl residue have at least one double bond and 8-40 carbon atoms, 0.1-10 wt % of structural units derived from monomers containing acid groups, and 50-98.9 wt % of structural units derived from (meth)acrylates having 1-6 carbon atoms in the alkyl residue, based on the weight of the (meth)acrylate segment.

EFFECT: invention enables to obtain dispersions with prolonged storage stability and coatings with high mechanical strength.

39 cl, 2 tbl, 7 ex

FIELD: chemistry.

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EFFECT: method is simple and enables to obtain dough-like and ready-to-use paint compositions.

FIELD: chemistry.

SUBSTANCE: invention relates to use of nanomaterials in wire enamel for improving thermal properties of enamel. The nanomodified wire enamels are usually used in making insulated winding wire. The polymer base of wire enamel is selected from a group comprising polyamideimide, polyester, polyesterimide, polyurethane and mixtures thereof. The nanomaterial is selected from a group comprising nano-oxides, metal nano-oxides, metal oxides or hydroxides of aluminium, tin, born, germanium, gallium, lead, transition metals, lanthanides, actinides and mixtures thereof. The nanomaterial is also selected from a group comprising nano-oxides, metal nano-oxides, metal oxides and hydroxides of aluminium, silicon, titanium, zinc, yttrium, vanadium, zirconium, nickel and mixtures thereof. After applying enamel on the wire and curing thereof, the wire exhibits improved thermal and mechanical properties.

EFFECT: improved thermal properties of enamel.

8 cl, 6 tbl

FIELD: chemistry.

SUBSTANCE: epoxy polyester paint composition contains the following (wt %): epoxy diane resin with epoxide equivalent weight of 1550-4000 g/eq 18.0-40.0, polyester resin based on a product of polycondensation of ethylene glycol with a saturated dibasic acid 5-15, methanol-esterified melamine-formaldehyde resin 3-5, pigments 6-14, nanofiller 5-10, texturing agent 0.1-0.3, orthophosphoric acid 0.5-0.8, dispersant 0.3-0.7, organic solvents- the balance.

EFFECT: invention reduces the drying temperature, increases hardness, bending strength, return shock and improves protective properties.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: polystyrene paint composition contains the following, wt %: film-forming agent - polystyrene or derivatives thereof 1-9, pigments 1-20, colloxylin 5-15, alkyd resins 10-15, plasticiser 1-15 and solvents - the balance.

EFFECT: obtaining coatings which provide high degree of protection from corrosion of components and surfaces in conditions of atmospheric exposure or exposure to a liquid or moist environment.

2 ex

FIELD: chemistry.

SUBSTANCE: branched amorphous macro-polyols are obtained by reacting at least one carbonic acid component and at least one alcohol component consisting of 10-25 mol % alcohol with at least three functional groups, and 75-90 mol % additional alcohol containing linear and/or branched aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols, in the presence of a cross-linking agent selected from a group comprising polyisocyanate and/or melamine resin and/or derivative thereof. The polyester is characterised by molecular weight of 2500-4500 g/mol, hydroxyl number of 0-200 mg KOH/g and acid number of 0-10 mg KOH/g. Described is a method of coating metal bands and coated metal bands obtained using said method.

EFFECT: sufficient flexibility of coating of metal bands combined with sufficient reactivity of cross linkage.

12 cl, 8 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to anticorrosion coating compositions and can be used to protect steel, zinc-coated steel, cast-iron and aluminium surfaces from corrosion. The anticorrosion paint coating is cured with polyisocyanate. The composition contains hydroxyl-containing acrylic or polyester resin, pigments, filler, polyester-modified polysiloxane, organic solvents, a texturing agent, a hydroxyl-containing fluoropolymer based on fluroethylene vinyl esters and a dispersant.

EFFECT: invention enables to obtain a coating with high light fastness, low dirt retention and high coating surface slipperiness.

2 tbl

FIELD: chemistry.

SUBSTANCE: curable body repair material contains a curable polymer resin and a plurality of hollow elements. The curable body repair contains less than 3% by number of hollow elements having a diameter greater than 80 mcm or greater than 70 mcm or greater than 60 mcm. The body repair method involves applying the curable compound, curing said compound and sanding the solid body repair material to expose the cavities of the hollow elements in the solid material.

EFFECT: improved properties of the compound.

19 cl, 5 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aqueous polyacrylate dispersions for coating. The dispersion contains a hydrophobic polymerisation product with hydroxyl functional groups, a hydrophilic polymerisation product with hydroxyl functional groups and contains, as a solvent, cosolvents consisting of at least one hydrophobic, water-immiscible hydrocarbon whose initial boiling point (according to ASTM D86-05) ranges from 170°C to 250°C and final boiling point (according to ASTM D86-05) ranges from 200°C to 280°C.

EFFECT: invention is suitable for producing aqueous two-component polyurethane lacquer with considerably larger thickness of the bubble-free layer.

8 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: method of producing alkyd resin involves feeding and mixing in a reactor an oil-containing component, glycerine and LiOH, and heating the mixture to 230-260°C, followed by vinylation, polyesterification and bringing to the required characteristics by adding a solvent, wherein vinylation is preceded by alcoholysis, distillation of water without an azeotrope and an alcohol test; after the alcohol test the mixture is cooled to 150-160°C and then undergoes vinylation in the presence of vinyl toluene, xylene, phthalic anhydride and di-tertiary butyl peroxide.

EFFECT: high efficiency of the process and low power consumption owing to a shorter time for synthesis of the alkyd mixture; the obtained resin has improved colour characteristics and shorter drying time to 3rd degree.

7 cl, 1 tbl

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