Thermosetting coating material

FIELD: thermosetting coating materials.

SUBSTANCE: claimed material contains polyester with carboxylic functional group and/or polyacrylate with carboxylic functional group, β-hydroxyalkylamide in which part of hydroxyls are chemically blocked, and/or fillers, and/or heat setting agent, and/or triboadditives, and/or additives such as flow controlling agent and degasification agent.

EFFECT: material of improved degasification and flow characteristics.

6 cl, 1 tbl, 3 ex

 

In the proposed invention thermosetting material to cover, which involves a complex polyester containing carboxyl functional group or polyacrylate, and specially selected crosslinking agent is masked β-hydroxyalkylated.

Coating of powder materials, which contain polyesters with carboxylic functional group and β-hydroxyalkylated as binding agents, has long been known.

In U.S. patent 4801680 described coating of powder materials based on polyesters with carboxylic functional group and β-hydroxyacetamido, and complex polyester has a glass transition temperature TD in the range of from 30°C to 85°C, acid number from about 20 to 85, and the ratio of equivalents equivalents β-hydroxyalkylated to equivalents of carboxylic acid is in the range from 0.6 to 1.6:1.

Safe from a Toxicological point of view of the coating of the powder materials based on polyesters with carboxylic functional group and/or polyacrylate with a carboxyl functional group and β-hydroxyalkylated show a very high stability in the external environment and, therefore, suitable for use outdoors. Used β-hydroxyalkylated must contain at least two βguide oxyalkylene groups per molecule, i.e. must have two functional groups.

However, at present mainly used β-hydroxyalkylated with a large number of functional groups, such as, for example, β-hydroxyalkylated with four functional groups - bis[N,N'-di(β-hydroxyethyl)]-adipate and bis[N,N'-di(β-hydroxypropyl)]adipamide.

Coating of powder materials, which contain β-hydroxyalkylated with a large number of functional groups (four groups and more) as hardeners, still have some drawbacks relating to surface defects. In case of a thicker layer of the problems associated with partly still inadequate characteristics of flow and degassing.

In U.S. patent 5216090 described coating of powder materials based on polyesters with carboxylic functional group and/or polyacrylate with a carboxyl functional group and mixtures β-hydroxyalkylated with two functional groups and β-hydroxyalkylated with a large number of functional groups, which clearly demonstrate the superior properties in terms of regulating flow and degassing.

The purpose of this invention is to partially mask the hydroxyl group in β-hydroxyalkylated to you re wirawati the number of functional groups with the aim of improving the properties of degassing and regulation of spreading the coating of powder materials on the basis of such modified β -hydroxyalkylated and polyesters with carboxylic functional group and/or polyacrylate with a carboxyl functional group.

This goal is achieved by the distinguishing characteristics of claim 1 of the claims. In dependent claims is shown a preferred embodiment of the invention.

Thus, in accordance with this invention proposed a thermosetting material to cover that combines sophisticated polyester with carbofunctional group and/or polyacrylate, as well as specially selected β-hydroxyalkylated as a hardener. β-Hydroxyalkylated in accordance with this invention has such a structure that a part of hydroxyl groups chemically masked, with the proviso, however, that there are at least two free Oh-groups for the formation of polymer in the final coating of the powder material.

Thus, preferably, if β-hydroxyalkylated described General formula I

where R1is hydrogen or C1-C5alkyl, a R2represents a

where R1has the above value, and one or two Oh-groups in this β-hydroxyethylamide with the General formula I is blocked. As the blocking agent can be in order to consider all currently known opportunities for masking the hydroxyl groups. Preferably, if the masking is performed with the use of the ester group. Preferred the ester group (formula II), which replaces the hydrogen atom in IT.

In formula II, R3is hydrogen or saturated or unsaturated aliphatic or cycloaliphatic or aromatic group containing up to 60 carbon atoms, the group can contain more carboxyl groups or a polymer, such as, for example, a complex polyester or polyacrylate.

In the General formula I, A is a chemical bond, or mono - or polyvalent organic group formed from a saturated, unsaturated or aromatic hydrocarbon group including a substituted hydrocarbon group having from 2 to 20 carbon atoms, m is from 1 to 2, n is from 0 to 2 and m+n is at least 2.

Preferred

bis[N,N'-di(β-hydroxyethyl)]-adipamide

bis[N,N'-di(β-hydroxypropyl)]-adipamide.

Getting β-hydroxyalkylated with the formula I is carried out by known methods by replacing the esters of the corresponding dicarboxylic acid alkanolamine when heated.

Suitable compounds with carboxyl functional group in obtaining β-hydroxyalkylated formula I are monobasic or politonalnye Ali is eticheskie (saturated or unsaturated), cycloaliphatic (saturated or unsaturated) or aromatic carboxylic acid containing up to 61 carbon atoms, and these carboxylic acids contain primary, secondary or tertiary carboxyl groups, with a preferred monobasic saturated aliphatic carboxylic acid containing up to 22 carbon atoms. Particularly preferred acetic acid. Also suitable chlorides of these carboxylic acids. Moreover, suitable polymers containing carboxyl group such as polyesters with carboxylic functional group and/or polyacrylates with a carboxyl functional group, which are described next.

Polyesters with carboxylic functional group suitable for receiving a coating of powder materials, you can get condensation methods known to obtain polyesters (esterification reaction and/or ester interchange). If necessary, you can also apply the appropriate catalysts. Such as, for example, oxide dibutylamine or tetrabutyl titanium.

Copolymers of esters with carboxylic functional group contain as the acid component mainly aromatic politonalnye carboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, pirone the lithium acid, trimellitate acid, 3,6-dichloroflua acid, tetrachlorophthalic acid and opportunities available to their anhydrides, chlorides or esters. They usually contain at least 50 mol.% terephthalic acid and/or isophthalic acid is preferably 80 mol.%. Missing up to 100 mol.% part of the acid include aliphatic and/or cycloaliphatic politonalnye acid, such as, for example, 1,4-cyclohexanecarbonyl acid, tetrahydrophtalic acid, hexahydroterephthalate acid, hexachlorethane acid, azelaic acid, sabotinova acid, decanedicarbonitrile acid, adipic acid, dodecadienol acid, succinic acid, maleic acid or dimeric fatty acids. Of course, if necessary, you can use hydroxycarboxylic acids and/or lactones, such as, for example, 12-eksisteeriva acid, Epsilon-caprolactone or esters of neopentyl glycol and oxybisethanol acid.

Also in small amounts can be applied monobasic carboxylic acids, such as, for example, benzoic acid, tertbutylbenzene acid, hexahydrobenzene acid and saturated aliphatic monobasic carboxylic acid.

As a suitable alcohol components may be mentioned aliphatic diols, such as ethylene glycol, 1,propandiol, 1,2-propandiol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-DIMETHYLPROPANE-1,3(neopentylglycol), 2,5-hexanediol, 1,6-hexanediol, 2,2[bis-(hydroxycyclohexyl)]propane, 1,4-dimethylcyclohexane, diethylene glycol, dipropyleneglycol and 2,2-bis-[4-(2-hydroxy)]phenylpropane. In small quantities it is also possible to use polyols, such as glycerin, hexanetriol, pentaerythritol, sorbitol, trimethylacetyl, trimethylolpropane and Tris(2-hydroxy)isocyanurate.

Instead of diols or polyols can also be applied epoxy composition. Preferably the part of neopentyl glycol and/or propylene glycol in the amount of alcohol component comprising at least 50 mol.% in the calculation of the total acid content.

Suitable for coatings from powder materials polyacrylates with carboxyl functional group have an acid number of from 10 to 300 mg KOH/g), while they get through copolymerization of a mixture of monomers including:

a) from 0 to 70 mass. h of methyl methacrylate,

b) from 0 to 60 mass. h complex (cyclo)alilovic esters of acrylic and/or methacrylic acid, where the alkyl or cycloalkyl group contains from 2 to 18 carbon atoms,

C) from 0 to 90 mass. h vinylaromatic connections

d) from 1 to 60 mass. h oleic unsaturated carboxylic acids, the total number of mass parts components shall ntow a)to d) is 100.

In the case of monomers (b) are preferred complex (cyclo)alkalemia esters of acrylic and/or methacrylic acid, where cycloalkyl group contains from 2 to 18 carbon atoms. Examples of suitable or preferred monomers (b) are: ethyl(methyl)acrylate, n-propyl(meth)acrylate, ISO-propyl(meth)acrylate, n-butyl(meth)acrylate, ISO-butyl(meth)acrylate, tertbutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexylmethyl, neopentylglycol, ISO-bornilacetate, 3,3,5-trimethylcyclohexylamine and sterilisability.

As examples of monomers (C) can be regarded styrene, vinyltoluene and β-atillery.

Examples of compounds (d), which are also preferably used are acrylic and methacrylic acid, and cretonne easy acid, taconova acid, fumaric acid, maleic acid and Tarakanova acid.

To get coprimary by copolymerization of the monomers described in (a)-(d) as an example, using conventional methods of radical polymerization, such as, for example, polymerization in solution, emulsion polymerization, polymerization in granules or polymerization in mass. The copolymerization of the monomers, thus, occurs at a temperature of from 60 to 160°C, preferably from 80 to 150°With, in the presence of initiator radicals and, when the necessity is, the molecular weight regulators.

Obtaining copolymers of acrylate with a carboxyl functional group takes place in inert solvents. Suitable solvents are, for instance, aromatic compounds such as benzene, toluene, xylene; esters, such as ethyl acetate, butyl acetate, exilerated, heptylate, methylsiliconate, acylglucuronide, methoxypropylacetate; ethers, such as tetrahydrofuran, dioxane, simple methyl ether of diethylene glycol; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amylketone, methylisobutylketone or any mixture of such solvents.

Obtaining copolymers can be conducted continuously or intermittently. Usually a mixture of monomers and initiator is metered continuously into the polymerization reactor continuously and simultaneously remove the appropriate amount of polymer. In this case, the copolymers that are almost chemically homogeneous, can be obtained according to preference. Almost chemically uniform copolymers can also be obtained by allowing the reaction mixture to flow at a constant speed in a mixing device, without deleting the polymer.

Part of the monomers can also be obtained, for example, in solvents of known type, and the residual monomers and auxiliary acid can be entered in this PE is aturu separately or together.

Typically, the polymerization proceeds at atmospheric pressure, but may also occur at pressures up to 25 bar (2.5 MPa). The initiators are used in quantities of from 0.05 to 15 wt.% in the calculation of the total number of monomers.

Suitable initiators are the conventional radical initiators, such as, for example, aliphatic azo compounds such as azodiisobutyronitrile, azo-bis-2-methylvalerate, 1,1'-azo-bis-1-cyclohexanediol and complex alkilany ether 2,2'-azo-bis-somaclonal acid; symmetrical peroxides DIALLA, such as, for example, acetyl peroxide, propionyl or buturla, peroxides, benzoyl, substituted bromine-, nitro-, methyl - or methoxy groups, peroxides Laurila; symmetric predicability, for example tert-butylperbenzoate, hydroperoxides, such as, for example, tert-butylhydroperoxide, the hydroperoxide has been studied, dialkylamide, such as peroxide of Dicumyl peroxide tert-butylamine or di-tert-butylperoxide.

To adjust the molecular weight of the copolymers in the method used conventional regulators. The purpose of the example we can mention mercaptopropionic acid, tert-dodecylmercaptan, n-dodecylmercaptan or diisopropylcarbodiimide. Regulators can be added in amounts from 0.1 to 10 wt.% in the calculation of the total number of monomers.

Solutions of the copolymers obtained by copolymerization, the m can be served without additional processing on the processes of evaporation or degassing, where the solvent is removed, for example in evaporation extruders or the spray dryer at a temperature of from about 120 to 160°and when the discharge from 100 to 300 mbar (0,01-0,03 MPa), and thus obtain the copolymers to be used according to this invention.

The ratio of equivalents equivalents β-hydroxyacetamido and equivalents of carboxylic acid is in the range from 0.6 to 1.6:1.

Upon receipt of the coatings from powder materials can also be used conventional pigments and/or fillers and/or additives.

As for supplements, they are chosen from the group including boosters, agents, regulatory spreading, degassing agents, thermal stabilizers, UV stabilizers and/or light stabilizers (HALS) and/or trimodality, and, if required, a matting agent, such as, for example, wax.

Coatings from powder materials produced preferably in foundries using co-extrusion of all the components in the formulation at a temperature of from 60 to 140°C. and Then extruded material is cooled, crushed and sieved to a particle size less than 90 μm. In principle also suitable for other ways of obtaining coatings of powder materials, such as, for example, mixing of ingredients in the solution and subsequent precipitation or distillation ostad the solvent.

The coating of the powder materials of the present invention are produced by methods that are typically used in the coatings of the powder materials, for example by electrostatic spray devices (Corona or Tribo) or by way fluidized bed.

Spreading define the coated metal sheets with a film thickness of approximately 60 μm. As the basis changes using gradation 1-5, 1 is most good spreading and 5 being the worst.

Degassing define the coated metal sheets with thickness increasing from 30 to 200 μm. The film thickness at which appear the first gas pores, serves as a limit degassing.

Comparative example

560,5 g Grilesta P 810 (copolymer with carboxyl functional group from the company UCB (b) with an acid number of 33 [mg KOH/g] and a glass transition temperature TD of approximately 60° (C)and 29.5 g Primid XL 552 (bis-[N,N'-di(β-hydroxyethyl)]-adipamide from EMS-Chemie AG (CH)), 400 g of Kronos CI 2160 (Tio2the company Kronos (D)), 8 g Resiflow PV 88 (agent regulating flow, based on polyacrylate, industrial product company Worlee-Chemie GmbH) and 2 g of benzoin mixed in dry form in a Henschel mixer at 700 rpm for 30 seconds and then ekstragiruyut on kneading machine (PLK 46) company Buss Co when the surface temperature is 100°and slaveholding screw and the rotation speed of the screw, equal to 150 rpm Extruded material is cooled, pulverized and sieved to particles of less than 90 microns.

Coating of the powder material is applied by electrostatic means (install Corona or Tribo) on sheets of aluminium (Q band Al - 365005 N 14/08 (0.8 mm)and utverjdayut in an electric furnace for 15 minutes at a firing temperature of 180°C.

Example 1

320 g (1 mol) of bis-[N,N'-di(β-hydroxyethyl)]-adipamide with a hydroxyl number of 700 mg KOH/and melted at 130°C. 60 g of acetic acid (100 %) are added into the molten mass at 130°within an hour, dropwise with stirring. After a reaction time at 130°C, 30 minutes at the same temperature impose a vacuum of 300 mbar (0,03 MPa) and remove the resulting reaction water. The molten mass is cooled and then is converted into a powder. The hydroxyl number of the product is 525 mg KOH/g

Example 2

554,6 g Grilesta P 810 (copolymer with carboxyl functional group from the company UCB (b) with an acid number of 33 [mg KOH/g] and a glass transition temperature TD of approximately 60°C)of 35.4 g of the product obtained in example 1, 400 g of Kronos Cl 2160 (Tio2from Kronos (D)), 8 g Resiflow PV 88 (agent regulating flow, based on polyacrylate, industrial product from Worlee-Chemie GmbH) and 2 g of benzoin mixed in dry form in a Henschel mixer at 700 rpm for 30 seconds is then ekstragiruyut on kneading machine (PLK 46) company Buss Co with the surface temperature of 100° C, cooled screw and the rotation speed of the screw equal to 150 rpm Extruded material is cooled, crushed and sieved to a particle size less than 90 μm.

Coating of the powder material is applied by electrostatic method (install Corona or Tribo) on sheets of aluminium (Q band Al - 365005 N 14/08 (0.8 mm)and utverjdayut in an electric furnace for 15 minutes at a firing temperature of 180°C.

Table 1 shows the properties of the coatings from powder materials.

Table 1
Time (sec) gelation DIN 55990 when

200°
Reverse impact (inch-pound) ASTM D2794Scale spreading 1-5Limit degassing mcm
Comparative example90160 (174,48 kg·cm)380
Example 2155160 (174,48 kg·cm)1120

1. Thermosetting material for coating, comprising (a) a complex of the polyester containing carboxyl functional group obtained by the condensation reaction of aliphatic and/or cycloaliphatic polyols and aliphatic and/or cycloaliphatic and/or aromatic polybasic carboxylic key is lots and anhydrides, moreover, this complex polyester has a glass transition temperature TD in the range of from 30 to 80°and an acid number from about 20 to 100 (mg KOH/g), and/or comprising polyacrylate with a carboxyl functional group obtained by polymerization of unsaturated compounds, polyacrylate has an acid number of from 20 to 300 mg KOH/g), and (b) β-hydroxyalkyl, which is defined by the formula I

where R1is hydrogen or C1-C5alkyl;

R2represents a

where R1has the above value,

and in which one or two of the Oh-group is blocked,

A is a chemical bond, or mono - or polyvalent organic group formed from a saturated, unsaturated or aromatic hydrocarbon group including a substituted hydrocarbon group having from 2 to 20 carbon atoms,

m is from 1 to 2,

n is from 0 to 2 and

m+n is at least 2, and the ratio of equivalents of β-hydroxyalkylated to equivalents of carboxylic acid is in the range from 0.6 to 1.6:1.

2. Thermosetting material for coating according to claim 1, characterized in that it further comprises pigments and/or fillers and/or stabilizers, and/or tribade is where it is refuelled, and/or additional additives, such as, for example, an agent that regulates the flow and degassing agent.

3. Thermosetting material for coating according to claim 1 or 2, characterized in that the said one or two OH-groups of blokirovana

where R3is hydrogen or a saturated, unsaturated aliphatic, cycloaliphatic or aromatic hydrocarbon group containing up to 60 carbon atoms, which group may contain an additional carboxyl group or a polymer, such as, for example, a complex polyester or polyacrylate.

4. Thermosetting material for coating according to any one of claims 1 to 3, characterized in that β-hydroxyethylamide with formula I are

bis[N,N'-di(β-hydroxyethyl)]-adipamide], bis[N,N'-di(β-hydroxypropyl)]-adipamide].

5. Thermosetting material for coating according to any one of claims 1 to 4, designed for use as protective layers.

6. A method of producing coatings of powder materials, characterized in that the extruded material was obtained from the melt using a co-extrusion of all the components in the formulation materials for the coating according to any one of claims 1 to 4, and also included the usual pigments and/or fillers and/or additives, at a temperature of from 60 to 140°and oksanyakimov material is then cooled, crushed and sieved to a particle size less than 90 μm.



 

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