阅读说明：本技术 生产结构化表面的涂料 (Coating for producing structured surfaces ) 是由 E·韦格纳 A·詹森 M·D·R·马加里诺斯 于 2018-04-10 设计创作，主要内容包括：本发明涉及涂料组合物,其包含：(i)至少一种多元醇组分(A),(ii)至少一种具有对组分(A)的羟基具有反应性的基团的交联剂组分(B),(iii)至少一种聚酰胺组分(P1),其中酰胺基通过具有6至10个碳原子的饱和脂族烃基连接,所述组分以颗粒形式使用,其中初级颗粒的粒度分布具有20至100μm的中值粒径(D<Sub>50</Sub>),和(iv)至少一种聚羧酰胺组分(P2),其中所述聚羧酰胺组分(P2)具有以下结构式<Image he="263" wi="700" file="DDA0002308412680000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中S为1、2或3,t为0或1,和s+t为2或3,R为特定的(s+t)价有机基团,并且基团R<Sup>1</Sup>和R<Sup>2</Sup>中的至少一个带有至少一个羟基。本发明还涉及这种涂料组合物的生产,其在多道油漆体系生产中的用途,以及作为涂料组合物中的添加剂的(P1)和(P2)的组合用于生产结构化涂膜,尤其是结构透明涂层的用途。(The present invention relates to a coating composition comprising: (i) at least one polyol component (a), (ii) at least one crosslinker component (B) having groups reactive toward the hydroxyl groups of component (a), (iii) at least one polyamide component (P1), in which the amide groups are linked by saturated aliphatic hydrocarbon groups having from 6 to 10 carbon atoms, the components being used in the form of particles, wherein the particle size distribution of the primary particles has a median particle diameter (D) of from 20 to 100 μm 50 ) And (iv) at least one polycarboxamide component(P2), wherein the polycarboamide component (P2) has the formula Wherein S is 1,2 or 3, t is 0 or 1, and S + t is 2 or 3, R is a specific (S + t) -valent organic radical, and the radical R is 1 And R 2 At least one of which carries at least one hydroxyl group. The invention also relates to the production of such coating compositions, to the use thereof in the production of multi-track paint systems, and to the use of the combination of (P1) and (P2) as additives in coating compositions for producing structured coating films, in particular structured clearcoats.)

1. A coating composition comprising:

(i) at least one polyol component (A),

(ii) at least one crosslinker component (B) having groups reactive with the hydroxyl groups of component (A),

(iii) at least one polyamide component (P1) in which the amide groups are linked by a saturated aliphatic hydrocarbon group having from 6 to 10 carbon atoms, said component being used in the form of particles in which the size distribution of the primary particles, determined by laser diffraction, has a median particle diameter (D) of from 20 to 100 [ mu ] m₅₀) And are and

(iv) at least one polycarboxamide component (P2), wherein

The polycarboxamide component (P2) has the formula

Wherein

s is 1,2 or 3,

t is 0 or 1, and

s + t is 2 or 3,

r is an (s + t) -valent organic group selected from:

(a) an aliphatic hydrocarbon group having 2 to 60 carbon atoms,

(b) an aliphatic or aliphatic-aromatic radical containing from 2 to 8 carboxamide groups and from 6 to 150 carbon atoms in the form of hydrocarbon radicals, and

(c) aliphatic radicals containing from 2 to 75 ether groups and a further 4 to 150 carbon atoms in the form of hydrocarbon radicals,

(d) an aromatic hydrocarbon group having 6 to 20 carbon atoms,

R¹is hydrogen or C_nH_2nR³Wherein n is 2 to 6 and R³Is hydrogen or of the structure (X)_p-R⁴Wherein p is 0 or 1, if p is 0, the radical R⁴Is OH, if p is 1, the radical X is an oxygen atom or a carboxylic esterThe base group is a group of a compound,

and R is⁴

i. Is an aliphatic hydrocarbon group having 1 to 3 hydroxyl groups and 2 to 80 carbon atoms, or

An aliphatic radical which contains from 1 to 3 hydroxyl groups, from 0 to 39 radicals from the group of ether and carboxylate groups and also from 2 to 80 carbon atoms in the form of hydrocarbon radicals,

and R is²Is a group C_nH_2n-(X)_p-R⁴(ii) a And is

-R '-NH-R' is

group-C_nH_2n-NH-C_nH_2n-(X)_p-R⁴

group-R^4’-X-C_nH_2n-NH-R¹Or

group-R^4’-X-C_nH_2n-NH-C_nH_2n-(X)_p-R⁴，

Wherein

R^4’Is an aliphatic hydrocarbon group having 0 to 2 hydroxyl groups and 2 to 80 carbon atoms, or

R^4’Aliphatic radicals which contain from 0 to 2 hydroxyl groups, from 0 to 39 radicals selected from ether and carboxylate groups and also from 2 to 80 carbon atoms in the form of hydrocarbon radicals.

2. The coating composition of claim 1, wherein the polyamide component (P1) is preparable by ring opening polymerization of a lactam of formula (I):

wherein n is 6 to 10; or

Prepared by polycondensation of an alpha, omega-aminocarboxylic acid of formula (I'):

HOOC-R-NH₂(I’)

wherein R ═ C_9-13An alkylene group.

3. The coating composition of claim 1 or 2, wherein

R is an (s + t) -valent organic group selected from:

(a) aliphatic hydrocarbon groups having 6 to 44, more preferably 34 to 42 carbon atoms,

(b) an aliphatic radical containing 2 carboxamide groups and a further 70 to 90 carbon atoms in the form of hydrocarbon radicals, and

(c) aliphatic radicals containing from 3 to 13 ether groups (-O-) and a further 6 to 26 carbon atoms in the form of hydrocarbon radicals.

4. A coating composition according to any one of claims 1 to 3, wherein the group R¹And R²Independently of one another are structure C_nH_2n-(X)_p-R⁴。

5. A coating composition according to any one of claims 1 to 4, wherein the polycarboxamide component (P2) is obtainable by reaction of:

(A) polycarboxylic acids (III) or esters (III)

Wherein

R, s and t are as defined in claims 1 to 4, and

R⁵is hydrogen or alkyl having 1 to 6 carbon atoms; or

Anhydrides of the formula (III

Wherein

R，R⁵S and t are as defined above,

and

(B) of the formula HNR¹R²Wherein R is¹And R²As defined in claims 1-4.

6. The coating composition of claim 5, wherein the amine NHR¹R²Is a reaction product of a dialkanolamine or dialkanolamine with a lactone or ethylene oxide.

7. The coating composition of any one of claims 1 to 6, wherein the coating composition is applied according to DIN ENISO 3146: the polyamide component (P1) of 2002-06 has a melting point of 160 ℃ to 350 ℃.

8. The coating composition according to any one of claims 1 to 7, wherein the polyol component (A) has a hydroxyl value of 80 to 250mg KOH/g and is selected from polyester polyols, polyurethane polyols, polysiloxane polyols and poly (meth) acrylate polyols.

9. The coating composition of claim 8, wherein the polyol component (a) is a poly (meth) acrylate polyol.

10. The coating composition according to any one of claims 1 to 9, wherein the crosslinker component (B) comprises one or more crosslinkers selected from crosslinkers having free isocyanate groups, crosslinkers having blocked isocyanate groups, amino resins and tris (alkoxycarbonylamino) triazine.

11. The coating composition according to claim 10, wherein the crosslinker component (B) comprises or consists of one or more crosslinkers selected from crosslinkers having free isocyanate groups.

12. The coating composition of claim 11, wherein the crosslinker is selected from hexamethylene 1, 6-diisocyanate, isophorone diisocyanate and 4,4' -methylenedicyclohexyl diisocyanate, their uretdione dimers, biuret dimers and/or isocyanurate trimers.

13. The coating composition of any one of claims 1 to 12, which is free of silica.

14. Coating composition according to any one of claims 1 to 12, comprising as matting agent (M) silica having a median particle diameter (D) of the particle size distribution of the primary particles of said silica₅₀) Below the median particle diameter of the particles of the polyamide component (P1) used in the coating.

15. A process for producing a coating composition according to claims 1 to 14, wherein the components which are liquid at 25 ℃ are contained wholly or partly in the initial charge and the components which are solid at 25 ℃ and any remaining components which are liquid at 25 ℃ are subsequently stirred.

16. A multi-track paint system comprising a coating layer as the outermost clear coat layer, said coating layer being obtained from the coating composition of any one of claims 1 to 14.

17. The multi-track paint system of claim 16 wherein the clear coat layer has a dry film thickness of 20 to 60 μ ι η.

18. Use of a formulation comprising at least one polyamide component (P1) according to any one of claims 1 to 14 and at least one polycarboxamide component (P2) according to any one of claims 1 to 14 as an additive in a coating composition for producing a structured coating.

Examples

All numbers are in parts by weight unless otherwise indicated.

Clearcoats B1 and B2 according to the invention were produced. The clear coating B1 of the invention was obtained from 100 parts by weight of base varnish S1 (see Table 1) and 33 parts by weight of curing agent H (see Table 2). The clear coating B2 of the invention was obtained from 106.7 parts by weight of base varnish S2 (see Table 1) and 33 parts by weight of curing agent H (see Table 2). Thus, the ratio of polyol component (a) to isocyanate component of the curing agent is the same for both inventive clearcoats.

TABLE 1

Base varnish	S1	S2
			Polyol component (A)1	67	67
Butyl diglycol acetate	6	6
			Butyl glycol acetate	3.6	3.6
Acetic acid butyl ester	5.4	5.4
			Solvent naphtha 160/180	2.7	2.7
Ethoxy propyl acetate	4.4	4.4
			Butanol	0.15	0.15
Ultraviolet absorber	1.0	1.0
			HALS	0.9	0.9
Polyether-modified polydimethylsiloxane (flow control agent)	0.35	0.35
			Polycarboxamide component (P2)2	0.2	0.2
Polyamide component (P1)3	5.5	15
			Flatting agent (M)4	2.8	0

¹A poly (meth) acrylate polyol component (65% form; drying: 1 hour at 150 ℃) based on 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate and acrylic acid; OH value: 180mg KOH/g, Mw: about 4650g/mol, acid number: about 7mg KOH/g;

²polyhydroxy carboxamides

³Polyamide 12, D₅₀：57μm

⁴Fumed silica D₅₀：10μm

The liquid base varnish components are pre-mixed. The solid was then added with stirring using a Lenart dish. The mixture was stirred for about 20 minutes. Mixing was carried out with a laboratory mixer (Vollrath 370W from Paul Vollrath GmbH & Co. KG, model "EWHV 0.5", rotation speed 1200rpm, toothed disc d 90mm) at 800-.

TABLE 2

Curing agent	H
		Aliphatic polyisocyanates based on HDI trimers (isocyanurates)	80.6
Solvent naphtha 160/180	9.7
		Acetic acid butyl ester	9.7

Comparison of different structurants

As an example of the invention, the clearcoat of example B1 (polyamide component (P1); polyamide 12, D) was used₅₀57 μm). To produce a clear coating not according to the invention, component P1 in base varnish S1 was replaced in equal amounts by the structuring agents 1 to 3 specified in table 3. Thus, comparative clear coats VB1 (structuring agent 1), VB2 (structuring agent 2) and VB3 (structuring agent 3) were obtained.

TABLE 3

The clear coats according to the invention of example B1 and the clear coats not according to the invention VB1, VB2 and VB3 were applied pneumatically to a metal substrate (dry film thickness: 40 μm; flash time: 7 minutes at 23 ℃ C.; drying: 20 minutes at 140 ℃ C.) which had been coated with a cathodic electrophoretic paint (Catheguard 500), a waterborne surfacer from BASF Coatings GmbH (FU 48-9000; dry film thickness: 25-30 μm; flash time: 10 minutes at 23 ℃ C.; drying: 70 ℃ C.; baking: 17 minutes at 155 ℃ C.), and a black waterborne primer from BASF Coatings GmbH (WB; dry film thickness: 1015 μm; flash time: 5 minutes at 23 ℃ C.).

The clear coating films formed from the coating materials of examples B1, VB1, VB2 and VB3 had a dry film thickness of 40 μm.

Measurement of Dry film thickness

The thickness of the dry film is measured microscopically in a ground profile method at a magnification of 500 times. For this purpose, a piece of about 2 cm by 2 cm of coated substrate is cut out. The sample was held vertically in a mount and placed in a mosaic mold (about 40mm diameter). A curable two-component epoxy inlay compound was mixed from 21 parts by weight of Epofix resin and 2.7 parts by weight of Epofix curing agent (both from Struers GmbH, willisch, germany) and the compound was then poured into an inlay mould. The mosaic compound was cured in the mosaic mold for 18 hours. The cured mosaic compound with the sample contained therein is then removed, ground and polished. The film thickness was measured by means of a microscope (Olympus BX 51; reflected light dark field and transmitted light). The dry film thickness of the structured clearcoat was measured at locations where the structuring agent particles were not evident.

Constant condensation condition test

To verify the adhesive strength, the samples were exposed to a coating in accordance with DIN EN ISO 6270-1: 2002-02 was tested for 240 hours at constant condensation conditions and then checked for blushing after one hour of reconditioning. The results are shown in Table 4.

Surface characterization (structural regularity)

Surface characterization was performed by the tactile quality of the surface and white light interferometry (μ surf mobile instrument from NanoFocus AG, olbhausen, germany) so that the structure of the surface could be determined. The term "regularity" denotes a uniform distribution of particles on the surface of the clear coat, which can in principle also be assessed visually. However, with the aid of a μ surf mobile instrument, it is additionally possible to determine the height of the particle fractions protruding from the clear coat, which fractions should exhibit little variation in the sense of regularity. The results are shown in Table 4.

Daimler gradient oven test

The resistance to fully demineralized water and pancreatin was specifically studied in a desmhler gradient oven test (desmhler test method PBODC 371). Only in the case of the polyamide component (P1), resistance to both substances may be found even at temperatures above 81 ℃. The results are shown in Table 4.

Scratch resistance (AMTEC)

Scratch resistance was determined according to AMTEC laboratory car wash test to DIN EN ISO 20566 (2007-01). The results are shown in Table 4.

TABLE 4

Testing	B1	VB1	VB2	VB3
					Constant condensation condition test	Minimal blushing	Very severe blushing	Severe blushing of hair	Slight whiting
Regularity of structure	+++	+	++	+
					Gradient oven test (Daimler)	+++	+	+++	++
Scratch resistance (AMTEC)	+++	++	++	+

+++: is very good

++: good taste

+: or good

Precipitation behavior

100g of the base varnish were introduced into a 200ml wide-necked glass bottle and stored at room temperature for 7 days.

TABLE 5

¹A poly (meth) acrylate polyol component (65% form; drying: 1 hour at 150 ℃) based on 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate and acrylic acid; OH value: 180mg KOH/g, Mw: about 4650g/mol, acid number: about 7mg KOH/g;

²polyhydroxy carboxamides

³Polyamide 12, D₅₀：57μm

⁴Fumed silica D₅₀：10μm

In the absence of component P2 according to the invention from the base varnish (comparative base varnish VS1), unwanted deposits were formed. There were no deposits in the base varnish of the present invention.

Determination of phase separation

The phase separation was measured using a ruler. Table 6 reports the results for different concentrations of base varnishes S4 to S7 and S8 to S11 of component P2.

TABLE 6

¹A poly (meth) acrylate polyol component (65% form; drying: 1 hour at 150 ℃) based on 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate and acrylic acid; OH value: 180mg KOH/g, Mw: about 4650g/mol, acid number: about 7mg KOH/g;

²polyhydroxy carboxamides

³Polyamide 12, D₅₀：57μm

⁴Polyamide 12, a; d₅₀：11μm

⁵Polyamide 12, D₅₀：6μm

Stability of circulation line

The stability of the recycle line was tested by pumping the base varnishes S1 and S2 (see Table 1) in the recycle line while subjecting it to a shear load, the main conditions being as follows:

pressure on the reflux monitor valve: 10bar

Round-trip per minute: 18

Volume (round trip): 0.6 liter

The gloss of the coating at 60 ° was measured before the shear load in the circulation line (TO 0) and after 100, 500, 720, 1500 and 2000 revolutions in the circulation line, respectively. Circulation line stability of the coating is sufficient when the gloss increase at an angle of 60 ° after shearing by pumping circulation in the circulation line does not exceed 10 gloss units. Gloss was measured using a commercial gloss meter from Byk Gardner, micro-TRI-gloss, cat.No.4520 at 60 ℃ in each case. The results are shown in Table 7.

TABLE 7