阅读说明：本技术 用于rma可交联的涂料组合物的涂料体系 (Coating systems for RMA crosslinkable coating compositions ) 是由 M·A·吉斯内 R·H·G·布林克威斯 于 2018-05-15 设计创作，主要内容包括：本发明涉及一种涂料体系,包含：I)底漆涂料组合物,其包含含有由酮或醛封端的伯胺官能团的粘结剂组分PA,含有乙酰乙酸酯或乙酰乙酰胺官能团的粘结剂组分PB,和II)RMA可交联的涂料组合物,其包含具有至少两个活化的亚甲基或次甲基中的酸性质子C-H的组分A,具有至少两个活化的不饱和C＝C基团的组分B,和碱交联催化剂C。本发明还涉及指定的底漆涂料组合物用于改善RMA可交联的涂料组合物,特别是对金属基材的粘附性的用途,用于涂覆基材的方法以及涂覆有本发明涂料体系的经涂覆的基材。(The present invention relates to a coating system comprising: I) a primer coating composition comprising a binder component PA comprising a primary amine functional group blocked by a ketone or an aldehyde, a binder component PB comprising an acetoacetate or an acetoacetamide functional group, and II) a RMA crosslinkable coating composition comprising a component a having at least two acidic protons C-H in activated methylene or methine groups, a component B having at least two activated unsaturated C ═ C groups, and an alkali crosslinking catalyst C. The invention also relates to the use of the specified primer coating composition for improving the adhesion of RMA crosslinkable coating compositions, in particular to metal substrates, a process for coating a substrate and a coated substrate coated with the coating system of the invention.)

1. A coating system, comprising:

I. a primer coating composition comprising:

a. a binder component PA containing primary amine functions terminated by ketones or aldehydes, preferably ketones,

b. a binder component PB comprising acetoacetate or acetoacetamide (preferably acetoacetate) functional groups,

wherein the components PA and PB form an organic binder network in the cured primer coating, and

a rma crosslinkable coating composition comprising:

a) component A having at least two acidic protons C-H of activated methylene or methine groups,

b) component B having at least two activated unsaturated C ═ C groups,

c) catalyst C for catalyzing the RMA crosslinking reaction between components A and B,

d) preferably, the reactivity regulator D,

wherein RMA components a and B form an organic binder network in the cured RMA crosslinked coating.

2. The coating system according to claim 1, wherein the primer coating composition further comprises one or more further binder components PC co-reactive with components PA or PB, preferably in an amount of less than 20 wt. -%, preferably less than 10 wt. -%, more preferably less than 5 wt. -%, relative to the total weight of binder solids in the primer coating composition.

3. A coating system according to claim 1 or 2, wherein the ketone or aldehyde (preferably ketone) in component PA is volatile, preferably having a boiling point of less than 200 ℃, preferably less than 160 ℃, 140 ℃ or even less than 120 ℃.

4. A coating system according to claims 1-3, wherein the number average functionality Fn of the ketimine or aldimine groups in component PA is at least 2, preferably 3, more preferably at least 4, and wherein Fn is preferably less than 20, preferably 10, more preferably 6, wherein the equivalent weight of the ketimine or aldimine of component PA is preferably at least 120g/mol, preferably 150g/mol, and typically less than 2000g/mol, preferably less than 1000 g/mol.

5. The coating system of claims 1-4, wherein component PA comprises the reaction product of:

a. an amine compound of formula I:

H₂N{-(CH₂)_n-NH}_m-(CH₂)_n-NH₂

wherein n is preferably 2 or 3, m is preferably 1 or 2, most preferably diethylenetriamine,

b. epoxide, isocyanate or electron-deficient unsaturated C ═ C double bonds, preferably acrylates, whose reactive functionality towards the secondary amino group-NH in the amine compound is preferably at least 2,

c. a primary aminoketone or aldehyde blocking the amine compound.

6. A coating system according to claims 1-5, wherein the number average acetoacetate/acetoacetamide functionality Fn of component PB is at least 2, preferably at least 3, more preferably at least 4, and preferably less than 20, more preferably less than 10, and the equivalent weight of the acetoacetate or acetoacetamide of component PB is preferably at least 100, more preferably at least 200, even more preferably at least 300, and preferably at most 2500, more preferably at most 1500, most preferably at most 1200 g/mol.

7. The coating system of claims 1-6, wherein component PB comprises an acrylic (co) polymer, wherein the acetoacetate functionality is introduced by:

a. by (co) polymerisation of acetoacetate-or acetoacetamide-functional (meth) acrylic comonomers, e.g. acetoacetoxyethyl methacrylate, or

b. Wherein acetoacetate functionality is introduced by transesterification of acetoacetates of low molecular weight alcohols with multifunctional hydroxyl structures having low, medium or high molecular weight (typically less than 1000, preferably less than 500, more preferably less than 250 g/mol).

8. The coating system according to claims 1-7, wherein in the primer composition component PB is a polyacrylic or polyester resin, preferably a polyacrylic resin, comprising acetoacetate functionality, wherein component PA is a ketimine modified acrylic or epoxy resin.

9. The coating system according to claims 1-8, wherein the total amount of binder component PA, binder component PB and optional further binder component PC in the primer composition is at least 50 wt%, preferably at least 60, 80 or 90 wt%, relative to the total dry solids weight of the primer composition excluding pigments.

10. A coating system according to claims 1-9, wherein the ratio of acetoacetate or acetoacetamide functionality in component PB to ketimine or aldehyde functionality in component PA is from 1:10 to 10:1, preferably from 1:5 to 5:1, more preferably from 1:3 to 3:1, most preferably from 1:2 to 2: 1.

11. The coating system according to claims 1-10, wherein the RMA crosslinkable coating composition comprises RMA crosslinkable components, wherein component a is predominantly malonate or acetoacetate, preferably malonate, and component B is acryloyl.

12. The coating system of claims 1-11, in the form of a kit of parts, wherein each part comprises one or more parts comprising components PA and PB of the primer coating composition, and one or more separate parts comprising components A, B and C of the RMA crosslinkable composition.

13. Use of a primer coating composition as a primer on a substrate for improving the adhesion of RMA crosslinkable coatings, wherein the primer coating composition comprises a ketimine or aldimine functional binder component PA, an acetoacetate or acetoacetamide functional binder component PB and optionally an organic solvent T1.

14. A method of applying an RMA crosslinked coating on a substrate comprising the steps of:

a) applying a layer of the primer coating composition according to any one of claims 1 to 12 on the surface of a substrate, preferably a metal substrate,

b) at least partially curing the layer of primer coating composition, preferably at ambient conditions, to form a primer layer,

c) applying on said primer layer a layer, preferably a topcoat layer, of an RMA crosslinkable coating composition as defined in any one of claims 1 to 12,

d) preferably, the RMA crosslinkable coating is cured under ambient conditions.

15. A coated substrate comprising a primer and a coating formed from the coating system of any one of claims 1 to 12 or obtainable by the process of claim 14.

Examples

The following is a description of certain embodiments of the invention, given by way of example only.

Adhesion test

The adhesion results described in the following examples are based on the cross-hatch adhesion test according to ISO/DIN 2409, ASTM D3359. The ratings are briefly as follows:

0: the edge of the cut is completely smooth; no peeling occurred in the squares within the lattice.

1: there was flaking of the coating at the intersection of the cuts, but less than 5% of the cross-hatched area was affected.

2: along the edges of the cuts and at the intersections of the cuts, the coating peeled off, with an affected cross-hatched area of 5-15%.

3: the coating is stripped off in strips along part or all of the edges of the cut and/or in different parts of the square, the coating is stripped off in part or all, and the area of the affected cross section is 15-35%.

4: the coating has long strips along the edges of the cuts and/or the same squares are partially or completely stripped. The cross-hatched area affected is 35-65%.

5: the degree of exfoliation was worse than 4.

Metal base material

To test forThe adhesion of the examples and comparative examples is established by applying the paint film to the metal substrate1000 above.Is the trade name of the german producer "Henkel".

General Process for preparing RMA crosslinkable coatings

Malonate containing polymer (RMA crosslinkable component a) is mixed with TMPTA (trimethylolpropane triacrylate) (RMA crosslinkable component B) and the diluent n-propanol and optionally with pigments or other coating additives and stirred until a homogeneous coating composition is obtained. All the mentioned formulations are activated by adding a defined amount of a latent base catalyst (i.e. a tetrabutylammonium hydroxide TBAH solution reactively blocked by dimethyl carbonate or diethyl carbonate, with a base concentration of 0.7-0.928meq/g solution) before application as a coating (see method for preparing the catalyst solution).

Preparation of malonate polyester resin MPE1

The preparation method of the resin comprises the following steps: a reactor equipped with a Raschig ring distillation column was charged with 382g of neopentyl glycol, 262.8g of hexahydrophthalic anhydride and 0.2g of butyl stannoic acid. The mixture was polymerized at 240 ℃ under nitrogen to an acid value of 0.2 mgKOH/g. The mixture was cooled to 130 ℃ and 355g of diethyl malonate were added. The reaction mixture was heated to 170 ℃ and ethanol was removed under reduced pressure. The resin was diluted with butyl acetate to a solids content of 85% to give a material with an OH number of 16mg KOH/g, a GPC Mn of 1750g/mol and a malonate equivalent weight of 350 (activated C-H EQW 175).

Preparation of Malonylated alkyd resin MA1

MA1 is a malonate-modified alkyd resin (Acure 510-300 from Al lnex) which uses coconut oil as the oil component, an oil length of 30%, an OH number of 108mg KOH/g, a GPC Mn of 1800g/mol and an Mw of 4350 g/mol. The malonate equivalent weight of this material was 360 (active C-H equivalent weight 180).

Preparing the paint: paint A, B and C

Paint a was prepared by mixing the components described in table 1 below. Paint A based on malonate-based polyester resinMPE1And TMPTA.

Table 1: real Michael addition ion varnish

Components	Paint A
		MPE1	10.00
TMPTA	3.47
		Silmer ACR-D2**	0.03
Methyl propyl ketone	5.00

Simmer ACR-D2 is a reactive siloxane comprising a multifunctional or linear difunctional siloxane prepolymer wherein the reactive end groups are acrylates.

The preparation method of the paint B comprises the following steps: real Michael Addition paints were prepared using TMPTA (550-100 in Table 2) to prepare mill bases, which were then diluted with malonate alkyd resin MA1 (510-300 in Table 2) and TMP-triacetoacetate (510-400 in Table 2) and TMPTA (550-100 in Table 2).

Table 2: real Michael Addition white paint B

Abrasive base

550-100	1005
		Disperbyk 163	63.6
Kronos 2310	2112

Diluting material

510-300	1390
		510-400	245
550-100	24
		Isopropanol (I-propanol)	227
80:20MAK:IBIB	433
		Part A totals	5499.25

MAK IBIB is methyl amyl ketone isobutyl isobutyrate.

Disperbyk 163 is a wetting dispersant from Byk

Kronos2310 is a titanium dioxide pigment

Catalyst preparation examples：

The catalyst compositions were prepared by mixing the components specified in table 3.

Table 3: catalyst composition

Components	Catalyst 1	Catalyst 2
			TBAH aqueous solution (40%)	35.8
TBAH aqueous solution (55%)		267.6
			Carbonic acid diethyl ester	0	121.19
Carbonic acid dimethyl ester	21.7	0
			N-propanol	0	182.4
2-propanol	1.5	0
			Deionized water	19.2	29.88