阅读说明：本技术 脲二酮分散体的催化剂体系 (Catalyst system for uretdione dispersions ) 是由 S·博伊克 S·德尔 H-J·拉斯 D·格雷茨塔-弗兰茨 N·尤瓦 R-G·博恩 于 2019-03-21 设计创作，主要内容包括：本发明涉及一种催化剂体系,其包含A)至少一种选自下述的化合物：唑类、噁唑类、噻唑类、苯并三唑、苯并咪唑、苯并噁唑和它们的盐；B)至少一种除酸剂,其包含至少一个环氧基团；和C)至少一种包含N,N,N’-三取代脒结构的脒基含量(作为CN2计算；分子量=40)为12.0至47.0重量％的催化剂。套件,其包含本发明的催化剂体系和脲二酮水性分散体,所述脲二酮水性分散体的酸值为1至100 mg KOH/g并且还具有至少一个羧基。用本发明的催化剂体系和所述脲二酮分散体制备聚氨酯层的方法,和由此得到的聚氨酯层,以及该催化剂体系在固化酸性的脲二酮水性分散体和/或在制备漆或涂料中的用途。(The present invention relates to a catalyst system comprising A) at least one compound selected from the group consisting of: azoles, oxazoles, thiazoles, benzotriazoles, benzimidazoles, benzoxazoles, and salts thereof; B) at least one acid scavenger comprising at least one epoxy group; and C) the content of at least one amidine group comprising an N, N, N' -trisubstituted amidine structure (calculated as CN 2; molecular weight =40) from 12.0 to 47.0 wt% of catalyst. A kit comprising a catalyst system of the invention and an aqueous uretdione dispersion having an acid value of from 1 to 100 mg KOH/g and also having at least one carboxyl group. The catalyst system according to the invention and the method for producing polyurethane layers from the uretdione dispersions described, and the polyurethane layers obtained therefrom, and the use of the catalyst system for curing acidic aqueous uretdione dispersions and/or for producing lacquers or coatings.)

1. A catalyst system comprising

A) At least one compound selected from the group consisting of: azoles, oxazoles, thiazoles, benzotriazoles, benzimidazoles, benzoxazoles, and salts thereof;

B) at least one acid scavenger comprising at least one epoxy group; and

C) at least one catalyst comprising an amidine group having a content of 12.0 to 47.0% by weight of an N, N, N' -trisubstituted amidine structure, said amidine group being calculated as CN 2; molecular weight = 40.

2. Catalyst system according to claim 1, characterized in that the at least one compound a) is selected from pyrazoles, imidazoles, 1,2, 3-triazoles, 1,2, 4-triazoles and benzotriazoles and salts thereof.

3. Catalyst system according to claim 1 or 2, characterized in that the at least one acid scavenger B) is selected from aliphatic or aromatic alcohols, diols, polyols, ethers and acids comprising at least one epoxy group.

4. Catalyst system according to one of the preceding claims, characterized in that the at least one catalyst C) comprising an N, N' -trisubstituted amidine structure having an amidine content of 12.0 to 47.0 wt. -% is selected from optionally substituted amidine bases having an alkyl, aralkyl or allyl group or any mixture of these amidines, wherein the CN double bond of the amidine structure may be either part of an open-chain molecule or part of a cyclic or bicyclic ring system or may be arranged outside the ring of the ring system, the amidine group being calculated as CN 2; molecular weight = 40.

5. The catalyst system according to any of the preceding claims, characterized in that a) and B) are mixed in a ratio of 1:1 to 10: 1 and/or a) to C) are present in a mass ratio of 0.5: 1 to 5: 1 and/or B) to C) are present in a mass ratio of 1: a mass ratio of 1 to 1: 10.

6. Kit comprising a catalyst system according to any one of claims 1 to 5 and, separately therefrom, an aqueous uretdione dispersion, which is characterized in that it has an acid number of from 1 to 100 mg KOH/g and also has at least one carboxyl group.

7. Kit according to claim 6, characterized in that the equivalent ratio of uretdione to hydroxyl groups used is from 0.5: 1 to 1: 0.5.

8. A method of making a polyurethane layer comprising the steps of:

i) providing an aqueous uretdione dispersion having an acid number of 1 to 100 mg KOH/g and at least one carboxyl group;

ii) adding the catalyst system of any one of claims 1 to 5;

iii) applying the mixture obtained under ii) to a substrate;

iv) drying the mixture from step iii), and

v) heating to 120 ℃ for up to 180 minutes to cure the mixture from step iv).

9. Polyurethane layer, in particular a polyurethane film, obtainable by the process according to claim 8.

10. Use of the catalyst system according to any one of claims 1 to 5 for curing uretdione aqueous dispersions having an acid number of from 1 to 100mg KOH/g and having at least one carboxyl group and/or for the preparation of lacquers or coatings, in particular polyurethane films.

Example (b):

the method and the material are as follows:

the method comprises the following steps:

all analytical methods refer to measurements at a temperature of 23 ℃ unless otherwise stated.

Pendulum hardness: pendulum hardness is according to DIN EN ISO 1522: 2007-04 measured on a glass plate and determined according to the kenig.

Solvent-and water tolerance:

The cured lacquer was tested for its resistance to p-xylene, 1-methoxy-2-propyl acetate, ethyl acetate, acetone and water. A piece of cotton soaked with the test substance was placed on the coated surface and covered with a watch glass. After a given exposure time, the cotton was removed, and the exposed sites were dried and immediately inspected. According to DIN EN ISO 4628-1: 2016-07 evaluates the softening or discoloration of the coating surface.

0 is unchanged, i.e. there is no appreciable change

1 very slight, i.e. only visible, change, e.g. slight, change in hue

2 recognizable, i.e. clearly perceptible, changes, e.g. softening, perceptible by fingernails

3 clearly perceptible changes, e.g. moderate hue changes, possible slight blistering

4 strong change, e.g. severe foaming

5 the coating is completely destroyed without any external influence.

Infrared measurement:

the ring opening of the uretdione was characterized by means of an FT-IR spectrometer (Tensor II with platinum ATR unit (diamond crystals) from Bruker). At (4000-^-1The spectrum is recorded in the wavenumber range of (a). The maximum uretdione peak was evaluated (about 1760 cm)^-1). The peak heights of the comparative systems were compared to the initial values set to 100% (uretdione film without catalyst, dried at room temperature). The uretdione peak height of the film cured at 180 ℃ for 30 minutes was set to 0%. The change from the 100 and 0% values (ratio formation) was determined.

When measured on an ATR crystal, the intensity of the spectrum depends on the coverage of the crystal surface (Besetzung). Since comparable crystal surface coverage cannot be ensured in comparable measurements due to sample preparation, it is necessary to form a ratio for this ratio by normalizing all spectra to CH stretching vibrations (wave number range) (3000-^-1) To correct for this effect. After the above peak height evaluation, the spectra were also substantially corrected.

The solids content (non-volatile content) was determined by heating a weighed sample to constant weight at 125 ℃. The solids content was calculated by weighing back the sample at constant weight.

The NCO content is determined by volume in accordance with DIN-EN ISO 11909. By means ofIn IR spectroscopy (at 2260 cm)^-1Band) to check for free NCO groups.

The viscosities given are in accordance with DIN 53019: 2016-10, determined with the aid of a rotational viscometer at 23 ℃ with the aid of a rotational viscometer using the rotational viscometer from Anton Paar Germany GmbH, Ostfildern, Germany, at a shear rate of 401/s.

The average particle diameter (number average given) of the polyurethane dispersions was determined by means of laser correlation spectroscopy after dilution with deionized water (instrument: Malvern Zetasizer 1000, Malvern Inst.Limited, London, UK).

The Zeta potential is measured by diluting a drop of the sample with 20ml of demineralized water and homogenizing by stirring. The Zeta potential was subsequently determined in a Malvern Nanosizer ZS90 (Malvern Instruments, Herrenberg, Germany) at 23 ℃.

The acid number of the respective dispersion is in accordance with DIN EN ISO 2114: 2002-06. Instead of as in DIN EN ISO 2114: 2002-06, using a mixture of acetone and ethanol (2: 1 by weight) as the solvent. The unit of acid number is mg KOH per g of sample analyzed.

Materials:

lupragen N700 (1, 8-diazabicyclo-5.4.0-undec-7-ene (DBU)): from BASF SE

Sodium 1,2, 4-triazole from Sigma Aldrich

Heloxy modifier TP polyfunctional glycidyl ether of trimethylolpropane, available from Hexion

Bayhydrol A2695-OH-functional polyacrylate Dispersion dilutable with Water; approximately 41% of the solution was neutralized with triethanolamine/dimethylethanolamine in water/1-butoxy-2-propanol, 7.2% of 1-butoxy-2-propanol, Covestro

Dowanol PnB propylene glycol mono-n-butyl Ether, Dow Co

Peroxan DB di-tert-butyl peroxide Pergan Co

Solvent naphtha 100 an aromatic solvent from Azelis

Butyl glycol Brenntag Co

Dimethylolpropionic acid (DMPS) Perstorp

Addocat SO 2-tin (II) ethylhexanoate, Rhein Chemie,

all acrylate monomers as well as amines (Sigma-Aldrich) were used as supplied.

Veova 9 vinyl Tertiary carbonate, Momentive

Other solvents and chemicals Sigma-Aldrich

Xylene (Xy), 1-methoxy-2-propyl acetate (MPA); ethyl Acetate (EA); acetone (Ac).