阅读说明：本技术 低光泽度混合粉末涂料 (Low gloss mixed powder coatings ) 是由 格尔德·施拉格尔 沃尔夫冈·沙伊内克尔 康拉德·塞巴斯蒂安·宾特 于 2018-05-04 设计创作，主要内容包括：一种可固化的粉末涂料组合物,所述组合物包含一种或多种羟基或羧基官能型聚酯(A)、一种或多种羟基或羧基官能型丙烯酸系树脂(B)、一种或多种能够与(A)和/或(B)反应的交联剂(C)。(A curable powder coating composition comprising one or more hydroxy-or carboxy-functional polyesters (a), one or more hydroxy-or carboxy-functional acrylic resins (B), one or more crosslinkers (C) capable of reacting with (a) and/or (B).)

1. A curable powder coating composition, the composition comprising:

One or more hydroxyl or carboxyl functional polyesters (a) in an amount of from 9 to 90 weight percent based on the entire powder coating composition, said functional polyesters (a) characterized by a Tg of greater than 35 ℃;

One or more hydroxyl-or carboxyl-functional acrylic resins (B) in an amount of from 9 to 90 percent by weight based on the entire powder coating composition, said hydroxyl-or carboxyl-functional acrylic resins (B) characterized by a Tg of greater than 35 ℃; and

One or more crosslinkers (C) capable of reacting with (A) and/or (B), the amount of crosslinker (C) being from 1 to 50% by weight based on the entire powder coating composition;

Wherein the difference in hydroxyl or acid values of (A) and (B) or, if a mixture of polyesters (A) and/or a mixture of acrylic resins (B) is present, the average hydroxyl or acid value of the mixture of polyesters (A) and/or of the mixture of acrylic resins (B) is greater than or equal to 20, in particular 30.

2. The powder coating composition of claim 1, wherein the hydroxyl number or average hydroxyl number of (B) is greater than or equal to 40.

3. A powder coating composition according to claim 2, wherein the hydroxyl number or average hydroxyl number is greater than or equal to 65.

4. The powder coating composition of claim 1, wherein the hydroxyl number or average hydroxyl number of (a) is greater than or equal to 200.

5. A powder coating composition according to claim 4, wherein the or an average hydroxyl number is greater than or equal to 250.

6. The powder coating composition according to claim 1, wherein the weight ratio of (B)/(A) is from 1.0 to 4.5.

7. The powder coating composition according to claim 1, wherein the weight ratio of (B)/(a) is from 1.5 to 3.0.

8. The powder coating composition according to claim 1, wherein the weight ratio of (B)/(a) is from 2 to 2.5.

9. The powder coating composition according to claim 1, further comprising one or more fluorine-containing organic compounds (D).

10. The powder coating composition according to claim 9, wherein the one or more fluorine-containing organic compounds (D) are fluorine-containing oligomers and/or polymers in a concentration of 0.5 to 19% by weight, based on the sum of (a), (B) and (D).

11. The powder coating composition according to claim 9, wherein the one or more fluorine-containing organic compounds (D) are fluorine-containing oligomers and/or polymers in a concentration of 1 to 10% by weight, based on the sum of (a), (B) and (D).

12. The powder coating composition according to claim 9, wherein the one or more fluoro organic compounds (D) are fluoro oligomers and/or polymers in a concentration of 1.5 to 3.5 wt. -%, based on the sum of (a), (B) and (D).

13. The powder coating composition of claim 1, wherein (C) comprises an isocyanate-based hardener.

14. The powder coating composition of claim 13, wherein the isocyanate-based hardener is a blocked isocyanate-based hardener.

15. Powder coating composition according to claim 14, wherein the blocked isocyanate based hardener is a caprolactam blocked isocyanate based hardener.

16. The powder coating composition of claim 13, wherein the isocyanate-based hardener is present at a weight concentration of (C) of greater than or equal to 50%.

17. The powder coating composition of claim 13, wherein the isocyanate-based hardener is present at a weight concentration of greater than or equal to 80% of (C).

18. The powder coating composition of claim 1, wherein (C) comprises a hardener comprising one or more carboxylic acids and/or carboxylic acid salts, the hardener being present in a weight concentration of less than or equal to 50% of (C).

19. the powder coating composition of claim 18, wherein the weight concentration is less than or equal to 20% of (C).

20. the powder coating composition of claim 18, wherein the weight concentration is less than or equal to 15% of (C).

21. The powder coating composition of claim 14, wherein (C) comprises a dodecanedioic acid and/or pyromellitic acid group.

22. The powder coating composition of claim 1, wherein (D) comprises perfluoroalkoxy and/or PTFE compounds.

23. The powder coating composition of claim 1, further comprising a polymer having a melting range of 50 ℃ to 200 ℃ and a viscosity of 10Pas to 500Pas measured by a plate/plate viscometer at a shear rate of 10 rad/s.

24. The powder coating composition of claim 23, wherein the melt range is from 100 ℃ to 150 ℃ and the viscosity is from 10Pas to 500Pas measured by a plate/plate viscometer with a shear rate of 10 rad/s.

25. The powder coating composition of claim 24, wherein the viscosity at 200 ℃ is 50Pas to 250Pas measured by a plate/plate viscometer with a shear rate of 10 rad/s.

26. The powder coating composition of claim 24, wherein the viscosity at 200 ℃ is 90Pas to 150Pas measured by a plate/plate viscometer with a shear rate of 10 rad/s.

27. The powder coating composition according to claim 12, wherein the polymer is a polyester-based material and/or an acrylic-based material.

28. The powder coating composition of claim 1, wherein the powder coating further comprises a phyllosilicate at a concentration of 3 to 30 weight percent, based on the weight of the entire powder coating formulation.

29. A powder coating composition according to claim 1, wherein the silicate is selected from the group consisting of china clay, montmorillonite clay, derivatives or organic derivatives thereof and mixtures thereof.

30. The powder coating composition according to claim 1, wherein the applied powder coating formulation has a gloss measured at 60 ° equal to or lower than 20.

Technical Field

The present invention relates to powder coating formulations, in particular powder coating compositions having improved chemical resistance and a matte surface.

Background

The need for elastomeric powder coatings is becoming more and more prevalent. Today, in the last decades, well-known basic powder chemicals have been used that meet standard durability requirements. However, most powder chemicals available in the industry today are not equipped with the proper chemical composition for use in extreme situations or environments. As ultra-durable powder coatings in this form become more prevalent, innovations in the composition of typical powder coating chemicals have placed a high demand.

Today, there are several well known chemical compositions in the industry defined as durable powder coatings. Examples of known durable powder chemicals include: polyester, polyester/isocyanate, acrylic and fluoropolymer powder coatings. Over 60% of the market uses polyester-based coatings that are formulated to withstand measurable amounts of standard outdoor environments, such as corrosion and ultraviolet radiation. Depending on the specification, these powder coatings have a wide gloss range, from high gloss to dull and dull. However, when these coatings are exposed to chemical, biological or decontamination agents, they will not withstand such harsh environments.

US 9,206,320B 1 relates to a matte-looking, chemical-resistant powder coating composition comprising a resin component, a polyisocyanate-containing uretdione cross-linking agent, a catalyst, and a flatting agent. The resin component may comprise a hydroxyl-containing resin and a hydroxyl-containing halogenated copolymer resin. Catalytic crosslinking of the uretdione isocyanate groups and the resin of the resin component during curing is preferably disclosed to produce a film in finished form having low gloss and shine and resistance to chemical agents.

US 9,012,556B 1 describes a low reflectance chemical resistant coating composition comprising a first acrylic powder resin having a hydroxyl number of at least about 180, a second acrylic powder resin having a hydroxyl number of less than about 45, a crosslinking agent that reacts with the hydroxyl functional acrylic resin and wollastonite.

US 8,969,577B 2 relates to curable compositions comprising a heat latent amidine base and an organic material which is polymerisable or crosslinkable with a basic or nucleophilic catalyst. In particular, this document describes curable coating compositions, in particular powder coating compositions, and curable binder compositions, and the use of heat-latent amidine bases as curing catalysts for thermally-induced base-catalyzed polymerization or crosslinking reactions. The polymerizable or crosslinkable organic material may be a two-component system comprising a hydroxyl-containing polyacrylate and/or polyester and an aliphatic or aromatic polyisocyanate.

Disclosure of Invention

The present invention relates to a curable, dull matte powder coating composition having excellent chemical resistance through a unique and innovative composite of hydroxyl functional polyesters and acrylic copolymers crosslinked with isocyanates, preferably blocked isocyanates and/or other suitable curing agents. It provides a system which exhibits high chemical resistance and good mechanical flexibility. Furthermore, in a particular and preferred embodiment of the invention, a fluorinated resin or an organic compound is added to the composition. In particular, such composites achieve optimal durability, viability, and resistance to chemical absorption by the addition of various PFA (perfluoroalkoxy polymer) and/or Polytetrafluoroethylene (PTFE) additives. While maintaining a matte surface. The present invention ultimately results in a leading mixed powder coating that is capable of maintaining durability in a wide variety of environments for any coated surface and resists absorption if exposed to or when exposed to chemicals, biological substances, and detergents. In a particular and preferred embodiment of the present invention, the final powder coating material may even result in a coated surface having improved resistance to chemicals, biological substances and detergents, such as mustard gas, so that the MIL-PRF-32348 specification may be met.

Drawings

For a more complete understanding of the present disclosure and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

Figure 1 shows an extrudate with 3% high molecular PTFE.

Figure 2 shows the negative results of the pliability test (example 2).

Figure 3 shows the positive results of the flexibility test (example 12).

Fig. 4 shows the negative result (evaluation value 3) of the DS2 test.

Fig. 5 shows the positive result (evaluation value 1) of the DS2 test.

Detailed Description

Slight variations above and below the given ranges can be used to achieve substantially the same results.

With regard to the invention, in particular with regard to the appended claims, it is to be understood that any combination of the subject matter of the different claims belongs to the inventive idea and the following disclosure, although dependent claims are, for formal reasons, only dependent on the main claim.

According to the invention, highly saturated polyester resin components of the hydroxyl or carboxyl functional type can be used as functional binders for powder coatings. The present invention is not limited to a particular polyester formulation. Typical examples of acid components include, but are not limited to, just a few of the following: terephthalic acid, isophthalic acid, trimellitic acid, adipic acid, polybasic acid, and pyromellitic acid (pyromellitic acid). Typical examples of alcohol components include, but are not limited to: ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and neopentyl glycol. In one or more polyesters, the polyester used may be hydroxyl functional, carboxyl functional or a combination thereof.

Some typical polyesters and monomers for such polyesters can be found in US 9,206,320B 1 and EP 1848782B 1.

unsaturated monomers such as alcohols and acids may also be used in the present invention.

Preferred hydroxy-functional polyester resins have about 1.2g/cm³A hydroxyl number of from about 10mg KOH/g to 350mg KOH/g, preferably from 200mg KOH/g to 250mg KOH/g and a Tg of greater than 30 ℃ and is prepared by polymerization of at least one acid component and at least one alcohol component.

Suitable monomers for polyesters and/or polyesters are well known in the art and are listed, for example, in US 9,206,320B 1.

Thus, for the present invention, one or more hydroxyl-or carboxyl-functional polyesters (A) are reacted with one or more hydroxyl-or carboxyl-acrylic copolymer resins having a Tg of greater than 30 ℃. It has surprisingly been found that resins based on hydroxy-or carboxy-functional acrylic (co) polymers (B) can achieve high chemical resistance and a matt appearance when combined with hydroxy-or carboxy-functional polyester resins to formulate powder coatings, provided that the amount of functional groups in the hydroxy-or carboxy-acrylic copolymer and the hydroxy-or carboxy-functional polyester resin is significantly different and that not only a certain low gloss can be achieved, but also sufficient mechanical flexibility can be obtained. Furthermore, it has surprisingly been found that for a matte appearance, a combination of acrylic and polyester resins with almost the same difference in acid or hydroxyl value gives a higher gloss reduction than a combination of polyester/polyester or acrylic/acrylic. The difference in functional group value between the hydroxyl or carboxyl functional polyester and one or more of the hydroxyl or carboxyl acrylic resin copolymers should be greater than or equal to 30.

Suitable monomers for the acrylic resin and/or acrylic resins are well known in the art and are listed, for example, in US 9,012,556B 1 and/or US 9,206,320B 1. In one or more polyesters, the acrylic resin used may be hydroxyl functional, carboxyl functional, or a combination thereof. The use of epoxy/GMA groups in the acrylic resin is likewise optional.

The powder coating compositions according to the invention also comprise one or more crosslinkers capable of reacting with the functional groups of the polyester and/or acrylic resin used, such as the following only to name a few: blocked isocyanates, uretdiones, cyclic amides and/or polyacid compounds. To obtain better chemical stability, blocked isocyanates are preferred over blocked uretdiones. In this case, glycoluril (glycouril) may also be selected. This combination according to the invention makes it possible to produce chemically resistant powder coatings having a gloss measured at an angle of 60 ℃ of ≦ 35 (as can be seen from the examples below, such as examples 1,4, 5, 6 and 9). The present invention has the ability, as strictly defined by the combination of (a) and (B), to provide powder coatings capable of producing a dull and matt finish (finish) with a gloss measured at 60 ° of less than 10. In the case of adding other raw materials, the measured gloss may be changed in either direction. Suitable cross-linking agents are well known in the art and are listed, for example, in US 9,012,556B 1 and US 9,206,320B 1.

In some embodiments of the invention, a blocked cycloaliphatic polyisocyanate is used as the crosslinking agent. In one embodiment, an epsilon-caprolactam blocked trimethylolpropane 4,4' -methylenedicyclohexyl diisocyanate (H12MDI) adduct having a Tg of 55 ℃ is used in combination with a hydroxyl or carboxyl functional polyester resin and a hydroxyl or carboxyl-acrylic copolymer to react with another hardener component to form an outdoor durable polyurethane. The starting materials exhibit faster reactivity, better hardness and flexibility than conventional isophorone isocyanate adducts. Preferred blocked cycloaliphatic polyisocyanates should have an NCO% of about 14.0, a functionality of 2.2 and a Tg of about or near 60 ℃.

In another embodiment of the invention, an epsilon-caprolactam blocked trimethylolpropane isophorone diisocyanate adduct, which should contain cyclic amide or caproic acid with a Tg of at or near 52 deg.C, is used to crosslink the hydroxyl functional groups of resins based on polyesters and acrylic copolymers. The addition of the blocked polyisocyanate adduct polyol has an effect on the mechanical properties of the powder coating and the blocked polyisocyanate remains stable during processing up to an unblocking temperature (unblocking temperature) of more than 160 ℃. The amount of polyisocyanate derivative may be from 1 to 50% by weight of the total powder coating composition.

Principle of reaction of isocyanate and alcohol to produce polyurethane

In another preferred embodiment of the invention, a polymer is added which has a melting range (melt area) of from 50 ℃ to 200 ℃, preferably from 100 ℃ to 150 ℃, and a viscosity of from 10Pas to 500Pas, preferably from 50Pas to 250Pas, most preferably from 90Pas to 150Pas, measured at 200 ℃ with a shear rate of 10rad/s with a plate/plate viscometer.

GRILTEX ES 502 is a suitable compound as a copolyester that changes the Gardner Impact Efficiency (Impact Efficiency) and flexibility (as measured by ASTM D522 (Mandrel Bend Test of Attached Organic Coatings)). The mandrel bend test according to ASTM D522 (method B using an 1/4 inch mandrel) is an integral part of MIL-PRF-32348. The optional impact modifier is an acrylic-based modifier that provides not only the impact modifier function, but also a multifunctional combination between impact resistance and weatherability.

In a further embodiment of the invention, the hardener (C) in the system comprises a hardener comprising one or more carboxylic acids and/or one or more salts of carboxylic acids, which hardener is present in a weight concentration of less than or equal to 50%, preferably less than or equal to 20%, most preferably less than or equal to 15% of (C). It has surprisingly been found that by adding this material to the hardener system C, the gloss can be further reduced even in the case of already low gloss.

Especially dicarboxylic acids such as azelaic acid, sebacic acid, undecanedioic acid, preferably dodecanedioic acid, in combination with compounds from 1,2,4, 5-benzenetetracarboxylic acid and 2-phenyl-2-imidazolinium pyromellitate (1: 1) (CAS 54553-90-1) are preferred because it shows an additional gloss reduction even at gloss levels below 3 (measured at an angle of 60 °).

In a particular embodiment of the present invention, it has surprisingly been found that a combination of dicarboxylic acids such as azelaic acid, sebacic acid, undecanedioic acid, preferably dodecanedioic acid, and melamine has an additional gloss-reducing effect at very low gloss levels in the range of less than 3 (measured at an angle of 60 °).

depending on the colour and the associated pigment volume concentration, different filler types can be used to further reduce the gloss, as is well known in the powder coating art. However, it has been found that the combination of crude barium sulfate and/or preferably kaolinite with a rheology modifier such as a derivative of montmorillonite clay has a very effective gloss reducing effect.

According to the invention, the flow-control agents may be added to the formulation in an amount of preferably 0 to 15% by weight of the total powder composition. In one embodiment, the carboxyl-functional acrylic polymer product, which has been converted to a free-flowing powder by adsorption onto a silica-type support, provides excellent recoatability, transparency, and appearance.

According to the invention, degassing agents may also be added to the formulation, if desired or preferred. A suitable reagent is, for example, benzoin (preferred), and may alternatively or in combination be used, for example, Powdermate 542DG from eston Chemical.

Pigments, with or without, whether organic or inorganic based, may be used in the present invention and meet the requirements of MIL-PRF-32348 specifications. Such suitable/unsuitable pigments include, but are not limited to, just a few examples as follows: titanium dioxide, antimony oxide, chromium oxide, zinc oxide, calcium carbonate, fumed silica and zinc phosphate. In addition, various forms of fillers may also be used, including but not limited to barium sulfate (e.g., barite) and/or calcium carbonate.

The fluoroorganic compound (D), preferably a fluorochemical oligomer and/or polymer, is added at a concentration of 0.5 to 19 wt. -%, preferably 1 to 10 wt. -%, most preferably 1.5 to 3.5 wt. -%, based on the sum of (a), (B) and (D), resulting in a further increase of the chemical resistance. In general, very high chemical resistance can be achieved by highly crosslinked systems. However, highly crosslinked systems show a clear lack of mechanical properties. It has surprisingly been found that the addition of high molecular weight PTFE (MW >1000000) as a surface modifier improves the resistance against chemical attack. PFA (perfluoroalkoxy polymer) as a copolymer also exhibits good mechanical properties and permeation resistance. PFA is similar to PTFE, but PTFE is not melt processable, whereas PFA is melt processable. This facilitates manufacturing. In addition to this, it has been found that the microstructuring effect of this material also has a positive effect on the reduction of the gloss, so that dull and matt coatings can be achieved. For the latter, other suitable compounds may also be used, such as polyethylene and PMMA (polymethyl methacrylate), with a suitable particle size distribution of 5 μm to 150 μm. In addition, it was found that scratch resistance can be improved and the coefficient of friction (COF) can be reduced by adding these materials.

It was found that further addition of PTFE and/or other suitable fluorocarbons (such as PFA) not only improves the matte appearance, increases scratch resistance, improves structuring and is used to obtain fine textured products, but also powder coating compositions with the following characteristics: improved resistance to chemicals, biologicals and detergents such as mustard gas (according to MIL-PRF-32348). Taking the fluorocarbon as an example, such fluorocarbon solids have a high molecular weight and consist primarily of carbon and fluorine. It was even found that the mustard gas test standard of MIL-PRF-32348 could be met. Also, according to the present invention, a fluoropolymer having functional groups suitable for reacting with at least one of the crosslinking agents C or C may be added. Such a material is for example FEVE, which is known under the trade name Lumiflon.

In yet another embodiment of the present invention, the use of additives in the form of a composition having a salt cyclic amide and/or one or more polyacid compounds reduces the overall gloss, thereby allowing the resulting product to retain high mechanical strength while having a matte and elegant appearance. The cyclic amide and/or polyacid solids used in accordance with the present invention typically have a melting point range between 190 ℃ and 240 ℃. The amount of cyclic amide and/or polyacid used in the present invention is from about 1% to 20% by weight of the total formulation composition.

Production of powder coatings

Powder coating compositions according to the invention may be produced by standard production procedures well known in the art, such as extruding the components of the coating composition, milling the cooled extrudate to a suitable particle size and applying the coating powder to a suitable substrate. The application can be performed using any available method, for example using an electrostatic spray gun or using a fluidized bed.

For some embodiments, it may be useful to produce two separate powder coatings, one comprising a hydroxyl or carboxyl functional polyester resin, one or more crosslinkers and fillers, and one comprising a hydroxyl or carboxyl-acrylic copolymer, one or more crosslinkers and fillers, and then to combine the two separately extruded and milled powder coating compositions together before applying them to a substrate (known in the art as a two-component powder coating system). However, based on experiments with powder coating compositions according to the invention, low gloss levels of up to 1 and below can be achieved even with so-called one-component systems.

The substrate to be coated may be provided at ambient or elevated temperature.

the powder coating composition according to the invention, once applied, can be cured for 5 to 50 minutes, mainly at a wide temperature range of about 130 to 250 ℃. However, the preferred cure cycle is 10 minutes at 200 ℃. If desired, the substrate may be pretreated by conventional methods known in the art, such as sandblasting, conversion coating, and the like, and/or one or more primer coatings may be applied prior to coating the substrate with the inventive coatings described herein.