Matting without mixing
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- Francine Anthony
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1 Seite/Page: 1 Matting without mixing The production of matte finish powder coatings currently requires dry blending of two incompatible resins, or expensive GMA or PUR chemistries for exterior coatings. A new single shot HAA-cured system allows low and reproducible gloss levels to be obtained by mixing two specific polyester resins together before extrusion. Gloss is controlled by selection of the polyesters and their mixing ratio. One-shot resin system creates reproducible low-gloss exterior finishes Benoit De Becker John Jacquin Alessandro Minesso Dietmar Fink* Powder coating has been developing for a number of years as an environmentally-friendly option for surface finishing applications. It has penetrated many segments in the coatings industry and powder-coated items can be found almost everywhere in our daily life. In many coating applications there is a preference in the market for matte finishes. Different methods and matting agents exist for indoor and outdoor durable powder coatings. The matting effect will in each case depend on the combination of the resin, hardener, matting agent and paint formulation. One area in which there are limitations in terms of reliability and adaptability of the matte level is that of powder coatings formulated for outdoor applications. A new technology is presented here that will make it possible to formulate outdoor hydroxyalkylamide (HAA)- based coatings to obtain a reproducible high quality matte finish with gloss level between 5 and 40 units with good overall properties. The new one-shot matte technology is based on patent-pending polyester chemistries used in combination with HAA for exterior grade powder coatings. Matte finishes serve many different purposes Matting effects in coatings can be desired for many different reasons. In some applications strong light reflection has to be minimised with the help of matte coatings. Matte finishes can also be used to conceal substrate defects, surface irregularities, or even dirt and dust particles on the coating surface. In most cases, however, matte powder coatings are used to achieve specific aesthetic and design aims. Matte finish paints are in high demand both in growth segments such as architectural applications and in high value speciality application such as sporting goods, glass coating and military applications. Some examples of critical applications include: Dull matte paints are used to give an elegant finish on glass bottles. High-end office furniture is typically painted with a matte to semi-matte finish that complements novel designs. Architectural elements such as window frames can now be powder coated with wood-effect designs that typically perform best at low gloss levels. Inside buildings, decorative and functional elements exposed to artificial light, such as ceiling panels or lamp holders, are often coated with matte or semi-matte UV-resistant powders to avoid excessive disturbing light reflections. Automotive trim parts are painted with matte to semi-matte powder coatings to offer an attractive contrast to the high gloss car body finish. Those applications typically require extended weather-resistance which can only be achieved with so-called super-durable polyester systems. Another application in the field of sporting equipment is dull matte powder coatings applied on bicycle frames. Military applications traditionally require a dull matte surface finish for functional reasons. Low gloss surfaces will be rendered less visible by reflecting less sunlight. These applications altogether represent about 20 % of the outdoor decorative powder market, or an overall volume of approximately 100,000 MT worldwide. Requirements in these markets, in addition to the lower gloss levels, will be those typical of high quality outdoor paints, which include superior weather resistance, flow and mechanical properties. Easy workability and reproducibility of results are also of the utmost importance for both the paint maker and applicator alike. The resin technology presented in this article will offer these performance levels in both standard and super-durable quality together with gloss levels between 5 and 40 units as measured at a 60 angle. Current matte finish technologies have limitations Most matte and semi-matte outdoor resistant powder coatings are based on dry-blend technology, where two powders with different reactivity levels have to be produced and mixed together either directly after the extrusion process as chips and then co-ground or mixed as previously fine ground powders. The matting effect is then generated during the curing process of the two different powders. When the reactive powder is already cross-linked, the slower reacting powder is still in the melting phase and embeds the other cured one. This causes a so-called incompatibility effect, which is visible as a lower gloss level in the powder film. The matte dry-blend technology has, however, some inherent limitations. Due to inhomogeneities in the cured film, a so-called sparkling effect is often visible. It varies with the particle size distribution of the dry-blended powders. The coarser the particle size, the stronger the sparkling effect. In addition, the mechanical properties are limited, due to the relatively weak bonding between the two phases of the powders. During recycling of the dry-blend powder in an automatic application booth, there is a danger of increasing the gloss over time, as the two phases of the dry-blended powder have different charging behaviour due to the different physical-chemical characteristics of the binder system and the slightly different particle size distribution, which leads to selective powder recovery and application.
2 Seite/Page: 2 There are additional costs associated with the production of dry-blended powder since two powder materials have to be produced to obtain a single matte dry-blend powder. Lack of reproducibility also translates into yield losses, which in turns also mean extra cost for the powder manufacturer and/or the applicator. Two main systems used for dull matte finishes Dull matte finishes can be achieved either by use of a glycidyl methacrylate (GMA) hardener or with a oneshot polyester powder system based on hydroxy-functional polyester blends cross-linked with blocked isocyanate, that is, PUR or polyurethane technology. These systems both provide superior dull-matte finishes that are typically used in speciality applications. However, as in the case of the matte dry-blend, those technologies suffer from some key limitations. Systems based on a GMA acrylic matting hardener show limitations in mechanical properties and to a certain extent, sensitivity to other binder systems in respect of contamination. It is also a rather expensive chemistry which has limited the penetration of the technology in niche applications. The one-shot PUR technology is the most expensive dull matte binder system, as it requires a large quantity of costly isocyanate hardener. The system is sensitive during the extrusion process, as different or varying dispersion conditions have a significant influence on the matting level. A new patent-pending "Crylcoat" technology is being developed to address the needs for matte finishes in the outdoor powder coating market. The target of the development is a binder system that allows premixing of all the ingredients necessary to produce in a single formulation a powder coating with the desired reproducible gloss level that uses standard production processing equipment. By selecting the right product pair in the new range of oneshot carboxylic polyesters it is possible to adjust the gloss to the desired level in a reproducible way. The products are available in standard and super-durable grades, and are designed to be used in combination with HAA. Dull-matte to matte finishes are readily achieved The new matte technology is very robust in relation to the production process. Either the twin-screw or monoscrew extruder technology used under standard conditions results in comparable matte gloss levels. The smoothness of the film surface will be dependent on the binder content. For speciality applications that require superior flow it is recommended, depending on the colour shade, to work with a relatively high concentration of resin. As regards the curing agent, a number of hydroxyalkylamide (HAA) hardeners are available on the market. "SF 45-10" is an HAA grade with lower functionality that yields gloss levels of about 10 units higher than the basic HAA grades when used as hardener for the new one-shot technology. Powders formulated with HAA modifications such as "QM 1260" and used in directly fired gasovens result, however, in significantly higher gloss levels, according to our experiments, and are not recommended. In order to formulate a robust, batch-to-batch reproducible matte powder coating, only ratios of polyester pairs that do not exceed the range 55/45 to 45/55 are recommended. More extreme ratios result in higher gloss levels, which might be useful for specific applications, but are not always reproducible see Figure 1. With the standard one-shot matte polyester resins one can obtain powder coatings with very good mechanical properties, better than any equivalents made by dry-blend technology. The system also shows good storage stability properties: powders do not change their reactivity, flow and flexibility. Physical stability is also good full properties are retained after 28 days at 40 C. Curing the one-shot matte HAA powders at different temperatures produces very consistent gloss levels. The weathering properties of the dull-matte combination polyester 1 (Ac-Nr. 90) and polyester 2 (Ac-Nr. 25) resins with HAA are good for GSB and Qualicoat approvals with gloss retention after 12 months in Florida (5 South) well above 50 %. As an alternative resin to polyester 2, one can use the super-durable polyester 3 (Ac-Nr. 30), which offers further improvements in weathering properties (see Figure 2). Different resins provide matte to semi-matte effects The two resins denoted as polyester 4 (Ac-Nr. 85) and polyester 5 (Ac-Nr. 33) can be used in ratios from 45/55 to 55/45 to formulate powders of different gloss levels from matte to semi-matte with good weathering resistance and good overall paint properties. Compared to dry-blend technology with polyester 6 (Ac-Nr. 48) and polyester 7 (Ac-Nr. 20) the new resin combination offers a homogeneous, non-sparkling matting effect, better mechanical properties and good reproducibility within the recommended formulation ratios (see Figures 3 and 4). There are four so-called super-durable types, polyester 8 (Ac-Nr. 90) and polyester 9 (Ac-Nr. 21) available which can be used to formulate powders with dull-matte glosslevels, and polyester 10 (Ac-Nr. 90) and polyester 11 (Ac- Nr. 30) for different gloss-levels from matte to semi-matte with excellent weathering properties and good overall paint properties. The new resin combinations offer homogeneous paint properties, non-sparkling matting effect and good reproducibility within the recommended formulation ratios. (Figure 5). Further improvements are being studied Ongoing developments in the area of one-shot technology for matte finishes are targeted at specific market needs for special applications. A number of modifications to the binder system are being investigated to achieve superior burnish resistance. The latter is a typical issue when formulating ultra-low gloss paint in dark shades. Resin design optimisation is continuing, to broaden the scope of pigments that can be used for producing oneshot matte coatings with superior flow. Flow modifiers and modifications to the resin are being investigated to further reduce the impact of binder content on flow. But already, a solution now exists that permits easy oneshot production of matte powder coatings. The patentpending technology presented here provides an adjustable gloss level in both standard and super-durable quality. The new system offers easier handling, with significant cost advantages to the production process, and better mechanical film properties. These had been two major limitations so far in the field of matte outdoor resistant powder coatings.
3 Seite/Page: 3 The different polyesters allow the production of matte paints in a wide range from 5 to 40 gloss units as measured at 60 incidence. In times when matte finishes are becoming more and more popular, and when the market is looking for cost-effective formulation options, this new technology is ideal to replace current technology systems for matting outdoor resistant powder coatings, and also to allow the penetration of near dull-matte finish in application segments where the former solutions were too expensive to be considered. Results at a glance There is a considerable demand for matte finishes to meet specific functional or aesthetic requirements in many different market sectors. However, this is one area of weakness for powder coatings, as gloss reduction must normally be achieved by mixing two incompatible powders. This dry blending process can produce problems such as sparkle and variation of gloss levels if powder is recycled during spraying. Where high exterior durability is required it is necessary to use expensive GMA or PUR chemistries. A new system for producing reproducible low gloss levels has been developed, in which two specific polyester resins are mixed together along with an HAA curing agent and extruded to produce a single shot matte powder. By selection of the right polyesters and altering the mixing ratio of the resins, low and very reproducible gloss levels can be obtained. Super-durable polyesters are available to provide very good exterior performance. * Corresponding Author: Dietmar Fink Cytec Tel. +32 (0) dietmar.fink@cytec.com
4 Seite/Page: 4 Figure 7: General comparison of properties between the new technology and standard dry-blend systems
5 Seite/Page: 5 Figure 1: Robustness of the new technology: low gloss levels are obtained and are highly reproducible so long as the mixing ratio of the resins is close to 50/50
6 Seite/Page: 6 Figure 2: Selection of a resin pair for dull matte finishes in relation to durability requirements
7 Seite/Page: 7 Figure 3: Gloss variations produced by changing the ratio between polyester 4 and polyester 5
8 Seite/Page: 8 Figure 4: Comparison of novel matte one-shot technology to existing matte HAA dry-blend powders
9 Seite/Page: 9 Figure 5: Properties of super-durable one-shot dull-matte to semi-matte (6-20 units to units 60 gloss) HAA powders
10 Seite/Page: 10 Figure 6: Gloss retention of superdurable one-shot dull-matte and semimatte HAA powders
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