EP2173819A2 - Pigments réfléchissant un rayonnement ir, leur procédé de production et leur utilisation - Google Patents

Pigments réfléchissant un rayonnement ir, leur procédé de production et leur utilisation

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Publication number
EP2173819A2
EP2173819A2 EP08759113A EP08759113A EP2173819A2 EP 2173819 A2 EP2173819 A2 EP 2173819A2 EP 08759113 A EP08759113 A EP 08759113A EP 08759113 A EP08759113 A EP 08759113A EP 2173819 A2 EP2173819 A2 EP 2173819A2
Authority
EP
European Patent Office
Prior art keywords
radiation
reflecting
pigments
core
pigment according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08759113A
Other languages
German (de)
English (en)
Inventor
Marco Greb
Michael GRÜNER
Thomas Schuster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eckart GmbH
Original Assignee
Eckart GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eckart GmbH filed Critical Eckart GmbH
Publication of EP2173819A2 publication Critical patent/EP2173819A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/642—Aluminium treated with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/66—Hue (H*)

Definitions

  • the invention relates essentially to dark pigments capable of reflecting IR radiation, processes for their preparation and their use.
  • paints, paints or varnishes are composed of a number of components such as solvents, pigments, additives, fillers, etc. These are capable, at least in part, of absorbing electromagnetic radiation, e.g. when exposed to solar radiation, leads to increased heating of the paint and the article (e.g., building facades) coated therewith.
  • Such warming is caused by the addition of colorant, dark pigments (e.g., carbon black), due to the specifically high absorbances in both the UV / Vis and IR spectral regions.
  • colorant e.g., carbon black
  • the interest in pigments and with these staggered applications, e.g. Paints that can reflect IR radiation is due to the fact that heating of the object can be significantly reduced by reflection of the heat radiation.
  • dark pigments generally show a higher absorptivity in the solar range compared to light, ie the spectral range of UV ⁇ / is-IR radiation. This occurs Phenomenon of warming by irradiated sunlight amplified. For this reason, dark IR-reflecting pigments are at the center of interest, for example for building paints, surface coatings or paints and coatings for textiles
  • IR-reflective pigments Another important application of IR-reflective pigments is the use for military camouflage colors.
  • the ability to reflect IR radiation implies a decreased absorbance in this spectral region, allowing objects to be changed in their IR signature.
  • WO 2005/007754 A1 describes an IR-reflecting pigment with a reflective core, an IR-transparent material as a partial or total coating on the surface.
  • the reflective core has a layer thickness of less than 0.2 ⁇ m.
  • the IR transparent material comprises a nonpolar or weakly polar organic polymer optionally containing a dye or colored material.
  • WO 2006/085563 A1 describes a dark color pigment for IR reflection consisting of mixed oxides with iron and cobalt as main components and Mg, Ca, Sr, Ba, Ti, Zn and Cu as minor component.
  • the pigments described have a particle size of 0.02-5 microns and an L * value ⁇ 30.
  • Such pigments are already commercially available in analog form. The ability to efficiently reflect IR rays is very limited here.
  • EP 1217044 B1 discloses composite pigments which reflect IR radiation.
  • IR radiation non-absorbing ie IR transparent colorants, ie at least one organic dark color pigment and a white pigment (eg TiO 2 , ZnO, etc.), which is coated with the corresponding IR-transparent organic black color pigment
  • a white pigment eg TiO 2 , ZnO, etc.
  • organic black color pigments are generally not lightfast.
  • the TiO 2 particles are photoactive. This leads to the decomposition of organic color pigments in outdoor applications.
  • the disclosed pigments are spherical and therefore limited in reflectance due to limited reflection geometry.
  • the document WO 2005/030878 A1 discloses an IR radiation-reflecting organic dark color pigment, which is composed proportionally of substituted copper phthalocyanine pigments and perylenetetracarboxylic acid diimide pigments.
  • organic color pigments are usually not long-term stable.
  • colored aluminum pigments are known in which color pigments are incorporated into a metal oxide matrix which is produced by a sol-gel process. The resulting aluminum pigments are colored, ie not dark, and also metallic shiny and therefore serve decorative purposes.
  • US Pat. No. 5,037,475 also discloses colored metal pigments wherein metallic pigments are coated with color pigments. These metallic and colored pigments are used for the production of light paints, printing inks or plastics. The binding of the color pigments takes place here on the one hand via a thermally polymerized, unsaturated polyfunctional carboxylic acid and on the other hand via a plastic coating. Another disadvantage is that the colored aluminum pigments produced in this way have a clearly metallic and therefore glossy appearance.
  • WO 91/04293 likewise discloses colored and metallically lustrous metal pigments.
  • DE 40 35 062 A1 discloses an IR-reflecting substrate, which is coated with a lacquer layer, which may contain white, gray, black or colored pigments.
  • a lacquer layer which may contain white, gray, black or colored pigments.
  • metal pigments and color pigments described have the disadvantage that the two pigments can separate in certain applications.
  • Sunlight which reaches as radiation up to the earth's surface, can be essentially divided into three subregions: 3% of the energy arriving on the surface covers the UV spectral range (295 -400 nm), nearly 50% of the visual range (400-700 nm) and 47% of the NIR range (700-2500 nm).
  • the MIR and FIR range above> 2500 nm contributes only small amounts of sunlight.
  • IR-reflecting pigments that do not bleed are in high demand. This applies in particular to the use in textiles, in which the IR radiation-reflecting pigments must have dark, inconspicuous camouflage colors.
  • An object of the invention is to provide pigments capable of efficiently reflecting IR radiation.
  • the pigments should be largely opaque, but have no decorative metallic effect, in particular not be metallic shiny. Furthermore, the pigments should not separate in the application medium, i. dark color effect, high IR reflection and lack of decorative metal effect should always be coupled to each other. Furthermore, a corrosion-stable pigment is to be provided which can be used, for example, in aqueous dyeing and coating systems.
  • the object of the invention is achieved by providing an IR radiation-reflecting pigment, comprising a platelet-shaped, metallic IR-reflecting core, wherein the IR radiation-reflecting core is provided with a substantially low-absorbing and substantially enveloping coating for IR radiation, and the IR-reflecting pigment is substantially dark.
  • Preferred embodiments are given in the dependent claims 2 to 18.
  • the object underlying the invention is further achieved by providing a method for producing an IR radiation-reflecting pigment according to any one of claims 1 to 18, wherein a platelet-shaped, metallic IR radiation-reflecting core having a substantially low-absorbing and dark for IR radiation Coating is coated.
  • the object of the invention is also achieved by the use of an IR radiation-reflecting pigment according to one of claims 1 to 18 in paints, lacquers, printing inks, security printing inks, textiles, military applications or plastics.
  • the object underlying the invention is achieved by a coating composition, wherein the
  • a coating composition containing an IR radiation-reflective pigment according to any one of claims 1 to 18.
  • a preferred embodiment is specified in dependent claim 26.
  • the object of the invention is also achieved by a coated article, wherein the article is coated with an IR radiation-reflecting pigment according to any one of claims 1 to 18 or a coating composition according to claim 25 or 26.
  • the inventors have surprisingly found that the metallic reflectivity of platelet-shaped metallic cores or substrates can be used effectively to reflect IR radiation and at the same time suppress the metallic luster, sparkle and flop.
  • metallic luster, sparkle and flop could not be suppressed or otherwise the IR reflectance would be significantly impaired.
  • metallic substrates such as metallic effect pigments, to suppress their typical properties, such as metallic luster, sparkle and flop, without significantly impairing the IR reflectivity.
  • the pigments of the invention may have different dark and, in particular, non-glossy colors.
  • the pigments according to the invention can be used in colorless applications for dyeing, so that correspondingly dark-colored solid shades are obtained. In colored applications, the resulting pigments can also be used for tinting.
  • the pigments according to the invention are largely free of any decorative metallic effect.
  • a decorative metallic effect is understood to mean typical properties of metallic effect pigments, such as the metallic luster, sparkle and light-dark-flop. These properties are further defined below.
  • dark is understood as meaning when the pigment according to the invention in a pigmented, opaque nitrocellulose lacquer (NC lacquer) has an L * value (CIELAB colorimetry, diffuse color measurement over all solid angles by means of an integration sphere with Minolta device CR). 410) of L * ⁇ 50, preferably L * ⁇ 45 and more preferably L * ⁇ 40.
  • Metallic effect pigments have a typical light-dark flop. To assess this property, in contrast to the diffuse measurement, a measurement over different solid angles is used.
  • the pigments of the invention exhibit a largely angle-independent brightness, i. have no significant brightness flop.
  • the brightness flop is determined by DuPont according to the following formula (A. BJ Rodriguez, JOCCA, (1992 (4)) pp. 150-153):
  • the flop index reflects the characteristic brightness flop, in particular of metallic effect pigments.
  • the pigments according to the invention have a brightness flop of from 0 to 2, preferably from 0.01 to 2 and particularly preferably from 0.05 to 1.0, in a correspondingly pigmented and opaque NC lacquer. These extremely low values show that the brightness flop otherwise typical for metal effect pigments having a flop index in a range from about 4 to 25 is completely or substantially suppressed in the pigments according to the invention.
  • a platelet-shaped, metallic IR-reflecting core with absorbing in the optical wavelength range, ie dark color pigments, coated substantially uniformly Under a platelet-shaped core is in the context of the invention Platelets with a form factor, ie the ratio of average size to average thickness, from 5 to 500, preferably from 10 to 200 and particularly preferably from 20 to 150 understood. Platelet-shaped cores or substrates, in contrast to spherical or ellipsoidal forms, have the greatest IR reflection with at the same time lowest material consumption. Platelet-shaped pigments have largely rectified reflection surfaces.
  • the platelet-shaped metal pigments are opaque to both optical light and IR radiation. Platelet-shaped metal pigments also produce the most effective directed and / or diffuse reflection of incident IR radiation on uneven surfaces.
  • platelet-shaped metal pigments it is preferred to use platelet-shaped pigments of aluminum, copper, zinc, tin, titanium, iron, silver and / or alloys of these metals.
  • Aluminum and alloys of aluminum are particularly preferred because of their extremely high IR reflection and the ready availability of these metal pigments.
  • the size, ie the dimensions of the length and width of the platelet-shaped metal pigments, are preferably in a range from 3 to 250 .mu.m and preferably from 10 to 200 .mu.m.
  • the mean of the sizes, ie the length or width of the platelet-shaped substrates, is represented as the d 50 value of the volume-averaged cumulative weight distribution. This is usually determined by laser diffraction methods.
  • the d ⁇ o value of the platelet-shaped, metallic substrates is preferably in a range from 25 to 150 ⁇ m, and preferably from 30 to 80 ⁇ m. These values are determined using a Cilas 1064 device from the French company Cilas.
  • the average thickness of the platelet-shaped metal pigment cores is preferably in a range from 0.25 to 4 ⁇ m, preferably from 0.3 to 3 ⁇ m and particularly preferably from 0.4 to 2 ⁇ m.
  • the specific surface area of the platelet cores or substrates is too high to permit uniform coating with dark color pigments.
  • the metal core is so thick that the proportion of the metal core and thus also the IR reflectivity in the pigment according to the invention is too low that no more effective IR reflectivity is achieved.
  • the mean pigment thickness can be determined by counting the thicknesses in the SEM or by spreading on a water surface in the usual manner known to the person skilled in the art.
  • the platelet-shaped cores or substrates preferably metallic effect pigments, preferably have BET specific surface areas of about 0.2 to about 5 m 2 / g.
  • Metal pigments or metallic effect pigments with a length or width of less than 3 ⁇ m have too high a specific surface area and can no longer be covered sufficiently well with a dark colored pigment.
  • the IR radiation is no longer optimally reflected by platelet-shaped cores or substrates of this size, since they are already smaller than the wavelength of the IR light to be reflected.
  • these metal pigments or metallic effect pigments can no longer be completely coated with dark pigments or incorporated into a coating accordingly.
  • the platelet-shaped metallic cores or substrates or metal pigments can be present in an already passivated form.
  • Examples are aluminum pigments coated with siue 2 (Hydrolan ®, PCX or PCS, Fa. Eckart) or chromated aluminum pigments (Hydrolux ®, Fa. Eckart).
  • the IR radiation substantially low absorbing and substantially enveloping the platelet-shaped core coating preferably comprises dark color pigments and a matrix.
  • the dark color pigments can be arranged in, on and / or under the matrix.
  • the dark color pigments are fixed by or in the matrix on the platelet-shaped core.
  • the dark color pigments are largely enveloped by the matrix or embedded in the matrix, so they are enclosed by the matrix.
  • the dark color pigments can also be arranged on the matrix and fixed for example via electrostatic forces with the matrix on the pigment surface.
  • the matrix together with the dark color pigments, preferably uniformly envelopes the platelet-shaped metal core.
  • This preferably enveloping matrix also protects the core from the corrosive influence of water or atmospheres.
  • a substantially enveloping coating is understood to mean that the IR-reflecting platelet-shaped core is enveloped by the coating in such a way that the core does not produce a perceptible, lustrous sensory impression in a viewer. Furthermore, the degree of cladding is so extensive that in the case of a metallic IR reflective core, for example aluminum plates, the occurrence of corrosion is suppressed or avoided.
  • the pigment of the invention Due to the uniform coating of the IR-reflecting core with opaque in the optical wavelength range and absorbing, thereby largely dark and low-IR radiation absorbing pigments, the pigment of the invention as a whole receives a largely dark appearance.
  • the resulting from the IR-reflecting core optical effect is largely, preferably completely, suppressed. Due to the low IR absorption of the applied dark color pigments, a high IR reflectance is surprisingly obtained in the pigment according to the invention
  • optical properties or “optical effect” always means those properties of the IR radiation-reflecting pigments visible to the human eye. These properties are determined essentially by the optical properties in the wavelength range from about 400 to about 800 nm.
  • dark is understood to mean that the pigments according to the invention absorb large areas of visible light and therefore appear dark to the human observer.
  • dark color pigments are understood as those which have a substantially low absorption in the IR spectral range, thus substantially an IR transparency and / or an IR reflectance. Preference is given to dark color pigments, preferably in the form of particles, which have low absorptions in the wavelength range of the NIR spectral range (0.8 to 2.5 ⁇ m) and are thus low in absorbing NIR.
  • the dark, in the IR range low absorbing dark, preferably black and / or brown, color pigments are particles having an average primary particle size of 10 nm to 1000 nm, preferably from 20 to 800 nm, more preferably from 30 nm to 400 nm. Below 10 nm average primary grain size, the dark color pigments are too finely divided to be uniformly applied to the metal pigment substrate surface, so that the decorative effects of the metallic core (gloss, flop, etc.) are effectively suppressed. Above 1000 nm, the specific coverage and thus the effect of the dark pigments is too low, so that again the optical properties of the metallic core become too prominent.
  • the dark color pigments can be selected, for example, from the group of complex inorganic colored pigments such as spinel mixed phases, iron oxides, iron-manganese mixed oxides.
  • the mixed-phase pigments are preferably copper-chromium spinels of the type CuCr 2 O 4 , chrome iron black Cr 2 O 3 (Fe), chrome iron brown (Fe 1 Cr) 2 O 3 and / or (Zn, Fe) (Fe 1 Cr ) 2 O 4 .
  • it may also be dark organic color pigments from the group of perylenes, such as Paliogen Black or Lumogen, (BASF, Germany), or consist of mixtures of all these exemplified here pigments.
  • the dark color pigments preferably have a low absorption capacity in the IR range; such color pigments are also referred to as "cold IR pigments".
  • spinel mixed-phase pigments or perylenes as marketed, for example, by the companies Ferro, USA, and Shepherd, USA, and BASF, Germany.
  • spinel mixed-phase pigments have the advantage of very high chemical and thermal stabilities.
  • the amount of dark color pigment used, which is applied or applied in the coating depends on the type, size and especially of the specific surface of the IR-reflecting platelet-shaped metallic core.
  • the specific surface area of the IR-reflecting core is understood to mean the surface of the IR-reflecting core per weight.
  • the specific surface of the IR-reflecting core is determined by the known BET method.
  • these preferably have dark color pigments in an amount of from 20 to 80% by weight, preferably from 30 to 70% by weight and particularly preferably from 40 to 65% by weight .-%, in each case based on the weight of the total IR-reflective pigment according to the invention, on.
  • the desired dark coverage of the IR-reflective pigments may be too low, which may cause the IR-reflective pigments to be metallic, which is undesirable.
  • too little IR reflection may occur because the proportion of the IR-reflecting core, based on the total pigment, may be too low.
  • this medium In order to obtain a good IR reflection in, for example, a paint or varnish with the latter pigments, this medium must be correspondingly highly pigmented.
  • High pigmentation i. a high content of pigment according to the invention in the application medium, on the one hand leads to high production costs. On the other hand, it can also lead to hyperpigmentation and thus poor performance characteristics of the paint or the paint.
  • per 1 m 2 surface of the platelet-shaped IR-reflecting metal core preferably 0.3 to 10 g, preferably 0.5 to 7 g, more preferably 0.7 to 3 g and particularly preferably 1, 0 to 2, 5 g of the dark pigment applied to the preferably platelet-shaped metal pigment or the platelet-shaped metallic core.
  • the coverage of the preferably platelet-shaped metal pigment with the dark color pigment (s) may be too low to give a satisfactory dark effect.
  • the dark effect is practically saturated and the proportion of the IR-reflecting core in the total pigment may be too low, so that such a pigment according to the invention may no longer have sufficient IR reflectivity.
  • Sunlight which reaches as far as the earth's surface as radiation, can be divided into three parts as mentioned above: 3% of the energy arriving on the surface covers the UV spectral range (295-400 nm), almost 50% the visual range (400-800 nm) and 47% IR (800-2500 nm).
  • the reflectivity of solar radiation of materials can be determined by ASTM E903.
  • the solar reflectance is determined from a measured against a gold standard reflectance over the wavelength range 300 to 2500 nm, weighted by the spectral intensity distribution of the solar radiation.
  • the reflectivity of the pigments according to the invention in applications can be determined as follows: With the aid of an FT-NIR spectrometer MPA-R from Bruker, the diffuse reflection can be measured over all solid angles by means of an integrating integration sphere (gold surface). For this purpose, a gold standard with a roughened surface is measured against an absolute black standard. A sample is measured against the black standard and then compared against the values of the gold sample. This results in a corresponding degree of reflection for each wavelength in the NIR range (800-2500 nm) (scaled in percent to the maximum reflection of the gold standard), which is weighted according to equation (1) as a function of wavelength against the solar radiation.
  • the pigments of the invention have a solar NIR reflectance p N i R (soi a r) ( ⁇ ) of at least 15% in opaque paint applications as determined above at 298 K. More preferably, the IR radiation-reflecting pigments have a reflectance of more than 25%, and more preferably of more than 30%. This means that with a solar NIR reflectance of 30%, 30% of the NIR content of the solar radiation is reflected in the range of 800 to 2500 nm.
  • the above-described NIR the above-described NIR
  • the value ⁇ NiR (soiar) ( ⁇ ) coating defined according to equation 3 is referred to in the context of this invention as the "NIR absorption coating".
  • the calculated ratio is preferably ⁇ 0.6, preferably ⁇ 0.3 and particularly preferably ⁇ 0.2. The lower the degree of absorption of the coating, the less the optimum NIR reflection of the uncoated metal core is reduced by the coating.
  • a coating which is essentially or largely transparent and essentially, preferably completely, enveloping is understood as meaning those coatings in which the pigment of the invention that reflects IR radiation has the abovementioned properties with regard to its IR reflectance.
  • the substantially completely or largely in the NIR low absorbing enveloping coating preferably has the dark appearance of improving or inducing dark color pigments.
  • the dark color pigments used may also be surface-treated and, for example, coated with metal oxides and / or be modified by surface-active substances such as dispersing agents, surfactants, organic polymers or be present together with them.
  • the dark color pigments with metal oxide (s), for example SiO ⁇ be coated or encapsulated of these.
  • the pigments of the invention preferably have in the spectral IR range of 800 nm up to an upper limit of 1500 nm, more preferably up to 2500 nm, even more preferably up to 15,000 nm, and more preferably up to 25,000 nm, a significant reflectivity.
  • the wavelength range in the NIR range of 800-1,500 nm and 800-2,500 nm, respectively, is crucial in considering thermal heating of objects.
  • This area is the higher-energy part of the heat radiation, in which the irradiated solar radiation is relatively high and which can be correlated with thermal heating.
  • High reflectivities over the entire IR range i. from 800 nm to 15,000 nm and up to 25,000 nm, respectively, are of particular interest for IR tinting inks.
  • the pigments according to the invention show both a high reflectivity in the NIR range (compare Figures 2 and 3, measured as a paint application on black ABS panels) and significant reflectivities in the MIR range (compare Figures 4 and 5, measured as 1, 5 % powder bed in KBr).
  • a characteristic of effect pigments is the high gloss of a dye or lacquer coating containing the effect pigments. Since the pigments of the invention this characteristic optical No longer show the gloss properties of the effect pigments, the lacquer coatings have very low gloss values.
  • the criterion used here is the gloss at 60 ° which was measured using a trigloss apparatus from Byk-Gardner, Germany, in accordance with the manufacturer's instructions.
  • the pigments according to the invention have a gloss of from 0.1 to 2, preferably from 0.2 to 1, units in a correspondingly pigmented and opaque NC lacquer finish.
  • the gloss in the case of effect pigments is in a range from about 30 to 160, which shows that the metallic gloss typical for metallic effect pigments is effectively suppressed in the pigments according to the invention.
  • the matrix of the IR radiation substantially low absorbing coating which largely, preferably completely covers both the core and the dark pigments, is optically largely.
  • the matrix preferably comprises or consists of metal oxides and / or one or more organic polymers and / or binder (s).
  • the dark pigments may also be applied to the substantially, preferably completely, enveloping coating or matrix.
  • the matrix is preferably substantially colorless in order not to impair the visual effect produced by the applied or introduced dark color pigments.
  • the metal oxides and / or organic polymers and / or binders have no significant intrinsic color, which can not be covered by the color effect generated by the dark color pigments.
  • the substantially colorless matrix material is preferably a metal oxide, since in this way the core can be very well protected against corrosion.
  • the metal oxide to be used for the matrix material and the amount thereof are selected in particular from the viewpoint that the pigment according to the invention absorbs as little IR radiation as possible. Any IR absorption of the pigments according to the invention leads to a reduced IR reflection and thus weakens the desired effect of the pigments according to the invention.
  • the matrix material causes adhesion of the color pigments to the IR radiation-reflecting core, so that the dark color pigments remain largely adhering to the IR radiation-reflecting core even after dispersion of the application medium.
  • metal oxides examples include silica and or partially hydrated silica, alumina, aluminum hydroxide, boria, boron hydroxide, zirconia or mixtures thereof. Particularly preferred is silica.
  • one or more organic polymers and / or binders are used as the matrix material.
  • those polymers which are also used as binders in paints, inks or printing inks are particularly preferred.
  • these are polyurethanes, polyesters, polyacrylates and / or polymethacrylates. It has been found that the pigments according to the invention can be incorporated very well into binders if the organic coating and the binder are very similar or identical to one another.
  • the binder further preferably have a glass transition temperature above 75 C C and more preferably above 90 0 C.
  • the matrix is so solid at room temperature that a detachment of dark pigments contained in the matrix does not take place.
  • the optically substantially colorless matrix is preferably present in a proportion of from 2 to 30% by weight, based on the weight of the total pigment.
  • the proportion is preferably 5 to 20% by weight and more preferably 6 to 15% by weight.
  • both the dark color pigments can be arranged reliably and uniformly on the surface of the platelet-shaped cores and corrosion resistance of these cores can be achieved in the case of metallic cores.
  • the pigments may not be sufficiently reliably disposed on the surface of the IR-reflecting core.
  • the required corrosion stability which requires the fullest possible coverage of the cores with the matrix, is not sufficiently given at these small quantities.
  • the IR absorption by the matrix material unfavorably increases and thereby the IR reflectance is greatly reduced.
  • the IR radiation-reflecting core is a platelet-shaped metal pigment, wherein the metal is preferably selected from the group consisting of aluminum, copper, zinc, iron, silver and alloys thereof
  • the IR-reflecting core consists of platelet-shaped aluminum and the optically largely colorless matrix of SiO 2 .
  • the dark color pigment is selected from the group of complex inorganic colored pigments such as spinel mixed phases, iron oxides, iron-manganese mixed oxides and mixtures thereof.
  • the mixed-phase pigments are preferably copper-chromium spinels of the type CuCr 2 O 4 , chrome iron black Cr 2 O 3 (Fe), chrome iron brown (Fe 1 Cr) 2 O 3 , and / or (Zn, Fe) (Fe 1 Cr) 2 O 4 .
  • Aluminum has the highest IR reflection and is very readily available commercially. SiO 2 is ideal for corrosion stabilization of aluminum.
  • the dark color pigments from the series of complex inorganic colored pigments are also characterized by low-absorbing properties in the NIR and they have a high chemical and thermal stability.
  • the pigments according to the invention have an organic surface modification.
  • the invention Pigments are preferably modified with leafing promoting agents.
  • the leafing-promoting agents cause the pigments according to the invention to float on the surface of the application medium, for example a paint, preferably an emulsion paint or a paint.
  • the fact that the pigments according to the invention are arranged on the surface of the application medium improves the IR reflectance in the applied state, since the IR radiation is already reflected on the surface of the application medium and does not first have to penetrate into the application medium, which leads to absorption losses can come.
  • the pigments according to the invention are surface-modified with long-chain saturated fatty acids such as stearic acid, or palmitic acid or long-chain alkylsilanes having 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms or with long-chain phosphoric acids or phosphonic acids or their esters and / or long-chain amines.
  • long-chain saturated fatty acids such as stearic acid, or palmitic acid or long-chain alkylsilanes having 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms or with long-chain phosphoric acids or phosphonic acids or their esters and / or long-chain amines.
  • a core which is substantially low absorbing and dark-absorbing for IR radiation is applied to a platelet-shaped core reflecting metallic IR radiation.
  • the platelet-shaped cores may be suspended in a corresponding coating solution containing, for example, dark color pigments and the components for forming a matrix in a suitable solvent, and thus coated.
  • the coating preferably comprises dark color pigments and a matrix.
  • the dark, for IR radiation substantially low-absorbing color pigments together with metal oxide using wet-chemical sol-gel process around the core, preferably completely enveloping applied, for example by precipitation, so that the dark color pigments in the Metal oxide layer are substantially embedded.
  • SiO 2 metal oxide with a wet-chemical sol-gel method, for example, with hydrolysis of tetraalkoxysilanes, applied to the IR-reflecting platelet-shaped core.
  • the inventive method comprises the following steps: a) dispersing the platelet-shaped IR-reflecting pigment core in a solvent, preferably in an organic solvent, b) adding water, a metal alkoxy compound and optionally a. Catalyst, wherein optionally heated to accelerate the reaction, c) addition of IR-transparent dark color pigments, preferably as a dispersion in a solvent, preferably in organic solvent.
  • the pigment according to the invention i. the coated with dark pigments and metal oxide platelet-shaped IR-reflecting platelet-shaped core, are separated from unreacted starting materials and the solvent. Thereafter, a drying and optionally a size classification can take place.
  • tetraalkoxysilanes such as tetramethoxysilane or tetraethoxysilane are preferably used to precipitate an SiO 2 layer having dark color pigments preferably embedded therein, and preferably enveloping the core.
  • Water-soluble solvents are preferably used as organic solvents. Particular preference is given to using alcohols such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol or glycols.
  • the amount of water should preferably be between 1.5 times and 30 times the stoichiometrically required amount for the sol-gel reaction. Preferably, the amount of water is between 2 and 10 times the stoichiometrically required amount.
  • the reaction rate of the sol-gel process is too slow, and above 30 times the stoichiometrically required amount, the layer formation may not be uniform enough.
  • the reaction temperature during the sol-gel reaction is preferably between 40 0 C and the boiling point of the solvent used.
  • weak acids or bases can be used in the sol-gel reaction.
  • acids organic acids such as acetic acid, oxalic acid, formic acid, etc. are preferably used.
  • the bases used are preferably amines. Examples of these are: ammonia, hydrazine, methylamine, ethylamine, triethanolamine, dimethylamine, diethylamine, methylethylamine, trimethylamine, triethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 1-propylmethylamine, 2-propylmethylamine, 1-butylmethylamine, 2-butylmethylamine, 1-propylethylamine, 2-propylethylamine, 1-butylethylamine, 2-butylethylamine, piperazine and / or pyridine.
  • the dark color pigments can, preferably before the addition to the coating suspension, be mechanically comminuted in order to have as many primary particles as possible. This can usually be done in an organic solvent, if appropriate with the addition of suitable dispersing additives and / or binders. The comminution can be done in the usual aggregates, such as three-roll mill, Co-BaII-MiII, gear dispersing mill, etc.
  • the pigments according to the invention are prepared by a spray-drying process.
  • a dispersion comprising a volatile, organic, solvent, IR radiation-reflecting platelet-shaped cores, dark color pigments and one or more organic polymer and / or binder is spray-dried by spraying.
  • the spray drying is carried out in a moving atmosphere, for example a fluidized bed, in order to avoid agglomeration.
  • the platelet-shaped cores are uniformly coated with the organic, preferably film-forming, polymer and / or binder and the dark color pigments.
  • the organic, preferably film-forming polymer and / or binder can be cured. This can preferably also be done in the spray-drying apparatus by, for example, the temperature of the feed gas is above the curing temperature of the binder.
  • the IR radiation-reflecting, preferably platelet-shaped, pigment can be obtained by coating the IR-reflecting cores with a matrix of suitable starting compounds and dark colored pigments in a fluidized bed process.
  • the IR radiation-reflecting, preferably platelet-shaped, pigments according to the invention are preferably used in paints, lacquers, printing inks, security printing inks, textiles, military applications or plastics.
  • Application media pigmented with the pigments according to the invention for example paints or lacquers, have a largely dark appearance.
  • the degree of darkening of these application media can optionally by further Addition of color pigments, which are optionally IR-transparent, eg Paliogen Black or Lumogen (BASF) can be further increased.
  • colorants such as organic or inorganic color pigments different colors or paints can be produced.
  • the dispersion paint contains the pigments according to the invention in such an amount that the proportion of IR radiation-reflecting cores, based on the weight of all, is not Volatile components of the emulsion paint, at 2 to 30 wt .-%, preferably 4 to 20 wt .-% and particularly preferably 7 to 15 wt .-%.
  • the other components of application medium such as binders or fillers also have the lowest possible IR absorption.
  • the pigmentation levels of the binders, fillers and / or dark color pigments can also be significantly lower than is usual in the prior art due to the additional pigmentation by the pigments according to the invention.
  • Figure 1 shows the correlation of thermal heating of painted ABS plastic panels after 30 minutes of irradiation with a 500 W radiator depending on calculated solar reflectance. (Dashed line: Balancing line)
  • FIG. 2 shows NIR reflection spectra of pigments of Inventive Example 1 in comparison to Comparative Examples 3 and 8 and FIG. 7.
  • FIG. 3 shows NIR reflection spectra of pigments of Inventive Example 2 in comparison to Comparative Examples 4 and 8 and FIG. 7.
  • FIG. 4 shows MIR reflection spectra of pigments of Inventive Example 1 compared to Comparative Examples 3 and 9.
  • Figure 5 shows MIR reflectance spectra of pigments of Inventive Example 2 compared to Comparative Examples 4 and 9.
  • Reaction time was a dispersion of 37.5 g of the dark color pigment Shepherd 20C980 (Shepherd, USA) with 30 g of tetraethoxysilane was added continuously over 2 h, wherein after 30, 60 and 90 min. 0.50 g of EDA in 10 g of isopropanol was added in each case. After the last addition, the reaction mixture was allowed to cool and stirred at 20 0 C for a further 16 h. The reaction mixture was filtered and washed with isopropanol and the resulting pigment was dried at 100 ° C. in vacuo.
  • the amount of dried pigment obtained was dispersed in 250 g of isopropanol and the procedure repeated again with 37.5 g of the color pigment Shepherd 20C980.
  • reaction mixture was filtered and washed with isopropanol and the resulting pigment was dried at 100 ° C. in vacuo.
  • NIR reflection spectra (wavelength range 0.8 to 2.5 microns)
  • the resulting pigment was incorporated 12% strength in a melamine-based paint and coated by spraying on opaque black ABS plastic panels (15 * 10 cm).
  • NIR reflection measurements were carried out on the painted sample using an FT-NIR spectrometer MPA-R from Bruker using an integrating integration sphere (gold surface) in accordance with the manufacturer's instructions. The obtained data was referenced against a gold standard and normalized. Spectral data obtained are shown in Figure 2.
  • MIR reflectance measurement (wavelength range 2.5 to 25 ⁇ m) was measured in diffuse reflection from a 1, 5% powder bed in KBr.
  • finely ground KBr was homogeneously mixed with pigment and a tablet-shaped sample chamber (diameter: 0.8 cm, depth 2.2 mm) was filled with the mixture and pressed on.
  • Specac Selector measuring unit
  • the IR reflection spectrum was measured in a quarter geometry (as the IR device Avatec 360 from Thermo with DTGS detector). As a reference, it was measured against pure KBr.
  • the spectral curve is shown in Figure 4.
  • the painted ABS panel was used to determine a temperature increase by irradiation with a commercial 500W spotlight for 30 min. irradiated at a distance of 35 cm and determined with a surface thermometer, the surface temperature.
  • the data obtained are listed in Table 1 and correlated in Figure 1 with the calculated solar NIR reflectance.
  • Example 1 To determine the NIR and MIR spectral data, the solar NIR reflectance and for color and gloss measurements, the procedure was analogous to Example 1 ( Figure 1, 3 and 5, Table 1 and 2).
  • the pigment Shepherd 20C980 in the application media was used.
  • the data of the NIR and MIR spectral measurements, the calculated solar NIR reflectance, color and gloss measurements were determined analogously to Example 1 (FIGS. 1, 2 and 4, Tables 1 and 2).
  • the pigment Shepherd 10C909A in the application media was used.
  • the data of the NIR and MIR spectral measurements, the calculated solar NIR reflectance, color and gloss measurements were determined analogously to Example 1 (FIGS. 1, 3 and 5, Tables 1 and 2).
  • a comparative example was a mixture of the pigment Shepherd 20C980 with an aluminum pigment STAPA Metallux 212 in the application medium
  • Nitrocellulose lacquer finish (12% 20C980, 8% Metallux 212.100 ⁇ m wet film thickness) incorporated.
  • Nitrocellulose lacquer finish (12% 10C909A, 8% Metallux 212.100 ⁇ m wet film thickness) incorporated.
  • an aluminum pigment STAPA Metallux 212 in the application medium nitrocellulose lacquer finish (8% Metallux 212.100 microns wet film thickness) was incorporated.
  • the carbon black pigment HelioBeit Black was used in the application media (spray lacquer application: 20% melamine-based lacquer on a black ABS plastic panel).
  • the data of the NIR spectral measurements and the calculated solar NIR reflectance were determined analogously to Example ( Figure 1, 2.3 and Table 1)
  • an SiO 2 -encapsulated aluminum pigment PCS 5000 (from Eckart) was used in accordance with Example 1 for recording the MIR reflection spectrum (FIGS. 4 and 5).
  • Table 1 Calculated solar NIR reflectance and temperature measurement after 30 min. Irradiation with a 500W spotlight
  • Example 1 12% 36 42
  • Example 2 12% 51 40
  • Comparative Example 8 20% 4 59 (HelioBeit Black) due to insufficient optical appearance
  • Pigments according to the invention show significant reflections in the IR spectral range, both for the NIR spectral range, as shown in FIGS. 2 and 3, and in the MIR range, as shown in FIGS. 4 and 5. This can be seen from the curves of the spectra.
  • the property of reflecting NIR radiation can be quantified by the solar NIR degree defined here, in which the reflectivities depend on the wavelengths emitted by the sun weighted by wavelength-dependent radiation intensities.
  • Inventive Examples 1 and 2 listed in Table 1 have solar NIR reflectivities of 36% and 51%. This means that these pigments can reflect 36% and 51% respectively of the NIR radiation emitted by the sun.
  • Other dark pigments (Comparative Examples 3,4 and 8) show significantly lower NIR solar reflectance.
  • Figure 1 shows that the reflectivity of pigments in paint applications correlates with the solar NIR reflectance.
  • the surface temperature is after 30 min. Irradiation with a 500W emitter for pigments with higher solar reflectivities is lower than for pigments with lower reflectivities. This shows that the significant reflectivity of the pigments according to the invention can be used to reduce thermal heating with pigments of coated articles according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne un pigment réfléchissant un rayonnement IR, comprenant un noyau réfléchissant un rayonnement IR, métallique lamellaire, caractérisé en ce que le noyau réfléchissant un rayonnement IR est pourvu d'un revêtement essentiellement enrobant, absorbant sensiblement faiblement un rayonnement IR, et en ce que le pigment réfléchissant IR est sensiblement foncé. L'invention concerne en outre un procédé de production de tels pigments ainsi que leur utilisation.
EP08759113A 2007-06-20 2008-06-09 Pigments réfléchissant un rayonnement ir, leur procédé de production et leur utilisation Withdrawn EP2173819A2 (fr)

Applications Claiming Priority (2)

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DE102007028842A DE102007028842A1 (de) 2007-06-20 2007-06-20 Dunkle, IR-Strahlung reflektierende Pigmente, Verfahren zu deren Herstellung und Verwendung derselben
PCT/EP2008/004581 WO2008155038A2 (fr) 2007-06-20 2008-06-09 Pigments réfléchissant un rayonnement ir, leur procédé de production et leur utilisation

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EP2173819A2 true EP2173819A2 (fr) 2010-04-14

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US (1) US20100242793A1 (fr)
EP (1) EP2173819A2 (fr)
JP (1) JP5684566B2 (fr)
KR (1) KR20100050465A (fr)
CN (1) CN101688072B (fr)
DE (1) DE102007028842A1 (fr)
WO (1) WO2008155038A2 (fr)

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DE102007028842A1 (de) 2008-12-24
KR20100050465A (ko) 2010-05-13
CN101688072B (zh) 2014-02-26
WO2008155038A3 (fr) 2009-06-18
CN101688072A (zh) 2010-03-31
US20100242793A1 (en) 2010-09-30
WO2008155038A2 (fr) 2008-12-24
JP2010530448A (ja) 2010-09-09
JP5684566B2 (ja) 2015-03-11

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