WO2013189699A1 - Additifs antiparasites, leur procédé de fabrication ainsi que leur utilisation dans des revêtements - Google Patents

Additifs antiparasites, leur procédé de fabrication ainsi que leur utilisation dans des revêtements Download PDF

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Publication number
WO2013189699A1
WO2013189699A1 PCT/EP2013/060904 EP2013060904W WO2013189699A1 WO 2013189699 A1 WO2013189699 A1 WO 2013189699A1 EP 2013060904 W EP2013060904 W EP 2013060904W WO 2013189699 A1 WO2013189699 A1 WO 2013189699A1
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WO
WIPO (PCT)
Prior art keywords
fouling
silica
modified
silicate
particle size
Prior art date
Application number
PCT/EP2013/060904
Other languages
German (de)
English (en)
Inventor
Katharina Schulz
Juri Tschernjaew
Rüdiger MERTSCH
Günther MICHAEL
Jürgen Meyer
Original Assignee
Evonik Industries Ag
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 Evonik Industries Ag filed Critical Evonik Industries Ag
Priority to EP13725655.8A priority Critical patent/EP2861674A1/fr
Priority to KR1020147035306A priority patent/KR20150024335A/ko
Priority to JP2015517653A priority patent/JP2015521664A/ja
Priority to CN201380032483.7A priority patent/CN104395410A/zh
Publication of WO2013189699A1 publication Critical patent/WO2013189699A1/fr

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09C1/28—Compounds of silicon
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/14—Pore volume
    • 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
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • Anti-fouling additives process for their preparation and their use in coatings
  • the present invention relates to anti-fouling additives, a process for their preparation and their use in coatings.
  • anti-fouling additives which function according to the chemical action principle, i. the antifouling mechanism of action is based on the release (leaching) of biocides, especially natural biocides, such as menthol, from the coating. Furthermore, anti-fouling additives are known, based on physical principles of action, such as
  • JP10025427A and JP09053612A Through the use of finely divided particles or fibers, a ternary boundary layer air-water-paint is formed, which has a positive effect on the
  • JP08268377A describes as an alternative the supply of air by means of compressors, which is of little relevance for certain applications.
  • CN101792534A discloses micro- and nanostructured surfaces with anti-fouling activity, which are made by molding the surface (molds). In this way, natural antifouling surfaces (e.g., sharkskin) based on physical principles of action may be ideal
  • nanostructured coating systems based on nanoscale hydrophobic particles are known from DE102006030055A1. However, these are less stable under mechanical stress, as the
  • structured surfaces e.g.
  • microorganisms use other feature sizes to macro-organisms such as mussels and algae.
  • EP1591509A1 describes the production of a lotus surface by ceramic hollow microspheres, which in turn
  • Nanoparticles e.g., aluminum oxides, alumina hydrates, titanium dioxides, zirconia dioxides
  • Nanoparticles are occupied and have improved life in the sense of conventional lotus effect applications (facades, buildings, roofs).
  • EP1283077A1 describes a self-cleaning
  • Particles which have antimicrobial properties, i. Agents are equipped so that the effect is not based solely on physical effects.
  • US20080241408A1 describes the generation of a lotus surface, i. a liquid-repellent surface, with
  • microstructured surfaces based on natural models can be done in addition to the use of particles by using fibers that adhere to
  • WO2007108679A1 describes the use of ym fibers by
  • electrostatic charge can be sprayed onto the wet paint and so a sea lion-like surface texture
  • structured surfaces can also by
  • Object of the present invention is a
  • fouling additive to be provided, which incorporated in coatings a fouling effect, based on non-toxic physical principles of action, achieved and the anti-fouling coating in the
  • Binder system be possible by adjusting the
  • a further object of the present invention is to provide growth-reducing additives which are largely or completely biodegradable and / or biologically harmless.
  • a further object is to provide fouling-reducing additives which ensure adequate anti-fouling protection both during travel and during lay periods of vessels or other objects in contact or coming into contact with water, in particular seawater.
  • the present invention refers to the ability of organic chemicals to biodegrade, that is, to decompose by living things or their enzymes. Ideally, this chemical metabolism progresses to the full extent
  • Ammonia is decomposed. This process can be analyzed analytically, e.g. be recorded by the indication of the half-life.
  • Fouling in the context of the present invention refers to the property of anti-fouling additives
  • the invention relates to a fouling-reducing additive containing at least
  • a modified or unmodified silica, silicate or silica gel having an average particle size d 50 of 100-500 ⁇ m, preferably of 100-300 ⁇ m,
  • a modified or unmodified silica, silicate or silica gel having a mean particle size d50 of 20-70 ym, preferably 20-50 ym and
  • the antifouling additive may be free of biocides or biocidal substances.
  • the silicas can be precipitated and / or pyrogenic silicas.
  • precipitated silicas can be used according to EP 1398301 A2, EP 1241135 A1, EP 1648824 A1, EP 0798348 A1, EP 0341383 A1 or EP 0922671 A1.
  • Precipitated or pyrogenic silicic acids and silica gels are already used as standard additives (for example for rheology control or matting) in paints, so that easy incorporation and uniform distribution of the additives according to the processes known to those skilled in the paint
  • the three silicic acids, silicates or silica gels a) -c) can be mixed with one another in variable ratios.
  • the mixing ratios and the amounts used can have a considerable influence on the resulting structures and thus on the anti-fouling effect.
  • the mixing ratio of the silicic acids, silicates or silica gels a): b): c), based on the mass, may preferably be 3: 2: 1 to 0.5: 0.5: 1.
  • other than the mentioned mixing ratios may prove to be advantageous.
  • the silicas, silicates or silica gels a) -c) can be used modified.
  • the modification can be done by a
  • Methods of surface modification can be any combination
  • silanes for surface modification it is possible, for example, to use the following silanes, individually or as a mixture:
  • R is the same or different and is alkyl, such as methyl, ethyl, n-propyl, i-propyl or butyl
  • X C1 or Br
  • R is the same or different and is alkyl, such as methyl, ethyl, n-propyl, i-propyl or butyl
  • alkyl such as methyl, ethyl, n-propyl, i-propyl or butyl,
  • X C1 or Br
  • m 0, l-20
  • R is the same or different and is alkyl, such as methyl, ethyl, n-propyl, i-propyl or butyl
  • Cyclic polysiloxanes D3, D4, D5 and their homologs where by D3, D4 and D5 cyclic polysiloxanes with 3, 4 or 5 units of the -0-Si (CH 3 ) 2 is understood, eg
  • R 10 or R 11 or R 12 can be (CH 2 ) V -NH 2 and
  • v 1-20
  • m ' 0, 1, 2, 3, ... 100,000
  • n' 0,1,2,3, ...
  • the following substances may preferably be used as surface modifiers: octyltrimethoxysilane,
  • Tridecaflourooctyltriethoxysilane Particularly preferred hexamethyldisilazane
  • Octyltriethoxysilane or dimethylpolysiloxanes are used.
  • the modification can be carried out by impregnation, for example with silicone oil, polyethylene glycol, polysaccharides, block copolymers, caprolactones, lactide and glycolide polymers,
  • Polyvinyl acetate, alginate, gelatin, agar or pectin can be achieved.
  • Silica gels can be incorporated into the coating systems analogously to the pure silicic acids, silicates or silica gels, with additional functionalities being produced which have a
  • Processing properties in the paint can modify.
  • the silicas, silicates or silica gels ac may be a mixture of unmodified and modified silicas.
  • One, two or three of the three silicic acids, silicates or silica gels may be ac modified.
  • Silicas and silicates a grindometer value of 10 to 45 ym, preferably 20 to 43 ym, and / or a tamped density of 50 to 350 g / 1 preferably 50 to 300 g / 1, and / or an oil number of 180 to 360 g / 100g and or a DBP number of 200 to 450 g / 100g, preferably 320 to 400 g / 100g, and / or a BET of 100 to 600 m 2 / g, preferably 200 to 550 m 2 / g, particularly preferably 300 to 550 m 2 / g, most preferably 350 to 500 m 2 / g, and / or a total pore volume of 6 to 14 ml / g (0.0042 - 414 MPa, 140 °) have.
  • the silicas and silicates have several of the above
  • Coating formulations coated surfaces can be created a microstructuring that affects biofilm growth and macro-fouling.
  • the BET surface area is important to a sufficient amount
  • the anti-fouling additive according to the invention may be a powder, preferably free-flowing powder. This means that the flowability of the product measured with the
  • Outlet funnels according to DIN 53492 preferably has the value 1.
  • the fouling-reducing additives according to the invention can therefore be processed and transported particularly well.
  • Another object of the invention is a process for the preparation of the growth-reducing additive according to the invention, which is characterized in that a modified or unmodified silica, silicate or silica gel a) having a particle size of 100-500 ym, preferably 100-300 ym , a modified or unmodified silica, silicate or silica gel b) having a particle size of 20-70 ⁇ m, preferably 20-50 ⁇ m and a modified or unmodified silica, silicate or silica gel c) having a particle size of ⁇ 20 ⁇ m, preferably from 10nm-10 ym, mixes.
  • the silicas, silicates or silica gels ac can be characterized in that a modified or unmodified silica, silicate or silica gel ac having a particle size of 100
  • the modification can be done by a
  • the mixing can be done, for example, in a kneader,
  • the temperature in the mixing unit can be between 5 ° C and 120 ° C.
  • the mixture can be done under air atmosphere.
  • the fouling-reducing additive according to the invention can be described in
  • Coating systems preferably paints used.
  • Anti-fouling additive may be applied to the surface of objects to protect the surface of objects in contact with or coming into contact with water, especially seawater.
  • Another object of the invention is a paint, which is characterized in that this at least a) a modified or unmodified silica, silicate or silica gel having an average particle size d 50 of 100-500 ⁇ m, preferably of 100-300 ⁇ m,
  • a modified or unmodified silica, silicate or silica gel having a mean particle size d50 of 20-70 ym, preferably 20-50 ym and
  • a modified or unmodified silica, silicate or silica gel having an average particle size d50 of ⁇ 20 ⁇ m, preferably of 10 nm-10 ⁇ m
  • the paint according to the invention can be free of biocides or
  • Silicates or silica gels a) -c) can be dispersed in any order in the finished paint formulation.
  • Another object of the invention is a paint, which is characterized in that it contains the fouling-reducing additive according to the invention.
  • the lacquer according to the invention may contain 1-40% by weight, preferably 10-20% by weight, of growth-reducing additive, based on the lacquer.
  • the antifouling additive can be dispersed with moderate shear stress in the finished paint formulation and the paint
  • the application technique can also have an influence on the resulting structure.
  • surface-active groups can take place by utilizing the hydrolysis taking place upon contact with water.
  • the silicas, silicates or silica gels for example, first modified or impregnated with a water-soluble polymer and then after the above
  • Water-soluble polymers can be biodegradable and not
  • the detachment of the polymer from the surface of the particles simultaneously removes the paint on the particle, thereby exposing the particle surface.
  • the particle remains sufficiently surrounded by the coating matrix, so that the silica, silicate or silica gel are not exposed from the paint system and can escape from the paint matrix.
  • hydrophilic spots can be generated in a hydrophobic matrix.
  • These alternating surfaces in turn have particularly good anti-fouling properties.
  • the paints prepared in this way show both in the laboratory bioassay against the test microorganism Ps.atlantica and in the field trial a fade-reducing effect in comparison to the reference system without the addition of the structuring elements.
  • Another advantage that results from using the additives described is the increase in mechanical strength, as well as
  • Biofouling are exposed. These are in particular sport boats, commercial ships, submerged in water structures and facilities such. B. Jetties, quay walls,
  • DBP absorption which is a measure of the absorbency of a porous particle, is determined in accordance with DIN 53601 as follows:
  • Granules will be the sieve fraction of 3.15 to 1 mm
  • the DBP recording is in the unit [g / (100g)] without
  • V consumption of DBP in ml
  • the correction value K When using moist support materials, in particular precipitated silicas or silica gels, the correction value K must be taken into account for calculating the DBP absorption. This value can be determined from the following correction table, eg. For example, a water content of the support material of 5.8% would mean a 33 g / (100 g) addition for DBP uptake.
  • the moisture of the carrier material is determined according to the method described below "Determination of moisture or dry loss".
  • the determination of the oil number is carried out according to DIN EN ISO 787-5 with linseed oil.
  • Carrier materials are determined according to ISO 787-2 after 2 hours of drying at 105 ° C. This
  • Drying loss consists mainly of water moisture.
  • execution In a dry weighing glass with ground cover (diameter 8 cm, height 3 cm) 10 g of the powdery, spherical or granular material are weighed to exactly 0.1 mg (weight E). The sample is dried with the lid open for 2 h at 105 ⁇ 2 ° C in a drying oven. Subsequently, the
  • the determination of the particle distribution of the product systems according to the invention is carried out according to the principle of laser diffraction on a laser diffractometer (Horiba, LA-920).
  • Dispersion with a weight fraction of about 1 wt .-% S1O 2 prepared by stirring the powder in water.
  • the particle size distribution is determined from a partial sample of the dispersion with the laser diffractometer (Horiba LA-920). For the measurement a relative refractive index of 1.09 has to be chosen. All measurements are carried out at room temperature.
  • the laser diffractometer Horiba LA-920.
  • the mean particle size dso is automatically calculated and graphed by the instrument.
  • the instructions in the operating instructions must be observed.
  • BET surface area The specific nitrogen surface area (hereinafter referred to as BET surface area) of the powdery, approximately spherical particles or granular silicic acid is disclosed in US Pat
  • the total pore volume is determined by means of mercury porosimetry. The method is based on the Hg
  • the amount of silica in the Penetrometer Type 10 is accurate to 0.001 g and is for a good
  • the reproducibility of the measurement is chosen such that the stem volume used, ie the volume of Hg volume used to fill the penetrometer, is 20% to 40%, then the penetrometer is slowly evacuated to 50 ym Hg and allowed to stand for
  • the operation of the Autopore device is carried out according to the
  • Indicated is the measuring vessel in which the powder just flows out without faltering.
  • Example 1 Lacquer with modified silicic acids
  • silica to be modified (Sipernat®22, Sipernat®50, Sipernat®50S) is initially charged in a mixer (Somakon laboratory mixer) according to the initial weight in Table 1 and the
  • Modification used polymer Polyethylene glycol 10,000 from Aldrich
  • aqueous solution 40 wt .-%)
  • the mixing process will be stopped after another 15 minutes.
  • the particles remain free-flowing. Subsequently, a drying step
  • Table 1 shows the weights for each
  • Sipernat®22, Sipernat®50 and Sipernat®50S are silicas from Evonik Industries.
  • the growth-reducing additive according to the invention is obtained by mixing the modified silicic acids 1-3 in a weight ratio of 6: 4: 5 (mod.Sipernat.RTM. 22: mod. Sipernat.RTM .50: mod. Sipernat.RTM ) with a tumble mixer at 25 ° C, 30 min.
  • composition paint a paint is prepared according to Table 2 (composition paint).
  • the first component is first prepared by means of a dissolver (Dispermat, diameter: 80 mm, 2000 rpm, 30 min).
  • Table 2 Table 2:
  • the hardener (DYNASYLA AMEO) and the anti-fouling additive are dispersed (Dispermat,
  • Diameter 40mm, 100pm, 10 minutes).
  • the paint is sprayed (gun Sata Jet 90,
  • Test surface are roughened PVC plates used (20x20cm for field trial; 7, 5x2, 5cm for laboratory test). After 8 hours, the coating according to the invention is cured and
  • sampling in the field trial was carried out under dynamic conditions (sample Karrussel with 8h rotation, 8h stoppage, about 5 knots) in the North Sea (Hooksiel). Subsequently, the evaluation was carried out on the basis of weighing, ie determination of the
  • the paint system according to the invention containing the fouling-reducing additive reduces the fouling mass by more than 30% in comparison to the reference paint without the fouling-reducing additive according to the invention.
  • Example 2 Lacquer With Mixture of 3 Silicic Acids
  • An inventive growth-reducing additive is prepared from the amounts of silicic acid types given in Table 3. The mixture is carried out in a tumble mixer at 25 ° C, 30 min.
  • Example 1 a lacquer is produced.
  • coating system according to the invention containing the fouling-reducing additive reduces the fouling mass by more than 40% compared to the reference coating without the fouling-reducing additive according to the invention.
  • the lacquer according to the invention is exposed to the colonization in the test medium (artificial seawater with test germ) for 24 hours Subsequently, the analysis of the surface growth of the lacquer according to the invention takes place in comparison with the reference system without fouling-reducing additive
  • the surface topography of the prepared paint surface according to the invention is determined by means of a stylus instrument (Hommelwerke, Turbo roughness V6.14). Table 4 shows the determined
  • Sipernat®820A is an al-silicate from Evonik Industries.
  • Anti-fouling additive (100% growth) increased microbial growth by> 50%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

La présente invention concerne un additif antiparasite contenant au moins (a) un acide silicique, silicate ou gel de silice modifié ou non modifié ayant une taille moyenne de particule d50 de 100-500 µm, b) un acide silicique, silicate ou gel de silice modifié ou non modifié ayant une taille moyenne de particule d50 de 20-70 µm et c) un acide silicique, silicate ou gel de silice modifié ou non modifié ayant une taille moyenne de particule d50 de <20 µm. L'additif antiparasite selon l'invention est produit par mélange. L'additif antiparasite peut être utilisé dans des peintures.
PCT/EP2013/060904 2012-06-19 2013-05-28 Additifs antiparasites, leur procédé de fabrication ainsi que leur utilisation dans des revêtements WO2013189699A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP13725655.8A EP2861674A1 (fr) 2012-06-19 2013-05-28 Additifs antiparasites, leur procédé de fabrication ainsi que leur utilisation dans des revêtements
KR1020147035306A KR20150024335A (ko) 2012-06-19 2013-05-28 부착물 방지 첨가제, 그의 제조 방법 및 코팅에서의 그의 용도
JP2015517653A JP2015521664A (ja) 2012-06-19 2013-05-28 汚損低減添加剤、その製造方法およびコーティングにおけるその使用
CN201380032483.7A CN104395410A (zh) 2012-06-19 2013-05-28 防污添加剂、其制备方法及其在涂料中的用途

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012210294.9 2012-06-19
DE102012210294A DE102012210294A1 (de) 2012-06-19 2012-06-19 Bewuchsmindernde-Additive, Verfahren zu deren Herstellung und deren Verwendung in Beschichtungen

Publications (1)

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WO2013189699A1 true WO2013189699A1 (fr) 2013-12-27

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EP (1) EP2861674A1 (fr)
JP (1) JP2015521664A (fr)
KR (1) KR20150024335A (fr)
CN (1) CN104395410A (fr)
AR (1) AR091472A1 (fr)
DE (1) DE102012210294A1 (fr)
TW (1) TW201418386A (fr)
WO (1) WO2013189699A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2017010459A1 (ja) * 2015-07-13 2017-07-20 富士シリシア化学株式会社 生物付着抑制塗料及びその製造方法、ならびに生物付着抑制塗膜
JP2018513240A (ja) * 2015-03-18 2018-05-24 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ 防汚性金属酸化物とヒュームドシリカとを含有する塗装系
JP2018526485A (ja) * 2015-07-13 2018-09-13 ヨトゥン アーエス 防汚組成物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021021394A1 (fr) * 2019-07-30 2021-02-04 Dow Global Technologies Llc Procédés de réduction de l'encrassement dans des réacteurs de valorisation
US20230183484A1 (en) * 2020-05-25 2023-06-15 Nanophos Sa Silicone-epoxy compositions and protective coatings

Citations (20)

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Publication number Priority date Publication date Assignee Title
EP0341383A2 (fr) 1988-05-07 1989-11-15 Degussa Aktiengesellschaft Silices de précipitation finement divisées de haute structure, procédé de préparation et utilisation
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CN104395410A (zh) 2015-03-04
AR091472A1 (es) 2015-02-04
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