WO2014157177A1 - フレーク状ステンレス顔料、それを配合してなる樹脂組成物、および該樹脂組成物により形成された塗膜を有する塗布物 - Google Patents
フレーク状ステンレス顔料、それを配合してなる樹脂組成物、および該樹脂組成物により形成された塗膜を有する塗布物 Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- 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
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- 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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- 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
Definitions
- the present invention relates to a flaky stainless pigment, a resin composition obtained by blending the same, and a coated product having a coating film formed from the resin composition.
- Metal pigments containing flaky metals are widely used for the purpose of imparting a metallic appearance to metal products such as automobiles, home appliances, cosmetics and building materials, plastic products and ceramic products.
- a coating film containing a metal pigment containing stainless steel exhibits a heavy metal appearance (for example, JP-A-2006-152299 (Patent Document 1)).
- a coating film containing stainless steel has attracted attention as a heavy anticorrosion paint because it has excellent corrosion resistance and high hardness.
- JP 2000-154338 A Patent Document 2
- JP 2002-273339 A Patent Document 3
- Patent Document 4 discloses a metal pigment having an enhanced rust prevention effect by mechanically coating zinc powder on the surface of a flaky stainless steel powder.
- Patent Document 5 discloses a technique for improving the light resistance of a metal plate by forming a coating film containing an ultraviolet absorber or a light stabilizer in addition to stainless steel powder. ing.
- the resin in the paint may be gelled by zinc covering the surface of stainless steel.
- the quality may be unstable due to segregation of the ultraviolet absorber or light stabilizer in the paint. That is, in the conventional technique, the corrosion resistance by the stainless pigment is not yet sufficient.
- the present invention has been made in view of the above situation, and the object of the present invention is to provide a flaky stainless pigment capable of exhibiting high corrosion resistance, a resin composition comprising the same, and the resin composition It is providing the coating material which has the coating film formed by.
- the flaky stainless pigment of the present invention has a 90% diameter of a volume cumulative particle size distribution of 55 ⁇ m or less, and a passing rate of a sieve having an opening of 38 ⁇ m is 99% by weight or more.
- the average thickness t is preferably 0.03 ⁇ m or more and 0.5 ⁇ m or less
- the average particle diameter D 50 is preferably 3 ⁇ m or more and 30 ⁇ m or less
- the ratio of the average particle diameter D 50 to the average thickness t is A certain average aspect ratio (D 50 / t) is preferably 5 or more and 500 or less, and more preferably 10 or more and 100 or less.
- the 90% diameter is preferably 40 ⁇ m or less.
- the present invention also relates to a resin composition obtained by blending the flaky stainless pigment and a coated product having a coating film formed from the resin composition.
- the flaky stainless pigment of the present invention a resin composition containing the same, and a coated product having a coating film formed from the resin composition have an excellent effect of exhibiting high corrosion resistance.
- FIG. 2 It is a figure which shows the state 250 hours after the crack in the coating film formed with the coating material which mix
- FIG. 2 It is a figure which shows the state 250 hours after the crack in the coating film formed with the coating material which mix
- FIG. 2 It is a figure which shows the state after 250 hours of the crack in the coating film formed with the coating material which mix
- FIG. It is a figure which shows the state after 250 hours of the crack in the coating film formed with the coating material which mix
- the flaky stainless pigment of the present invention a resin composition obtained by blending the same, and a coated product having a coating film formed from the resin composition will be described in more detail.
- the flaky stainless steel pigment of the present invention has a 90% diameter (D 90 ) of a volume cumulative particle size distribution of 55 ⁇ m or less, and a passing rate of a sieve having an opening of 38 ⁇ m is 99% by weight or more.
- volume cumulative particle size distribution means a volume cumulative particle size distribution obtained by measuring the volume average particle size of a flaky stainless pigment, and the “90% diameter is 55 ⁇ m or less”.
- the volume cumulative particle size distribution curve in which the vertical axis is the cumulative frequency (%) and the horizontal axis is the particle diameter ( ⁇ m), it means that the particle diameter at 90% accumulation is 55 ⁇ m or less.
- the volume average particle diameter can be obtained by calculating the volume average based on the particle size distribution measured by the laser diffraction method.
- the flaky stainless pigment of the present invention having the above characteristics can exhibit higher corrosion resistance than conventional flaky stainless pigments.
- a coating film formed from a resin composition obtained by blending the flaky stainless pigment of the present invention can have high corrosion resistance.
- the coating film can have high wear resistance and high slidability.
- the orientation of the flaky stainless steel pigment in the coating film decreases. Tend to. For this reason, the flaky stainless pigment becomes easier to protrude from the coating film, and cracks are generated from the protruding portion, so that sufficient corrosion resistance cannot be exhibited.
- the flaky stainless pigment becomes easier to protrude from the coating film, and cracks are generated from the protruding portion, so that sufficient corrosion resistance cannot be exhibited.
- cavities are likely to occur in the coating film, and peeling is likely to occur from the cavities. In such a coating film, naturally, abrasion resistance and sliding resistance are also lowered.
- the 90% diameter (D 90 ) of the volume cumulative particle size distribution is 55 ⁇ m or less, and the passing rate of a sieve having an aperture of 38 ⁇ m is 99. Both features of being greater than or equal to weight percent are required. The reason for this is not clear, but the following can be considered.
- the above-mentioned definition relating to the 90% diameter of the accumulated cumulative particle size distribution cannot sufficiently exclude the mixing of coarse particles that adversely affect the appearance of the coating film, and the aperture is 38 ⁇ m.
- the above-mentioned regulations regarding the passage rate of the sieves of particles the mixing of irregularly shaped particles such as rod-like particles cannot be sufficiently eliminated.
- the above-described effects of the present invention can be exhibited only when both of the above-mentioned regulations are satisfied.
- D 90 is more preferably 40 ⁇ m or less. Furthermore, it is possible to form a coating film with fewer defects, and thus to exhibit even higher corrosion resistance, wear resistance, and slidability.
- the passing rate of a sieve having an opening of 38 ⁇ m is preferably 99.9% or more. Also in this case, a coating film with fewer defects can be formed, and thus higher corrosion resistance, wear resistance, and slidability can be exhibited.
- the type of stainless steel is not particularly limited, and conventionally known stainless steels such as ferritic stainless steel, austenitic stainless steel, martensitic stainless steel, and two-phase stainless steel can be used. .
- ferritic stainless steel or austenitic stainless steel in terms of having high corrosion resistance and high workability.
- ferritic stainless steels SUS430 and NSS445M2 and NSS447M1 manufactured by Nisshin Steel Co., Ltd. are preferable, and among austenitic stainless steels, SUS304, SUS316, and SUS316L are preferable.
- NSSURC manufactured by Nisshin Steel Co., Ltd.
- stainless steel may contain inevitable impurities, and the composition is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of corrosion resistance and workability, the content of inevitable impurities in the flaky stainless pigment Is preferably 1% or less.
- the average thickness (t) is preferably 0.03 ⁇ m or more and 0.5 ⁇ m or less, and the average particle diameter (D 50 ) is preferably 3 ⁇ m or more and 30 ⁇ m or less. More preferably, t is 0.03 ⁇ m to 0.33 ⁇ m, D 50 is 3 ⁇ m to 20 ⁇ m, more preferably t is 0.09 ⁇ m to 0.33 ⁇ m, and D 50 is 5 ⁇ m to 20 ⁇ m. It is as follows.
- the flaky stainless steel pigment is suitably laminated even in a thin coating film, for example, in a coating film having a thickness of 10 ⁇ m or less, the labyrinth effect (blocking effect) against corrosive substances can be enhanced.
- D 50 means a particle size having a cumulative degree of 50% in the above-mentioned volume cumulative particle size distribution.
- the average aspect ratio (D 50 / t), which is the ratio of the average particle diameter D 50 to the average thickness t, is preferably 5 or more and 500 or less, more preferably 10 or more and 100 or less.
- the average aspect ratio is less than 5, a sufficient shielding effect cannot be exhibited in the coating film.
- the average aspect ratio exceeds 500, in the resin composition, the viscosity tends to increase greatly. It becomes difficult to ensure an appropriate blending amount in the resin composition.
- the average aspect ratio exceeds 500 the bulk specific gravity of the flaky stainless pigment is small, so that there are many gaps between the flaky stainless pigment in the coating film. As a result, many voids are generated in the resin, and as a result, the corrosion resistance of the coating film tends to decrease.
- the flaky stainless pigment of the present invention can include any other configuration other than the above configuration, for example, a coating layer that covers the surface of the flaky stainless steel.
- a coating layer that covers the surface of the flaky stainless steel.
- the coating film is made of only flaky stainless steel and does not have other components such as a coating layer.
- the flaky stainless pigment of the present invention can exhibit high corrosion resistance, and thus is excellent in coating applications, and is preferably used for coating a substrate exposed to a particularly severe environment. it can. Moreover, since the flaky stainless steel pigment of the present invention has the above-described characteristics, it is expected to improve other characteristics such as heat shielding properties, heat resistance, flame retardancy, and lightning surge protection function.
- the flaky stainless pigment of the present invention described above can be produced by the following method.
- stainless steel powder as a raw material is prepared (preparation process).
- this stainless steel powder a powder obtained by a known atomizing method, crushing method, rotating disk method, rotating electrode method, cavitation method, melt spinning method or the like can be used.
- the prepared stainless steel powder is deformed into flakes (deformation process).
- the method of deforming into flakes include a method of flattening the stainless steel powder by pulverizing the stainless steel powder with a wet ball mill, a dry ball mill, a bead mill or the like. In particular, it is preferable to use a wet ball mill from the viewpoint of safety and workability.
- the flattened flaky stainless powder is sieved using a sieve having an opening of 38 ⁇ m or less (sieving step).
- the flaky stainless steel pigment of the present invention can be obtained.
- the D 90 of the stainless powder is preferably 5 ⁇ m or more and 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the recovery rate of the finally obtained flaky stainless pigment can be increased.
- D 90 may exceed 20 [mu] m, since the flake-form stainless steel powder coarsened through the deformation process occurs in a large amount, the recovery of flake stainless steel pigments ultimately obtained is greatly reduced.
- the sieving process may take a long time.
- D 90 is less than 5 ⁇ m, it is difficult to handle, and for example, it may take a long time in a solid-liquid separation operation accompanying pulverization with a wet ball mill.
- D 50 of stainless steel powder is preferably 2 ⁇ m or more 10 ⁇ m or less.
- the recovery rate of the finally obtained flaky stainless pigment can be increased as described above.
- the recovery rate indicates the ratio of the finally obtained flaky stainless pigment to the weight of the used stainless steel powder.
- the meaning of D 90 and D 50 of the stainless steel powder, and the calculation method thereof is the same as D 90 and D 50 of flake stainless pigment, description thereof will not be repeated.
- the sieving step it is preferable to use a sieve made of stainless steel having a diameter of 200 mm or more and 2000 mm or less. In this case, there is little abrasion and damage of a sieve, and it can be sieved efficiently.
- transformation process is a slurry state
- the sieve opening used may be 35 ⁇ m or less, more preferably 25 ⁇ m or less. In this case, a flaky stainless pigment having a D 90 of 23 ⁇ m or less and a sieve having a mesh opening of 38 ⁇ m and having a passage rate of 99.9% by weight or more can be more reliably produced.
- the flaky stainless pigment of the present invention can be produced by the production method detailed above.
- the manufacturing method of the flaky stainless steel pigment of this invention is not restricted to said each process, Other processes can be included.
- the present invention also relates to a resin composition comprising the above flaky stainless pigment.
- the resin composition can contain a resin component and a solvent in addition to the flaky stainless steel pigment.
- Such a resin composition of the present invention can form a coating film having higher corrosion resistance than before by blending the flaky stainless pigment.
- the resin composition can be used as a paint, an adhesive, a lining agent, a plastic, FRP, or the like.
- the blending amount of the flaky stainless pigment in the resin composition of the present invention is preferably 5 parts by weight or more and 120 parts by weight or less, and 30 parts by weight or more and 120 parts by weight or less with respect to 100 parts by weight of the total solid content in the resin composition. It is more preferable that the amount is not more than parts.
- the blending amount of the flaky stainless pigment is less than 5 parts by weight, the concealability of the formed coating film is reduced, and when the blending amount exceeds 120 parts by weight, the adhesion of the resin composition is decreased, As a result, cracks are likely to occur in the coating film.
- the total solid content indicates the remaining solid content excluding the fluid resin and solvent in the resin composition.
- the resin component examples include epoxy resin, polyester resin, alkyd resin, acrylic resin, acrylic silicone resin, vinyl resin, silicon resin (inorganic binder), polyamide resin, polyamideimide resin, fluororesin, synthetic resin emulsion, boil oil, Two or more combinations of chlorinated rubber, natural resin and amino resin, phenol resin, polyisocyanate resin, urea resin, etc. are preferably used.
- the solvent examples include organic solvents such as alcohols, glycols, ketones, esters, ethers and hydrocarbons, water, and the like. Moreover, when a resin composition does not contain a solvent, a resin composition turns into what is called a powder coating material.
- the resin composition of the present invention can also contain a color developing agent.
- Preferred color developing agents include epoxy resins (high adhesion, high altitude, high corrosion resistance, wear resistance), polyester resins (high corrosion resistance, high altitude), acrylic resins (high weather resistance, high design properties), fluororesins ( High corrosion resistance, high weather resistance), polyamideimide resin (high hardness, high heat resistance, flame resistance, wear resistance), and chlorinated rubber (high weather resistance, workability) are exemplified.
- additives other pigments and the like may be blended as necessary.
- additives include pigment dispersants, antifoaming agents, anti-settling agents, curing catalysts, and lubricants.
- pigments include organic coloring pigments, inorganic coloring pigments, extender pigments, pearl mica. Examples thereof include color pigments such as flaky aluminum and plate-like iron oxide.
- a resin composition used as a solid lubricant coating composition for the purpose of sliding as a lubricant, polytetrafluoroethylene, ethylene / tetrafluoroethylene copolymer, polychlorotrifluoroethylene, polyfluoride, Fluorine resin such as vinyl fluoride, polyvinylidene fluoride, hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, fluorinated ethylene polypropylene copolymer, fluorine monomer such as tetrafluoroethylene, silicone oil, molybdenum disulfide, disulfide It is preferable to blend tungsten, boron nitride, graphite or the like. For the reasons described above, it is preferable not to add an ultraviolet absorber or a light stabilizer.
- the compounding amount of the resin component in the resin composition used as a coating is preferably 20 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the resin composition, and the solvent compounding amount is 100 parts by weight of the resin composition. On the other hand, it is preferably 20 parts by weight or more and 80 parts by weight or less. If the resin component is less than 20 parts by weight, the adhesion is lowered, and this causes cracks in the coating film. If the resin component is more than 80 parts by weight, the concealability and the labyrinth effect are lowered.
- the amount of the solvent is less than 20 parts by weight, the dispersibility of the flaky stainless pigment in the resin composition becomes insufficient, and when the amount is more than 80 parts by weight, the environment is caused by a solvent that evaporates when the resin composition is dried and cured. Contamination is a problem.
- a powder coating material it is as above-mentioned that a solvent is not contained in a resin composition.
- the resin composition of the present invention includes not only a final kneaded product for paint use, but also a master batch containing the flaky stainless steel pigment of the present invention, which is used for the purpose of blending into a base material resin, Intermediate work in progress such as colored pellets obtained by kneading batch and base material resin for coloring purpose into pellets is also included.
- the present invention also relates to a coated product having a coating film formed from the resin composition containing the flaky stainless pigment.
- the resin composition can inherit the effect of the flaky stainless steel pigment of the present invention. Therefore, a coated product having a coating film formed of the resin composition on a substrate is also used.
- the effect of the flaky stainless pigment of the present invention can be inherited. That is, since the coated material of the present invention has a coating film exhibiting high corrosion resistance on its surface, for example, the deterioration of the substrate is sufficiently suppressed even in a severe environment.
- the coating film in the coated product of the present invention are shown in the following (1) to (4).
- the number average of the inclination angle of the flaky stainless pigment located on the most surface side of the coating film with respect to the surface of the substrate is 5 degrees or less, more preferably 3 degrees or less.
- flaky stainless pigments having a number average of 2 or more exist in the normal direction (thickness direction) of the coating film.
- the film thickness of the coating film is 10 to 500 times the average thickness t of the flaky stainless pigment.
- the porosity is 5% or less.
- the film thickness of the coating film is less than 10 times the average thickness t, since the flake-like stainless steel pigment is not suitably laminated in the thickness direction, the labyrinth effect of the coating film is reduced and the corrosion resistance is reduced. There is a case.
- the film thickness of a coating film exceeds 500 times the average thickness t, since the clearance gap between flake-like stainless steel pigments becomes large, a labyrinth effect may become small and corrosion resistance may fall.
- bubbles may be easily generated in the coating film due to the volatilization of the solvent, or the workability of coating may be deteriorated. Further, since the solvent tends to remain in the coating film, the performance of the coating film may be deteriorated.
- the material thereof is not particularly limited, such as metal, plastic, ceramic products, glass, wood, concrete, cloth, paper and the like.
- the shape is also, for example, columns, bridges, guard rails, fastening parts (bolts, nuts, rivets, etc.), sliding parts (seat belt parts, machine tool parts, etc.), mounts (photovoltaic panel mounts, etc.), tanks,
- a three-dimensional structure such as a vehicle or an outdoor storage box (such as a cubicle), a planar object such as a pre-coated metal, a plate material, a wall material, a roof material, or a sheet can be used, and is not particularly limited.
- substrate can employ
- the coating material of this invention may have another layer, and it is preferable to have a base-treatment layer especially between the said coating film and a base
- the base treatment layer By having the base treatment layer, the adhesion between the substrate and the coating film can be enhanced, and the effects of the present invention can be more suitably exhibited.
- the base treatment layer examples include a hot-dip plating layer, a thermal spray plating layer, an electrolytic plating layer, an electroless plating layer, a vapor deposition layer, a chemical conversion treatment layer, an electrodeposition coating layer, an organic primer layer, and a zinc rich primer layer.
- a hot dip galvanized layer, an electrolytic galvanized layer, a chemical conversion treatment layer with an inorganic salt, and an organic primer layer are preferable.
- Particularly preferable base treatment layers include hot dip galvanization, electrogalvanization, chemical conversion treatment with inorganic salts, organic primers, and the like.
- a coating film having high corrosion resistance can be formed.
- Such a coating film can sufficiently suppress deterioration even under severe conditions.
- the coating film can exhibit high wear resistance and high slidability, even if the base material is a sliding part that is exposed to a highly corrosive environment, the effect is sufficiently exhibited. can do.
- Example 1 A flaky stainless steel pigment was produced according to the following production method.
- the slurry in the ball mill was washed out with mineral spirits and recovered as a slurry, and the recovered slurry was sieved using a sieve having openings shown in Table 1 (sieving step).
- the inner diameter of the sieve was 495 mm and the depth was 50 mm.
- the cake that passed through the sieving was kneaded with a kneader mixer to obtain a paste containing a flaky stainless steel pigment (see Table 1).
- Example 2 to 6 and Comparative Example 1 were the same as Example 1 except that the stainless steel powder, steel balls, grinding and deformation treatment times used, and sieve openings used were changed as shown in Table 1. By the method, a paste containing a flaky stainless pigment was obtained.
- the paste obtained in a 100 ml beaker was collected and dispersed by adding about 5 ml of mineral spirits. Next, this was left to stand in a dryer maintained at 105 ° C. ⁇ 2 ° C. for 3 hours to be dried, and then allowed to cool to room temperature in a desiccator. And the weight of the residue in a beaker was measured and solid content (weight%) was computed by following formula (1). The results are shown in Table 2.
- the prepared paint was applied to a transparent PET film having a thickness of 12 ⁇ m using a 1 mil (25 ⁇ m) doctor blade.
- coating was 15 micrometers.
- V-570 UV-visible near-infrared spectrophotometer
- Passing rate of sieve having an opening of 38 ⁇ m The passing rate (% by weight) of a sieve having an opening of 38 ⁇ m was calculated for the obtained paste by a wet sieving method. Specifically, first, 30 g of each paste obtained in Examples 1 to 6 and Comparative Example 1 was transferred into a 100 ml beaker, and 100 ml of mineral spirit was gradually added thereto to prepare a sample in which the paste was dispersed. did. Next, a sieve having an aperture of 38 ⁇ m (inner diameter: 200 mm, depth: 50 mm) was fixed on the collection container (container 1), and the prepared sample was poured onto the sieve mesh. Further, the sample remaining in the beaker was washed with a small amount of mineral spirit, and this washing solution was also poured onto the mesh of the sieve.
- mineral spirit was added into a collection container (container 2) having a size capable of accommodating the sieve, and up to about half of the depth was filled with mineral spirit.
- the said sieve was put in this container 2, and the mesh of the said sieve was immersed in the liquid level of the mineral spirit.
- the sample remaining on the mesh was immersed in the mineral spirit in the container 2.
- sieving was performed by making the mesh of the screen slant with respect to the liquid level, moving up and down from the liquid level, and moving the sieve left and right.
- the mineral spirit in the container 2 was taken out, a new mineral spirit was added into the container 2, and the above sieving operation was performed again.
- the sieve with the sample remaining on the mesh was placed in a dryer maintained at 105 ⁇ 2 ° C. and dried, and then allowed to cool. Finally, the dried flaky stainless pigment on the mesh was collected, and the passage rate (% by weight) of a sieve having a mesh size of 38 ⁇ m in the flaky stainless pigment in the paste was calculated according to the following formula (4).
- the weight of the flaky stainless pigment before sieving is the same as that of the flaky stainless pigment obtained by placing 10 g of the paste in a dryer maintained at 105 ⁇ 2 ° C., drying, and then allowing to cool. Of weight.
- the results are shown in Table 2.
- Example 5 Using each paste of Example 5 and Comparative Example 1, a coating film was formed by the following method, and its corrosion resistance was confirmed.
- a resin composition an epoxy resin and a paste were mixed to prepare a paint so that the paste content was 80 parts by weight with respect to 100 parts by weight of the resin solid content (including the curing agent).
- the paint was diluted with a solvent until the viscosity of the paint became an optimum viscosity for spray coating.
- the solvent used was a ketone solvent, and the final addition amount of the solvent was about 20 to 50 parts by weight with respect to 100 parts by weight of the paint.
- this was baked and dried at 200 ° C. for 20 minutes on a zinc phosphate-treated steel plate (ponderite treatment # 144) to form a coating film having a thickness of 15 ⁇ 5 ⁇ m on the steel plate.
- FIGS. 1 and FIG. 2 are diagrams showing a state after 250 hours of cracking in a coating film formed from a paint containing the paste of Example 5.
- FIG. 3 and 4 are diagrams showing a state after 250 hours of cracks in a coating film formed from a paint containing the paste of Comparative Example 1.
- FIG. 1 and FIG. 2 are diagrams showing a state after 250 hours of cracking in a coating film formed from a paint containing the paste of Example 5.
- FIG. 3 and 4 are diagrams showing a state after 250 hours of cracks in a coating film formed from a paint containing the paste of Comparative Example 1.
- ⁇ Corrosion resistance 2> Using each paste of Examples 1 to 6 and Comparative Example 1, a coating film was prepared in the same manner as in ⁇ Corrosion Resistance 1>, and an X-shaped crack was formed in the coating film. Then, a salt spray test (based on JIS Z 2371: 2000) was performed for 3000 hours on this coating film, and the change was confirmed.
- the coating film formed from the paint containing the pastes of Examples 1 to 6 did not rust even after the 3000 hour salt spray test, or generated in a dot-like manner even when it occurred. It was only to do. In particular, the occurrence of rust was not observed in the paints blended with the pastes of Examples 1, 5, and 6 in which the average aspect ratio of the flaky stainless pigment was in the range of 10 to 100. On the other hand, the paint containing the paste of Comparative Example 1 was rusted on the entire surface. From this, it was confirmed that the coating film formed with the coating material which mix
- a paste and a resin solution (trade name: “Nippe Acrylic Auto Clear Super”, manufactured by Nippon Paint Co., Ltd.) were kneaded so that the solid content was 6 parts by weight to prepare 30 g of paint.
- the solid content corresponds to the amount of the flaky stainless pigment contained in the paste.
- this paint was applied on a glass plate using a 9 Mils doctor blade applicator, and naturally dried to form a coating film on the glass plate.
- the formed coating film had a thickness of 25 ⁇ m.
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Abstract
Description
本発明のフレーク状ステンレス顔料は、体積累積粒度分布の90%径(D90)が55μm以下であり、目開き38μmの篩いの通過率が99重量%以上である。
通過率(重量%)={(S1-S2)/S1}×100・・・(1)
すなわち、本発明のフレーク状ステンレス顔料は、フレーク形状を有する粒子の集合体であり、その集合体のうちの90体積%以上の粒子が55μm以下の体積平均粒子径を有し、その集合体のうちの99重量%以上が目開き38μmの篩いを通過するものということができる。
上述の本発明のフレーク状ステンレス顔料は、以下の方法により製造することができる。
本発明は、上記フレーク状ステンレス顔料を配合してなる樹脂組成物にもかかわる。該樹脂組成物は、フレーク状ステンレス顔料の他に、樹脂成分と溶剤とを含むことができる。このような本発明の樹脂組成物は、上記フレーク状ステンレス顔料が配合されることにより、従来よりも高い耐食性を有する塗膜を形成することができる。樹脂組成物は、具体的には、塗料、接着剤、ライニング剤、プラスチック、FRPなどとして使用することができる。
本発明は、上記フレーク状ステンレス顔料を配合した上記樹脂組成物により形成された塗膜を有する塗布物にもかかわる。上記樹脂組成物は、上述のように、本発明のフレーク状ステンレス顔料の効果を引き継ぐことができるものであり、したがって、この樹脂組成物により形成された塗膜を基体上に有する塗布物もまた、本発明のフレーク状ステンレス顔料の効果を引き継ぐことができる。すなわち、本発明の塗布物は、高い耐食性を発揮する塗膜をその表面に有するため、たとえば、厳しい環境下においても十分に基体の劣化が抑制されることになる。
(1)塗膜の任意の断面において、塗膜の最も表面側に位置するフレーク状ステンレス顔料の基体の表面に対する傾斜角度の個数平均が、5度以下、より好ましくは3度以下である。
(2)塗膜の任意の断面の95%以上の領域において、塗膜の法線方向(厚み方向)に個数平均2個以上のフレーク状ステンレス顔料が存在する。
(3)塗膜の膜厚がフレーク状ステンレス顔料の平均厚みtの10~500倍である。
(4)塗膜の任意の断面において、空隙率が5%以下である。
以下の製造方法に従って、フレーク状ステンレス顔料を製造した。
実施例2~6および比較例1においては、用いるステンレス粉末、スチールボール、粉砕および変形処理時間、ならびに用いた篩いの目開きを表1に示すように変更した以外は、実施例1と同様の方法により、フレーク状ステンレス顔料を含むペーストを得た。
実施例1~5および比較例1で得られた各ペーストについて、ペーストに含まれる固形分量(重量%)を確認した。なお、この固形分量(重量%)は、ペースト中のフレーク状ステンレス顔料の重量(%)に相当するものである。また、ペースト中のフレーク状ステンレス顔料のD50およびD90、平均厚み、アスペクト比、ならびに目開き38μmの篩いの通過率について確認した。
得られたペーストについて、次の方法により、固形分量(重量%)を算出した。
(式(1)中、W1は乾燥前のペーストの重量を示し、W2は乾燥および放冷後の残渣の重量を示す。)
2.D50およびD90
得られたペーストについて、次の方法により、ペーストに含まれるフレーク状ステンレス顔料のD50およびD90を算出した。
得られた実施例1のペーストについて、以下の手順(i)~(vi)に従がって、ペーストに含まれるフレーク状ステンレス顔料の平均厚みを求めた。その結果を表2に「厚み」として示す。
S=S0×0.5/W・・・(2)。
t=10000/S×ρ・・・(3)
なお、上記式(3)においてρはステンレスの密度であってその値は7.8となる。
実施例1~6および比較例1で得られた各ペーストにおいて、ペーストに含まれるフレーク状ステンレス顔料のD50(μm)をその厚みt(μm)で除した値(D50/t)をアスペクト比とした。算出した結果を表2に示す。
得られたペーストについて、湿式篩い法により、目開き38μmの篩いの通過率(重量%)を算出した。具体的には、まず、実施例1~6および比較例1で得られた各ペースト30gを100mlのビーカー内に移し、これにミネラルスピリット100mlを徐々に加えて、ペーストを分散させた試料を調製した。次に、目開き38μmの篩い(内径200mm、深さ50mm)を回収容器(容器1)の上に固定し、この篩いの網目上に調製した試料を流し込んだ。また、ビーカー内に残った試料を少量のミネラルスピリットで洗浄し、この洗浄液も篩いの網目上に流し込んだ。
(式(4)中、S1は湿式篩いによる篩い分けを行う前のフレーク状ステンレス顔料の重量を示し、S2は該篩い分けを行った後に篩いに残留したフレーク状ステンレス顔料の重量を示す)。
実施例5および比較例1の各ペーストを用いて、次の方法により塗膜を形成し、その耐食性を確認した。
実施例1~6および比較例1の各ペーストを用いて、<耐食性1>と同様の方法により塗膜を作製し、該塗膜にX形状の亀裂を形成した。そして、この塗膜に対して塩水噴霧試験(JIS Z 2371:2000に基づく)を3000時間行い、その変化を確認した。
実施例1~6および比較例1の各ペーストを用いて、次の方法により塗膜を形成し、その表面粗さを確認した。
Claims (7)
- 体積累積粒度分布の90%径が55μm以下であり、
目開き38μmの篩いの通過率が99重量%以上である、フレーク状ステンレス顔料。 - 平均厚みtが0.03μm以上0.5μm以下であり、
平均粒子径D50が3μm以上30μm以下である、請求項1に記載のフレーク状ステンレス顔料。 - 平均厚みtに対する平均粒子径D50の比である平均アスペクト比(D50/t)が5以上100以下である、請求項1または2に記載のフレーク状ステンレス顔料。
- 平均厚みtに対する平均粒子径D50の比である平均アスペクト比(D50/t)が10以上100以下である、請求項1または2に記載のフレーク状ステンレス顔料。
- 前記90%径が40μm以下である、請求項1から4のいずれか1項に記載のフレーク状ステンレス顔料。
- 請求項1から5のいずれか1項に記載のフレーク状ステンレス顔料を配合してなる、樹脂組成物。
- 請求項6に記載の樹脂組成物により形成された塗膜を有する塗布物。
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JP2015508533A JP6690940B2 (ja) | 2013-03-29 | 2014-03-25 | フレーク状ステンレス顔料、それを配合してなる樹脂組成物、および該樹脂組成物により形成された塗膜を有する塗布物 |
CN201480017957.5A CN105102156A (zh) | 2013-03-29 | 2014-03-25 | 片状不锈钢颜料、配合该颜料而成的树脂组合物、以及具有由该树脂组合物形成的涂膜的涂布物 |
US14/780,589 US20160040015A1 (en) | 2013-03-29 | 2014-03-25 | Flaky stainless-steel pigment, resin composition formulated with the same, and coated product provided with coating film formed from resin composition |
EP14774800.8A EP2979779A4 (en) | 2013-03-29 | 2014-03-25 | STAINLESS STEEL PIGMENT PIGMENT, RESIN COMPOSITION CONTAINING THE SAME, AND COATED PRODUCT HAVING A COATING FILM FORMED FROM THE RESIN COMPOSITION |
KR1020157030888A KR20150136117A (ko) | 2013-03-29 | 2014-03-25 | 플레이크상 스테인리스 안료, 그것을 배합하여 이루어지는 수지 조성물, 및 그 수지 조성물에 의해 형성된 도막을 갖는 도포물 |
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US (1) | US20160040015A1 (ja) |
EP (1) | EP2979779A4 (ja) |
JP (1) | JP6690940B2 (ja) |
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Cited By (2)
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JP2021161152A (ja) * | 2020-03-30 | 2021-10-11 | 大日本塗料株式会社 | 塗料組成物 |
WO2022196441A1 (ja) * | 2021-03-15 | 2022-09-22 | 東洋アルミニウム株式会社 | 塗料組成物 |
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KR102434646B1 (ko) * | 2017-09-18 | 2022-08-19 | 대우조선해양 주식회사 | Lngc 화물창용 워시 프라이머 코팅제 |
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US20160040015A1 (en) | 2016-02-11 |
JP6690940B2 (ja) | 2020-04-28 |
CN105102156A (zh) | 2015-11-25 |
JPWO2014157177A1 (ja) | 2017-02-16 |
KR20150136117A (ko) | 2015-12-04 |
EP2979779A4 (en) | 2016-11-30 |
EP2979779A1 (en) | 2016-02-03 |
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