WO1996038506A1 - Nouveau pigment metallique enduit de resine et matiere d'enduction metallique contenant le pigment - Google Patents

Nouveau pigment metallique enduit de resine et matiere d'enduction metallique contenant le pigment Download PDF

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Publication number
WO1996038506A1
WO1996038506A1 PCT/JP1996/001450 JP9601450W WO9638506A1 WO 1996038506 A1 WO1996038506 A1 WO 1996038506A1 JP 9601450 W JP9601450 W JP 9601450W WO 9638506 A1 WO9638506 A1 WO 9638506A1
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Prior art keywords
resin
polymerizable double
metal pigment
monomer
coated
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PCT/JP1996/001450
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English (en)
Japanese (ja)
Inventor
Shunsuke Takase
Yasunobu Imasato
Shinji Hayami
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Asahi Kasei Metals Limited
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Application filed by Asahi Kasei Metals Limited filed Critical Asahi Kasei Metals Limited
Priority to JP53636896A priority Critical patent/JP3903325B2/ja
Priority to KR1019970707377A priority patent/KR100327274B1/ko
Publication of WO1996038506A1 publication Critical patent/WO1996038506A1/fr

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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
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds

Definitions

  • the present invention relates to a novel resin-coated metal pigment, and more particularly, to a metallic pigment which, when used as a paint pigment, has excellent chemical resistance, gloss, and weather resistance, and has storage stability in a water-based paint.
  • the present invention relates to a resin-coated metal pigment having excellent resistance.
  • the present invention also relates to a novel metallic paint comprising the above resin-coated metal pigment, paint resin, and diluent. More specifically, the present invention provides a metallic paint film having excellent chemical resistance, gloss, weather resistance, etc. And a coating material having extremely excellent storage stability. Background art
  • metal pigments have been used for metallic paints, printing inks, kneading plastics, and the like for the purpose of obtaining a cosmetic effect emphasizing metallic feeling.
  • coating films and resin molded products obtained using conventional metal pigments have the disadvantages of insufficient chemical resistance such as acid resistance and alkali resistance and water resistance, and poor weather resistance. I have.
  • the use of the pigment is limited due to the discoloration of the coated surface and the decrease in gloss over time, and the provision of a metal pigment that is excellent in chemical resistance and weather resistance and also has excellent storage stability. Is strongly desired.
  • the aluminum paste is dispersed in an organic solvent, firstly, radically polymerizable unsaturated carboxylic acid or the like is adsorbed, and then, a polymer formed from a monomer having three or more radically polymerizable double bonds is formed.
  • a method of surface coating has been proposed. JP-A-11-49764). In this method, it is necessary to add a considerable amount of a coating resin monomer in order to achieve sufficient alkali resistance, and at the same time, the gloss is lowered and the metallic feeling is significantly different. I have.
  • Japanese Patent Application Laid-Open No. Hei 7-31885 describes a metal pigment composed of a siloxane coating and a three-dimensionally crosslinked synthetic resin coating covalently bonded to the siloxane coating.
  • this metal pigment even with this metal pigment, the chemical resistance was not sufficient.
  • the present inventors have conducted intensive studies to solve the problems of the conventional metal pigments, and as a result, have found that a radical polymerizable unsaturated carboxylic acid, a phosphoric acid or a phosphonic acid having a radical polymerizable double bond, Monomers or diesters and / or coupling agents with radically polymerizable double bonds are added at the same time as the polymerization initiator with a monomer having three or more radically polymerizable double bonds in one molecule By adding a monomer having three or more radically polymerizable double bonds or a polymerization initiator, and coating the surface of the metal pigment with a resin.
  • the present inventors have found the fact that the object can be achieved, and have reached the present invention.
  • the present invention includes the embodiments described below.
  • (B) a monomer having three or more radically polymerizable double bonds and (C) a polymerization initiator (A) is added first to treat the metal pigment, and then (B) and (B) C) a resin-coated metal pigment in which a polymer layer is formed on the surface by gradually adding at least one of (C) and (2) a monomer having at least three radically polymerizable double bonds of (B).
  • a monomer having three radical polymerizable double bonds and a monomer having four or more radical polymerizable double bonds, and a monomer having four or more radical polymerizable double bonds The resin-coated metal pigment according to the first embodiment, in which the amount is 10% to 60% by weight relative to the total amount of the monomers having three or more radical polymerizable double bonds,
  • the resin-coated metal pigment according to the present invention exhibits excellent chemical resistance, which has never been seen before, while maintaining the luster of the metal pigment as a raw material and having excellent storage stability.
  • the metal pigments used in the present invention include aluminum, copper, zinc, iron, nickel, and / or alloys thereof, and a preferred example is aluminum. Its shape is flakes, spheres, needles, and other granular forms.
  • the preferred particle size of the metal pigment depends on the application. For paints and printings, the average particle size is preferably about 1 to 100 ⁇ , and for kneading plastics, it is about 1 to 200 ⁇ , but it is particularly limited to these ranges. is not.
  • radical polymerizable unsaturated carboxylic acid in the present invention examples include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and the like, and one or more of them are used in combination.
  • the amount used depends on the type and properties of the metal pigment, especially on its surface area, but is generally between 0.01 and 10 parts by weight, more preferably 0.1 part by weight, based on the metal pigment. Parts to 5.0 parts by weight.
  • the effects of the invention that is, the chemical resistance such as alkali resistance and acid resistance are not sufficiently exhibited, and the monomer having three or more polymerizable double bonds is a metal pigment.
  • the polymer system may gel, making it impossible to stir. Further, even if the amount exceeds 10 parts by weight, the effect such as chemical resistance does not increase.
  • phosphoric acid or phosphonic acid ester having a radical polymerizable double bond in the present invention a mono- or di-ester of phosphoric acid or phosphonic acid is used, and specific examples thereof include 2-methacryloyxixyl.
  • Phosphate di-2-methacryloyloxyshethyl phosphate, tree 2-methacryloyloxyshethyl phosphate, 2-acryloyloxyshethyl phosphate, di-2-acryloyloxyshethyl phosphate 1-triacryl-2-oxacryloyl phosphate, diphenyl 1-2-acryloyloxyshethyl phosphate, dibutyl 1-methyl-2-hexyl chloride , Dioctyl 2- 2-acrylic acid kissil phosphate, 2-methacryloyloxy propyl phosphate, bis (2-chloro ethyl) vinyl And diaryldibutylphosphonosuccinate. One or a mixture of two or more thereof is used.
  • a preferred example is a phosphoric acid monoester. This is because the phosphate group has two OH groups, which are more firmly fixed to the aluminum particle surface. It is presumed to be caused by More preferred monoesters of phosphoric acid include monoesters having a methacryloyloxy group and an acryloyloxy group. Examples thereof include 2-methacryloyl mouth xicetyl phosphate and 2-acroiroxicetyl phosphite.
  • the amount used depends on the type and properties of the metal pigment, especially on its surface area, but is generally between 0.01 and 30 parts by weight per 100 parts by weight of the metal pigment. . More preferably, the amount is 0.1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the effect of the present invention, that is, the chemical resistance such as alkali resistance is not sufficiently exhibited, and even if the amount exceeds 20 parts by weight, the effect cannot be expected to increase.
  • Examples of the coupling agent having a radical polymerizable double bond in the present invention include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
  • silane coupling agent examples include methacryloxypropyl trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl tris (; 5-methoxetoxy) silane, and the like.
  • titanate-based coupling agents examples include isopropyl isostearyl diacryl titanate.
  • aluminum-based coupling agents examples include acetoalkoxyaluminum diisopropylate, zircoaluminate and the like.
  • the amount of the coupling agent having a radically polymerizable double bond to be used varies depending on the type and properties of the metal pigment, particularly the surface area, but is generally from 0.01 to 20 parts by weight to 100 parts by weight of the metal pigment. Between the departments. More preferably, it is between 0.1 parts by weight and 10 parts by weight. If the amount is less than 0.01 part by weight, the effect of the invention, that is, the chemical resistance such as alkali resistance is not sufficiently exhibited, and even if the amount exceeds 20 parts by weight, the effect does not increase.
  • treatment in an inert solvent is desirable to prevent the reaction between the metal pigment itself and water.
  • the radically polymerizable unsaturated ruponic acid and / or mono- or diester phosphonic acid having a radically polymerizable double bond are generally used in inert solvents. It has a high solubility, so that uniform dispersion can be relatively easily achieved, and it is preferable because storage stability in a water-based paint is hardly reduced.
  • Examples of the monomer (B) having three or more radically polymerizable double bonds in the present invention include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethanetetraacrylate, and tetramethylolprono.
  • monomers having four or more radically polymerizable double bonds include di-trimethylolpropanetetraacrylate and pentaerythritoltetraacrylate.
  • Preferable examples include acrylate and dipentaerythritol hexaacrylate.
  • the amount of the monomer (B) having three or more radical polymerizable double bonds in the present invention is between 2 parts by weight and 50 parts by weight based on 100 parts by weight of the metal component of the metal pigment. More preferably, the amount is 3 parts by weight to 40 parts by weight. If the amount is less than 2 parts by weight, the effect of the invention, that is, the chemical resistance is reduced, and if it exceeds 50 parts by weight, the effect cannot be expected to increase, and the basic properties as a metallic paint such as glitter and gloss. And it is difficult to put to practical use.
  • the monomer having three or more radical polymerizable double bonds (B) includes a monomer having three radical polymerizable double bonds and a monomer having four or more radical polymerizable double bonds.
  • the ratio of the monomer having four or more radical polymerizable double bonds to the total amount of the monomer (B) having three or more radical polymerizable double bonds is 10 to 60 by weight. %, And more preferably 20% to 50%.
  • a monomer having four or more radically polymerizable double bonds is used in combination, it exhibits excellent performance in chemical resistance such as alkali resistance and acid resistance.
  • the molecular weight per functional group of the monomer having four or more radically polymerizable double bonds is 30 or more and 200 or less, since this effect is further increased. The reason for this is not clear, but it is thought to be due to highly three-dimensional crosslinking.
  • a monomer having one or two polymerizable double bonds in one molecule may be used as long as the effects of the present invention are not impaired. Examples include acrylates such as styrene, ⁇ -methylstyrene and methyl acrylate, methacrylates such as methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, and ethylene glycol diethylene glycol. Methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol diacrylate, 1, 6
  • the amount used is between 0.1 and 10 parts by weight per 100 parts by weight of metal pigment. If the amount used exceeds 10 parts by weight, the effects of the invention, that is, when a metallic coating film is formed using the obtained resin-coated metal pigment, the properties are reduced, and the heat stability of the metal pigment is also reduced. It is difficult to put into practical use.
  • the resin-coated metal pigment of the present invention is obtained by first dispersing an untreated metal pigment in an organic solvent, then heating and stirring ( ⁇ ) to form a radical polymerizable unsaturated carboxylic acid and a radical polymerizable double bond.
  • the surface of the metal pigment is treated by adding at least one selected from phosphoric acid or phosphonic acid mono- or diesters and a coupling agent having a radical polymerizable double bond.
  • a monomer having three or more radically polymerizable double bonds and (C) at least one of the polymerization initiators are gradually and continuously polymerized to form a resin layer on the surface of the metal pigment. It is obtained by doing.
  • the untreated metal pigment is dispersed in an organic solvent, then the mixture is heated, and the process of adding ( ⁇ ) with stirring is not particularly limited, but the weight concentration of the metal pigment in the organic solvent is 1 to 30%. It is desirable to perform in. If it is less than 1%, a uniform dispersion can be obtained, but it is not preferable because the amount of the solvent for handling becomes excessive and labor for removing it later is required. If it exceeds 30%, the dispersion of the metal pigment tends to be uneven, which is not preferable.
  • This treatment is preferably performed at a temperature of 40 ° C. to 150 ° C. for about 5 minutes to 10 hours. If the temperature is lower than 40 ° C, it takes time to raise the temperature to the polymerization temperature of (B). If the temperature is higher than 150 ° C, sufficient consideration must be given to the ignition of the vapor of the organic solvent, which is not preferable. Also, the processing time
  • a resin layer is formed on the surface of the metal pigment by gradually and continuously adding (B) a monomer having three or more radically polymerizable double bonds and (C) a polymerization initiator while gradually adding the monomer. .
  • a highly three-dimensionally crosslinked resin layer is formed on the metal surface by gradually and continuously adding at least one of (B) and (C) and polymerizing.
  • the polymerization temperature is not particularly limited, it is preferably from 60 ° C. to 150 ° C.
  • an atmosphere of an inert gas such as nitrogen or helium.
  • dilute (B) and (0) in an organic solvent or the like it is preferable to dilute (B) and (0) in an organic solvent or the like and feed it at a constant rate using a quantitative pump or the like.
  • the polymerization time is not particularly limited, but is about 2 hours to 10 hours, where the polymerization time is the time when both (B) and (C) are simultaneously present in the reaction system.
  • the feed time is preferably 90% or less of the polymerization time in order to shorten the time, and is preferably 70% or less in order to further shorten the reaction time and increase the productivity.
  • the specific surface area of the resin-coated metal pigment of the present invention is slightly increased compared to the metal pigment before the treatment, it is significantly smaller than the increase of the resin-coated metal pigment obtained by the conventional method, and the oil absorption is small. It is characteristic. This is considered to be because the resin layer formed on the metal surface was uniform and highly three-dimensionally cross-linked, and the chemical resistance, gloss, and weather resistance of the coating film using the resin-coated metal pigment of the present invention were considered. It shows excellent characteristics.
  • the organic solvent used in the polymerization in the present invention includes aliphatic hydrocarbons such as hexane, heptane, octane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, and solvent naphtha; Ethers such as tetrahydrofuran and getyl ether; and esters such as ethyl acetate and butyl acetate.
  • the polymerization initiator used in the present invention is generally known as a radical generator, and includes benzoyl peroxide, lauroyl peroxide, bis- (4- t-butylcyclohexyl) peroxides such as peroxydicarbonate and azo compounds such as 2,2'-azobis-isobutyronitrile and 2,2'-azobis_2,4-dimethylvaleronitrile.
  • the amount used is not particularly limited in the present invention, but is about 0.1 to 50 parts by weight based on 100 parts by weight of the monomer having three or more radical polymerizable double bonds.
  • the resin-coated metal pigment of the present invention exhibits extremely excellent alkali resistance when used in a coating. This is presumably because the surface of the metal pigment is covered with a highly three-dimensionally crosslinked resin layer, and it is difficult for the metal to reach the surface of the metal pigment even if the metal enters the coating.
  • the alkali resistance shown in the examples indicates a value of 0.01 to 2.0.
  • the metallic paint of the present invention can be used as a solvent-based paint, a water-based paint, etc., and mainly comprises three basic components, namely, (a) A resin for paint, (b) a resin-coated metal pigment, and (c) a diluent.
  • any of the coating resins conventionally used in metallic coatings can be used.
  • the resin include acrylic resin, alkyd resin, oil-free alkyd resin, vinyl chloride resin, urethane resin, melamine resin, unsaturated polyester resin, urea resin, cellulose resin, epoxy resin, fluororesin, etc. These may be used alone or as a mixture.
  • the amount of the resin-coated metal pigment used in the solvent-type paint is preferably from 0.1 to 100 parts by weight, more preferably from 1 to 50 parts by weight, based on 100 parts by weight of the resin for the paint. Preferably, it is used. If the resin-coated metal pigment is less than 0.1 part by weight, the metallic luster required for the metallic paint is insufficient, and if it exceeds 100 parts by weight, the amount of the metal pigment in the paint is reduced. It is not practical because the paint workability is deteriorated and the physical properties of the coating film are inferior.
  • Diluents for solvent-based paints include aromatic compounds such as toluene and xylene, aliphatic compounds such as hexane, heptane and octane, alcohols such as ethanol and butanol, ethyl acetate and butyl acetate. Examples include ketones such as estyls and methylethyl ketone, chlorine compounds such as trichloroethylene, and cellosolves such as ethylene glycol monoethyl ether. These diluents may be used alone or in combination of two or more. Used mixed. The composition is determined in consideration of solubility in coating resins, coating film forming properties, coating workability, and the like.
  • Additives commonly used in the paint industry such as pigments, dyes, wetting agents, dispersants, anti-segregation agents, leveling agents, slip agents, anti-skinning agents, anti-gelling agents, and defoamers Can be added.
  • the pigment of the present invention can also be used for water-based paints by using the resin for water-based paints.
  • the resin for water-based paints is a water-soluble resin or a water-dispersible resin. Or it may be a mixture.
  • the types vary widely depending on the purpose and application, and are not particularly limited, but generally include resins for aqueous coatings such as acrylic, acryl-melamine, polyester, and polyurethane. Of these, acrylic-melamine is most commonly used.
  • the amount of the resin-coated metal pigment used in the water-based paint is 0.1 to 100 parts by weight based on 100 parts by weight of the resin for the paint. In particular, it is preferable to use 1 part by weight to 50 parts by weight. If the amount of the resin-coated metal pigment is less than 0.1 part by weight, the metallic luster required for the metallic paint is insufficient, and if it exceeds 100 parts by weight, the metal pigment in the paint is Is too large, coating workability is deteriorated, and physical properties of the coating film are inferior.
  • additives examples include, for example, dispersants, thickeners, anti-sagging agents, fungicides, ultraviolet absorbers, film forming aids, surfactants, other organic solvents, water, and the like. It can be added as long as it can be used normally and does not impair the effects of the present invention.
  • the metallic paint in the present invention can be used as a general-purpose paint in addition to the solvent-based paint and the water-based paint, and examples thereof include a powder paint.
  • the lower half of the coated plate is immersed in a beaker containing a 2.5 N—NaOH aqueous solution and left at 20 ° C. for 24 hours. After the coated plate after the test was washed with water and dried, the immersed part and the unimmersed part were measured in color according to the condition d (8-d method) of JIS-Z-8722 (19982), ) Calculate the color difference E by 6.3.2.
  • the unreacted amount of trimethylolpropane trimethacrylate in the filtrate sampled at this time was analyzed by gas chromatography, and it was found that 99.5% or more of the added amount had reacted.
  • the slurry was filtered to obtain a resin-coated aluminum paste.
  • the nonvolatile content of this paste (according to JIS—K—910) was 65.0% by weight.
  • the resin coating amount based on 100 parts by weight of the aluminum metal was 8.3 parts by weight.
  • trimethylolpropane trimethacrylate and ditrimethylolpropane tetraacrylate used in Example 1
  • trimethylolpropane trimethacrylate A resin-coated aluminum paste was produced in the same manner as in Example 1 except that 3.5 g of acrylate was used.
  • the nonvolatile content (according to JIS-K-5910) of this paste was 62.0% by weight.
  • the resin coating amount with respect to 100 parts by weight of aluminum metal was 11.6 parts by weight. From these results, 98% or more of acrylic acid, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and 2,2'-azobis-isobutyronitrile account for at least 98% of the aluminum surface. It is presumed to have adhered to the top.
  • Resin-coated aluminum paste was prepared in the same manner as in Example 1 except that trimethylolpropane trimethacrylate was changed to 1.0 g and Geetrimethylolpropanetetraaphthalate was changed to 2.5 g. It was created.
  • the nonvolatile content (according to JIS-K-910) of this paste was 60.0%.
  • Example 7 trimethylolpropane trimethacrylate 2.5 g, di-trimethylolpropane tetraacrylate 1.0 g, 2,2'-azobis-1,2,4-dimethylvaleronitrile 0.
  • Resin coating was performed in the same manner as in Example 1 except that a solution prepared by dissolving 35 g in 19 g of mineral spirit was added by a metering pump at a rate of about 0.32 gZmin over 1.2 hours.
  • Aluminum paste was made.
  • the nonvolatile content (according to JIS-K-5910) of this paste was 65.0%.
  • the resin coating amount based on 100 parts by weight of the aluminum metal was 8.3 parts by weight. From these results, 98% or more of vinyltrimethoxysilane, trimethylolpropane trimethacrylate, ditrimethylolpropane tetratetraacrylate, 2,2′-azobis-1,2,4-dimethylvaleronitrile adhered to the aluminum surface. It is presumed to have been done.
  • a resin-coated aluminum paste was obtained in the same manner as in Example 1 except that acrylic acid was changed to 2-methacryloyl quinethyl acid phosphate (manufactured by Daihachi Chemical, MR-200).
  • the nonvolatile content (according to JIS-K-5910) of this paste was 65.0% by weight. From these results, it was found that 98% or more of 2-methacryloyloxyshetyl acid phosphate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraatalylate, and 2,2′-azobis-2,4-dimethylvalero nitrile had an aluminum surface of at least 98%. It is presumed that it adhered to the top.
  • a resin-coated aluminum paste was produced in the same manner as in Example 1, except that the monomer (B) and the polymerization initiator were added all at once without performing the continuous addition operation using the pump of Example 1.
  • a resin-coated aluminum paste was prepared in the same manner as in Example 2, except that the monomer (B) and the polymerization initiator were added all at once without performing the continuous additional operation using the pump of Example 2.
  • Example 2 In the same manner as in Example 1, 2.5 g of trimethylolpropane trimethacrylate, 1.0 g of ditrimethylolpropanetetraacrylate, and 2,2 ′ azobis-1,2,4-dimethylvaleronitrile 0 3 5 g of mineral sp A resin-coated aluminum base was prepared in the same manner as in Example 1 except that the solution dissolved in 19 g of lit was added by a metering pump at a rate of about 0.76 g / min over 0.5 hours. . The non-volatile content (according to JI SK-59010) of this paste was 60.0%.
  • Example 1 instead of acrylic acid, 0.888 g of vinyltrimethoxysilane, 0.06 g of phosphoric acid, 0.06 g of water and 1.00 g of 2-butanol were used, and trimethylolpropane trimethacrylate was used.
  • trimethylolpropane trimethacrylate 3.5 g instead of D-trimethylolpropane triacrylate, a solution prepared by dissolving trimethylolpropane trimethacrylate in 19 g of mineral spirit was pumped by a metering pump.
  • a resin-coated aluminum base was prepared in the same manner as in Example 1 except that the addition was performed at a rate of 0.78 g / in over 0.5 hours.
  • the nonvolatile content (according to JIS-K-910) of this paste was 60.0%.
  • Comparative Example 4 Same as Comparative Example 4 except that a solution prepared by dissolving trimethylol mouth pantrimethacrylate in 19 g of mineral spirit was added at once without continuous addition by a metering pump. To prepare a resin-coated aluminum paste. The nonvolatile content (according to JIS-K-910) of this paste was 60.0%. Table 2 shows the best performance of Examples 1 to 8 and Comparative Examples 1 to 5.
  • the compounding ratio of the polyfunctional monomer is the ratio of the monomer having four or more radical polymerizable double bonds to the total amount of monomers having three or more radical polymerizable double bonds (the Quantitative ratio).
  • Example 9 Using vinylidene fluoride-type fluororesin as the resin material, paint it by applying the paint shown in Table 5, apply it to an aluminum plate with a bar coater to a film thickness of 30 ⁇ , and further heat it at 240 ° C. The coating was prepared by drying for 5 minutes. A chemical resistance spot test was performed in the same manner as in Example 9. As a result, the coating film using the resin-coated aluminum paste of Example 1 exhibited extremely excellent chemical resistance as in Example 9.
  • Example 6 Using the resin-coated aluminum paste of Example 1 and the resin-coated aluminum paste of Comparative Example 2 to prepare an acrylic paint with the paint formulation shown in Table 6, the film thickness was 30 as in Example 10. Was spray-painted on an ABS resin plate. After drying at room temperature for 24 hours, the gloss of the coating film was measured at 60 degrees. As a result, the coating film using the resin-coated aluminum paste of Example 1 exhibited a high gloss of 65%. The resin of Comparative Example 2 The gloss of the coating film using the coated aluminum paste was 53%. Table 6 Paint formulation (parts by weight)
  • the specific surface areas of the resin-coated aluminum paste of Example 1, the resin-coated aluminum paste of Comparative Example 2, and the non-resin-coated aluminum paste (MG-51: manufactured by Asahi Chemical Industry Co., Ltd.) were measured. Table 8 shows the results.
  • the specific surface area of the resin-coated aluminum paste of Example 1 is 1.9 times that of the non-resin-coated aluminum paste, and that of Comparative Example 2 is 3.0 times that of the resin-coated aluminum paste. It is considered that it is covered with three-dimensionally cross-linked resin.
  • the resin-coated metal pigment of the present invention is coated with a resin having a high crosslinking density, it is excellent in chemical resistance, weather resistance and storage stability. Further, since the specific surface area is small and the amount of oil absorption is small, it is possible to minimize a decrease in gloss due to resin coating.
  • the resin-coated metal pigment of the present invention can be suitably used for metallic paints, printing inks, and kneading plastics.
  • the metallic paint of the present invention has excellent weather resistance, it is required to be used in the fields of automobile bodies, bumpers, side mirrors, and other components, tiles, roofs, walls, and other construction and home appliances that require durability. It can be used preferably.

Abstract

Pigment métallique enduit de résine que l'on prépare en utilisant (A) au moins un composant sélectionné parmi des acides carboxyliques insaturés à polymérisation radicalaire, des mono- et diesters d'acide phosphorique et d'acide phosphonique possèdant chacun une double liaison à polymérisation radicalaire et des agents de couplage ayant chacun une double liaison à polymérisation radicalaire, (B) un monomère à trois ou plusieurs doubles liaisons à polymérisation radicalaire et (C) un déclencheur de polymérisation, selon un procédé qui consiste à: traiter un pigment métallique avec le composant (A), puis à former une couche de résine sur la surface du pigment par addition graduelle d'au moins un des composants (B) et (C) pour induire la polymérisation. Le pigment s'avère excellent en termes de résistance aux intempéries, résistance chimique, brillance et stabilité en stockage dans des matières d'enduction aqueuses et permet la formation d'un finissage métallique. L'invention comporte également une matière d'enduction métalllique contenant le pigment métallique enduit de résine.
PCT/JP1996/001450 1995-05-30 1996-05-29 Nouveau pigment metallique enduit de resine et matiere d'enduction metallique contenant le pigment WO1996038506A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP53636896A JP3903325B2 (ja) 1995-05-30 1996-05-29 樹脂被覆金属顔料の製造方法
KR1019970707377A KR100327274B1 (ko) 1995-05-30 1996-05-29 신규수지피복금속안료및,그안료를함유하는금속도료

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Application Number Priority Date Filing Date Title
JP13182895 1995-05-30
JP7/131828 1995-05-30

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WO1996038506A1 true WO1996038506A1 (fr) 1996-12-05

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JP (1) JP3903325B2 (fr)
KR (1) KR100327274B1 (fr)
CN (1) CN1093155C (fr)
MY (1) MY121596A (fr)
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Cited By (24)

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Publication number Priority date Publication date Assignee Title
JP2000044835A (ja) * 1998-07-27 2000-02-15 Asahi Chem Ind Co Ltd 樹脂被覆金属顔料およびそれを用いたメタリック塗料
JP2001115061A (ja) * 1999-10-14 2001-04-24 Showa Aluminum Powder Kk 金属顔料及びその製造法
JP2001139887A (ja) * 1999-11-11 2001-05-22 Asahi Kasei Metals Kk メタリック粉体塗料組成物
JP2003020413A (ja) * 2001-07-10 2003-01-24 Cemedine Co Ltd 高意匠性組成物
WO2004089316A1 (fr) * 2003-04-08 2004-10-21 Fujikasei Co., Ltd. Pigment pour preparation cosmetique et preparation cosmetique contenant ledit pigment
WO2005007755A1 (fr) * 2003-07-18 2005-01-27 Toyo Aluminium Kabushiki Kaisha Pigment sous forme de paillettes, materiau de revetement et composition de revetement en poudre contenant ce pigment, et agent de traitement de surface pour particule en paillettes associe
JP2006124676A (ja) * 2004-09-28 2006-05-18 Seiko Epson Corp カプセル化無機微粒子及びその製造方法、カプセル化無機微粒子を含むコーティング組成物及びそのコーティング方法、並びに、カプセル化無機微粒子を含む印刷用組成物及びその印刷方法
JP2006169393A (ja) * 2004-12-16 2006-06-29 Toyo Aluminium Kk メタリック顔料およびこれを含む塗料
WO2007052447A1 (fr) * 2005-10-31 2007-05-10 Toyo Aluminium Kabushiki Kaisha Pigment metallique enduit de resine, son procede de fabrication et peinture a base d’eau utilisant le pigment
US7223476B2 (en) 2004-06-14 2007-05-29 Ppg Industries Ohio, Inc. Composite flakes and methods for making and using the same
JP2008106154A (ja) * 2006-10-25 2008-05-08 Techno Polymer Co Ltd 押出成形用樹脂組成物、成形品及び積層品
JP2008201821A (ja) * 2007-02-16 2008-09-04 Asahi Kasei Chemicals Corp 金属顔料組成物
JPWO2007043453A1 (ja) * 2005-10-13 2009-04-16 東洋アルミニウム株式会社 被覆金属顔料およびその製造方法、ならびにそれを含む塗料組成物
JP2010254934A (ja) * 2009-04-28 2010-11-11 Tokai Rika Co Ltd 金属調塗料及び金属調インキ、金属調塗膜、並びにこれらの製造方法
US7837777B2 (en) 2004-03-24 2010-11-23 Toyo Aluminium Kabushiki Kaisha Metallic pigment composition and UV metallic ink composition or UV metallic coating composition using the same
WO2014041692A1 (fr) * 2012-09-14 2014-03-20 東洋アルミニウム株式会社 Pigment métallique coloré et son procédé de production
JP2014088508A (ja) * 2012-10-30 2014-05-15 Asahi Kasei Chemicals Corp 樹脂被覆金属顔料及び塗料組成物
JP2014114326A (ja) * 2012-12-06 2014-06-26 Seiko Epson Corp 紫外線硬化型インクジェット用組成物および記録物
US8883255B2 (en) 2009-09-18 2014-11-11 Asahi Kasei Chemicals Corporation Process for producing resin-coated metal pigment
US9296906B2 (en) 2010-06-08 2016-03-29 Asahi Kasei Chemicals Corporation Metallic pigment composition
JP6168266B1 (ja) * 2016-09-06 2017-07-26 Dic株式会社 樹脂被覆無機又は金属顔料
WO2018047360A1 (fr) * 2016-09-06 2018-03-15 Dic株式会社 Pigment d'aluminium revêtu de résine
WO2018047359A1 (fr) * 2016-09-06 2018-03-15 Dic株式会社 Pigment inorganique ou métallique enrobé de résine
WO2020161490A2 (fr) 2019-02-05 2020-08-13 Silberline Limited Nouveau produit

Families Citing this family (4)

* Cited by examiner, † Cited by third party
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DE10361437A1 (de) * 2003-12-23 2005-07-28 Eckart Gmbh & Co. Kg Metallpigmente mit vernetzbarer Bindemittelbeschichtung, Beschichtungszusammensetzung, Verfahren zur Herstellung der beschichteten Metallpigmente und deren Verwendung
FR2879613B1 (fr) * 2004-12-22 2007-01-26 Toyal Europ Sa Sa Composition de pigments metalliques
AU2012338962A1 (en) * 2011-11-15 2014-06-12 Apceth Gmbh & Co. Kg Polymer modified substrates, their preparation and uses thereof
KR20230001525A (ko) * 2021-06-28 2023-01-04 아사히 가세이 가부시키가이샤 금속 안료 조성물의 곤포체

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59224102A (ja) * 1983-06-03 1984-12-17 Ricoh Co Ltd 磁性粉の表面処理方法
JPH0149746B2 (fr) * 1985-09-07 1989-10-25 Asahi Kasei Metaruzu Kk
JPH0420578A (ja) * 1990-05-16 1992-01-24 Asahi Kasei Metals Kk 低温硬化性一液型塗料用アルミニウム顔料組成物
JPH0692546B2 (ja) * 1988-06-16 1994-11-16 昭和アルミパウダー株式会社 着色メタリック顔料およびその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4750940A (en) * 1985-09-07 1988-06-14 Asahi Kasei Metals Limited Novel resin-coated metallic pigment and a process for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59224102A (ja) * 1983-06-03 1984-12-17 Ricoh Co Ltd 磁性粉の表面処理方法
JPH0149746B2 (fr) * 1985-09-07 1989-10-25 Asahi Kasei Metaruzu Kk
JPH0692546B2 (ja) * 1988-06-16 1994-11-16 昭和アルミパウダー株式会社 着色メタリック顔料およびその製造方法
JPH0420578A (ja) * 1990-05-16 1992-01-24 Asahi Kasei Metals Kk 低温硬化性一液型塗料用アルミニウム顔料組成物

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000044835A (ja) * 1998-07-27 2000-02-15 Asahi Chem Ind Co Ltd 樹脂被覆金属顔料およびそれを用いたメタリック塗料
JP2001115061A (ja) * 1999-10-14 2001-04-24 Showa Aluminum Powder Kk 金属顔料及びその製造法
JP2001139887A (ja) * 1999-11-11 2001-05-22 Asahi Kasei Metals Kk メタリック粉体塗料組成物
JP2003020413A (ja) * 2001-07-10 2003-01-24 Cemedine Co Ltd 高意匠性組成物
WO2004089316A1 (fr) * 2003-04-08 2004-10-21 Fujikasei Co., Ltd. Pigment pour preparation cosmetique et preparation cosmetique contenant ledit pigment
WO2005007755A1 (fr) * 2003-07-18 2005-01-27 Toyo Aluminium Kabushiki Kaisha Pigment sous forme de paillettes, materiau de revetement et composition de revetement en poudre contenant ce pigment, et agent de traitement de surface pour particule en paillettes associe
JP4553844B2 (ja) * 2003-07-18 2010-09-29 東洋アルミニウム株式会社 フレーク顔料、それを含む塗料および粉体塗料、それに用いるフレーク粒子の表面処理剤
JPWO2005007755A1 (ja) * 2003-07-18 2007-04-12 東洋アルミニウム株式会社 フレーク顔料、それを含む塗料および粉体塗料、それに用いるフレーク粒子の表面処理剤
US7837777B2 (en) 2004-03-24 2010-11-23 Toyo Aluminium Kabushiki Kaisha Metallic pigment composition and UV metallic ink composition or UV metallic coating composition using the same
US7223476B2 (en) 2004-06-14 2007-05-29 Ppg Industries Ohio, Inc. Composite flakes and methods for making and using the same
JP2006124676A (ja) * 2004-09-28 2006-05-18 Seiko Epson Corp カプセル化無機微粒子及びその製造方法、カプセル化無機微粒子を含むコーティング組成物及びそのコーティング方法、並びに、カプセル化無機微粒子を含む印刷用組成物及びその印刷方法
JP2006169393A (ja) * 2004-12-16 2006-06-29 Toyo Aluminium Kk メタリック顔料およびこれを含む塗料
JP5068170B2 (ja) * 2005-10-13 2012-11-07 東洋アルミニウム株式会社 被覆金属顔料およびその製造方法、ならびにそれを含む塗料組成物
US8580382B2 (en) 2005-10-13 2013-11-12 Toyo Aluminium Kabushiki Kaisha Coated metal pigment, method for production of the same, and coating composition containing the same
JPWO2007043453A1 (ja) * 2005-10-13 2009-04-16 東洋アルミニウム株式会社 被覆金属顔料およびその製造方法、ならびにそれを含む塗料組成物
JP4611176B2 (ja) * 2005-10-31 2011-01-12 東洋アルミニウム株式会社 樹脂被覆金属顔料の製造方法
EP2784134A1 (fr) 2005-10-31 2014-10-01 Toyo Aluminium Kabushiki Kaisha Pigment métallique enduit de résine et peinture à base d'eau utilisant le pigment
US8734908B2 (en) 2005-10-31 2014-05-27 Toyo Aluminium Kabushiki Kaisha Resin-coated metal pigment, method for producing the same, and water base paint using the same
WO2007052447A1 (fr) * 2005-10-31 2007-05-10 Toyo Aluminium Kabushiki Kaisha Pigment metallique enduit de resine, son procede de fabrication et peinture a base d’eau utilisant le pigment
US8283397B2 (en) 2005-10-31 2012-10-09 Toyo Aluminium Kabushiki Kaisha Resin-coated metal pigment, method for producing the same, and water base paint using the same
JP2007119671A (ja) * 2005-10-31 2007-05-17 Toyo Aluminium Kk 樹脂被覆金属顔料およびその製造方法、ならびにこれを用いた水性塗料
JP2008106154A (ja) * 2006-10-25 2008-05-08 Techno Polymer Co Ltd 押出成形用樹脂組成物、成形品及び積層品
JP2008201821A (ja) * 2007-02-16 2008-09-04 Asahi Kasei Chemicals Corp 金属顔料組成物
JP2010254934A (ja) * 2009-04-28 2010-11-11 Tokai Rika Co Ltd 金属調塗料及び金属調インキ、金属調塗膜、並びにこれらの製造方法
US8883255B2 (en) 2009-09-18 2014-11-11 Asahi Kasei Chemicals Corporation Process for producing resin-coated metal pigment
US8900708B2 (en) 2009-09-18 2014-12-02 Asahi Kasei Chemicals Corporation Resin-coated metal pigment, and process for producing same
US9296906B2 (en) 2010-06-08 2016-03-29 Asahi Kasei Chemicals Corporation Metallic pigment composition
US9499696B2 (en) 2012-09-14 2016-11-22 Toyo Aluminum Kabushiki Kaisha Colored metallic pigment and method for producing the same
WO2014041692A1 (fr) * 2012-09-14 2014-03-20 東洋アルミニウム株式会社 Pigment métallique coloré et son procédé de production
JP2014088508A (ja) * 2012-10-30 2014-05-15 Asahi Kasei Chemicals Corp 樹脂被覆金属顔料及び塗料組成物
JP2014114326A (ja) * 2012-12-06 2014-06-26 Seiko Epson Corp 紫外線硬化型インクジェット用組成物および記録物
JP6168266B1 (ja) * 2016-09-06 2017-07-26 Dic株式会社 樹脂被覆無機又は金属顔料
WO2018047360A1 (fr) * 2016-09-06 2018-03-15 Dic株式会社 Pigment d'aluminium revêtu de résine
WO2018047359A1 (fr) * 2016-09-06 2018-03-15 Dic株式会社 Pigment inorganique ou métallique enrobé de résine
CN109415576A (zh) * 2016-09-06 2019-03-01 Dic株式会社 树脂被覆无机或金属颜料
JPWO2018047360A1 (ja) * 2016-09-06 2019-03-07 Dic株式会社 樹脂被覆アルミニウム顔料
US11186722B2 (en) 2016-09-06 2021-11-30 Dic Corporation Resin coated inorganic or metallic pigment
WO2020161490A2 (fr) 2019-02-05 2020-08-13 Silberline Limited Nouveau produit

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CN1093155C (zh) 2002-10-23
KR100327274B1 (ko) 2002-09-27
CN1185798A (zh) 1998-06-24
KR19990007854A (ko) 1999-01-25
TW425419B (en) 2001-03-11
JP3903325B2 (ja) 2007-04-11
MY121596A (en) 2006-02-28

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