WO1996038506A1 - Novel resin-coated metallic pigment and metallic coating material containing the pigment - Google Patents

Novel resin-coated metallic pigment and metallic coating material containing the 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
Prior art date
Application number
PCT/JP1996/001450
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French (fr)
Japanese (ja)
Inventor
Shunsuke Takase
Yasunobu Imasato
Shinji Hayami
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Asahi Kasei Metals Limited
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Publication date
Application filed by Asahi Kasei Metals Limited filed Critical Asahi Kasei Metals Limited
Priority to KR1019970707377A priority Critical patent/KR100327274B1/en
Priority to JP53636896A priority patent/JP3903325B2/en
Publication of WO1996038506A1 publication Critical patent/WO1996038506A1/en

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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

A resin-coated metallic pigment which is prepared by using (A) at least one member selected from among radical-polymerizable unsaturated carboxylic acids, mono- and di-esters of phosphoric acid and phosphonic acid each having a radical-polymerizable double bond and coupling agents each having a radical-polymerizable double bond, (B) a monomer having three or more radical-polymerizable double bonds and (C) a polymerization initiator according to a process characterised by treating a metallic pigment with the component (A) and thereafter forming a resin layer on the surface of the resulting pigment by gradually adding at least one of the components (B) and (C) to cause polymerization and which is excellent in weathering resistance, chemical resistance, gloss and storage stability in aqueous coating materials and permits the formation of a metallic finish; and a metallic coating material containing the resin-coated metallic pigment.

Description

明 細 書 新規な樹脂被覆金属顔料およびそれを用いたメタリック塗料 技術分野  Description New resin-coated metal pigments and metallic coatings using them
本発明は、 新規な樹脂被覆金属顔料に関し、 さらに詳しくは、 塗料顔料として 使用したとき、 耐薬品性、 光沢、 耐候性に優れたメタリック塗膜を与え、 かつ水 性塗料中での貯蔵安定性に優れた樹脂被覆金属顔料に関するものである。 また、 上記樹脂被覆金属顔料、 塗料用樹脂、 及び稀釈剤からなる新規なメタリック塗料 に関するものであり、 さらに詳しくは、 耐薬品性、 光沢、 耐候性等に優れたメタ リック塗膜を与え、 力、つ極めて貯蔵安定性に優れた塗料に関するものである。 背景技術  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
従来、 メタリック塗料用、 印刷インキ用、 プラスチック練り込み用等に、 メタ リック感を重視する美粧効果を得る目的で金属顔料が使用されている。  Conventionally, 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.
ところが、 従来の金属顔料を用いて得られた塗膜や樹脂成形品は、 耐酸、 耐ァ ルカリ性等の耐薬品性および耐水性が十分でなく、 また耐候性が劣るという欠点 を有している。 すなわち、 経時的に塗面が変色したり光沢が低下するためにその 使用用途が限定されており、 耐薬品性、 耐候性に優れており、 かつ、 貯蔵安定性 にも優れた金属顔料の提供が強く望まれている。  However, 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. In other words, 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.
この課題の改善策として、 金属顔料成分に樹脂被覆を施す方法が提案されてい 。  As a measure for solving this problem, a method of applying a resin coating to the metal pigment component has been proposed.
アルミペーストをエチレン性不飽和モノマ一を溶解させた有機溶剤中に分散さ せ、 重合開始剤の共存下で加熱することにより、 耐薬品性に優れる樹脂被覆アル ミペーストが得られることが知られている （特開昭 5 1 - 1 1 8 1 8号公報） 。 しかし、 この方法によって製造される樹脂被覆アルミペーストは十分な耐薬品性 を有しておらず、 実用水準に達していない。  It is known that a resin-coated aluminum paste with excellent chemical resistance can be obtained by dispersing an aluminum paste in an organic solvent in which an ethylenically unsaturated monomer is dissolved and heating it in the presence of a polymerization initiator. (Japanese Unexamined Patent Publication No. 51-111818). However, the resin-coated aluminum paste produced by this method does not have sufficient chemical resistance and has not reached a practical level.
また、 アルミペーストを有機溶媒中に分散し、 まずはじめにラジカル重合性不 飽和カルボン酸等を吸着させ、 次いでラジカル重合性二重結合を 3個以上有する 単量体から生成される重合体によつて表面被覆する方法が提案されている （特公 平 1一 4 9 7 4 6号公報） 。 この方法では、 十分な耐アルカリ性を実現するため には被覆樹脂単量体を相当量添加することが必要となり、 このとき同時に光沢の 低下をもたらし、 メタリック感が著しく異なってしまうという問題点を有してい 。 In addition, 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.
また、 特開平 7— 3 1 8 5号公報には、 シロキサン被覆とこのシロキサン被覆 に共有結合した 3次元架橋した合成樹脂被覆とで構成される金属顔料が記載され ている。 しかしながら、 この金属顔料においても耐薬品性は十分とはいえなかつ た。 ，  Further, 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. However, even with this metal pigment, the chemical resistance was not sufficient. ,
さらに、 上記の樹脂被覆アルミペーストおよび樹脂被覆のないアルミペースト を水性媒体中で使用した場合、 水と反応して水素ガスを発生して金属光沢が大幅 に低下する。 また、 水性塗料として使用する時は、 ガス抜き等の対策が必要であ つ τ乙。  Furthermore, when the above-mentioned resin-coated aluminum paste and aluminum paste without resin coating are used in an aqueous medium, they react with water to generate hydrogen gas, and the metallic luster is greatly reduced. When using as a water-based paint, measures such as degassing are required.
被覆樹脂膜の均一性、 平滑性を向上させることを目的として、 ラジカル重合性 のモノマーとオリゴマーの共重合体により被覆する方法が提案されている （特開 昭 6 4— 4 0 5 6 6号公報） 。 この方法でも上記のように水性塗料として使用し た場合、 水素ガス力《多量に発生し、 また、 金属光沢が大幅に低下するため、 貯蔵 安定性に問題があった。  In order to improve the uniformity and smoothness of the coating resin film, a method of coating with a copolymer of a radically polymerizable monomer and oligomer has been proposed (Japanese Patent Application Laid-Open No. Sho 644-40566). Gazette). Even in this method, when used as a water-based paint as described above, a large amount of hydrogen gas power was generated, and the metallic luster was significantly reduced, so that there was a problem in storage stability.
発明の開示  Disclosure of the invention
本発明者らは、 このような従来の金属顔料の問題点を解決すベく鋭意研究を続 けた結果、 ラジカル重合性不飽和カルボン酸、 ラジカル重合性二重結合を有する リン酸またはホスホン酸のモノまたはジエステル、 およびラジカル重合性二重結 合を有するカツプリング剤から選ばれた少なくとも一種に 1分子中にラジカル重 合性二重結合を 3個以上有する単量体を重合開始剤と同時に連続追加添加するか、 もしくはラジカル重合性二重結合を 3個以上有する単量体または重合開始剤のど ちらか一方を連続追加添加して得られた共重合体によって金属顔料の表面を樹脂 被覆することにより、 目的を達成し得る事実を見い出し本発明に至った。  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.
すなわち、 本発明は、 以下に既述するような態様を含むものである。  That is, the present invention includes the embodiments described below.
(1) (A) ラジカル重合性不飽和カルボン酸、 及び Zまたは、 ラジカル重合性二 重結合を有するリン酸またはホスホン酸のモノまたはジエステル、 及び Zまたは、 ラジカル重合性二重結合を有するカツプリング剤から選ばれた少なくとも 1種と、(1) (A) a radically polymerizable unsaturated carboxylic acid and Z or a mono- or diester of a phosphoric acid or phosphonic acid having a radically polymerizable double bond, and Z or At least one selected from a coupling agent having a radical polymerizable double bond,
(B) ラジカル重合性二重結合を 3個以上有する単量体と、 （C) 重合開始剤とを用 い、 先ず (A) を添加して金属顔料を処理した後、 （B) と（C) の少なくとも一方を 徐々に追加添加して重合した樹脂層をその表面に形成させた樹脂被覆金属顔料、 (2) (B) のラジカル重合性二重結合を 3個以上有する単量体として、 ラジカル 重合性二重結合を 3個有する単量体とラジカル重合性二重結合を 4個以上有する 単量体を併用し、 かつ該ラジカル重合性二重結合を 4個以上有する単量体の量が 前記ラジ力ル重合性二重結合を 3個以上有する単量体全量に対して重量比で 1 0 %〜 6 0 %である第 1の態様として記載の樹脂被覆金属顔料、 Using (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,
(3) 上記 (B) と上記 (C) の少なくとも一方を全重合時間の 2 0 %以上の時間を かけて追加添加する第 1〜第 2の態様として記載の樹脂被覆金属顔料、  (3) The resin-coated metal pigment according to the first or second aspect, wherein at least one of the above (B) and the above (C) is additionally added over a period of 20% or more of the total polymerization time,
(4) ラジカル重合性 2重結合を 4個以上有する単量体の官能基当たりの分子量 が 3 0以上 2 0 0以下である第 1ないし第 3の態様のいずれかとして記載の樹脂 被覆金属顔料、  (4) The resin-coated metal pigment according to any one of the first to third aspects, wherein 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. ,
(5) 耐アルカリ性が 2 . 0以下である第 1ないし第 4の態様のいずれかとして 記載の樹脂被覆金属顔料、  (5) The resin-coated metal pigment according to any one of the first to fourth aspects, which has an alkali resistance of 2.0 or less,
(6) 第 1ないし第 5の態様のいずれかとして記載の樹脂被覆金属顔料を含有す るメタリツク塗料、  (6) a metallic paint containing the resin-coated metal pigment according to any one of the first to fifth aspects,
(7) (A) ラジカノレ重合性不飽和カルボン酸、 および Zまたは、 ラジカル重合性 二重結合を有するリン酸またはホスホン酸のモノまたはジエステル、 および/ま たは、 ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも 一種と、 （B) ラジカル重合性二重結合を 3個以上有する単量体と、 （C) 重合開始 剤とを用い、 先ず、 (A) を添加し金属顔料を処理した後、 （B) と（C) の少なくと も一方を徐々に追加添加することを特徵とする重合し樹脂層をその表面に形成し た樹脂被覆金属顔料の製法。  (7) (A) Radicanole polymerizable unsaturated carboxylic acid, and Z or a mono- or diester of phosphoric acid or phosphonic acid having a radical polymerizable double bond, and / or having a radical polymerizable double bond Using at least one selected from coupling agents, (B) a monomer having three or more radical polymerizable double bonds, and (C) a polymerization initiator, (A) is first added, and a metal pigment is added. A method for producing a resin-coated metal pigment having a polymerized resin layer formed on its surface, characterized by gradually adding at least one of (B) and (C) after the treatment.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
本発明による樹脂被覆金属顔料は、 従来にない卓越した耐薬品性を示すととも に、 原料の金属顔料の持つ光沢を維持し、 かつ、 優れた貯蔵安定性を有するもの こ、 'ある。 本発明に使用される金属顔料として、 アルミニウム、 銅、 亜鉛、 鉄、 ニッケル、 及び/またはこれらの合金が含まれ、 好ましい例としてアルミニウムを挙げるこ とができる。 その形状はフレーク状、 球状、 針状等の粒状である。 金属顔料の好 ましい粒度は用途により異なる。 塗料用、 印刷用としては、 平均粒径が 1〜1 0 0〃程度が良く、 プラスチック練り込み用としては、 約 1〜2 0 0〃程度がよい が、 特にこれらの範囲に限定されるものではない。 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.
本発明におけるラジカル重合性不飽和カルボン酸としては、 ァクリル酸、 メ夕 クリル酸、 ィタコン酸、 フマル酸等が含まれ、 その一種または二種以上を M合し て使用する。 その使用量は該金属顔料の種類と特性、 特にその表面積によって異 なるが、 一般には金属顔料に対して 0 . 0 1重量部から 1 0重量部の間であり、 更に好ましくは 0 . 1重量部〜 5 . 0重量部である。 0 . 0 1重量部未満では、 発明の効果、 即ち、 耐アルカリ性や耐酸性などの耐薬品性が良好に発揮されず、 また、 重合性二重結合を 3個以上有する単量体を金属顔料表面に重合する時、 重 合系がゲル化し、 攪拌できなくなることがある。 また、 1 0重量部を越えて使用 しても耐薬品性等の効果に増大がない。  Examples of the radical polymerizable unsaturated carboxylic acid in the present invention 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. When the amount is less than 0.01 part 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. When polymerizing on the surface, 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.
本発明におけるラジカル重合性二重結合を有するリン酸またはホスホン酸エス テルとして、 リン酸またはホスホン酸のモノまたはジエステルが用いられる力く、 その具体的な例としては、 2—メタクリロイ口キシェチルホスフヱ一卜、 ジ一 2 —メタクリロイロキシェチルホスフエ一ト、 トリー 2—メタクリロイロキシェチ ルホスフェート、 2—ァクリロイロキシェチルホスフェート、 ジ一 2—ァクリロ イロキシェチルホスフヱ一ト、 トリ一 2—ァクリロイロキシェチルホスフエ一ト、 ジフエニル一 2—ァクリロイロキシェチルホスフエ一ト、 ジブチル一 2—メ夕ク リロイ口キシェチルホスフヱ一ト、 ジォクチル一 2—ァクリロイ口キシェチルホ スフェート、 2—メタクリロイロキシプロピルホスフェート、 ビス （2—クロ口 ェチル） ビニルホスホネート、 ジァリルジブチルホスホノサクシネート等が挙げ られ、 その一種または二種以上を混合して使用する。  As the 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.
ラジカル重合性二重結合を有するリン酸またはホスホン酸エステルの中で、 好 ましいものとしてリン酸モノエステルを挙げることができる。 これはリン酸基の 持つ O H基が 2個あることにより、 より強固にアルミニウム粒子表面に固定され ることに起因すると推定される。 より好ましいリン酸モノエステルとして、 メタ クリロイロキシ基およびァクロイロキシ基を有したモノエステルが挙げられ、 例 えば、 2—メタクリロイ口キシェチルホスフェート、 2—ァクロイロキシェチル ホスフエ一トカ《挙げられる。 Among the phosphoric acid or phosphonic acid esters having a radical polymerizable double bond, 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.
その使用量は、 金属顔料の種類と特性、 特にその表面積によって異なるが、 一 般には該金属顔料 1 0 0重量部に対して 0 . 0 1重量部から 3 0重量部の間であ る。 更に好ましくは 0 . 1重量部〜 2 0重量部である。 0 . 0 1重量部未満では、 本発明の効果、 即ち、 耐アルカリ性などの耐薬品性が良好に発揮されず、 2 0重 量部を越えて使用してもその効果の増大は期待できない。  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.
本発明におけるラジカル重合性二重結合を有するカップリング剤としては、 シ ランカップリング剤、 チタネート系カップリング剤、 アルミニウム系カップリン グ剤等が挙げられる。  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.
シランカップリング剤の例としては、 ァ一メタクリロキシプロビルトリメ トキ シシラン、 ビニルトリクロルシラン、 ビニルトリエトキシシラン、 ビニルトリメ トキシシラン、 ビニル · トリス （；5—メ トキシェトキシ） シラン等が挙げられる。 チタネート系カツプリング剤の例としては、 イソプロピルイソステアロイルジ アクリルチタネート等が挙げられる。  Examples of the silane coupling agent include methacryloxypropyl trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl tris (; 5-methoxetoxy) silane, and the like. Examples of titanate-based coupling agents include isopropyl isostearyl diacryl titanate.
アルミニウム系力ップリング剤の例としては、 ァセトアルコキシアルミニウム ジイソプロビレート、 ジルコアルミネー卜等が挙げられる。  Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate, zircoaluminate and the like.
使用されるラジカル重合性二重結合を有するカツプリング剤の量は金属顔料の 種類と特性、 特に表面積によって異なるが、 一般に金属顔料 1 0 0重量部に対し て 0 . 0 1重量部から 2 0重量部の間である。 更に好ましくは、 0 . 1重量部〜 1 0重量部の間である。 0 . 0 1重量部未満では、 発明の効果、 即ち耐アルカリ 性などの耐薬品性が良好に発揮されず、 2 0重量部を越えて使用しても効果の増 大がない。  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.
一般に、 金属顔料を処理する場合には、 金属顔料自身と水との反応を防ぐため に、 不活性溶媒中での処理が望ましい。  Generally, when treating a metal pigment, treatment in an inert solvent is desirable to prevent the reaction between the metal pigment itself and water.
ラジカル重合性不飽和力ルポン酸、 およびノまたは、 ラジカル重合性二重結合 を有するリン酸ホスホン酸モノまたはジエステルは、 一般に、 不活性溶剤に対す る溶解度が高いため、 比較的容易に均一分散が可能となり、 耐薬品性 ·水系塗料 中での貯蔵安定性低下を起こしにく く、 好ましい。 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.
本発明におけるラジカル重合性二重結合を 3個以上有する単量体 (B) としては、 トリメチロールプロパントリアクリレート、 トリメチロールプロパントリメタク リレート、 テトラメチロールメタンテトラァクリレート、 テトラメチロールプロ ノ、。ンテトラァクリレート、 ジ一トリメチロールプロパンテトラァクリレート、 ジ 一トリメチロールプロパンへキサァクリレート、 ペン夕エリスリ トールテトラァ クリレート、 ジ一ペン夕エリスリ トールへキサァクリレート等が挙げることがで き、 これらの 1種又は 2種以上混合し使用する。  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. Methacrylate, ditrimethylolpropanetetraacrylate, ditrimethylolpropanehexaacrylate, pentaerythritol tetraacrylate, dipentyerythritol hexaacrylate, and one of these. Or use a mixture of two or more.
ラジカル重合性二重結合を 3個以上有する単量体 (B) の中でラジカル重合性二 重結合を 4個以上有する単量体としては、 ジ—トリメチロールプロパンテトラァ クリレート、 ペンタエリスリ トールテトラァクリレート、 ジ一ペンタエリスリ ト ールへキサァクリレ一卜が好ましい例として挙げられる。  Among the monomers (B) having three or more radically polymerizable double bonds, monomers having four or more radically polymerizable double bonds include di-trimethylolpropanetetraacrylate and pentaerythritoltetraacrylate. Preferable examples include acrylate and dipentaerythritol hexaacrylate.
本発明におけるラジカル重合性二重結合を 3個以上有する単量体 (B) の使用量 は、 金属顔料の金属分 1 0 0重量部に対して 2重量部から 5 0重量部の間であり、 更に好ましくは、 3重量部〜 4 0重量部である。 2重量部未満では、 発明の効果、 即ち、 耐薬品性が低下し、 5 0重量部を越えると、 効果の増大も期待できず、 ま た、 光輝性、 光沢などのメタリック塗料としての基本特性が低下し実用に供し難 い。  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.
本発明の中でラジカル重合性二重結合を 3個以上有する単量体 (B) として、 ラ ジカル重合性二重結合を 3個有する単量体とラジカル重合性二重結合を 4個以上 有する単量体を併用すると本発明の効果が増大する。 その割合はラジカル重合性 二重結合を 3個以上有する単量体 (B) の総量に対して、 ラジカル重合性二重結合 を 4個以上有する単量体が、 重量比で 1 0〜6 0 %であり、 更に好ましくは 2 0 %〜5 0 %である。 ラジカル重合性二重結合を 4個以上有する単量体を併用する と耐アルカリ性や耐酸性の耐薬品性が卓越した性能を示す。 また、 ラジカル重合 性二重結合を 4個以上有する単量体の官能基当たりの分子量が 3 0以上 2 0 0以 下である場合、 更にこの効果が増大するので好ましい。 この理由は明らかでない が、 高度に 3次元架橋するためと考えられる。 本発明の効果を損なわない範囲で 1分子中に重合性二重結合を 1ないし 2個有 する単量体を使用しても良い。 その例としては、 スチレン、 α—メチルスチレン、 ァクリル酸メチル等のァクリル酸エステル類、 メタクリル酸メチル等のメタクリ ル酸エステル類、 アクリロニトリル、 メタクリロニトリル、 酢酸ビニル、 プロピ オン酸ビニル、 エチレングリコールジメタクリレート、 ジエチレングリコールジ メタクリレート、 トリエチレングリコールジメタクリレー卜、 1， 3—ブチレン グリコールジメタクリレート、 ネオペンチルグリコールジァクリレート、 1， 6In the present invention, 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. When a monomer is used in combination, the effect of the present invention is increased. 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%. When 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. Further, it is preferable that 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, α-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
—へキサンジオールジァクリレ一ト、 ジビニルベンゼン等を挙げることができ、 これらの 1種又は 2種以上を混合して使用する。 その使用量は金属顔料の 1 0 0 重量部に対して 0 . 1重量部から 1 0重量部の間である。 使用量が 1 0重量部を 越えると、 発明の効果、 即ち、 得られる樹脂被覆金属顔料を使用しメタリック塗 膜を作成した時、 特性が低下し、 又、 金属顔料の耐熱安定性も低下し、 実用に供 し難い。 本発明の樹脂被覆金属顔料は、 先ず未処理の金属顔料を有機溶剤中に分 散後、 加温し、 攪拌しながら (Α) ラジカル重合性不飽和カルボン酸、 ラジカル重 合性二重結合を有するリン酸またはホスホン酸モノまたはジエステル、 およびラ ジ力ル重合性二重結合を有するカップリング剤から選ばれた少なくとも 1種を添 加し金属顔料の表面を処理をする。 次に（Β) ラジカル重合性二重結合を 3個以上 有する単量体と（C) 重合開始剤の少なくとも一方を徐々に連続的に追加しながら 重合して、 金属顔料表面に樹脂層を形成させることで得られる。 —Hexanediol diacrylate, divinylbenzene and the like can be mentioned, and one or more of these can be used in combination. 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 (Α) 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. Next, (Β) 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.
先ず未処理の金属顔料を有機溶剤に分散後、 加温し、 攪拌しながら（Α) を添加 して行う処理は、 特に限定されないが有機溶剤中の金属顔料の重量濃度は 1〜 3 0 %で行うことが望ましい。 1 %未満では均一な分散は得られるが、 取り扱いの 溶剤量が過大となりあとで取り除くための労力を要し好ましくない。 3 0 %を越 えると金属顔料の分散が不均一となりやすく好ましくない。 なお、 この処理は 4 0 °C〜1 5 0 °Cの温度で、 5分〜 1 0時間程度が好ましい。 4 0 °C未満では（B) の重合温度まで昇温するのに時間を要し、 1 5 0 °Cを越えると有機溶剤の蒸気の 発火等に対する配慮を充分にしなければならず好ましくない。 また、 処理時間が First, the untreated metal pigment is dispersed in an organic solvent, then the mixture is heated, and the process of adding (Α) 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
5分未満では (A) の拡散が不充分となり易く、 1 0時間を越えても効果の増大は 無く時間を要するのみで好ましくない。 次に (B) ラジカル重合性二重結合を 3個以上有する単量体と（C) 重合開始剤の 少なくとも一方を徐々に連続的に追加しながら重合して金属顔料表面に樹脂層を 形成させる。 本発明では (B) と（C) の少なくとも一方を連続的に追加添加するこ とが肝要である。 具体的には (B) と（C) 両方を徐々に、 （C) を先に添加後 (B) の みを徐々に、 または（B) を先に添加後 (C) のみを徐々に連続的に追加添加するこ とであり、 何れの方法を取ってもよい。 本発明では、 （B) と（C) の少なくとも一 方を徐々に連続的に追加して重合することで金属表面に高度に三次元架橋した樹 脂層が形成すると考えられる。 重合温度は特に限定されないが 6 0 °C〜1 5 0 °C が好ましく、 重合効率を高めるため窒素、 ヘリウム等の不活性ガス雰囲気下が望 ましい。 また、 連続的に添加するには (B) 、 (0 を有機溶剤等に希釈し定量ボン プ等を用い一定速度でフィードすることが好ましく、 フィード時間、 すなわち、 追加添加時間は重合時間の 2 0 %以上が好ましい。 重合時間は特に限定されない が、 2時間〜 1 0時間程度である。 ここで、 重合時間とは、 （B) と（C) 両者が反 応系中に同時に存在した時点から、 （B) の未反応物が 1 %未満になるまでをいう。 フィード時間が重合時間の 2 0 %未満であると連続的に添加した効果が小さく好 ましくない。 また、 反応時間を早めるためにはフィード時間は重合時間の 9 0 % 以下が好ましく、 更に反応時間を早め生産性を高めるためには、 7 0 %以下にす ることが望ましい。 If the time is less than 5 minutes, the diffusion of (A) tends to be insufficient, and if the time exceeds 10 hours, the effect is not increased and it takes time, which is not preferable. Next, 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. . In the present invention, it is important to continuously add at least one of (B) and (C). Specifically, both (B) and (C) are gradually added, (C) is added first and then (B) only, or (B) is added first and only (C) is gradually added. It is possible to use any method. In the present invention, it is considered that 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. Although the polymerization temperature is not particularly limited, it is preferably from 60 ° C. to 150 ° C. In order to increase the polymerization efficiency, it is desirable to use an atmosphere of an inert gas such as nitrogen or helium. For continuous addition, 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. From the time when the unreacted substance of (B) becomes less than 1% When the feed time is less than 20% of the polymerization time, the effect of the continuous addition is small, which is not preferable. 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.
本発明の樹脂被覆金属顔料は、 処理前の金属顔料に比べて比表面積の増加は若 干認められるが、 従来法で得られた樹脂被覆金属顔料の増加に比べ大幅に小さく、 吸油量が小さいのが特徴である。 このことは、 金属表面に形成した樹脂層が均一 で、 かつ高度に三次元架橋したためであると考えられ、 本発明の樹脂被覆金属顔 料を使用した塗膜の耐薬品性、 光沢、 耐候性等に優れた特性を示すものである。 本発明に於ける重合の際に使用される有機溶剤は、 へキサン、 ヘプタン、 ォク タン、 ミネラルスピリッ ト等の脂肪族炭化水素、 ベンゼン、 トルエン、 キシレン、 ソルベントナフサ等の芳香族炭化水素、 テトラヒドロフラン、 ジェチルエーテル 等のエーテル類、 酢酸ェチル、 酢酸ブチル等のエステル類が挙げられる。  Although 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.
本発明に用いられる重合開始剤は、 一般にラジカル発生剤として知られるもの であり、 ベンゾィルパーオキサイド、 ラウロイルパーオキサイド、 ビス一 （4— tーブチルシクロへキシル） パーォキシジカーボネート等のパ一ォキサイド類、 および 2， 2 ' —ァゾビス一イソブチロニトリル、 2， 2 ' —ァゾビス _ 2， 4 —ジメチルバレロニトリル等のァゾ化合物が挙げられる。 使用される量は本発明 では特に限定されないが、 ラジカル重合性二重結合を 3個以上有する単量体 1 0 0重量部に対して、 0 . 1重量部〜 5 0重量部程度である。 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. No. 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.
本発明の樹脂被覆金属顔料は塗料に使用した時の塗膜の耐ァルカリ性が極めて 優れた特性を示す。 これは金属顔料表面が高度に三次元架橋した樹脂層で被覆さ れているため、 アル力リが塗膜内に侵入しても金属顔料表面へ到達し難いためと 考えられ、 本発明の実施例に示した耐アルカリ性は 0 . 0 1〜2 . 0の値を示す c 本発明のメタリック塗料は、 溶剤型塗料、 水性塗料等として使用可能であり、 主として 3つの基本成分、 即ち（a) 塗料用樹脂、 (b) 樹脂被覆金属顔料、 及び (c) 稀釈剤からなる。 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. C 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.
溶剤型塗料の塗料用樹脂としては、 従来メタリック塗料で用いられている塗料 用樹脂の中の任意のものを用いることができる。 その樹脂としては、 ァクリノレ樹 脂、 アルキッ ド樹脂、 オイルフリーアルキッ ド樹脂、 塩化ビニル樹脂、 ウレタン 樹脂、 メラミン樹脂、 不飽和ポリエステル樹脂、 尿素樹脂、 セルロース系樹脂、 エポキシ樹脂、 フッ素樹脂等が挙げられ、 これらは単独で用いてもよいし混合し て用いてもよい。  As the coating resin for the solvent type coating, any of the coating resins conventionally used in metallic coatings can be used. Examples of 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.
溶剤型塗料に使用される樹脂被覆金属顔料は、 塗料用樹脂 1 0 0重量部に対し て 0 . 1重量部〜 1 0 0重量部であることが好ましく、 更に 1重量部〜 5 0重量 部用いることが好ましい。 この樹脂被覆金属顔料が 0 . 1重量部未満であると、 メタリツク塗料として必要な金属光沢が不十分であり、 また、 1 0 0重量部を越 えて用いると、 塗料中の金属顔料の量が多くなり過ぎて、 塗装作業性が悪くなり、 かつ、 塗膜物性も劣り実用的でない。  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.
溶剤型塗料での希釈剤としては、 トルエン、 キシレン等の芳香族系化合物、 へ キサン、 ヘプタン、 オクタン等の脂肪族系化合物、 エタノール、 ブタノ一ル等の アルコール類、 酢酸ェチル、 酢酸ブチル等のエスチル類、 メチルェチルケトン等 のケトン類、 トリクロロエチレン等の塩素化合物、 エチレングリコールモノェチ ルェ一テル等のセロソルブ類が挙げられ、 これらの希釈剤は単独または二種以上 混合して使用される。 その組成は塗料用樹脂に対する溶解性、 塗膜形成特性、 塗 装作業性等を考慮して決定される。 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.
塗料業界で一般に使用されている顔料、 染料、 湿潤剤、 分散剤、 色分れ防止剤、 レべリング剤、 スリップ剤、 皮張り防止剤、 ゲル化防止剤、 消泡剤等の添加剤を 加えることができる。  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.
本発明の顔料は水性塗料用樹脂を用いることにより水性塗料にも使用可能であ るカ^ ここで水性塗料用樹脂とは、 水溶性樹脂または水分散性樹脂であって、 こ れらは単独または混合物であってもよい。 その種類は目的、 用途により千差万別 であり、 特に限定されるものではないが、 一般にはアクリル系、 アクリル一メラ ミン系、 ポリエステル系、 ポリウレタン系等の水性塗料用樹脂が挙げられ、 中で もアクリル一メラミン系が最も汎用的に使用されている。  The pigment of the present invention can also be used for water-based paints by using the resin for water-based paints. Here, 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.
水性塗料に使用される樹脂被覆金属顔料は、 塗料用樹脂 1 0 0重量部に対して 0 . 1重量部〜 1 0 0重量部である。 特に 1重量部〜 5 0重量部用いることが好 ましい。 この樹脂被覆金属顔料が 0 . 1重量部未満であると、 メタリック塗料と して必要な金属光沢が不十分であり、 また、 1 0 0重量部を越えて用いると、 塗 料中の金属顔料の量が多くなり過ぎて、 塗装作業性が悪くなり、 かつ、 塗膜物性 も劣り実用的でない。  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.
また、 各種添加剤としては、 例えば、 分散剤、 増粘剤、 タレ防止剤、 防カビ剤、 紫外線吸収剤、 成膜助剤、 界面活性剤、 その他の有機溶剤、 水等、 当該分野に於 いて通常使用され得るものであって、 本発明に於ける効果を損なわないもの及び 量であれば、 添加しても差し支えない。  Examples of various additives 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.
本発明におけるメタリック塗料は、 溶剤型塗料、 水性塗料以外にも汎用の塗料 で使用可能であり、 その例としては、 粉体塗料等が挙げられる。  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.
実施例  Example
次に、 本発明の実施例を示すが、 本発明はこれに限定されるものではない。 ま た、 本実施例で用し、る試験方法および測定方法を以下に詳述する。  Next, examples of the present invention will be described, but the present invention is not limited thereto. The test method and the measurement method used in this example are described in detail below.
(1) 評価用塗板の作製  (1) Preparation of coated plate for evaluation
樹脂被覆アルミペーストを使用し、 表 1に示す塗料配合にて、 耐ァルカリ性評 価用のメタリック塗料を調製する。 表 1 塗料配合 （重量部） Using a resin-coated aluminum paste, prepare a metallic paint for evaluation of alkali resistance with the paint formulation shown in Table 1. Table 1 Paint composition (parts by weight)
Figure imgf000013_0001
Figure imgf000013_0001
* 1 酢酸ブチル （30部） 、 トルエン （45部）  * 1 butyl acetate (30 parts), toluene (45 parts)
イソプロピルアルコール （20部） 、  Isopropyl alcohol (20 parts),
ェチルセ口ソルブ （5部） を混合したもの  A mixture of Echilse mouth solve (5 parts)
* 2 ァクリディック A— 1 66 (不揮発分； 45%)  * 2 Acrylic A-166 (non-volatile content; 45%)
(大日本インキ化学 （株） 製、 常乾型アクリル樹脂） (Dai Nippon Ink Chemical Co., Ltd., dry acrylic resin)
* 3 L I G 1/2 (不揮発分 70%) * 3 L I G 1/2 (70% non-volatile content)
(旭化成工業 （株） 製、 工業用硝化綿）  (Industrial nitrified cotton manufactured by Asahi Kasei Kogyo Co., Ltd.)
をシンナー * 1で不揮発分が 1 6 %になるように調製したもの。 該塗料の粘度を上記表 1に示したシンナーを用いて 1 3秒 （FC#4、 20 °C) に調整し、 ABS樹脂板に膜厚が 1 0 になるように吹き付け塗装した。 そ の後 50°Cで 3 0分乾燥し、 評価用塗板を作製する。  Prepared with thinner * 1 so that the non-volatile content is 16%. The viscosity of the paint was adjusted to 13 seconds (FC # 4, 20 ° C.) using the thinner shown in Table 1 above, and sprayed onto the ABS resin plate so that the film thickness became 10. Then, it is dried at 50 ° C for 30 minutes to prepare a coated board for evaluation.
(2) 耐ァルカリ性の測定  (2) Alkali resistance measurement
上記塗板の下半分を 2. 5 N— N a OH水溶液を入れたビーカーに浸漬し、 2 0°Cで 24時間放置する。 試験後の塗板を水洗、 乾燥したのち、 浸漬部と未浸漬 部を、 J I S— Z— 8722 ( 1 98 2 ) の条件 d (8— d法） により測色し、 J I S-Z-8730 (1 980 ) の 6. 3. 2により色差厶 Eを求める。  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.
(3) 光沢保持率  (3) Gloss retention
上記塗板について、 光沢計を用いて 60度光沢 （入射角、 反射角とも 60度） を測定する。 未処理アルミべ一ストの 60度光沢を G、 樹脂被覆アルミペースト の 60度光沢を G' とし、 光沢保持率 Rを下式によって求める。  For the above coated plate, measure the gloss at 60 degrees (both incident and reflection angles are 60 degrees) using a gloss meter. Let G be the 60-degree gloss of the untreated aluminum base and G 'be the 60-degree gloss of the resin-coated aluminum paste, and calculate the gloss retention R by the following formula.
R= (C /G) X 1 00  R = (C / G) X 1 00
(4) 吸油量 樹脂被覆アルミペーストを 1 0 5 °Cで 3時間加熱処理したものを試料とし、 J I S K 6 2 2 1— 1 9 8 2の Β法 （へら練り法） に従いジブチルフタレート を用いて測定する。 (4) Oil absorption The resin-coated aluminum paste is heat-treated at 105 ° C for 3 hours, and the sample is measured using dibutyl phthalate according to the JISK6221—19882 method (spatula kneading method).
(5) 比表面積  (5) Specific surface area
ァセトン置換によってアルミペース卜の溶剤を除去してパウダー状になったサ ンプルの表面を B E T 1点式比表面積計 （島津フローソープ 2 3 0 0 ) により測 Lする。  Measure the surface of the powdered sample by removing the solvent from the aluminum paste by acetone substitution using a BET one-point specific surface area meter (Shimadzu flow soap 230,000).
実施例 1 Example 1
容積 1 リッ トルの四つ口フラスコに、 アルミペース卜 （旭化成工業株式会社製 MG— 5 1、 金属分 6 7 %) 7 5 gおよびミネラルスピリッ ト 3 0 0 gを加え、 窒素ガスを導入しながら攪拌し、 系内の温度を 8 0 °Cに昇温した。 次いで、 ァク リル酸 0 . 3 7 5 を添加し 8 0 °Cで 3 0分攪拌を続けた。 次にトリメチロール プロパントリメタクリレート 2 . 5 gとジ一トリメチロールプロパンテトラァク リレート （官能基当たりの分子量 1 1 6 . 5 ) 1 . 0 gと 2， 2 ' —ァゾビス一 2 , 4—ジメチルバレロニトリル 0 . 3 5 gをミネラルスピリッ ト 1 9 gに溶解 させ、 その溶液を定量ポンプにより約 0 . 1 3 g/m i n . の速度で 3時間かけ て添加し、 その後系内の温度を 8 0 °Cに保ちながら合計 6時間重合した。 この時 点でサンプリングしたろ液中のトリメチロールプロパントリメタァクリレー卜の 未反応量をガスクロマトグラフィで分析したところ、 添加量の 9 9 . 5 %以上が 反応していた。 重合終了後、 スラリーを濾過し、 樹脂被覆アルミペーストを得た。 このペーストの不揮発分 （J I S— K— 5 9 1 0による） は、 6 5 . 0重量％で あった。 アルミニウム金属分 1 0 0重量部に対する樹脂被覆量は 8 . 3重量部で あった。 この結果から、 アクリル酸、 トリメチロールプロパントリメタクリレー ト、 ジ一トリメチロールプロパンテトラァクリレート、 2， 2 ' —ァゾビス一 2， 4—ジメチルバレロニトリルの 9 8 %以上がアルミニウム表面上に付着したもの と推定される。  To a one-liter four-necked flask, add 75 g of aluminum paste (MG-51 from Asahi Kasei Corporation, metal content 67%) and 300 g of mineral spirit, and introduce nitrogen gas. While stirring, the temperature in the system was raised to 80 ° C. Next, 0.375 of acrylic acid was added, and stirring was continued at 80 ° C for 30 minutes. Next, 2.5 g of trimethylolpropane trimethacrylate and 1.0 g of di-trimethylolpropane tetraacrylate (molecular weight per functional group: 1 16.5) and 2,2'-azobis-1,2,4-dimethyl 0.35 g of valeronitrile was dissolved in 19 g of mineral spirit, and the solution was added by a metering pump at a rate of about 0.13 g / min over 3 hours. While maintaining the temperature at 0 ° C, polymerization was performed for a total of 6 hours. 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. After completion of the polymerization, 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. From this result, more than 98% of acrylic acid, trimethylolpropane trimethacrylate, di-trimethylolpropane tetraacrylate, 2,2'-azobis-1,2,4-dimethylvaleronitrile adhered to the aluminum surface It is estimated that they have done so.
実施例 2 Example 2
実施例 1で用いたトリメチロールプロパントリメタクリレートとジ一トリメチ ロールプロパンテトラァクリレー卜の代わりにトリメチロールプロパントリメタ クリレート 3. 5 gを用いたこと以外は実施例 1と同様にして樹脂被覆アルミべ —ストを作製した。 Instead of 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.
実施例 3 Example 3
容積 1 リットルの四つ口フラスコに、 アルミペースト （旭化成工業株式会社製 MG— 5 1、 金属分 6 7 %) 7 5 gおよびミネラルスピリッ ト 3 0 0 gを加え、 窒素ガスを導入しながら攪拌し、 系内の温度を 6 0°Cに昇温した。 次いで、 ァク リル酸を 0. 3 7 5 gを添加し、 6 0°Cで 3 0分攪拌を続けた。 次に卜リメチロ ールプロパントリァクリレート 6. 4 gとジ一ペンタエリスリ トールへキサァク リレー卜 （官能基当たりの分子量 9 6. 3) 1. 6 gを系内に分散させた。 次に 2, 2 ' —ァゾビス一 2， 4—ジメチルバレロニトリル 0. 8 gをミネラルスピ リッ ト 1 9 gに溶解させ、 その溶液を定量ポンプにより約 0. 0 8 g/ i n. の速度で 4時間かけて添加し、 その後系内の温度を 6 0°Cに保ちながら合計 7時 間重合した。 重合終了後、 スラリーを濾過し、 樹脂被覆アルミペーストを得た。 このペーストの不揮発分 （J I S— K— 5 9 1 0による） は、 6 0. 0重量％で あった。 アルミニウム金属分 1 0 0重量部に対する樹脂被覆量は 1 8. 2重量部 であった。 この結果から、 アタリノレ酸、 トリメチロールプロパントリァクリレー ト、 ジ一ペンタエリスリ トールへキサァクリレート、 2， 2 ' —ァゾビス一 2， 4—ジメルバレロ二トリルの 9 9 %以上がアルミニウム表面上に付着したものと 推定される。  To a 1-liter four-necked flask, add 75 g of aluminum paste (MG-51 from Asahi Kasei Corporation, metal content 67%) and 300 g of mineral spirits, and stir while introducing nitrogen gas. Then, the temperature in the system was raised to 60 ° C. Next, 0.375 g of acrylic acid was added, and stirring was continued at 60 ° C for 30 minutes. Next, 6.4 g of trimethylolpropane triacrylate and 1.6 g of di-pentaerythritol hexacrylate (molecular weight per functional group: 96.3) were dispersed in the system. Next, 0.8 g of 2,2'-azobis-1,2,4-dimethylvaleronitrile was dissolved in 19 g of mineral spirits, and the solution was pumped at a rate of about 0.08 g / in. Over 4 hours, and then polymerization was carried out for a total of 7 hours while maintaining the temperature in the system at 60 ° C. After completion of the polymerization, the slurry was filtered to obtain a resin-coated aluminum paste. The nonvolatile content of this paste (according to JIS-K-590) was 60.0% by weight. The resin coating amount relative to 100 parts by weight of the aluminum metal was 18.2 parts by weight. The results show that at least 99% of atalinoleic acid, trimethylolpropane triacrylate, dipentapentaerythritol hexacrylate, and 2,2'-azobis-1,2,4-dimervaleronitrile adhered to the aluminum surface. Presumed.
実施例 4 Example 4
容積 1 リッ トルの四つ口フラスコに、 アルミペースト （旭化成工業株式会社製 MG— 5 1、 金属分 6 7 %) 7 5 gおよびミネラルスピリッ ト 3 0 0 gを加え、 窒素ガスを導入しながら攪拌し、 系内の温度を 7 0°Cに昇温した。 次いで、 ァク リル酸 0. 4 gを添加し、 8 0°Cで 3 0分攪拌を続けた。 次に 1， 6—へキサン ジオールジァクリレート 0. 5 g、 トリメチロールプロパントリメタクリレート 3. 0 g、 ペンタエリスリ トールテトラァクリレート （官能基当たりの分子量 8 8) 1. 5 gとァゾビスイソブチロニトリル 0. 5 gをミネラルスピリッ ト 3 8 gに溶解させ、 その溶液を定量ポンプにより約 0. 2 4 g/m i n. の速度で 3 時間かけて添加し、 その後系内の温度を 8 0°Cに保ちながら合計 6時間重合した。 重合終了後、 スラリーを濾過し、 樹脂被覆アルミペーストを得た。 このペースト の不揮発分 （J I S— K— 5 9 1 0による） は、 62. 0重量％であった。 アル ミニゥム金属分 1 0 0重量部に対する樹脂被覆量は 1 1. 6重量部であった。 こ の結果から、 アクリル酸、 1， 6—へキサンジォ一ルジァクリレート、 トリメチ ロールプロパントリメタクリレート、 ペンタエリスリ トールテトラァクリレー卜、 2, 2 ' —ァゾビス一イソブチロニトリルの 9 8 %以上がアルミニウム表面上に 付着したものと推定される。 To a one-liter four-necked flask, add 75 g of aluminum paste (MG-51 from Asahi Kasei Kogyo Co., Ltd., 67% metal content) and 300 g of mineral spirit, and introduce nitrogen gas. After stirring, the temperature in the system was raised to 70 ° C. Then, 0.4 g of acrylic acid was added, and stirring was continued at 80 ° C for 30 minutes. Then, 0.5 g of 1,6-hexanedioldiol diacrylate, 3.0 g of trimethylolpropane trimethacrylate, 1.5 g of pentaerythritol tetraacrylate (molecular weight of 88 per functional group) and 1.5 g of azo 0.5 g of bisisobutyronitrile was dissolved in 38 g of mineral spirit, and the solution was added at a rate of about 0.24 g / min by a metering pump over 3 hours. The polymerization was carried out for a total of 6 hours while maintaining the temperature at 80 ° C. After the polymerization, the slurry was filtered to obtain a resin-coated aluminum paste. 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.
実施例 5 Example 5
実施例 1と同様にして、 トリメチロールプロパン卜リメタァクリレートを 1. 0 g、 ジートリメチロールプロパンテトラアタリレートを 2. 5 gとした以 外は実施例 1と同様にして樹脂被覆アルミペーストを作成した。 このペーストの 不揮発分 （J I S-K- 5 9 1 0による） は 6 0. 0 %であった。  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%.
実施例 6 Example 6
実施例 1と同様にして、 トリメチロールプロパントリメタァクリレート 2. 5 g、 ジ一 トリメチロールプロパンテトラァクリレート 1. 0 g、 2， 2 ' ァゾビ ス一 2， 4—ジメチルバレロニトリル 0. 3 5 gをミネラルスピリッ ト 1 9 gに 溶解させた溶液を定量ポンプにより約 0. 3 2 gZm i nの速度で 1. 2時間か けて添加した以外は実施例 1と同様にして、 樹脂被覆アルミペーストを作成した。 このペース卜の不揮発分 （J I S-K- 5 9 1 0による） は 6 5. 0 %であった。 実施例 7  As in Example 1, 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%. Example 7
容積 2リットルの四つ口フラスコに、 アルミペースト （旭化成工業株式会社製 MG- 5 1、 金属分 6 7 %) 1 5 0 gおよび 2—プロピルアルコール 6 0 0 gを 加え、 窒素ガスを導入しながら攪拌し、 系内の温度を 7 0°Cに昇温した。 次いで、 ビニルトリメ トキシシラン 7 gと精製水 7 gを加え、 5時間攪拌した。 次にスラ リーをろ過し、 ミネラルスピリッ トでよく洗浄した。 このようにして得られたぺ —スト 7 5 gとミネラルスピリッ ト 3 0 0 gを容積 1 リッ トルの四つ口フラスコ に加え、 窒素ガスを導入しながら攪拌し、 系内の温度を 8 0°Cに昇温した。 次に トリメチロールプロパントリメタクリ レート 2. 5 gとジ一 トリメチロールプロ パンテトラァクリレート 1. 0 gと 2， 2 ' —ァゾビス一 2， 4—ジメチルバレ ロニトリノレ 0. 3 5 gをミネラルスピリッ ト 1 9 gに溶解させ、 その溶液を定量 ポンプにより約 0. 1 3 gZm i n. の速度で 3時間かけて添加し、 その後系内 の温度を 8 0°Cに保ちながら合計 6時間重合した。 重合終了後、 スラリーを濾過 し、 樹脂被覆アルミペーストを得た。 このペース卜の不揮発分 （J I S-K-5 9 1 0による） は、 6 5. 0重量％であった。 アルミニウム金属分 1 0 0重量部 に対する樹脂被覆量は 8. 3重量部であった。 この結果から、 ビニルトリメ トキ シシラン、 トリメチロールプロパントリメタクリ レート、 ジー トリメチロールプ 口パンテトラァクリ レート、 2， 2 ' —ァゾビス一 2, 4—ジメチルバレロニ卜 リルの 9 8 %以上がアルミニゥム表面上に付着したものと推定される。 To a 2 liter four-necked flask, 150 g of aluminum paste (MG-51 from Asahi Kasei Corporation, metal content 67%) and 600 g of 2-propyl alcohol were added, and nitrogen gas was introduced. The temperature in the system was raised to 70 ° C while stirring. Next, 7 g of vinyltrimethoxysilane and 7 g of purified water were added, and the mixture was stirred for 5 hours. The slurry was then filtered and washed well with mineral spirits. 75 g of the thus obtained paste and 300 g of mineral spirit were added to a one-liter four-necked flask, and the mixture was stirred while introducing nitrogen gas, and the temperature in the system was reduced to 800 g. The temperature was raised to ° C. Next, 2.5 g of trimethylolpropane trimethacrylate and 1.0 g of di-trimethylolpropane tetraacrylate and 2,2′-azobis-1,2,4-dimethylvale Dissolve 0.35 g of Lonitrinole in 19 g of mineral spirits and add the solution by a metering pump at a rate of about 0.13 g Zmin over 3 hours, then raise the temperature in the system to 80 While maintaining the temperature at ° C, polymerization was carried out for a total of 6 hours. After completion of the polymerization, the slurry was filtered to obtain a resin-coated aluminum paste. The nonvolatile content (according to JI SK-5910) of this paste 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. 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.
実施例 8 Example 8
実施例 1のァクリル酸を 2—メタクリロイ口キンェチルァシッ ドホスフヱ一ト (大八化学製、 MR— 2 0 0 ) に変える以外同様にして、 樹脂被覆アルミペース トを得た。 このペーストの不揮発分 （J I S-K- 5 9 1 0による） は、 6 5. 0重量％であった。 この結果から、 2—メタクリロイロキシェチルァシッ ドホスフェート、 トリメチロールプロパントリメタクリ レート、 ジトリメチロー ルプロパンテトラアタリ レート、 2， 2 ' —ァゾビスー2， 4ージメチルバレロ 二トリルの 9 8 %以上がアルミニウム表面上に付着したものと推定される。  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.
比較例 1 Comparative Example 1
実施例 1のポンプによる連続追加添加操作をせずに、 単量体 (B) 、 重合開始剤 を一括して添加したこと以外は実施例 1と同様にして樹脂被覆アルミペーストを 作製した。  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.
比較例 2 Comparative Example 2
実施例 2のポンプによる連続追加添加操作をせずに、 単量体 (B) 、 重合開始剤 を一括して添加したこと以外は実施例 2と同様にして樹脂被覆アルミペーストを 作製した。  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.
比較例 3 Comparative Example 3
実施例 1と同様にして、 トリメチロールプロパントリメタァクリレートを 2. 5 g、 ジ一 トリメチロールプロパンテトラァクリレートを 1. 0 gと 2, 2 ' ァゾビス一 2， 4—ジメチルバレロニトリル 0. 3 5 gをミネラルスピ リッ ト 1 9 gに溶解させた溶液を定量ポンプにより約 0. 7 6 g/m i nの速度 で 0. 5時間かけて添加した以外は実施例 1と同様にして、 樹脂被覆アルミベー ストを作製した。 このペース卜の不揮発分 （J I S-K- 5 9 1 0による） は 6 0. 0 %であった。 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%.
比較例 4 Comparative Example 4
実施例 1において、 ァクリル酸の代わりにビニルトリメ トキシシラン 0. 8 8 g、 リン酸 0. 06 、 水0. 0 6 gおよび 2—ブタノール 1. 00 gを用い、 トリメチロールプロパントリメタァクリレー卜とジートリメチロールプロパンテ トラァクリレー卜の代わりに卜リメチロールプロパントリメタァクリレート 3. 5 gを用い、 トリメチロールプロパントリメタァクリレートをミネラルスピ リッ ト 1 9 gに溶解させた溶液を定量ポンプにより約 0. 7 8 g/ i nの速度 で 0. 5時間かけて添加した以外は実施例 1と同様にして、 樹脂被覆アルミベー ストを作製した。 このペーストの不揮発分 （J I S-K- 5 9 1 0による） は 6 0. 0 %であった。  In 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. Using 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%.
比較例 5 Comparative Example 5
比較例 4において、 定量ポンプによる連続追加添加をせずにトリメチロ一ルプ 口パントリメタァクリレートをミネラルスピリッ ト 1 9 gに溶解させた溶液を一 括して添加した以外は比較例 4と同様にして樹脂被覆アルミペーストを作製した。 このペーストの不揮発分 （J I S-K- 5 9 1 0による） は 6 0. 0 %であった。 実施例 1〜 8、 比較例 1〜 5のべ一スト性能を表 2に示す。  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.
表 2中、 多官能単量体配合率は、 ラジカル重合性二重結合を 3個以上有する単 量体総量中にラジカル重合性二重結合を 4個以上有する単量体が含まれる率 （重 量比） を示す。 表 2 ペース卜性能 In Table 2, 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). Table 2 Paste performance
Figure imgf000019_0001
Figure imgf000019_0001
* 1 ラジカル重合性 =重結合を 4個以上有する単量体 * 2 成分 (Β) 及び Ζ又は成分 (C) のフィード時間が重合時 間に占めるパーセント  * 1 Radical polymerizable = monomer having 4 or more heavy bonds * 2 Percentage of feed time of component (Β) and Ζ or component (C) in polymerization time
* 3 水系塗料中の貯蔵安定性  * 3 Storage stability in water-based paint
〇：ガス発生量 1 0 (c cZg) 以下  〇: Gas generation 10 (c cZg) or less
X ：ガス発生量 1 0 (c c/g) 超過  X: Gas generation amount exceeds 10 (c c / g)
実施例 9 Example 9
実施例 1で得られた樹脂被覆アルミペーストと比較例 2で得た樹脂被覆アルミ ペースト、 未樹脂被覆処理アルミペースト （MG— 5 1 ：旭化成工業株式会社 製） 、 およびフッ素樹脂を使用し、 表 3の塗料配合により塗料化後、 エアースプ レ一塗装で膜厚が 3 0 / になるようにアルミ板 （1 X 7 0 X 1 5 0mm) に塗装し た。 その後、 1 0 0°Cで 3 0分間乾燥してフッ素樹脂系のメタリック塗膜を作製 し 表 3 塗料配合 （重量部） Using the resin-coated aluminum paste obtained in Example 1 and the resin-coated aluminum paste obtained in Comparative Example 2, an unresin-coated aluminum paste (MG-51: manufactured by Asahi Kasei Kogyo Co., Ltd.), and a fluororesin, After forming the paint by the paint formulation of 3, the aluminum plate (1 × 70 × 150 mm) was applied by air spray coating so that the film thickness became 30 /. Then, it was dried at 100 ° C for 30 minutes to produce a fluororesin-based metallic coating. Table 3 Paint composition (parts by weight)
Figure imgf000020_0001
Figure imgf000020_0001
* 1…旭硝子 （株） 製  * 1: Made by Asahi Glass Co., Ltd.
* 2…旭化成工業 （株） 製  * 2: Made by Asahi Kasei Industry Co., Ltd.
* 3…トルェン Zキシレン Z酢酸ェチル /酢酸ブチルの重量 比 = 30Z2 0Z20/30  * 3: Toluene Z-xylene Z-ethyl acetate / butyl acetate weight ratio = 30Z2 0Z20 / 30
このメタリツク塗膜を用いて 20 °Cでの耐薬品性スポッ 卜試験を 1 0日間実施 後、 塗膜の変色度合いを評価した。 また、 同じ塗膜でサンシャインゥヱザオメ一 ター （SWOM) による 30 00時間の暴露試験を行った。 なお、 耐薬品性に用 いた薬品は、 各々 1 0 %塩酸、 1 0 %N a OH、 1 0 %硫酸の水溶液とした。 そ の結果を表 4に示した。  Using this metallic coating film, a chemical resistance spot test at 20 ° C. was performed for 10 days, and then the degree of discoloration of the coating film was evaluated. In addition, the same coating film was subjected to an exposure test for 3 000 hours using a Sunshine Zomeometer (SWOM). The chemicals used for the chemical resistance were aqueous solutions of 10% hydrochloric acid, 10% NaOH, and 10% sulfuric acid, respectively. Table 4 shows the results.
表 4 塗膜の変色度合評価  Table 4 Evaluation of degree of discoloration of coating film
Figure imgf000020_0002
Figure imgf000020_0002
〇：変色なし 〇: No discoloration
△ :やや変色が認められる  △: Some discoloration is observed
X ：大きな変色が認められる  X: Large discoloration is observed
その結果、 本発明の実施例 1の樹脂被覆アルミペーストを使用した塗膜は耐薬 品性試験において塗膜に全く変化が認められなかった。 また、 サンシャインゥェ ザオメ一ターによる試験においても、 本発明の実施例 1の樹脂被覆アルミペース トを使用した塗膜は塗膜外観の変化はほとんど認められず、 優れた耐候性を示し ノ As a result, in the coating film using the resin-coated aluminum paste of Example 1 of the present invention, no change was observed in the coating film in the chemical resistance test. Also, in a test using a sunshine laser meter, the resin-coated aluminum paste of Example 1 of the present invention was used. The coating using the paint shows almost no change in the appearance of the coating, showing excellent weather resistance.
実施例 1 0 Example 10
樹脂系をフッ化ビ二リデン型フッ素樹脂を使用し表 5の塗料配合により塗料化 後、 バーコ一ターで膜厚 3 0 ^になるようにアルミ板に塗装し、 さらに 2 4 0 °C で 5分間乾燥して塗膜を作製した。 実施例 9と同様に耐薬品性スポット試験を実 施した。 その結果、 実施例 1の樹脂被覆アルミペーストを使用した塗膜は、 実施 例 9と同様に極めて優れた耐薬品性を示した。  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.
表 5 塗料配合 （重量部）  Table 5 Paint composition (parts by weight)
Figure imgf000021_0001
Figure imgf000021_0001
* 1…ローム ' アンド ·ハース社製  * 1… ROHM 'and Haas
* 2…イソホ πン /ジメチルフタレ-ト /トル Iン /イソブチルァセテ-ト / チルァセテ -トの重量比 * 2 ... Weight ratio of isophthalic acid / dimethyl phthalate / toluene / isobutyl acetate / til acetate
= 4 5 / 2 4 Z 1 5 / 8 / 8 = 4 5/2 4 Z 15/8/8
* 3…ダイキン工業 （株） 製  * 3: manufactured by Daikin Industries, Ltd.
実施例 1 1 Example 1 1
実施例 1の樹脂被覆アルミぺ一ストと比較例 2の樹脂被覆アルミペーストを用 い、 表 6の塗料配合にてアクリル系の塗料を作製後、 実施例 1 0と同様に膜厚が 3 0 になるように A B S樹脂板にエアースプレー塗装した。 室温で 2 4時間乾 燥後、 塗膜の 6 0度光沢を測定した結果、 実施例 1の樹脂被覆アルミペーストを 使用した塗膜は 6 5 %と高い光沢を示した力 比較例 2の樹脂被覆アルミペース トを使用した塗膜の光沢は、 5 3 %であつた。 表 6 塗料配合 （重量部） 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)
Figure imgf000022_0001
Figure imgf000022_0001
* 1…大日本インキ化学 （株） 製  * 1: Made by Dainippon Ink and Chemicals, Inc.
* 2…酢酸 Iチル /酢酸ブチル /トルエン/キシレン/ブ πピルメトキ'ンアセテ-ト の重量比 * 2 ... Weight ratio of I-yl acetate / butyl acetate / toluene / xylene / butyl pi-pyrmethoxane acetate
= 2 0/3 0/3 0/1 5/5 = 2 0/3 0/3 0/1 5/5
実施例 1 2 Example 1 2
実施例 1〜 8、 比較例 1〜 5の樹脂被覆アルミペーストについて、 表 7の配合 により水系塗料中での貯蔵安定性を評価した。 2 00mlの三角フラスコに上記塗 料 1 0 0 gを入れ、 ゴム栓付きメスピぺッ トを取り付け、 5 0°Cで 2 4時間放置 後のガス発生状態を上記の表 2に示す。 さらに、 実施例 1の樹脂被覆アルミべ一 ストを用いて表 7の配合により水性塗料を作製した後、 エア一スプレー塗装で膜 厚 3 0 になるようにアルミ板に塗装し、 1 7 0°Cで 2 0分乾燥して塗膜を作製 したところ、 優れたメタリック感を有する塗膜が得られた。 With respect to the resin-coated aluminum pastes of Examples 1 to 8 and Comparative Examples 1 to 5, storage stability in a water-based paint was evaluated according to the formulation in Table 7. The above-mentioned coating solution (100 g) was placed in a 200 ml Erlenmeyer flask, a rubber stopper was attached, and the gas generation state after standing at 50 ° C. for 24 hours is shown in Table 2 above. Further, a water-based paint was prepared by using the resin-coated aluminum base of Example 1 according to the formulation shown in Table 7, and then applied to an aluminum plate so as to have a film thickness of 30 by air spray coating. After drying with C for 20 minutes to prepare a coating film, a coating film having an excellent metallic feeling was obtained.
表 7 塗料配合 （重量部） Table 7 Paint composition (parts by weight)
Figure imgf000023_0001
Figure imgf000023_0001
* 1 アルマテックス WA- 911 (三井東圧化学㈱製）  * 1 Armatex WA-911 (Mitsui Toatsu Chemicals)
に、 ジメチルエタノールアミンを加え、 pHを  And add dimethylethanolamine to adjust the pH
9 . 5に調整したもの  Adjusted to 9.5
* 2 サイメル 3 5 0 (三井サイテック㈱製）  * 2 Cymel 350 (Mitsui Cytec Corporation)
実施例 1 3 Example 13
実施例 1の樹脂被覆アルミペースト、 比較例 2の樹脂被覆アルミペースト、 未 樹脂被覆処理アルミペースト （M G— 5 1 ：旭化成工業株式会社製） の比表面積 を測定した。 その結果を表 8に示した。 実施例 1の樹脂被覆アルミペーストの比 表面積は未樹脂被覆処理アルミペース卜の 1 . 9倍、 比較例 2では 3 . 0倍とな り、 実施例 1の樹脂被覆アルミペーストの方が高度に三次元架橋した樹脂で被覆 されていると考えられる。  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.
表 8 比表面積  Table 8 Specific surface area
Figure imgf000023_0002
Figure imgf000023_0002
実施例 1 4 Example 14
実施例 1で用いたアルミペーストを MH— 8 8 0 1 (旭化成工業株式会社製、 金属分 6 5 %) に変更した以外は実施例 1と同様にして樹脂被覆アルミべ一スト を作製した。 得られた樹脂被覆アルミペース卜を用い、 耐アルカリ性を測定した ところ、 色差は Δ Ε = 0 . 3で、 優れた耐アルカリ性を示した。 比較例 6 A resin-coated aluminum paste was produced in the same manner as in Example 1 except that the aluminum paste used in Example 1 was changed to MH-8801 (Metal content: 65%, manufactured by Asahi Kasei Corporation). When the alkali resistance was measured using the obtained resin-coated aluminum paste, the color difference was ΔΕ = 0.3, indicating excellent alkali resistance. Comparative Example 6
比較例 2で用いたアルミペーストを MH— 8 8 0 1 (旭化成工業株式会社製、 金属分 6 5 %) に変更した以外は比較例 2と同様にして樹脂被覆アルミペースト を作製した。 得られた樹脂被覆アルミペーストを用い、 その耐アルカリ性を測定 したところ、 色差は厶 E = 3 . 1であった。  A resin-coated aluminum paste was produced in the same manner as in Comparative Example 2, except that the aluminum paste used in Comparative Example 2 was changed to MH-8801 (Metal content: 65%, manufactured by Asahi Kasei Corporation). The alkali resistance of the obtained resin-coated aluminum paste was measured, and the color difference was E = 3.1.
実施例 1 5 Example 15
実施例 1 4の樹脂被覆アルミペースト、 比較例 6の樹脂被覆アルミペースト、 未樹脂被覆処理アルミペースト （MH— 8 8 0 1 ：旭化成工業株式会社製） の比 表面積を測定した。 その結果を表 9に示した。 実施例 1 4の樹脂被覆アルミべ一 ストの比表面積は未処理アルミべ一ストの 1 . 5倍、 比較例 6では 3 . 0倍とな り、 実施例 1 3の樹脂被覆アルミペーストの方が高度に三次元架橋した樹脂で被 覆されていると考えられる。 表 9 比表面積  The specific surface areas of the resin-coated aluminum paste of Example 14, the resin-coated aluminum paste of Comparative Example 6, and the non-resin-coated aluminum paste (MH-8801: manufactured by Asahi Kasei Corporation) were measured. Table 9 shows the results. The specific surface area of the resin-coated aluminum base in Example 14 was 1.5 times that of the untreated aluminum base, and 3.0 times in Comparative Example 6. Thus, the resin-coated aluminum paste of Example 13 was smaller. Is considered to be covered with highly three-dimensionally crosslinked resin. Table 9 Specific surface area
Figure imgf000024_0001
Figure imgf000024_0001
本発明の樹脂被覆金属顔料は、 架橋密度の高い樹脂で被覆されているため、 耐 薬品性、 耐候性および貯蔵安定性に優れる。 また比表面積が小さく吸油量が小さ いため、 樹脂被覆に起因する光沢の低下を最小限に抑えることができる。  Since 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.
これらの理由から本発明の樹脂被覆金属顔料はメタリック塗料用、 印刷ィンキ 用、 プラスチック練り込み用途に好適に使用できる。  For these reasons, the resin-coated metal pigment of the present invention can be suitably used for metallic paints, printing inks, and kneading plastics.
また、 本発明のメタリック塗料は優れた耐候性を有するため、 耐久性を要求さ れる自動車のボディーやバンパー、 サイドミラー等の部品、 瓦、 屋根、 壁等の建 築外装、 家電等の分野に好適に使用できる。  In addition, since 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.

Claims

請 求 の 範 囲 The scope of the claims
1. (A) ラジカル重合性不飽和カルボン酸、 および Zまたは、 ラジカル重合 性二重結合を有するリン酸またはホスホン酸モノまたはジエステル、 および/ま たは、 ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも 一種と、 （B) ラジカル重合性二重結合を 3個以上有する単量体と、 （C) 重合開始 剤とを用い、 先ず、 （A) を添加し金属顔料を処理した後、 （B) と（C) の少なくと も一方を徐々に追加添加して重合した樹脂層を表面に形成した樹脂被覆金属顔料。 1. (A) Radical polymerizable unsaturated carboxylic acid, and Z or phosphoric acid or phosphonic acid mono or diester having a radical polymerizable double bond, and / or coupling having a radical polymerizable double bond Using at least one selected from the group consisting of (B) a monomer having three or more radically polymerizable double bonds and (C) a polymerization initiator, first adding (A) to treat the metal pigment After that, at least one of (B) and (C) is gradually added to form a polymerized resin layer on the surface of the resin-coated metal pigment.
2. (B) のラジカル重合性二重結合を 3個以上有する単量体として、 ラジカ ル重合性二重結合を 3個有する単量体とラジカル重合性二重結合を 4個以上有す る単量体を併用し、 ラジカル重合性二重結合を 4個以上有する単量体の量が重量 比で 1 0〜 6 0 %である請求項 1に記載の樹脂被覆金属顔料。  2. As a monomer having three or more radical polymerizable double bonds in (B), a monomer having three radical polymerizable double bonds and four or more radical polymerizable double bonds 2. The resin-coated metal pigment according to claim 1, wherein the amount of the monomer having four or more radical polymerizable double bonds in combination with the monomer is 10 to 60% by weight.
3. (B) と（C) の少なくとも一方を重合時間の 2 0 %以上の時間をかけて追 加添加する請求項 1又は 2に記載の樹脂被覆金属顔料。  3. The resin-coated metal pigment according to claim 1, wherein at least one of (B) and (C) is additionally added over 20% of the polymerization time.
4. ラジカル重合性二重結合を 4個以上有する単量体の官能基あたりの分子 量が 3 0以上 2 0 0以下である請求項 1ないし 3に記載の樹脂被覆金属顔料。  4. The resin-coated metal pigment according to claim 1, wherein the molecular weight per functional group of the monomer having four or more radically polymerizable double bonds is from 30 to 200.
5. 耐アルカリ性が 2 . 0以下である請求項 1ないし 4に記載の樹脂被覆金 Jk顔^。  5. The resin-coated gold Jk face according to claim 1, which has an alkali resistance of 2.0 or less.
6. 請求項 1ないし 5のいずれかに記載の樹脂被覆金属顔料を含むメタリッ ク塗料。  6. A metallic paint containing the resin-coated metal pigment according to any one of claims 1 to 5.
PCT/JP1996/001450 1995-05-30 1996-05-29 Novel resin-coated metallic pigment and metallic coating material containing the pigment WO1996038506A1 (en)

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MY121596A (en) 2006-02-28
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TW425419B (en) 2001-03-11
CN1185798A (en) 1998-06-24
KR100327274B1 (en) 2002-09-27
CN1093155C (en) 2002-10-23

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