JP2005120284A - Black complex particle powder and coating and resin composition each containing the black complex particle powder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide black complex particle powder excellent in dispersibility and filling property in vehicles and exhibiting excellent blackness in slight addition amount. <P>SOLUTION: In the black complex particle powder, at least parts of particle surfaces of carbon product particle powder of furnace black, channel black, acetylene black, etc., are coated with a surface treating agent and a carbon component exists on the each surface of the coat and/or the particles. The black complex particle powder has ≤20% rate of change of compressive density. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a black composite particle powder having excellent dispersibility and filling properties in a vehicle and exhibiting excellent blackness with a small addition amount.

  Currently, black pigments such as inks, paints, rubbers and plastics are mixed with black pigments such as carbon black, graphite and black iron oxide, black organic pigments such as perylene black, and two-color pigments that are complementary to each other. A black pigment obtained by the above method is known.

However, these black pigments, particularly carbon black, which is most commonly used, is a fine particle powder having an average particle size of about 0.005 to 0.05 μm, and therefore, into a vehicle or a resin composition. It is known that it is difficult to disperse, and the bulk density is about 0.1 g / cm ³ , so that it is difficult to handle and the workability is poor.

  Therefore, there is a need for a black pigment that is excellent in dispersibility and filling properties in a vehicle and that exhibits excellent blackness with a small amount of addition.

  Until now, for the purpose of obtaining a high optical density, it is known to use a mixture of carbon black and graphite, and to use two or more types of carbon black having different average particle diameters (Patent Document 1). Thru 3).

  In addition, for the purpose of obtaining a black composite particle powder having excellent light resistance, coloring power and dispersibility in the vehicle, the surface of the white inorganic particle powder having a refractive index of less than 2.0 is blackened via a paste. A black composite particle powder to which a pigment is attached is known (Patent Document 4).

JP-A-11-349898 Japanese Patent Laid-Open No. 9-133806 Japanese Patent Laid-Open No. 9-178931 JP 2003-147228 A

  A black pigment that is excellent in dispersibility and filling property in a vehicle and that exhibits excellent blackness with a small amount of addition is currently most demanded, but has not yet been obtained.

  That is, in the above-mentioned patent documents 1 to 3, it is described that carbon black and graphite or two or more types of carbon black having different average particle diameters are mixed and used. It is difficult to disperse in and it is difficult to say that it is excellent in dispersibility and filling property because it behaves as an agglomerate.

  Moreover, although the above-mentioned patent document 4 describes the black composite particle powder in which the black pigment adheres to the particle surface of the white inorganic particle powder having a refractive index of less than 2.0 via a paste. Since the core particles are transparent or white, it is difficult to say that they have better blackness.

  Accordingly, it is a technical object of the present invention to provide a black composite particle powder that is excellent in dispersibility and filling properties in a vehicle and exhibits excellent blackness with a small addition amount.

  The technical problem can be achieved by the present invention as follows.

  That is, the present invention provides a black composite characterized in that at least a part of the particle surface of the carbon product particle powder is coated with a surface treatment agent and a carbon component is present on the surface of the coating and / or the particle. It is a particle powder (Invention 1).

  Further, the present invention is a black composite particle powder in which at least a part of the particle surface of the carbon product particle powder is coated with a surface treatment agent and the coating and / or the surface of the particle has a carbon component. The black composite particle powder is characterized in that the change rate of the compression density of the black composite particle powder is 20% or less (Invention 2).

  In addition, the present invention is a paint characterized in that the black composite particle powder of the present invention 1 or 2 is contained in a paint-constituting substrate (Invention 3).

  Moreover, this invention is a resin composition characterized by coloring using the black composite particle powder of this invention 1 or this invention 2 (this invention 4).

  The black composite particle powder according to the present invention is suitable as a coloring material for paints, inks, resins, and the like because it is excellent in dispersibility and filling properties in a vehicle and exhibits excellent blackness with a small addition amount.

  The configuration of the present invention will be described in more detail as follows.

  First, the black composite particle powder according to the present invention will be described.

  In the black composite particle powder according to the present invention, at least a part of the particle surface of the carbon product that is the core particle powder is coated with the surface treatment agent, and the surface treatment agent-coated particle and / or the carbon product particle. It consists of composite particles in which a carbon component is present on the particle surface.

  As the carbon product in the present invention, carbon black and graphite such as furnace black, channel black and acetylene black can be used, and carbon black is preferable.

  The particle shape of the carbon product may be any shape such as a spherical shape, a granular shape, a polyhedral shape, a needle shape, a spindle shape, a rice granular shape, a flake shape, a scale shape, and a plate shape.

  The particle size of the carbon product may be appropriately selected according to the use, but the average particle size is preferably 0.001 to 5.0 μm, more preferably 0.005 to 4.0 μm, and still more preferably 0.01 to 3.0 μm.

  When the average particle diameter exceeds 5.0 μm, the resulting black composite particle powder becomes coarse particles, which is not preferable because the coloring power is reduced.

BET specific surface area value of the carbon product is at 0.1m ² / g~500m ² / g or more, preferably 0.3m ² / g~400m ² / g, more preferably 0.5 m ^2/300 m ² / G.

The blackness of the carbon product in the present invention has an L ^* value of 33.0 or less, preferably 32.0 or less, more preferably 31.0 or less.

The hiding power of the carbon product in the present invention is preferably 2,000 cm ² / g or more, more preferably 2,500 cm ² / g or more, and still more preferably 3,000 cm ² / g or more.

In the light resistance of the carbon product in the present invention, the lower limit value of the ΔE ^* value usually exceeds 5.0 and the upper limit value is 12.0, preferably 11.0, more preferably 10.0, according to an evaluation method described later. It is.

  At least a part of the surface of the carbon product particles used in the present invention is coated with a surface treatment agent. Any surface treating agent may be used as long as it can adhere a carbon component to the particle surface of the carbon product. Examples of the surface treating agent include alkoxysilane, fluoroalkylsilane, silane coupling agent and organopolysiloxane. Preferably used are organosilicon compounds such as siloxane, coupling agents such as titanate, aluminate and zirconate, low molecular weight or high molecular surfactants and the like. More preferred are organosilicon compounds such as alkoxysilanes, fluoroalkylsilanes, silane coupling agents, and organopolysiloxanes.

  Examples of organosilicon compounds include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, ethyltriethoxysilane, and propyl. Alkoxysilanes such as triethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane and decyltriethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadeca Fluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorodecyltriethoxysilane And fluoroalkylsilanes such as tridecafluorooctyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, Silane coupling such as γ-methacryloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane Agents, organopolysiloxanes such as polysiloxane, methyl hydrogen polysiloxane, and modified polysiloxane.

  Titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate titanate, tetra (2,2 diallyl) Examples include oxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tribotoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  Examples of the low molecular surfactant include alkylbenzene sulfonate, dioctyl sulfone succinate, alkylamine acetate, alkyl fatty acid salt and the like. Examples of the polymeric surfactant include polyvinyl alcohol, polyacrylate, carboxymethylcellulose, acrylic acid-maleate copolymer, and olefin-maleate copolymer.

  The coating amount of the surface treatment agent is preferably 0.02 to 5.0% by weight in terms of a metal element contained in the surface treatment agent with respect to the carbon product. More preferably, it is 0.03-3.0 weight%, More preferably, it is 0.05-2.0 weight%. In the case of less than 0.02% by weight, it is difficult to attach 1 part by weight or more of carbon component to 100 parts by weight of the carbon product. When the amount exceeds 5.0% by weight, 1 to 500 parts by weight of the carbon component can be attached to 100 parts by weight of the carbon product, so there is no meaning to cover more than necessary.

  The carbon component present on the particle surface of the carbon product in the present invention is composed of carbon black such as furnace black, channel black, and acetylene black.

  The total amount of the carbon component is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the carbon product as the core particle.

  In the case of less than 1 part by weight and in the case of exceeding 500 parts by weight, it is difficult to obtain the black composite particle powder that is the object of the present invention. More preferably, it is 2-400 weight part, More preferably, it is 5-300 weight part.

  The particle shape and particle size of the black composite particle powder according to the present invention greatly depend on the particle shape and particle size of the carbon product as the core particle, and have a particle form similar to the core particle.

  That is, the average particle size of the black composite particle powder according to the present invention is preferably 0.001 to 5.0 μm, more preferably 0.005 to 4.0 μm, and still more preferably 0.01 to 3.0 μm.

  When the average particle diameter of the black composite particle powder according to the present invention according to the present invention exceeds 5.0 μm, the coloring power is reduced because the particle size is too large.

BET specific surface area value of the black composite particles according to the present invention according to the present invention is preferably 0.1m ² / g~500m ² / g, more preferably 0.3m ² / g~400m ² / g, preferably more than is 0.5m ² / g~300m ² / g. When the BET specific surface area value is less than 0.5 m ² / g, the particles are coarse and the coloring power is reduced.

The blackness of the black composite particle powder according to the present invention has an L ^* value of 32.0 or less, preferably 31.0 or less, more preferably 30.0 or less. When the L ^* value exceeds 32.0, the brightness is too high, and it is difficult to say that the blackness is excellent.

The black composite particle powder according to the present invention is preferably 3,000 cm ² / g or more, more preferably 4,000 cm ² / g or more, still more preferably 4,500 cm ² / g or more, most preferably 5,000 cm ² / g. That's it. When the hiding power is less than 3,000 cm ² / g, it is difficult to say that the hiding power is excellent.

  The coloring power of the black composite particle powder according to the present invention is preferably 105% or more, more preferably 110% or more, and most preferably 115% or more according to an evaluation method described later.

In the evaluation method described later, the light resistance of the black composite particle powder according to the present invention is preferably 5.0 or less, more preferably 4.5 or less in terms of ΔE ^* value.

  The rate of change in compression density of the black composite particle powder according to the present invention is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less, in the evaluation method described later.

  Next, a paint containing the black composite particle powder according to the present invention will be described.

The coating composition containing the black composite particle powder according to the present invention preferably has a storage stability of ΔE ^* value of 1.5 or less, more preferably 1.2 or less. In the case of a coating film, the blackness L ^* value is preferably 32.0 or less, more preferably 31.0 or less, and most preferably 30.0 or less. The glossiness is preferably 75 to 110%, more preferably 80 to 110%. The light resistance ΔE ^* value of the coating film is preferably 5.0 or less, more preferably 4.0 or less.

The water-based paint containing the black composite particle powder according to the present invention has a storage stability of preferably 1.5 or less, more preferably 1.2 or less in terms of ΔE ^* value. In the case of a coating film, the blackness L ^* value is preferably 32.0 or less, more preferably 31.0 or less, and most preferably 30.0 or less. The glossiness is preferably 70 to 110%, more preferably 75 to 110%. The light resistance ΔE ^* value of the coating film is preferably 5.0 or less, more preferably 4.0 or less.

  The blending ratio of the black composite particle powder in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint constituting base material, and considering the handling of the paint, Preferably it is 1.0-100 weight part.

  As the paint constituent base material, a resin, a solvent, and if necessary, fats and oils, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.

  Resins include acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin, vinyl chloride resin, silicone resin, gum rosin that are usually used for solvent-based paints and oil-based printing inks. Rosin resins such as lime rosin, maleic acid resin, polyamide resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, rosin modified phenolic resin, rosin modified maleic resin and other rosin modified resins, petroleum resins and the like can be used. . For water-based paints, water-soluble acrylic resins, water-soluble styrene-maleic acid resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urethane emulsion resins, water-soluble epoxies commonly used for water-based paints and water-based inks Resins, water-soluble polyester resins, and the like can be used.

  Solvents include soybean oil, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Glycol ether solvents, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, alicyclic hydrocarbon solvents such as cyclohexane, and petroleum-based solvents such as mineral spirits Solvents, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, aliphatic hydrocarbons, and the like can be used.

  Water-based paint solvents include water and alcohol-based solvents usually used for water-based paints such as ethyl alcohol, propyl alcohol and butyl alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and other glycol ether solvents, diethylene glycol , Oxyethylene or oxypropylene addition polymers such as triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, alkylene glycol such as ethylene glycol, propylene glycol, 1,2,6-hexanetriol, glycerin, It can be used by mixing with a water-soluble organic solvent such as 2-pyrrolidone.

  As oils and fats, boil oils obtained by processing dry oils such as linseed oil, persimmon oil, sea lion oil, safflower oil and the like can be used.

  Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Commercially available products such as manufactured by Co., Ltd., Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.

  Next, the resin composition containing the black composite particle powder according to the present invention will be described.

In the resin composition according to the present invention, the blackness L ^* value is preferably 32.0 or less, more preferably 31.0 or less, and most preferably 30.0 or less. As for the dispersibility in a resin composition, 4 or 5 is preferable by the evaluation method mentioned later, More preferably, it is 5. The light resistance ΔE ^* value is 5.0 or less, preferably 4.0 or less, and the aging resistance is 15% or less, preferably 10% or less, and the proportion of the discolored portion when heated at 190 ° C. for 120 minutes Preferably it is 5% or less.

  The compounding ratio of the black composite particle powder in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the resin, and considering the handling of the resin composition. The amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.

  As a constituent substrate in the resin composition according to the present invention, black composite particle powder and a known thermoplastic resin, and additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers, if necessary. Blended.

  Examples of the resin include polyolefins such as polyethylene, polypropylene, polybutene, and polyisobutylene, polyvinyl chloride, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, styrene-acrylic acid ester copolymer, styrene-vinyl acetate copolymer, Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-EPDM-styrene copolymer, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane and other thermoplastic resins, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, Silicone resin, rosin ester, rosin, natural rubber, synthetic rubber and the like can be used.

  The amount of the additive may be 50% by weight or less with respect to the total of the black composite particle powder and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.

  The resin composition according to the present invention is obtained by thoroughly mixing a resin raw material and black composite particle powder in advance, and then applying a strong shearing action under heating using a kneader or an extruder, thereby agglomerating the black composite particle powder. After the black composite particle powder is uniformly dispersed in the resin composition, it is molded into a shape suitable for the purpose and used.

  The resin composition according to the present invention can also be obtained via a master batch pellet.

  The masterbatch pellets in the present invention are a blender such as a ribbon blender, a Nauter mixer, a Henschel mixer, a super mixer, etc., if necessary, with a binder resin as a constituent substrate of the paint and resin composition and the black composite particle powder. After mixing, kneaded with a well-known single-screw kneading extruder or twin-screw kneading extruder, molded and then cut, or kneaded product obtained by kneading the above mixture with a Banbury mixer, pressure kneader or the like Manufactured by crushing or molding and cutting.

  As for the supply of the binder resin and the black composite particle powder to the kneader, each of them may be supplied at a predetermined ratio, or a mixture of both may be supplied.

  The master batch pellet in the present invention has an average major axis of 1 to 6 mm, preferably 2 to 5 mm. The average minor axis is 2 to 5 mm, preferably 2.5 to 4 mm. When the average major axis is less than 1 mm, the workability at the time of producing the pellet is poor, which is not preferable. When the thickness exceeds 6 mm, the difference from the size of the binder resin for dilution is large, and it becomes difficult to sufficiently disperse. Moreover, the shape can be various, and can be indefinite and spherical, cylindrical, flakes, and the like.

  As the binder resin used for the master batch pellet in the present invention, the same resin as the resin for resin composition can be used.

  The composition of the binder resin in the masterbatch pellet may be the same resin as the diluent binder resin or a different resin, but if different resins are used, What is necessary is just to determine in consideration of the various characteristics determined by the compatibility.

  The amount of the black composite particle powder blended in the master batch pellet is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is less than 1 part by weight, the melt viscosity at the time of kneading is insufficient, and it is difficult to achieve good dispersion mixing of the black composite particle powder. When the amount exceeds 200 parts by weight, since the binder resin for the black composite particle powder is small, it is difficult to disperse and mix the black composite particle powder. Since the content of the black composite particle powder blended in is greatly changed, it is difficult to prepare a desired content, which is not preferable. Also, mechanical wear is severe and not suitable.

  Next, a method for producing the black composite particle powder according to the present invention will be described.

  The black composite particle powder according to the present invention is obtained by mixing a carbon product and a surface treatment agent, coating at least a part of the particle surface of the carbon product with the surface treatment agent, and then coating the carbon coated with the surface treatment agent. It can be obtained by mixing the product and the carbon component.

  In the present invention, the surface of the carbon product with the surface treatment agent is coated on the particle surface by mechanically mixing and stirring the carbon product and the surface treatment agent or the solution of the surface treatment agent. Alternatively, mechanical mixing and stirring may be performed while spraying the surface treatment agent. Almost all of the added surface treatment agent is coated on the particle surface of the carbon product.

  As a device for mixing and stirring the carbon product and the surface treatment agent, and mixing and stirring the carbon component and the carbon product whose particle surface is coated with the surface treatment agent, a shear force is applied to the powder layer. It is preferable to use a device that can simultaneously perform shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, and a roll-type kneader. A kneader can be used more effectively.

  Examples of the wheel-type kneader include an edge runner (synonymous with “mix muller”, “simpson mill”, “sand mill”), multi-mal, stotz mill, wet pan mill, conner mill, ring muller, etc., preferably edge Runners, multi-mals, stocks mills, wet pan mills and ring mullers, more preferably edge runners. Examples of the ball kneader include a vibration mill. Examples of the blade-type kneader include a Henschel mixer, a planetary mixer, and a nauter mixer. Examples of the roll-type kneader include an extruder.

  The conditions at the time of mixing and stirring the carbon product and the surface treatment agent were such that the line load was 19.6 to 1960 N / cm (2 to 200 kg) so that the surface treatment agent was coated as uniformly as possible on the particle surface of the carbon product. / Cm), preferably 98 to 1470 N / cm (10 to 150 Kg / cm), more preferably 147 to 980 N / cm (15 to 100 Kg / cm), treatment time 5 minutes to 24 hours, preferably 10 minutes to 20 What is necessary is just to adjust process conditions suitably in the range of time. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.

  The addition amount of the surface treatment agent is preferably 0.15 to 45 parts by weight with respect to 100 parts by weight of the carbon product. With the addition amount of 0.15 to 45 parts by weight, 1 to 500 parts by weight of the carbon component can be present with respect to 100 parts by weight of the carbon product.

  After the surface treatment agent is coated on the surface of the carbon product particles, the carbon component is added and mixed and stirred to adhere or coat the carbon component on the particle surface of the carbon product or the surface treatment agent coating. If necessary, drying or heat treatment may be further performed.

  The carbon component is added little by little over a period of 5 minutes to 24 hours, preferably 5 minutes to 20 hours, or 5 to 25 weights per 100 parts by weight of the carbon product. Part of the carbon component is preferably added in portions until the desired addition amount is reached.

  The conditions at the time of mixing and stirring are such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm), preferably 98 to 1470 N / cm (10 to 10%) so that the carbon component exists as uniformly as possible on the particle surface. 150 Kg / cm), more preferably 147 to 980 N / cm (15 to 100 Kg / cm), and the processing time may be appropriately adjusted within the range of 5 minutes to 24 hours, preferably 10 minutes to 20 hours. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.

  The addition amount of the carbon component is 1 to 500 parts by weight, preferably 2 to 400 parts by weight, and more preferably 5 to 300 parts by weight with respect to 100 parts by weight of the carbon product. When the addition amount of the carbon component is outside the above range, the target black composite particle powder cannot be obtained.

  In the case of performing drying or heat treatment, the heating temperature is usually preferably 40 to 150 ° C, more preferably 60 to 120 ° C, and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours. .

<Action>
The most important point in the present invention is that at least a part of the particle surface of the carbon product particle powder is coated with a surface treatment agent, and the surface treatment agent-coated particle and / or the carbon surface of the carbon product particle is coated with carbon. This is the fact that the black composite particle powder containing the components is excellent in dispersibility and filling properties in the vehicle and exhibits excellent blackness with a small addition amount.

  The reason why the black composite particle powder according to the present invention has excellent dispersibility is that the present inventor found that the fine carbon black that normally behaves as an aggregate due to the fine particles is the black color according to the present invention. In the case of the composite particle powder, the individual carbon black functions more effectively without being agglomerated by being coated or attached to the particle surface of the carbon product having a large particle diameter via a surface treatment agent. I believe that.

As a reason why the black composite particle powder according to the present invention is excellent in packing properties, the present inventors, as described above, simply mixed fine carbon black (carbon component) and a carbon product having a large particle diameter. In addition, since fine carbon black (carbon component) behaves as an aggregate, it is difficult to efficiently enter a gap between carbon products having a large particle diameter (carbon black). In this case, it is possible to effectively fill the voids by coating or adhering the carbon component to the particle surface of the carbon product having a large particle diameter via a surface treatment agent in advance, and the filling rate in the coating film Is estimated to have improved.

  Hereinafter, embodiments of the present invention will be described to specifically describe the present invention.

  The average particle size of each particle was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.

  The specific surface area value was indicated by a value measured by the BET method.

  The coating amount of the surface treatment agent coated on the particle surface of the carbon product uses “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Corporation) for the metal elements contained in each surface treatment agent. , Measured in accordance with “General X-ray fluorescence analysis rules” of JIS K0119.

  Confirmation of the presence of the surface treatment agent and the carbon component coated on the surface of the carbon product particles is obtained by treating the sample powder with a resin and cutting the cross section with a microtome, EPMA “Electron Probe Microanalyzer JXA-8900RL” (Nippon Denshi Co., Ltd.) was used to perform color map analysis on carbon and metal elements contained in the surface treatment agent.

The blackness of the carbon product and the black composite particle powder was determined by mixing 0.5 g of a sample and 0.5 ml of castor oil with a Hoover-type Mahler to form a paste, and adding 4.5 g of clear lacquer to this paste to knead and paint. Then, an application piece (coating thickness: about 30 μm) coated on a cast-coated paper using a 150 μm (6 mil) applicator was prepared, and “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.) The color index L ^* was shown in accordance with JIS Z 8929.

The coloring power of the carbon product and the black composite particle powder is as follows. First, each of the primary color enamel and the color development enamel prepared according to the following method is applied onto a cast coated paper using a 150 μm (6 mil) applicator. The L ^* value was measured using a “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.), and the difference was taken as the ΔL ^* value.

Next, as a standard sample of the black composite particle powder, using a mixed pigment obtained by simply mixing a carbon product and a carbon component at the same ratio as the black composite particle powder, the primary color enamel and the color development enamel are applied in the same manner as described above. A piece was prepared, the L ^* value of each coated piece was measured, and the difference was taken as the ΔLs ^* value.

The value calculated according to the following Equation 1 using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the obtained black composite particles shown as tinting strength (%).

(Equation 1)
Tinting strength (%) = 100 + {( ΔLs * value -Delta L ^* value) × 10}

Production of primary color enamel:
10 g of the above sample powder, 16 g of amino alkyd resin and 6 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed for 45 minutes with a paint shaker, and then 50 g of amino alkyd resin was added. Further, it was dispersed with a paint shaker for 5 minutes to produce a primary color enamel.

Production of color-enamel:
12 g of the primary color enamel and 40 g of amylac white (titanium dioxide-dispersed aminoalkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to produce a color-enamel.

  The hiding power of the carbon product and the black composite particle powder was indicated by a value obtained according to the cryptometer method of JIS K 5101 8.2 using the primary color enamel prepared for measuring the above-mentioned coloring power.

The light resistance of the carbon product and the black composite particle powder is that the primary color enamel prepared for measuring the coloring power is 150 μm on a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141). Coating with a thickness and drying to form a coating film, half of the obtained coating for measurement is covered with a metal foil, and ultraviolet rays are applied using “I Super UV Tester SUV-W13” (manufactured by Iwasaki Electric Co., Ltd.). After being irradiated continuously for 6 hours at an irradiation intensity of 100 mW / cm ² , the hue (L ^* value, a ^* value, b ^* value) between the portion not irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays by covering with metal foil The ΔE ^* values calculated according to the following formula 2 are shown based on the measured values of the portions not irradiated with ultraviolet rays.

(Equation 2)
ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2
ΔL ^* value: difference in L ^* value of sample to be compared with UV irradiation Δa ^* value: difference in a ^* value of sample to be compared with UV irradiation Δb ^* value: b ^* value of sample to be compared with UV irradiation difference

The rate of change in the compression density of the carbon product and black composite particle powder is as follows. First, 0.3 g of the sample powder is measured and placed in a cylindrical mold having a diameter of 13 mm, and a KBr tablet molding machine (Shimadzu Corporation) is used. Then, pressure forming is performed at a pressure of 0.98 × 10 ⁷ Pa (100 Kg / cm ² ) and 4.90 × 10 ⁷ Pa (500 Kg / cm ² ), and from the thickness of the obtained powder layer, The compression densities CD ₁₀₀ (g / cm ³ ) and CD ₅₀₀ (g / cm ³ ) at pressure were determined, and the measured values were inserted into the following Equation 3 to determine the compression density change rate (%).

(Equation 3)
Rate of change in compression density (%) = {(CD ₁₀₀ −CD ₅₀₀ ) / CD ₁₀₀ )} × 100

The L ^* value of the solvent-based paint and the water-based paint using the black composite particle powder is 150 μm on each cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) prepared according to the formulation described later. About the coating piece for measurement obtained by coating and drying at a thickness to form a coating film, measurement is performed using a “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.), and as defined in JIS Z 8929 According to the color index L ^* value. Further, the L ^* value of the resin composition colored using the black composite particle powder is determined by using a spectrocolorimeter CM-3610d (manufactured by Minolta Co., Ltd.) as a colored resin plate produced by a method described later. Measurement was performed in the same manner as described above.

  The glossiness of the coating film was shown by the glossiness at an incident angle of 60 ° using the “Glossmeter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). It shows that the dispersibility of the coating material which mix | blended black composite particle powder is excellent, so that glossiness is high.

The light resistance of the coating film using each paint was determined by covering half of the coating piece for measurement prepared in order to measure the L ^* value of the above-mentioned paint with a metal foil, “I Super UV Tester SUV-W13” (Iwasaki) (Electrical Co., Ltd.), and continuously irradiating ultraviolet rays at an irradiation intensity of 100 mW / cm ² for 6 hours, and then covering with a metal foil, the hue between the portion not irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays (L ^* Value, a ^* value, b ^* value) were measured, and indicated by the ΔE ^* value calculated according to the above equation 2 based on the measured value of the portion not irradiated with ultraviolet rays.

In addition, the light resistance of each resin composition was determined by covering half of the resin plate prepared for measuring the L ^* value of the resin composition described above with a metal foil, “I Super UV Tester SUV-W13” (Iwasaki Electric Co., Ltd.). The color (L ^* value) between the part that was not irradiated with ultraviolet rays and the part that was irradiated with ultraviolet rays by covering it with a metal foil after continuously irradiating ultraviolet rays with an irradiation intensity of 100 mW / cm ² for 6 hours. , A ^* value, b ^* value) were measured, respectively, and indicated by ΔE ^* value calculated according to the above equation 2 based on the measured value of the portion not irradiated with ultraviolet rays.

The storage stability of the paint is a coating film produced by applying each paint prepared according to the formulation described later to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS-G-3141) at a thickness of 150 μm and drying. L ^* value, a ^* value, and b ^* value, and L ^* value of a coating film produced by applying the paint obtained by allowing the paint to stand at 25 ° C. for 1 week on a cold-rolled steel sheet and drying, The a ^* value and the b ^* value were measured and indicated by the ΔE ^* value obtained according to the following equation 4.

(Equation 4)
ΔE ^* value = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^1/2
ΔL ^* value: difference in L ^* value before and after standing of the coating film to be compared Δa ^* value: difference in a ^* value before and after standing of the coating film to be compared Δb ^* value: b before and after standing of the coating film to be compared ^* Value difference

Regarding the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared according to the formulation described below is measured using an E type viscometer (cone plate type viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.) and a shear rate D = 1. The value at 92 sec ⁻¹ was determined.

The dispersibility of the black composite particle powder in the resin composition was evaluated in five stages by visually determining the number of undispersed aggregated particles on the surface of the obtained colored resin plate. 5 indicates the best dispersion state.
5: Undispersed material is not recognized,
4: 1 to less than 5 per 1 cm ²
3: 5 or more and less than 10 per 1 cm ²
2: 10 to less than 50 per 1 cm ²
1: 50 or more per 1 cm ² .

Aging resistance is the area S of the portion where the colored resin plate (1.5 cm long × 1.5 cm wide × 1 mm thick) kneaded with the black composite particle powder is discolored and the resin deteriorates when heated at 190 ° C. The ratio S / S ₀ between the surface area of the colored plate before heating and the surface area S ₀ (1.5 × 1.5 = 2.25 cm ² ) of the colored plate was determined in 5% increments.

That is, when (S / S ₀ ) × 100 is 0%, there is no deterioration, and when (S / S ₀ ) × 100 is 100%, the resin is completely deteriorated.

<Manufacture of black composite particle powder>
Example 1
Carbon product particle 3 (type: carbon black, particle shape: granular, average particle size 0.303 μm, BET specific surface area value 8.6 m ² / g, L ^* value 27.94, hiding power 4,200, light resistance ΔE ^* Value 13.71, compression density change rate 22.1%) 5.0kg, methyl hydrogen polysiloxane (trade name: TSF484: manufactured by GE Toshiba Silicone Co., Ltd.) 100g, carbon generation while running the edge runner The mixture was stirred for 30 minutes with a linear load of 588 N / cm (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, carbon product particles 1 (type: carbon black, particle shape: granular, average particle size 0.022 μm, BET specific surface area value 134.0 m ² / g, L ^* value 25.63, hiding power 14,300 cm ² / G, light resistance ΔE ^* value 12.65, rate of change of compression density 30.4%) is added over 30 minutes while the edge runner is running, and a linear load of 588 N / cm (60 Kg / cm) is added. The mixture was stirred for 30 minutes to deposit or coat the carbon component, and then heat-treated at 105 ° C. for 60 minutes using a dryer to obtain black composite particle powder. The stirring speed at this time was 22 rpm.

The obtained black composite particle powder was a granular particle powder having an average particle size of 0.305 μm. The BET specific surface area value is 8.9 m ² / g, the blackness L ^* value is 25.91, the coloring power is 118%, the hiding power is 5,900 cm ² / g, and the light resistance ΔE ^* value is 3.61. The rate of change in compression density was 3.8%. The coating amount of methyl hydrogen polysiloxane was 0.41% by weight in terms of Si.

  As a result of EPMA analysis, it was confirmed that the surface treatment agent and the carbon product were present on the surface of the carbon product.

Examples 2-6, Comparative Examples 1-3:
The type of additive in the coating process with the surface treatment agent, the amount added, the line load and time for edge runner treatment, the type of carbon product in the adhesion or coating process of the carbon component, the amount added, the line load and time for edge runner treatment. A black composite particle powder was obtained in the same manner as in Example 1 except that various changes were made.

  The production conditions at this time are shown in Table 2, and the characteristics of the obtained black composite particle powder are shown in Table 3. In addition, the particles 1-5 which have the characteristic shown in Table 1 as a carbon product were used.

  In Example 6, 95.0 parts by weight of carbon product particles 1 were gradually added over 90 minutes with respect to 100.0 parts by weight of the core particles.

<Manufacture of solvent-based paint containing black composite particle powder>
Example 7
10 g of the black composite particle powder, amino alkyd resin and thinner were blended in the following proportions and added together with 90 g of 3 mmφ glass beads to a 140 ml glass bottle, and then mixed and dispersed in a paint shaker for 90 minutes to prepare a mill base.

12.2 parts by weight of black composite particle powder,
19.5 parts by weight of amino alkyd resin,
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 7.3 parts by weight.

  Using the mill base, an amino alkyd resin was blended so as to have the following ratio, and further mixed and dispersed with a paint shaker for 15 minutes to obtain a solvent-based paint containing black composite particle powder.

39.0 parts by weight of mill base,
Aminoalkyd resin 61.0 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The solvent-based paint obtained had a paint viscosity of 893 cP, and the storage stability of the paint was 0.93 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the solvent-based paint to a cold-rolled steel sheet (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 83%, L ^* The value was 26.12, and the light resistance ΔE ^* value was 2.12.

Examples 8-12, Comparative Examples 3-11:
A solvent-based paint was obtained in the same manner as in Example 7 except that the type and amount of the black particle powder were variously changed.

  Table 4 shows various properties of the obtained paint and various properties of the coating film.

<Manufacture of water-based paint containing black composite particle powder>
Example 13
The black composite particle powder (7.62 g) and water-soluble alkyd resin and the like were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads at the following ratio, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.

12.4 parts by weight of black composite particle powder,
9.0 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
4.8 parts by weight of water,
Butyl cellosolve 4.1 parts by weight.

  Using the mill base, the paint composition was blended at the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain an aqueous paint containing black composite particle powder.

30.4 parts by weight of mill base,
46.2 parts by weight of a water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
12.6 parts by weight of a water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
9.1 parts by weight of water,
Butyl cellosolve 1.6 parts by weight.

The resulting water-based paint had a paint viscosity of 1,263 cP and a storage stability of 0.92 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the water-based paint to a cold rolled steel sheet (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 81%, L ^* value Was 26.15 and the light resistance ΔE ^* value was 2.10.

<Water-based paint>
Examples 14-18, Comparative Examples 12-19:
A water-based paint was obtained in the same manner as in Example 13 except that the type and amount of black particle powder were variously changed.

  Table 5 shows various properties of the obtained paint and various properties of the coating film.

<Manufacture of resin composition>
Example 19
The black composite particle powder 2.5 g and the polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.) 47.5 g were weighed, put into a 100 ml poly beaker and mixed well with a spatula to obtain a mixed powder.

  After adding 0.5 g of calcium stearate to the obtained mixed powder and mixing it, and setting the clearance of the hot roll heated to 160 ° C. to 0.2 mm, the mixed powder was kneaded with a roll little by little to obtain a resin composition The kneading was continued until the products were integrated, and then the resin composition was peeled from the roll and used as a colored resin plate raw material.

Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press-molded at a pressure of 9.8 × 10 ⁷ Pa (1 ton / cm ² ). A colored resin plate having a thickness of 1 mm was obtained. The dispersion state of the obtained colored resin plate was 5, the hue was L ^* value 26.15, and the light resistance was ΔE ^* value 2.13.

Three test pieces obtained by cutting a colored resin plate into a 1.5 cm square were put in a gear oven heated to 190 ° C., and taken out one by one every 30 minutes to examine the state of resin deterioration. The degree of resin deterioration (S / S ₀ × 100) was 0%, the degree of resin deterioration after 60 minutes was 0%, and the degree of resin deterioration after 120 minutes was 0%.

Examples 20-24, Comparative Examples 16-21:
A resin composition was obtained in the same manner as in Example 19 except that the type and addition amount of the black particle powder were variously changed.

  Table 6 shows the production conditions and various characteristics of the obtained resin composition.

The black composite particle powder according to the present invention is suitable as a coloring material for paints, inks, resins, and the like because it is excellent in dispersibility and filling properties in a vehicle and exhibits excellent blackness with a small addition amount.

Claims (4)

A black composite particle powder characterized in that at least a part of the particle surface of the carbon product particle powder is coated with a surface treating agent and a carbon component is present on the surface of the coating and / or the particle. A black composite particle powder in which at least a part of the particle surface of the carbon product particle powder is coated with a surface treatment agent and a carbon component is present on the surface of the coating and / or the particle, the black composite particle powder The black composite particle powder is characterized in that the change rate of the compression density of the powder is 20% or less. A paint comprising the black composite particle powder according to claim 1 or 2 blended in a paint constituting base material. A resin composition colored using the black composite particle powder according to claim 1.