JP5481907B2 - Black composite particle powder and method for producing the same, and paint, resin composition and optical material using the black composite particle powder - Google Patents

Description

  The present invention comprises a resin particle powder coated with carbon black on the particle surface, a black composite particle powder excellent in fluidity, coloring power and light absorption, and a dispersibility formed by blending the black composite particle powder. The present invention relates to a paint, a resin composition, and an optical material excellent in light resistance and light absorption.

  Today, many optical display devices using liquid crystal or the like have been developed. In such an optical display device, a light diffusing sheet for improving the visibility of an observer, or a light emission angle is controlled so that image information cannot be seen from surrounding people who can see the observer. A viewing angle control sheet may be incorporated.

  The light diffusion sheet has so far been (1) filled with inorganic particles or bubbles having a refractive index different from that of the film, (2) filled with organic resin particles having a refractive index different from that of the film, and (3) translucent light. (4) The surface is coated with particles having different refractive indexes, (5) The surface is filled with black light-absorbing particles to absorb incident stray light, etc. (For example, refer to Patent Document 1). The light-absorbing particles or the light-absorbing material is also used for the viewing angle control sheet (see, for example, Patent Document 2).

  For such light-absorbing particles and light-absorbing materials, carbon black, black inorganic pigments, resin particles colored with black pigments and dyes are generally used. Regarding the resin particles colored with black pigment, the applicant has also developed black composite particles in which the resin particle surface is coated with carbon black as black particles with excellent fluidity, coloring power and light resistance, and has already filed a patent application. (For example, refer to Patent Document 3).

JP 2008-90324 A JP 2008-175975 A JP 2004-300350 A

  The light-absorbing particles used for the light diffusion sheet and the like are required to have high light absorption and excellent handling properties. However, while carbon black has excellent light absorption properties, carbon black has poor dispersibility because it is a fine particle, and has a large bulk density, which causes many problems in handling. Black inorganic pigments generally have low blackness and do not have sufficient light absorption. Resin particles colored with a black pigment or dye are excellent in handling properties, but cannot be said to have sufficient light absorption. The black composite particles in which the resin particle surfaces described in Patent Document 3 are coated with carbon black are excellent in blackness and handling properties, but have sufficient light absorptivity as a light absorbing material for a light diffusion sheet or a viewing angle control sheet. It can not be said. As described above, until now, there is no particle powder having excellent handling properties and high light absorption required as a light absorption material for optical display devices, and development is awaited. Such a particle powder having excellent blackness and high light absorption and excellent handling properties is also required as a colorant for paints or resin compositions.

  An object of the present invention is to provide a black composite particle powder that is excellent in fluidity, coloring power, light absorption and handling properties and can be suitably used as an optical material.

  The object can be achieved by the present invention as follows.

That is, the present invention, after the resin particles and the surface modifier mixed and stirred by coating the surface modifier on the particle surfaces of the resin particles, carbon black was added, mixed and stirred to surface modification Carbon black is adhered to the particle surface of the agent-coated resin particles , and then heat-treated at a temperature of 100 ° C. or higher and lower than the glass transition point of the resin powder particles, and further comprising classified powder particles. A black composite particle powder having a geometric standard deviation of particle size of 1.50 or less (Invention 1).

In the present invention, 2 g of the measured particle powder and 20 ml of ethanol are added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed in a paint shaker for 60 minutes, and then centrifuged at 10,000 rpm for 15 minutes. The measured particle powder and the solvent portion are separated, the obtained measured particle powder is dried at 60 ° C. for 5 hours, and is detached in the field of view shown in the electron micrograph or optical micrograph. The number of carbon blacks desorbed from the composite particle powder and re-aggregated when measured by a method of visually observing the number of reaggregated carbon blacks is less than 30 per 100 composite particle powders. The black composite particle powder according to claim 1 (Invention 2 ).

Moreover, this invention is a coating material characterized by mix | blending the black composite particle powder of Claim 1 or 2 in the coating-material base material (this invention 3 ).

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

Moreover, this invention is an optical material obtained using the black composite particle powder of Claim 1 or 2 (Invention 5 ).

  The black composite particle powder according to the present invention is excellent in fluidity, coloring power and light absorption because carbon black adheres to the surface of the resin particle powder via the surface modifier and the geometric standard deviation of the particle size is small. Also, it can be suitably used as a light absorbing material for an optical display device. In addition, other black composite particle powders according to the present invention are excellent in fluidity, coloring power and light absorption, because carbon black is firmly attached to the surface of the resin particle powder via the surface modifier. It can also be suitably used as a light absorbing material for display devices.

  The paint and resin composition according to the present invention uses the above-mentioned black composite particle powder as a color pigment, and thus is excellent in dispersibility and light resistance, and is suitable as a paint and resin composition.

  In addition, since the optical material according to the present invention is obtained using the above black composite particle powder, it has high light absorption and is suitable as an optical material.

  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.

  The black composite particle powder according to the present invention is a composite particle powder in which the particle surface of the resin particle powder is coated with a surface modifier, and carbon black is adhered to the particle surface of the surface modifier-coated resin particle. The geometric standard deviation of the particle size of the composite particle powder is 1.50 or less. In another black composite particle powder according to the present invention, the particle surface of the resin particle powder is coated with a surface modifier, and carbon black is adhered to the particle surface of the surface modifier-coated resin particle. The number of carbon blacks made of the composite particle powder and desorbed from the composite particle powder and reaggregated when measured by a predetermined method is less than 30 per 100 composite particle powders.

  Among the black composite particle powders according to the present invention, a more preferable black composite particle powder is obtained by coating the surface of the resin particle powder with a surface modifier, and carbon black on the surface of the surface modifier-coated resin particle. Carbon black which is composed of composite particle powder to which is adhered, and whose geometric standard deviation of the particle size of the composite particle powder is 1.50 or less and which is separated from the composite particle powder and reaggregates when measured by a predetermined method Is less than 30 per 100 composite particle powders.

  As the resin particles in the present invention, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, thermoplastic resins include olefin resins (polyethylene, polypropylene, polybutylene), acrylic resins, styrene resins, vinyl resins, polyamide resins, polyester resins, polyurethanes, fluorinated resins, and fiber-based resins. As the thermosetting resin, silicone resin, phenol resin, urea resin, melamine resin, allyl resin, furan resin, unsaturated polyester resin, epoxy resin, polyimide, or the like can be used. The resin particles may be selected according to required properties and applications, but are preferably acrylic resins, olefin resins, styrene resins, polyamide resins, polyester resins, silicone resins, phenol resins, and epoxy resins.

  The particle shape of the resin particles may be any shape such as spherical shape, granular shape, needle shape, spindle shape, rice granular shape, flake shape, plate shape, and irregular shape. When the obtained black composite particle powder is used as a colorant such as a paint or a resin composition, or when used as an optical material such as a light diffusing sheet or a light absorbing material for a viewing angle control sheet, the sphericity (average particle diameter / A spherical or granular form having an average shortest diameter (hereinafter referred to as “sphericity”) of 1.0 or more and less than 2.0 is preferable, and the sphericity is more preferably 1.0 to 1.5.

  The particle size of the resin particle powder is not particularly limited and may be appropriately selected depending on the intended use of the resulting black composite particle powder. However, the surface of the resin particle powder is uniformly coated with a surface modifier and carbon black. In consideration of the uniform adhesion treatment by, the average particle diameter is preferably 0.01 μm to 1 cm.

  In particular, when the resulting black composite particle powder is used as a colorant for paints and resin compositions, the average particle size of the resin particle powder is preferably 0.01 to 300 μm, more preferably 0.015 to 200 μm, even more preferably 0.02 to 100 μm. In this case, if the average particle diameter exceeds 300 μm, the resulting black composite particles become coarse particles, which is not preferable because the coloring power is reduced. Moreover, when using the obtained black composite particle powder for a light absorbing material or the like, the average particle diameter of the resin particle powder is preferably 0.05 to 200 μm, more preferably 0.1 to 150 μm, and still more preferably 0. .2 to 100 μm. In this case, if the average particle diameter exceeds 200 μm, the resulting black composite particles become coarse particles, which is not preferable because the light absorption ability is reduced.

The BET specific surface area value of the resin particle powder is preferably 0.005 to 700 m ² / g in consideration of the uniform coating treatment with the surface modifier and the uniform adhesion treatment with carbon black on the particle surface of the resin particle powder.

In particular, when the obtained black composite particle powder is used as a colorant for paints and resin compositions, the BET specific surface area value of the resin particle powder is preferably 0.005 to 700 m ² / g, more preferably. It is 0.01-500 m < ² > / g, More preferably, it is 0.01-400 m < ² > / g. In this case, when the BET specific surface area value is less than 0.005 m ² / g, the resulting black composite particles become coarse particles, which is not preferable because the coloring power is reduced. Further, when the obtained black composite particle powder is used as a light absorbing material of an optical material, the BET specific surface area value of the resin particle powder is preferably 0.01 to 300 m ² / g, more preferably 0.01. 200 m ² / g, even more preferably 0.01~100m ² / g. In this case, when the BET specific surface area value is less than 0.01 m ² / g, the resulting black composite particles become coarse particles, which is not preferable.

The hue of the resin particle powder in the present invention is preferably as colorless as possible, the L ^* value is 70.0 or more, more preferably 75.0 or more, and the C ^* value is 18.0 or less, preferably Is 15.0 or less, more preferably 12.0 or less, and even more preferably 9.0 or less. When the L ^* value and the C ^* value are out of the above ranges, it is difficult to say that the hue is colorless and it is difficult to obtain the black composite particle powder having excellent blackness as the object of the present invention. .

  The fluidity of the resin particle powder in the present invention varies depending on the shape and the like, but generally has 55 or more. In particular, those having a spherical particle shape have high fluidity, and in this case, 60 or more.

With respect to the light resistance of the resin particle powder 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.

  Any surface modifier may be used as the surface modifier in the present invention as long as it can attach carbon black to the particle surface of the resin particles, and preferably alkoxysilane, fluoroalkylsilane, silane coupling agent and organopolysiloxane. 1 type or 2 types or more of coupling agents such as organosilicon compounds such as titanate series, aluminate series and zirconate series, low molecular or high molecular surfactants, etc., more preferably alkoxysilane, fluoroalkylsilane, silane Coupling agents, organosilicon compounds such as organopolysiloxanes, titanates, aluminates and zirconates.

  Examples of organosilicon compounds include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, ethyltriethoxysilane, 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, Silanes such as γ-methacryloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, trimethylchlorosilane And coupling agents, organopolysiloxanes such as polysiloxane, methyl hydrogen polysiloxane, and modified polysiloxane.

  Examples of titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2- Examples include 2-diallyloxymethyl-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 tributoxymonoethylacetoacetate, 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 modifying agent is preferably 0.02 to 5.0% by weight in terms of the element of the metal contained in each surface modifying agent with respect to the surface modifying agent-coated resin particle powder, more preferably 0. It is 03 to 4.0 weight%, Most preferably, it is 0.05 to 3.0 weight%. In the case of a surfactant that does not contain a metal, 0.01 to 15.0% by weight in terms of C with respect to the surface modifier-coated resin particle powder is preferable, and more preferably 0.02 to 12.5. % By weight, most preferably 0.03 to 10.0% by weight.

  When the amount is less than the lower limit, it is difficult to attach 0.001 part by weight or more of carbon black to 100 parts by weight of the resin particle powder. When the above upper limit is exceeded, 0.001 to 2000 parts by weight of carbon black can be attached to 100 parts by weight of the resin particle powder, so there is no point in covering more than necessary.

  As the carbon black used for the adhesion treatment, carbon black particle powders such as furnace black, channel black, and acetylene black can be used.

  Specifically, as carbon black, # 3050, # 3150, # 3250, # 3750, # 3950, MA100, MA7, # 1000, # 2400B, # 30, MA77, MA8, # 650, MA11, # 50, # 52, # 45, # 2200B, MA600, etc. (all are trade names of Mitsubishi Chemical Corporation), Seast 9H, Seast 7H, Seast 6, Seast 3H, Seast 300, Seast FM, etc. These are all trade names of Tokai Carbon Co., Ltd.), Raven 1250, Raven 860, Raven 1000, Raven 1190 ULTRA (all are trade names of Colombian Chemicals Company). , Ketjen Black EC, Ketjen Black EC600 D (all are trade names of Ketjen Black International Co., Ltd.), BLACK PEARLS-L, BLACK PEARLS 1000, BLACK PEARLS 4630, VULCAN XC72, REGAL 660, REGAL 400 (all above) Cabot Specialty Chemicals, Inc. (trade name), etc.) can be used.

  The amount of carbon black attached varies depending on the surface area of the resin particle powder, but is preferably 0.001 to 2000 parts by weight, more preferably 0.005 to 1000 parts by weight, and still more preferably 100 parts by weight of the resin particle powder. Is 0.01 to 500 parts by weight.

  When the amount is less than 0.001 part by weight, the amount of carbon black covering the particle surface of the resin particles is too small, so that it is difficult to obtain black composite particle powder having high coloring power and light absorptivity targeted by the present invention. It becomes. When the amount exceeds 2000 parts by weight, the carbon black adheres so much that the carbon black is easily detached, and as a result, dispersibility in the paint vehicle and the resin composition is lowered. Similarly, when used as a light absorbing material or the like, the dispersibility and the light absorbing property are lowered.

  The fluidity of carbon black in the present invention is usually around 20, and in the case of granulated carbon black, it has a slightly high value.

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

  The particle shape of the black composite particle powder according to the present invention may be any shape such as spherical shape, granular shape, needle shape, spindle shape, rice granular shape, flake shape, plate shape, and irregular shape. When the black composite particle powder according to the present invention is used as a colorant such as a paint or a resin composition, or when used as a light absorber or the like, a sphere having a sphericity of 1.0 or more and less than 2.0 is preferred. More preferably, it is 1.0-1.5.

  The particle size of the black composite particle powder according to the present invention is not particularly limited and may be appropriately selected depending on the intended use. The average particle diameter is preferably 0.01 μm to 1 cm.

  In particular, when the black composite particle powder according to the present invention is used as a coloring material for paints and resin compositions, the average particle diameter of the black composite particle powder is preferably 0.01 to 300 μm, more preferably 0.00. It is 015-200 micrometers, More preferably, it is 0.02-100 micrometers. When the average particle diameter exceeds 300 μm, the particle size is too large, so that the coloring power is lowered, which is not preferable as a coloring material for paints and resin compositions. Further, when the average particle size is less than 0.01 μm, it may be difficult to disperse in the paint vehicle or the resin composition.

  In addition, when the obtained black composite particle powder is used as a light absorbing material or the like, the average particle diameter of the black composite particle powder is preferably 0.05 to 200 μm, more preferably 0.1 to 150 μm, and still more preferably. 0.2 to 100 μm. When the average particle diameter exceeds 200 μm, the particle size is too large, so that the light absorptivity is lowered and it is not preferable as a light absorbing material for optical materials.

  The black composite particle powder according to the present invention preferably has a geometric standard deviation of an average particle diameter of 1.50 or less. By setting the geometric standard deviation of the average particle diameter to 1.50 or less, the particle size distribution becomes sharp. Particularly when used as a light absorbing material such as a light diffusion sheet, the dispersibility is improved and the light absorbing property is increased. .

The BET specific surface area value of the black composite particle powder according to the present invention is not particularly limited and may be appropriately selected depending on the application, but is preferably 0.005 to 700 m ² / g.

In particular, when the black composite particle powder according to the present invention is used as a coloring material for paints and resin compositions, the BET specific surface area value of the black composite particle powder is preferably 0.005 to 700 m ² / g, more preferably. Is 0.01 to 500 m ² / g, and even more preferably 0.01 to 400 m ² / g. When the BET specific surface area value is less than 0.005 m ² / g, it becomes coarse particles and the coloring power is lowered, which is not preferable as a coloring material for paints and resin compositions. When the BET specific surface area value exceeds 700 m ² / g, it is difficult to disperse in the paint vehicle or the resin composition. In addition, when the black composite particle powder according to the present invention is used as a light absorbing material for an optical material, the BET specific surface area value of the black composite particle powder is preferably 0.01 to 300 m ² / g, more preferably 0.00. 01~200m ² / g, even more preferably 0.01~100m ² / g. When the BET specific surface area value is less than 0.01 m ² / g, it is not preferable because it becomes coarse particles and the light absorptivity decreases.

The blackness of the black composite particle powder according to the present invention is preferably an L ^* value of 50.0 or less, more preferably 45.0 or less, and most preferably 40.0 or less. When the L ^* value exceeds 50.0, it is difficult to say that the brightness is high and the blackness is excellent. The lower limit of the L ^* value is preferably as low as possible, but industrially it is about 16.0.

  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 still more preferably 115% or more according to the evaluation method described later.

  The fluidity of the black composite particle powder according to the present invention maintains the fluidity of the resin particle powder as the core particle even when carbon black having poor fluidity is adhered to the particle surface, and has a fluidity of 55 or more. . In particular, those having a spherical particle shape have 60 or more, preferably 65 or more.

In the evaluation method described later, the light resistance of the black composite particle powder according to the present invention is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less in ΔE ^* value.

  The degree of carbon black desorption from the black composite particle powder according to the present invention is determined by the number of carbon blacks desorbed and re-aggregated from the black composite particle powder in the visual evaluation in a later evaluation method. Less than 30 per hit is preferred. More preferably, the number of carbon blacks desorbed and reaggregated from the black composite particle powder is less than 10 per 100 black complex particle powders, and even more preferably desorbed from the black composite particle powder and reaggregates. The number of carbon blacks is less than 5 per 100 black composite particle powders. If the degree of carbon black desorption is less than 30 per 100 black composite particle powders, the desorbed carbon black does not inhibit uniform dispersion in the paint vehicle or resin composition, and uniform hue. Can be obtained. Similarly, when blended in a light diffusion sheet or the like, if the degree of carbon black desorption is less than 30 per 100 black composite particle powders, uniform dispersion is not hindered by the desorbed carbon black, which is high. Shows light absorption.

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

When the paint containing the black composite particle powder according to the present invention is used as a coating film, the light resistance ΔE ^* value of the coating film is preferably 5.0 or less, more preferably 4.2 or less. Further, the transmittance of the coating film is 10.0 or less, preferably 9.0 or less in the evaluation method described later, and the optical density is 2.00 or more, preferably 2.03 or more, in the evaluation method described later. It is.

When the water-based paint blended with the black composite particle powder according to the present invention is used as a coating film, the light resistance ΔE ^* value of the coating film is preferably 5.0 or less, more preferably 4.2 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 ether solvents such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve, and 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 colored using the black composite particle powder according to the present invention will be described.

The resin composition colored using the black composite particle powder according to the present invention has a dispersion state by visual observation of 3, 4 or 5, preferably 4 or 5, more preferably 5, according to the following evaluation method. The light resistance ΔE ^* value of the composition is 5.0 or less, preferably 4.0 or less.

The dispersibility of the black composite particle powder in the resin composition is 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 was not recognized,
4: 1 or more and 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 .

  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 known thermoplastic resins, and additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, various stabilizers, etc., as 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.

  In the resin composition according to the present invention, the resin raw material and the black composite particle powder are mixed well in advance, and then a strong shearing action is applied under heating using a kneader or an extruder, so that the black composite is contained in the resin composition. After the particle powder is uniformly dispersed, it is molded into a shape suitable for the purpose and used.

  Next, an optical material obtained using the black composite particle powder according to the present invention will be described.

  The optical material according to the present invention is an optical display device or the like incorporating a light diffusion sheet, a viewing angle control sheet, or the like filled with the black composite particle powder according to the present invention as a light absorbing material for absorbing incident stray light. .

  As the resin constituting the light diffusion sheet and the viewing angle control sheet in the present invention, urethane acrylate having ionizing radiation curability can be used.

  The blending ratio of the black composite particle powder in the resin composition constituting the light diffusion sheet and the viewing angle control sheet in the present invention is preferably 10 to 70% by weight, more preferably 20 to 60% by weight.

  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 resin particle powder and a surface modifier, coating the particle surface of the resin particle powder with the surface modifier, and then coating the resin particles with the surface modifier. It can be obtained by mixing powder and carbon black, adhering carbon black to the particle surface of the surface modifying agent-coated resin particles, drying it if necessary, and then classifying these.

  In another black composite particle powder according to the present invention, the resin particle powder and the surface modifier are mixed, the particle surface of the resin particle powder is coated with the surface modifier, and then coated with the surface modifier. The resin particle powder and carbon black are mixed, and the carbon black is adhered to the surface of the surface modifier-coated resin particles, and then heat-treated at a temperature of 100 ° C. or higher and lower than the glass transition point of the resin powder particles. Can be obtained at

  Of the black composite particle powders according to the present invention, a more preferable black composite particle powder is obtained by mixing resin particle powder and a surface modifier, coating the particle surface of the resin particle powder with the surface modifier, and then modifying the surface. The resin particle powder coated with the material and carbon black are mixed, and the carbon black is adhered to the particle surface of the surface modifier-coated resin particles, and then the temperature is 100 ° C. or higher and below the glass transition point of the resin powder particles. It can be obtained by heat treatment at a temperature and further classifying them.

  The surface of the resin particle powder with the surface modifier is coated by mechanically mixing and stirring the resin particle powder and the surface modifier or a solution of the surface modifier. What is necessary is just to mix and stir mechanically, spraying a solution or a surface modifier. Almost all of the added surface modifier is coated on the particle surface of the resin particle powder.

  As a device for mixing and stirring the resin particle powder and the surface modifier, and mixing and stirring the carbon black and the resin particle powder whose surface is coated with the surface modifier, a shear force is applied to the powder layer. A device capable of simultaneously performing shearing, spatula and compression, for example, a wheel-type kneader, a ball-type kneader, a blade-type kneader, a roll-type kneader, and a wheel can be used. A mold kneader and a ball 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-type kneader include a vibration mill, a rotary mill, a sand grinder, and preferably 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.

  After the surface modifier is coated on the surface of the resin particle powder, carbon black is added, mixed and stirred to adhere the carbon black to the surface modifier-coated resin particle surface.

  The heating temperature when heat treatment is performed after carbon black is attached is 100 ° C. or higher, preferably 110 ° C. or higher, more preferably 120 ° C. or higher. The upper limit of the heating temperature is the glass transition point of the resin particle powder. The heating time when the heat treatment is performed is preferably 10 minutes to 6 hours, more preferably 30 minutes to 3 hours.

  In addition, when alkoxysilane and fluoroalkylsilane are used as surface modifiers, the fluorosilane containing organosilane compound or fluoroalkylsilane finally produced from alkoxysilane is obtained through these steps. It is coated as a silane compound.

  In the case of performing classification treatment, any of dry classification, wet classification, and sieving may be used as a technique, but from the industrial viewpoint, dry classification and sieving that can be performed by a dry process are preferable.

  A typical embodiment of the present invention is as follows.

  The average particle size of particles having a particle size of less than 100 μm was photographed using an electron microscope, the particle size of 350 particles shown therein was measured, and the average value was shown. For particles having a particle size of about 100 μm to 5 mm, photographs were taken using an optical microscope, the particle diameters of 350 particles shown therein were measured, and the average value was shown. In the case of particles having a particle size of 5 mm or more, 100 particle diameters were measured using calipers, and the average value was shown.

  The particle size distribution of the particle size was indicated by a geometric standard deviation value obtained by the following method.

  That is, the value obtained by measuring the particle diameter by the above method is calculated from the measured value, and the particle diameter is plotted on the horizontal axis on the lognormal probability paper from the actual particle diameter and the number of particles determined according to the statistical method, and the vertical axis. The cumulative number of particles belonging to each of the predetermined particle diameter sections (under the integrated sieve) is plotted as a percentage. Then, from this graph, the particle diameter values corresponding to the number of particles of 50% and 84.13% are read, and the geometric standard deviation value = particle diameter under integrated fluid 84.13% / under integrated fluid 50%. The value was calculated according to the particle diameter (geometric mean diameter). The closer the geometric standard deviation value is to 1, the better the particle size distribution of the particle diameter.

  The sphericity is indicated by the ratio between the average particle diameter (average longest diameter) and the average shortest diameter.

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

  The flowability of the resin particle powder, carbon black and black composite particle powder is determined by using a powder tester (manufactured by Hosokawa Micron Co., Ltd.), the angle of repose (degree), the degree of compression (%), the spatula angle (degree), and the degree of aggregation. Each powder characteristic value was measured, each index was obtained by replacing each measured value with a numerical value of the same standard, and each index was indicated as a total fluidity index. The closer the fluidity index is to 100, the better the fluidity.

The hue of the resin particle powder, the blackness of the carbon black and the black composite particle powder are prepared by pasting 0.5 g of a sample and 0.5 ml of castor oil with a Hoover-type Mahler into a paste, and adding 4.5 g of clear lacquer to this paste. Then, an application piece (coating thickness: about 30 μm) was prepared by kneading, coating, and applying onto a cast-coated paper using a 150 μm (6 mil) applicator, and “spectral colorimeter CM-3610d” ( Measurement was performed using Minolta Co., Ltd., and the color index was shown in accordance with JIS Z 8729. The C ^* value represents saturation and can be determined according to the following formula (1).

C ^* value = ((a ^* value) ² + (b ^* value) ² ) ^1/2 (1)

  The coating amount of the surface modifier coated on the surface of the resin particle powder is “X-ray fluorescence analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) for the metal contained in each surface modifier. Was measured in accordance with “General X-ray fluorescence analysis rules” of JIS K0119.

  The coating amount of carbon black adhering to the black composite particle powder is measured by the following procedure using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 Model” (manufactured by Horiba, Ltd.). Was determined by The amount of carbon per unit weight of the resin particle powder that is the core particle is measured in advance, and then the amount of carbon of the black composite particle powder is measured. The amount was determined.

  The degree of desorption of the carbon black adhering to the black composite particle powder was evaluated visually in five stages by the following method. 5 indicates that the amount of carbon black desorbed from the particle surface of the composite particle is small.

  2 g of particles to be measured and 20 ml of ethanol are added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed in a paint shaker for 60 minutes, and then centrifuged at 10,000 rpm for 15 minutes to measure particles to be measured. The powder and solvent part were separated. The obtained particles to be measured were dried at 60 ° C. for 5 hours, and the number of detached and re-aggregated carbon black present in the field of view shown in the electron micrograph or optical micrograph was visually observed, and the resin The particle powder and carbon black were evaluated in five stages as compared with an electron micrograph or an optical micrograph of a mixed particle powder simply mixed without using a surface modifier.

1: The same level as when resin particle powder and carbon black are simply mixed without a surface modifier.
2: 30 or more and less than 50 per 100 black composite particle powders.
3: 10 or more and less than 30 per 100 black composite particle powders.
4: About 5 or more per 100 black composite particle powders.
5: Less than 5 per 100 black composite particle powders.

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

Next, as a standard sample of the black composite particle powder, a mixed particle powder obtained by simply mixing carbon black and resin particle powder in the same proportion as the black composite particle powder was used, and the primary color enamel and the color-enameled enamel were processed in the same manner as described above. A coated piece was prepared, the L ^* value of each coated piece was measured, and the difference was taken as the ΔLs ^* value.

Using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the obtained black composite particles showed the calculated value as the tinting strength (%) according to the following equation (2).

Tinting strength (%) = 100 + {( ΔLs * value -Delta L ^* value) × 10} ··· (2)

Production of primary color enamel:
3 g of the above sample powder, 16 g of aminoalkyd resin and 10 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 60 minutes with a paint shaker, and then 50 g of aminoalkyd 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 light resistance of the resin particle powder, carbon black, and black composite particle powder is determined by using the primary color enamel prepared for measuring the coloring power as described above as a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141). 150 μm thick, coated and dried to form a coating film, half of the obtained coating for measurement was covered with a metal foil, and “I Super UV Tester SUV-W13 (Iwasaki Electric Co., Ltd.) was used. , After continuously irradiating with ultraviolet rays at an irradiation intensity of 100 mW / cm ² for 6 hours, the hue (L ^* value, a ^* value, b ^*) between the portion not irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays by covering with metal foil Value) was measured, and indicated by ΔE ^* value calculated according to the following formula (3) with reference to the measured value of the portion not irradiated with ultraviolet rays.

ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2 (3)
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

  A coating film for measuring the transmittance of the solvent-based paint using the black composite resin particle powder was prepared by the following method. 0.1 g of sample and 0.5 ml of castor oil were kneaded with a Hoover-type Mahler to make a paste. To this paste, 4.5 g of clear lacquer was added, kneaded and coated, and a 150 μm (6 mil) applicator was used on the transparent film. A coated piece (coating thickness: about 30 μm) was prepared. The transmittance was measured using a “Shimadzu spectrophotometer, UV-2100 (PC) S” (manufactured by Shimadzu Corporation), and indicated by the transmittance at a wavelength of 550 nm.

  A coating film for measuring the optical density of the solvent-based paint using the black composite resin particle powder was prepared by the following method. 0.25 g of sample and 0.5 ml of castor oil were kneaded with a Hoover-type Mahler to form a paste. To this paste, 4.5 g of clear lacquer was added, kneaded and coated, and a 150 μm (6 mil) applicator was used on cast-coated paper. A coated piece (coating thickness: about 30 μm) was prepared. The optical density was measured using “X-Rite 939” (manufactured by X-Rite Co., Ltd.).

The light resistance of the coating film using each paint was applied to each cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) with a thickness of 150 μm and dried by preparing each paint prepared according to the formulation described below. Half of the coating for measurement obtained by forming the coating film was covered with a metal foil, and using “I Super UV Tester SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.), ultraviolet rays were applied at an irradiation intensity of 100 mW / cm ² . After 6 hours of continuous irradiation, the hue (L ^* value, a ^* value, b ^* value) of the part that was not irradiated with ultraviolet light and the part that was irradiated with ultraviolet light was measured by covering with a metal foil. Based on the measured value of the part that was not performed, it was shown by the ΔE ^* value calculated according to the equation (3).

  The most important point in the present invention is a composite particle powder in which the particle surface of the resin particle powder is coated with a surface modifier, and carbon black is attached to the surface modifier-coated resin particle surface, The black composite particle powder having a geometric standard deviation of the particle size of the composite particle powder of 1.50 or less suppresses the detachment of carbon black from the particle surface of the resin particle powder, and has fluidity, coloring power and light. It is the fact that it has excellent absorbency.

  Regarding the reason why the flowability of the black composite particle powder according to the present invention is excellent, the present inventor generally added that carbon black having poor flowability is prevented from desorbing from the particle surface of the resin particles. In addition, the aggregated state of the carbon black is unraveled, and an adhesion layer is formed on the surface of the resin particles that are the core particles in a refined state. This is thought to be due to the fact that it could be expressed as it was without being inhibited. Further, it is considered that the geometric standard deviation of the particle size is as small as 1.50 or less and the sharp particle size distribution contributes to the improvement of fluidity.

  And when the coating material which mix | blended the said black composite particle powder was used as the coating film, it is the fact that light absorptivity is excellent, specifically, the transmittance | permeability is small and optical density is large.

  In the case of the black composite particle powder according to the present invention, the present inventors have suppressed the detachment of carbon black from the particle surface for the reason that the light absorption is excellent when the paint according to the present invention is used as a coating film. In addition, since the geometric standard deviation of the particle size is as small as 1.50 or less and the particle size distribution is sharp, it is considered that the dispersibility when formed into a coating film is improved and the light absorption is increased.

  In the present invention, the most important point is that the particle surface of the resin particle powder is coated with a surface modifier, and the composite particle powder in which carbon black is adhered to the surface modifier-coated resin particle surface. The black composite particle powder in which the number of carbon blacks desorbed and reaggregated from the composite particle powder when measured by a predetermined method is less than 30 per 100 composite particle powders is the particle surface of the resin particle powder. This is the fact that the detachment of carbon black from the resin is suppressed and the fluidity, coloring power and light absorption are excellent.

  In the present invention, the reason why the detachment of the carbon black from the particle surface of the resin particle powder is suppressed is as follows. By performing the heat treatment at a temperature not higher than the glass transition point of the resin powder particles as described above, the reaction of the surface modifier is completed, and the carbon black, the surface modifier, and the surface reformer on which the carbon black is adhered. This is because the agent is firmly bonded to the particle surface of the resin particles.

Next, examples and comparative examples are shown.

Core particles 1-9:
Resin particle powder having the characteristics shown in Table 1 was prepared as the core particle powder. PMMA is an abbreviation for polymethyl methacrylate.

Carbon black A to C:
Carbon black having various characteristics shown in Table 2 was prepared as carbon black.

Example 1
<Manufacture of black composite particle powder>
Resin particle powder (core particle 1) (type: polymethyl methacrylate (PMMA), particle shape: spherical, average particle size: 2.18 μm, sphericity: 1.03, BET specific surface area value: 2.50 m ² / g, 700 g of fluidity: 70, light resistance ΔE ^* value: 9.59) was put into a vibration mill “MB1” (media: φ1 / 4 inch chrome hard ball 10 kg) (product name, Chuo Kako Co., Ltd.) 35 g of 3-aminopropyltriethoxysilane (trade name: GENIOSIL GF91: manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was added, and the mixture was stirred for 30 minutes at a rotation speed of 1200 rpm and an amplitude of 6 mm.

Next, carbon black A (type: channel black, particle shape: granular, average particle size: 0.011 μm, BET specific surface area value: 324.7 m ² / g, fluidity: 18, blackness L ^* value: 25. 2) 140 g was added, and further mixed and stirred for 30 minutes. After carbon black was deposited on the 3-aminopropyltriethoxysilane coating, heat treatment was performed at 120 ° C. for 90 minutes using a dryer. Thereafter, the mixture was cooled and classified to obtain black composite particle powder.

The obtained black composite particle powder was a spherical particle powder having an average particle diameter of 2.53 μm and a sphericity of 1.03. The BET specific surface area value is 22.82 m ² / g, the fluidity is 71, the blackness L ^* value is 24.9, the coloring power is 118%, the light resistance ΔE ^* value is 3.41, and the geometric standard deviation σg is 1. 42. Desorption degree of carbon black was 5. The coating amount of 3-aminopropyltriethoxysilane is 0.601% by weight in terms of Si, and the amount of adhering carbon black is 16.80% by weight in terms of C (based on 100 parts by weight of resin particle powder). Equivalent to about 20 parts by weight).

  As a result of observing an electron micrograph, since almost no carbon black was observed, it was confirmed that almost all of the carbon black was attached to the 3-aminopropyltriethoxysilane coating.

Examples 2 to 9 , Comparative Examples 1 and 2:
Other than changing the type and amount of additive in the coating step with the surface modifier, the type and amount of carbon black in the carbon black adhesion step, the heat treatment temperature in the heat treatment step, the heat treatment time and the presence or absence of classification Produced black composite particle powder in the same manner as in Example 1. In addition, the comparative example 2 is resin particle powder (trade name: Love Color: manufactured by Dainichi Seika Kogyo Co., Ltd.) enclosing carbon black.

  The production conditions at this time are shown in Table 3, and various characteristics of the obtained black composite particle powder are shown in Table 4. From Table 4, it can be seen that by performing the heat treatment, the separation rate of carbon black is improved.

Example 10
<Manufacture of solvent-based paint containing black composite particle powder>
10 g of the black composite particle powder obtained in Example 1 above, 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, then mixed and dispersed for 90 minutes with a paint shaker, mill base Was made.

3.8 parts by weight of black composite particle powder,
Amino alkyd resin 20.3 parts by weight,
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 12.7 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.

36.8 parts by weight of mill base,
Aminoalkyd resin 63.3 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The light resistance ΔE ^* value of the coating film obtained by applying the solvent-based paint to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 3.71. there were.

  Moreover, the coating film for a transmittance | permeability measurement was separately produced by the above-mentioned method using 0.1 g of black composite particle powder obtained in Example 1. The transmittance of the coating film was 6.9%.

  Moreover, the coating film for an optical density measurement was produced separately by the above-mentioned method using 0.25g of the black composite particle powder obtained in Example 1. The optical density of the coating film was 2.28.

Examples 11 to 15 and Comparative Examples 3 and 4
A solvent-based paint was obtained in the same manner as in Example 10 except that the type of the black particle powder was variously changed. Further, the transmittance and optical density of the coating film were evaluated in the same manner as in Example 10 .

  Table 5 shows the production conditions and various properties of the coating film. By producing a paint using the black composite particle powder according to the present invention and making it a coating film, the transmittance is reduced and the optical density is lower than when the black composite particle powder shown in the comparative example is used. Rose.

Claims (5)

After the resin particles and the surface modifier mixed and stirred by coating the surface modifier on the particle surfaces of the resin particles, adding carbon black, particles of mixed stirred to surface modifier coating resin particles Carbon black is adhered to the surface, and then heat-treated at a temperature of 100 ° C. or higher and lower than the glass transition point of the resin powder particles, and further classified , and the geometric standard deviation of the particle size of the composite particle powder Is a black composite particle powder, characterized in that it is 1.50 or less.   2 g of particles to be measured and 20 ml of ethanol are added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed in a paint shaker for 60 minutes, and then centrifuged at 10,000 rpm for 15 minutes to measure particles to be measured. The powder and solvent portion are separated, and the obtained particle powder to be measured is dried at 60 ° C. for 5 hours, and is detached and re-agglomerated in the field of view shown in the electron micrograph or optical micrograph. The number of carbon blacks desorbed from the composite particle powder and reaggregated when measured by a method of visually observing the number of particles is less than 30 per 100 composite particle powders. The black composite particle powder described.   A paint comprising the black composite particle powder according to claim 1 blended in a paint constituting base material.   A resin composition colored using the black composite particle powder according to claim 1.   An optical material obtained by using the black composite particle powder according to claim 1.